scholarly journals Thermodynamic and Structural Modelling of Non-Stoichiometric Ln-Doped UO2 Solid Solutions,Ln = {La, Pr, Nd, Gd}

2021 ◽  
Vol 9 ◽  
Author(s):  
Victor L. Vinograd ◽  
Andrey A. Bukaemskiy ◽  
G. Modolo ◽  
G. Deissmann ◽  
D. Bosbach
Keyword(s):  
Solid Solutions ◽  
Thermodynamic Model ◽  
Structural Model ◽  
Chemical Potential ◽  
Configurational Entropy ◽  
Lattice Parameter ◽  
Lattice Contraction ◽  
Coordination Numbers ◽  
Ideal Mixing ◽  
The One

Available data on the dependence of the equilibrium chemical potential of oxygen on degrees of doping, z, and non-stoichiometry, x, y, in U1-zLnzO2+0.5(x-y) fluorite solid solutions and data on the dependence of the lattice parameter, a, on the same variables are combined within a unified structural-thermodynamic model. The thermodynamic model fits experimental isotherms of the oxygen potential under the assumptions of a non-ideal mixing of the endmembers, UO2, UO2.5, UO1.5, LnO1.5, and Ln0.5U0.5O2, and of a significant reduction in the configurational entropy arising from short-range ordering (SRO) within cation-anion distributions. The structural model further investigates the SRO in terms of constraints on admissible values of cation coordination numbers and, building on these constraints, fits the lattice parameter as a function of z, y, and x. Linking together the thermodynamic and structural models allows predicting the lattice parameter as a function of z, T and the oxygen partial pressure. The model elucidates contrasting structural and thermodynamic changes due to the doping with LaO1.5, on the one hand, and with NdO1.5 and GdO1.5, on the other hand. An increased oxidation resistance in the case of Gd and Nd is attributed to strain effects caused by the lattice contraction due to the doping and to an increased thermodynamic cost of a further contraction required by the oxidation.

Structure, Stability and Water Adsorption on Ultra-Thin TiO2 Supported on TiN

2019 ◽  
Author(s):  
Jose Julio Gutierrez Moreno ◽  
Marco Fronzi ◽  
Pierre Lovera ◽  
alan O'Riordan ◽  
Mike J Ford ◽  
...  
Keyword(s):  
Density Functional ◽  
Water Adsorption ◽  
Chemical Potential ◽  
Energy Gap ◽  
Molecular Water ◽  
Structure Stability ◽  
Ambient Conditions ◽  
Rutile Structure ◽  
The Stability ◽  
The One

<p></p><p>Interfacial metal-oxide systems with ultrathin oxide layers are of high interest for their use in catalysis. In this study, we present a density functional theory (DFT) investigation of the structure of ultrathin rutile layers (one and two TiO<sub>2</sub> layers) supported on TiN and the stability of water on these interfacial structures. The rutile layers are stabilized on the TiN surface through the formation of interfacial Ti–O bonds. Charge transfer from the TiN substrate leads to the formation of reduced Ti<sup>3+</sup> cations in TiO<sub>2.</sub> The structure of the one-layer oxide slab is strongly distorted at the interface, while the thicker TiO<sub>2</sub> layer preserves the rutile structure. The energy cost for the formation of a single O vacancy in the one-layer oxide slab is only 0.5 eV with respect to the ideal interface. For the two-layer oxide slab, the introduction of several vacancies in an already non-stoichiometric system becomes progressively more favourable, which indicates the stability of the highly non-stoichiometric interfaces. Isolated water molecules dissociate when adsorbed at the TiO<sub>2</sub> layers. At higher coverages the preference is for molecular water adsorption. Our ab initio thermodynamics calculations show the fully water covered stoichiometric models as the most stable structure at typical ambient conditions. Interfacial models with multiple vacancies are most stable at low (reducing) oxygen chemical potential values. A water monolayer adsorbs dissociatively on the highly distorted 2-layer TiO<sub>1.75</sub>-TiN interface, where the Ti<sup>3+</sup> states lying above the top of the valence band contribute to a significant reduction of the energy gap compared to the stoichiometric TiO<sub>2</sub>-TiN model. Our results provide a guide for the design of novel interfacial systems containing ultrathin TiO<sub>2</sub> with potential application as photocatalytic water splitting devices.</p><p></p>

Comparison of a Non Electrostatic Surface Complexation Model and Surface Phase Theories for Prediction of Future Sorption Properties.

2004 ◽  
Vol 824 ◽  
Author(s):  
Allan T. Emrén ◽  
Anna-Maria Jacobsson
Keyword(s):  
Aqueous Solution ◽  
Chemical Potential ◽  
Surface Complexation ◽  
Sorption Properties ◽  
Phase Method ◽  
Detailed Knowledge ◽  
Surface Phase ◽  
Surface Complexation Model ◽  
Advantages And Disadvantages ◽  
The One

AbstractIn performance assessments, sorption of radionuclides dissolved in groundwater is mostly handled by the use of fixed Kd values. It has been well known that this approach is unsatisfying. Only during the last few years, however, tools have become available that make it possible to predict the actual Kd value in an aqueous solution that differs from the one in which the sorption properties were measured.One such approach is surface complexation (SC) that gives a detailed knowledge of the sorption properties. In SC, one tries to find what kinds of sorbed species are available on the surface and the thermodynamics for their formation from species in the bulk aqueous solution. Recently, a different approach, surface phase method (SP), has been developed. In SP, a thin layer including the surface is treated as a separate phase. In the bulk aqueous solution, the surface phase is treated as a virtual component, and from the chemical potential of this component, the sorption properties can be found.In the paper, we compare advantages and disadvantages of the two kinds of models. We also investigate the differences in predicted sorption properties of a number of radionuclides (Co, Np, Th and U). Furthermore, we discuss under which circumstances, one approach or the other is preferable.

The Solid Solutions Gd2Cu2In1–xMgx – Drastic Increase of the Curie Temperature upon In/Mg Substitution

2010 ◽  
Vol 65 (12) ◽  
pp. 1516-1520 ◽  
Author(s):  
Wilfried Hermes ◽  
Falko M. Schappacher ◽  
Rainer Pöttgen
Keyword(s):  
Curie Temperature ◽  
Intermetallic Compounds ◽  
Solid Solutions ◽  
Temperature Increase ◽  
Magnesium Content ◽  
Lattice Parameter ◽  
Weiss Constant ◽  
Drastic Increase ◽  
Complete Set ◽  
Mg Substitution

The Mo2B2Fe-type intermetallic compounds Gd2Cu2In and Gd2Cu2Mg form a complete set of solid solutions Gd2Cu2In1−xMgx. The a lattice parameter, the Weiss constant and the Curie temperature increase with increasing magnesium content in an almost Vegard-like manner, while the c parameter remains almost constant. All members of the solid solutions show ferromagnetism with TCs between 114 and 80 K.

scholarly journals EFFECT OF A LOCALLY REPULSIVE INTERACTION ON s-WAVE SUPERCONDUCTORS

2010 ◽  
Vol 22 (03) ◽  
pp. 233-303 ◽  
Author(s):  
J.-B BRU ◽  
W. DE SIQUEIRA PEDRA
Keyword(s):  
Phase Transition ◽  
Chemical Potential ◽  
Large Deviation ◽  
Coulomb Repulsion ◽  
Meissner Effect ◽  
Repulsive Interaction ◽  
S Wave ◽  
Insulator Phase Transition ◽  
The One ◽  
Strong Repulsion

The thermodynamic impact of the Coulomb repulsion on s-wave superconductors is analyzed via a rigorous study of equilibrium and ground states of the strong coupling BCS-Hubbard Hamiltonian. We show that the one-site electron repulsion can favor superconductivity at fixed chemical potential by increasing the critical temperature and/or the Cooper pair condensate density. If the one-site repulsion is not too large, a first or a second order superconducting phase transition can appear at low temperatures. The Meißner effect is shown to be rather generic but coexistence of superconducting and ferromagnetic phases is also shown to be feasible, for instance, near half-filling and at strong repulsion. Our proof of a superconductor-Mott insulator phase transition implies a rigorous explanation of the necessity of doping insulators to create superconductors. These mathematical results are consequences of "quantum large deviation" arguments combined with an adaptation of the proof of Størmer's theorem [1] to even states on the CAR algebra.

scholarly journals X-Ray and Neutron Diffraction of Amorphous Nickel-Zirconium-Alloys as Prepared in Different Ways

1991 ◽  
Vol 46 (6) ◽  
pp. 491-498 ◽  
Author(s):  
L. Schultz ◽  
P. Lamparter ◽  
S. Steeb
Keyword(s):  
Neutron Diffraction ◽  
Short Range ◽  
Melt Spinning ◽  
Short Range Order ◽  
Pair Correlation ◽  
Zirconium Alloys ◽  
X Ray ◽  
Coordination Numbers ◽  
Structure Factors ◽  
The One

AbstractThe structure of amorphous NiχZr100-χ-alloys (Χ= 30, 31, 34, 63.7, and 65), which were produced by melt spinning (MS), mechanical alloying (MA), and sputtering (SP) was studied by X-ray- and neutron diffraction yielding structure factors, pair correlation functions, coordination numbers, atomic distances, and Warren-Cowley chemical short range order parameters. The atomic arrangement within the first coordination sphere is independent of the method of preparation while in the second and higher spheres it differs between the MS- and the MA-alloys on the one side and the SP-specimens on the other side. Thus one understands that some physical properties of the different specimens differ

The Free Energy Simulation Approach to Grain Boundary Segregation In Cu-Ni

1990 ◽  
Vol 209 ◽  
Author(s):  
H. Y. Wang ◽  
R. Najafabadi ◽  
D. J. Srolovitz ◽  
R. Lesar
Keyword(s):  
Monte Carlo ◽  
Free Energy ◽  
Grain Boundary ◽  
Chemical Potential ◽  
Boundary Segregation ◽  
Configurational Entropy ◽  
Accurate Method ◽  
Increasing Temperature ◽  
Atomic Coordinates ◽  
Good Agreement

ABSTRACTA new, accurate method for determining equilibrium segregation to defects in solids is employed to examine the segregation of Cu to grain boundaries in Cu-Ni alloys. The results are in very good agreement with the ones given by Monte Carlo. This method is based upon a point approximation for the configurational entropy, an Einstein model for vibrational contributions to the free energy. To achieve the equilibrium state of a defect in an alloy the free energy is minimized with respect to atomic coordinates and composition of each site at constant chemical potential. One of the main advantages this new method enjoys over other methods such as Monte Carlo, is the efficiency with which the atomic structure of a defect, segregation and thermodynamic properties can be determined. The grain boundary free energy can either increase or decrease with increasing temperature due to the competition between energetic and configurational entropy terms. In general, the grain boundary free energy increases with temperature when the segregation is strongest.

Synthesis of ZrO2–Y6WO12 solid solution powders by a polymerized complex method

1998 ◽  
Vol 13 (4) ◽  
pp. 939-943 ◽  
Author(s):  
Junfeng Ma ◽  
Masahiro Yoshimura ◽  
Masato Kakihana ◽  
Masatomo Yashima
Keyword(s):  
Solid Solution ◽  
Crystallite Size ◽  
Surface Area ◽  
Solid Solutions ◽  
Lattice Parameter ◽  
Cubic Phase ◽  
Complex Method ◽  
Amorphous Precursor ◽  
Fine Powders ◽  
Polymerized Complex Method

A series of solid solutions (1 − x) ZrO2 · xY0.857 W0.143 O1.714 (1/7Y6WO12) of metastable cubic phase were synthesized at 800 °C through a polymerized complex method. Lattice parameter a0 of solid solutions varies linearly with Y0.857 W0.143 O1.714 content (x). Crystallization began to occur above 400 °C from amorphous precursor to yield at 800 °C fine powders of 6–10 nm and 19–40 m2/g for crystallite size and surface area, respectively.

Habit modification of nearly perfect single crystals of potassium dihydrogen phosphate (KDP) by trivalent manganese ions studied using synchrotron radiation X-ray multiple diffraction in Renninger scanning mode

2003 ◽  
Vol 36 (5) ◽  
pp. 1230-1235 ◽  
Author(s):  
X. Lai ◽  
K. J. Roberts ◽  
L. H. Avanci ◽  
L. P. Cardoso ◽  
J. M. Sasaki
Keyword(s):  
Synchrotron Radiation ◽  
Potassium Dihydrogen Phosphate ◽  
Lattice Parameter ◽  
Dihydrogen Phosphate ◽  
Multiple Diffraction ◽  
Lattice Contraction ◽  
X Ray ◽  
Wave Measurements ◽  
Impurity Species ◽  
Habit Modification

The X-ray multiple diffraction technique using synchrotron radiation is applied in the preliminary study of the habit modification of KDP samples as induced by incorporation of the trivalent transition metal cation Mn3+. High-resolution Renninger scans of pure and doped KDP were carried out using 400 as the primary reflection, echoing the fact that these impurity species were segregated in the {100} growth sector. The analysis of the Renninger scans of the doped KDP crystals is consistent with the presence of the impurity species chemically bound within the KDP crystal structure, as confirmed through the suppression of the huge observed peak asymmetry, characteristic of perfect crystals. In addition, an extra Renninger-scan peak measured for the doped material is indicative of the impurity atoms occupying interstitial crystallographic sites in the lattice, a result consistent with X-ray standing-wave measurements. Renninger-scan reflection curve widths and lattice parameter measurements reveal the decrease in crystalline perfection (increased mosaic spread, η) and lattice contraction ofca0.4% in theaandclattice directions at the surface plane for the Mn3+-doped KDP samples in comparison with the undoped crystals.

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