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At least 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Low- and high-order accurate boundary conditions: From Stokes to Darcy porous flow modeled with standard and improved Brinkman lattice Boltzmann schemes

The present contribution focuses on the accuracy of reflection-type boundary conditions in the Stokes–Brinkman–Darcy modeling of porous flows solved with the lattice Boltzmann method (LBM), which we operate with the two-relaxation-time (TRT) collision and the Brinkman-force based scheme (BF), called BF-TRT scheme. In parallel, we compare it with the Stokes–Brinkman–Darcy linear finite element method (FEM) where the Dirichlet boundary conditions are enforced on grid vertices. In bulk, both BF-TRT and FEM share the same defect: in their discretization a correction to the modeled Brinkman equation appears, given by the discrete Laplacian of the velocity-proportional resistance force. This correction modifies the effective Brinkman viscosity, playing a crucial role in the triggering of spurious oscillations in the bulk solution. While the exact form of this defect is available in lattice-aligned, straight or diagonal, flows; in arbitrary flow/lattice orientations its approximation is constructed. At boundaries, we verify that such a Brinkman viscosity correction has an even more harmful impact. Already at the first order, it shifts the location of the no-slip wall condition supported by traditional LBM boundary schemes, such as the bounce-back rule. For that reason, this work develops a new class of boundary schemes to prescribe the Dirichlet velocity condition at an arbitrary wall/boundary-node distance and that supports a higher order accuracy in the accommodation of the TRT-Brinkman solutions. For their modeling, we consider the standard BF scheme and its improved version, called IBF; this latter is generalized in this work to suppress or to reduce the viscosity correction in arbitrarily oriented flows. Our framework extends the one- and two-point families of linear and parabolic link-wise boundary schemes, respectively called B-LI and B-MLI, which avoid the interference of the Brinkman viscosity correction in their closure relations. The performance of LBM and FEM is thoroughly evaluated in three benchmark tests, which are run throughout three distinctive permeability regimes. The first configuration is a horizontal porous channel, studied with a symbolic approach, where we construct the exact solutions of FEM and BF/IBF with different boundary schemes. The second problem refers to an inclined porous channel flow, which brings in as new challenge the formation of spurious boundary layers in LBM; that is, numerical artefacts that arise due to a deficient accommodation of the bulk solution by the low-accurate boundary scheme. The third problem considers a porous flow past a periodic square array of solid cylinders, which intensifies the previous two tests with the simulation of a more complex flow pattern. The ensemble of numerical tests provides guidelines on the effect of grid resolution and the TRT free collision parameter over the accuracy and the quality of the velocity field, spanning from Stokes to Darcy permeability regimes. It is shown that, with the use of the high-order accurate boundary schemes, the simple, uniform-mesh-based TRT-LBM formulation can even surpass the accuracy of FEM employing hardworking body-fitted meshes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Permutation-adapted complete and independent basis for atomic cluster expansion descriptors

Atomic cluster expansion (ACE) methods provide a systematic way to describe particle local environments of arbitrary body order. For practical applications it is often required that the basis of cluster functions be symmetrized with respect to rotations and permutations. Existing methodologies yield sets of symmetrized functions that are over-complete. These methodologies thus require an additional numerical procedure, such as singular value decomposition (SVD), to eliminate redundant functions. In this work, it is shown that analytical linear relationships for subsets of cluster functions may be derived using recursion and permutation properties of generalized Wigner symbols. From these relationships, subsets (blocks) of cluster functions can be selected such that, within each block, functions are guaranteed to be linearly independent. It is conjectured that this block-wise independent set of permutation-adapted rotation and permutation invariant (PA-RPI) functions forms a complete, independent basis for ACE. Along with the first analytical proofs of block-wise linear dependence of ACE cluster functions and other theoretical arguments, numerical results are offered to demonstrate this. The utility of the method is demonstrated in the development of an ACE interatomic potential for tantalum. Using the new basis functions in combination with Bayesian compressive sensing sparse regression, some high degree descriptors are observed to persist and help achieve high-accuracy models.

Angular momentum↗
DOE OSTI2025

Machine learning models for volumetric swelling in uranium nitride

Machine learning methods are applied to predict the volumetric swelling rate of the nuclear fuel uranium nitride (UN) over various temperatures, irradiation conditions, and power densities. Both kernel-based methods and symbolic regression models for UN swelling are developed and compared with multiple experimental datasets. We find that the UN pellet geometry and dimensions must be taken into account to accurately model swelling behavior. Strong agreement is observed between the developed machine learning models and the data. The predictive error generated by the machine learning models improves on empirical models taken from the literature. Sensitivity analysis is performed to determine which properties such as temperature, burnup, and power density, are most important in the swelling process. We find that machine learning can be used to quickly develop accurate swelling models for nuclear materials. In conclusion, the presented results illustrate the potential of machine learning to determine volumetric swelling in UN.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Pressure-induced development of bonding in NiAs type compounds and polymorphism of NiP

A reversible, displacive, pressure-induced structural phase transition has been found to occur in nickel monophosphide NiP at approximately 3.5 GPa by means of in situ synchrotron single-crystal X-ray diffraction. The new phase, with Pearson symbol oC56, assumes an orthorhombic structure with Cmc2{sub 1} space group and unit cell parameters a=23.801(2) {angstrom}, b=5.9238(6) {angstrom}, and c=4.8479(4) {angstrom} at 5.79 GPa. The high-pressure phase is a superstructure of the ambient, oP16 phase with multiplicity of 3.5. The phosphorous sublattice gradually converts from the net of isolated P{sub 2} dimers found in the ambient NiP, towards zig-zag polymeric P{infinity} chains found in MnP-type structures. The transformation involves development of triatomic phosphorous clusters and interconnected Ni slabs with diamondoid topology. The high-pressure phase, which represents intermediate polymerization step, is a commensurately modulated superstructure of the NiAs aristotype. The phase transformation in NiP bears resemblance to the effect of successive substitution of Si or Ge in place of P found in the series of stoichiometric inhomogeneous linear structures in ternary NiP{sub 1-x}Si{sub x} and NiP{sub 1-x}Ge{sub x} systems.

Dera, Przemyslaw↗
DOE OSTI2011

Synthesis, structural characterization and magnetic properties of RE{sub 2}MgGe{sub 2} (RE=rare-earth metal)

A series of rare-earth metal-magnesium-germanides RE{sub 2}MgGe{sub 2} (RE=Y, Nd, Sm, Gd-Tm, Lu) has been synthesized by reactions of the corresponding elements at high temperature. Their structures have been established by single-crystal and powder X-ray diffraction and belong to the Mo{sub 2}FeB{sub 2} structure type (space group P4/mbm (No. 127), Z=2; Pearson symbol tP10). Temperature dependent DC magnetization measurements indicate Curie-Weiss paramagnetism in the high-temperature regime for all members of the family, excluding Y{sub 2}MgGe{sub 2}, Sm{sub 2}MgGe{sub 2}, and Lu{sub 2}MgGe{sub 2}. At cryogenic temperatures (ca. 60 K and below), most RE{sub 2}MgGe{sub 2} phases enter into an antiferromagnetic ground-state, except for Er{sub 2}MgGe{sub 2} and Tm{sub 2}MgGe{sub 2}, which do not undergo magnetic ordering down to 5 K. The structural variations as a function of the decreasing size of the rare-earth metals, following the lanthanide contraction, and the changes in the magnetic properties across the series are discussed as well. - Graphical Abstract: The structure of RE{sub 2}MgGe{sub 2} (RE=Y, Nd, Sm, Gd-Tm, Lu) can be best viewed as 2-dimensional slabs of Mg and Ge atoms (anionic sub-lattice), and layers of rare-earth metal atoms (cationic sub-lattice) between them. Within this description, one should consider the Ge-Ge dumbbells (formally Ge{sup 6-}{sub 2}), interconnected with square-planar Mg atom as forming flat [MgGe{sub 2}] layers (z=0), stacked along the c-axis with the layers at z=1/2, made of rare-earth metal cations (formally RE{sup 3+}). Highlights: > RE{sub 2}MgGe{sub 2} (RE=Y, Nd, Sm, Gd-Tm, Lu) are new ternary germanides. > Their structures can be recognized as a 1:1 intergrowth of CsCl- and AlB{sub 2}-like slabs. > Ge atoms are covalently bound into Ge{sub 2} dumbbells. > Most RE{sub 2}MgGe{sub 2} phases are antiferromagnetically ordered at cryogenic temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Thermodynamic restrictions on mechanosynthesis of strontium titanate

Chemical potential phase stability diagrams were calculated from relevant thermodynamic properties and used to predict the thermodynamic driving force under prospective conditions of room temperature mechanosynthesis. One analysed the dependence of chemical potential diagrams on temperature and partial pressure of evolving gases such as oxygen or carbon dioxide, as expected on using strontium peroxide or strontium carbonate as precursor reactants for the alkali earth component. Thermodynamic calculations were also obtained for changes in titania precursor reactants, including thermodynamic predictions for reactivity of strontium carbonate with amorphous titania. Experimental evidence showed that strontium titanate can be obtained by mechanosynthesis of strontium carbonate+anatase mixtures, due to previous amorphization under high energy milling. Ability to perform mechanosynthesis with less energetic milling depends on the suitable choice of alternative precursor reactants, which meet the thermodynamic requirements without previous amorphization; this was demonstrated by mechanosynthesis from anatase+strontium peroxide mixtures. - Graphical abstract: X-Ray diffractograms of the starting TiO{sub 2} (anatase)+SrCO{sub 3} mixture and after mechanical activation at 650 rpm, for 1, 2, and 7 h. Different symbols are used to identify reflections ascribed to anatase (diamonds), SrCO{sub 3} (squares) and SrTiO{sub 3} (triangles). Highlights: Black-Right-Pointing-Pointer Prediction of thermodynamic driving force for room temperature mechanosynthesis. Black-Right-Pointing-Pointer Dependence of chemical potential diagrams on temperature and partial pressure. Black-Right-Pointing-Pointer Thermodynamic calculations for changes in titania precursor. Black-Right-Pointing-Pointer Experimental support for thermodynamic predictions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Eleven new compounds in the RE-Cd-Ge systems (RE=Pr, Nd, Sm, Gd-Yb; Y): Crystal chemistry of the RE{sub 2}CdGe{sub 2} series

A large new family of rare-earth metal-cadmium-germanides RE{sub 2}CdGe{sub 2} (RE=Y, Pr, Nd, Sm, Gd-Yb) has been synthesized and structurally characterized. All eleven structures have been established from single-crystal X-ray diffraction data and have been found to belong to the tetragonal Mo{sub 2}FeB{sub 2} structure type (ordered ternary variant of the U{sub 3}Si{sub 2} structure type-space group P4/mbm (No. 127), Z=2; Pearson symbol tP10). The structural variations among the three series of isostructural RE{sub 2}MgGe{sub 2}, RE{sub 2}InGe{sub 2}, and RE{sub 2}CdGe{sub 2} compounds are discussed, as well as the crystal chemistry changes as a function of the decreasing size of the rare-earth metals (lattice constants a=7.176(2)-7.4589(12) A and c=4.1273(14)-4.4356(13) A). The experimental results have been complemented by tight-binding linear muffin-tin orbital (TB-LMTO) electronic structure calculations. - Graphical abstract: More than 300 compounds have been reported to crystallize with the tetragonal U{sub 3}Si{sub 2} structure type, or the Mo{sub 2}FeB{sub 2} structure type, which is its ordered ternary variant. Among them, there are several large RE{sub 2}CdX{sub 2} classes, where the X-elements are typically late transition metals such as Cu, Ni, Au, Pd, Pt, and Rh. The new RE{sub 2}CdGe{sub 2} phases (RE=Y, Pr, Nd, Sm, Gd-Yb) increase the diversity and represent the first cadmium germanides. Highlights: Black-Right-Pointing-Pointer RE{sub 2}CdGe{sub 2} (RE=Y, Pr, Nd, Sm, Gd-Yb) are new ternary germanides. Black-Right-Pointing-Pointer Their structures can be recognized as a 1:1 intergrowth of CsCl- and AlB{sub 2}-like slabs. Black-Right-Pointing-Pointer The Ge atoms are covalently bound into Ge{sub 2} dumbbells. Black-Right-Pointing-Pointer Almost all RE{sub 2}CdGe{sub 2} phases are the first structurally characterized phases in the respective ternary RE-Cd-Ge systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Ternary CaCu{sub 4}P{sub 2}-type pnictides AAg{sub 4}Pn{sub 2} (A=Sr, Eu; Pn=As, Sb)

Four ternary pnictides AAg{sub 4}Pn{sub 2} (A=Sr, Eu; Pn=As, Sb) were prepared by reactions of the elements at 850 Degree-Sign C and their crystal structures were determined from single-crystal X-ray diffraction studies. These silver-containing pnictides AAg{sub 4}Pn{sub 2} adopt the trigonal CaCu{sub 4}P{sub 2}-type structure (Pearson symbol hR21, space group R3-bar m, Z=3; a=4.5555(6) A, c=24.041(3) A for SrAg{sub 4}As{sub 2}; a=4.5352(2) A, c=23.7221(11) A for EuAg{sub 4}As{sub 2}; a=4.7404(4) A, c=25.029(2) A for SrAg{sub 4}Sb{sub 2}; a=4.7239(3) A, c=24.689(2) A for EuAg{sub 4}Sb{sub 2}), which can be derived from the trigonal CaAl{sub 2}Si{sub 2}-type structure of the isoelectronic zinc-containing pnictides AZn{sub 2}Pn{sub 2} by insertion of additional Ag atoms into trigonal planar sites within [M{sub 2}Pn{sub 2}]{sup 2-} slabs built up of edge-sharing tetrahedra. Band structure calculations on SrAg{sub 4}As{sub 2} and SrAg{sub 4}Sb{sub 2} revealed that these charge-balanced Zintl phases actually exhibit no gap at the Fermi level and are predicted to be semimetals. - Graphical abstract: SrAg{sub 4}As{sub 2} and related pnictides adopt a CaCu{sub 4}P{sub 2}-type structure in which additional Ag atoms enter trigonal planar sites within slabs built from edge-sharing tetrahedra. Highlights: Black-Right-Pointing-Pointer AAg{sub 4}Pn{sub 2} are the first Ag-containing members of the CaCu{sub 4}P{sub 2}-type structure. Black-Right-Pointing-Pointer Ag atoms are stuffed in trigonal planar sites within CaAl{sub 2}Si{sub 2}-type slabs. Black-Right-Pointing-Pointer Ag-Ag bonding develops through attractive d{sup 10}-d{sup 10} interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Crystal structure, electrical resistivity, and X-ray photoelectron spectroscopy of BaAg{sub 2}As{sub 2}

The ternary arsenide BaAg{sub 2}As{sub 2} has been prepared by reaction of the elements at 850 Degree-Sign C. Single-crystal and powder X-ray diffraction analysis revealed that it adopts the ThCr{sub 2}Si{sub 2}-type structure (Pearson symbol tI10, space group I4/mmm, Z=2, a=4.6025(3) A, c=10.8672(6) A at 295 K) featuring [Ag{sub 2}As{sub 2}] layers interconnected by homoatomic As-As bonds along the c-direction. Band structure calculations indicate no gap at the Fermi level, and support the occurrence of strong As-As and weak Ag-Ag bonding. The asymmetric lineshape and the absence of a BE shift in the Ag 3d{sub 5/2} core-line peak relative to the element suggest delocalization of the Ag valence electrons. A significant negative BE shift (1.0 eV) in the As 3d{sub 5/2} core-line peak relative to the element confirms the presence of anionic As atoms. A reversible transition is observed at 175 K in the electrical resistivity, and is probably related to a structural phase transition. - Graphical abstract: BaAg{sub 2}As{sub 2} adopts a ThCr{sub 2}Si{sub 2}-type structure with As-As pairs and undergoes a transition at 175 K in its electrical resistivity. Highlights: Black-Right-Pointing-Pointer BaAg{sub 2}As{sub 2} fills the gap within the BaM{sub 2}As{sub 2} series containing 4d metals. Black-Right-Pointing-Pointer [Ag{sub 2}As{sub 2}] layers are linked by As-As pairs. Black-Right-Pointing-Pointer XPS studies support the assignment of monovalent Ag and anionic As atoms. Black-Right-Pointing-Pointer An anomaly is observed at 175 K in the electrical resistivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

A 3D complex containing novel 2D Cu{sup II}-azido layers: Structure, magnetic properties and effects of 'Non-innocent' reagent

A novel copper-azido coordination polymer, [Cu{sub 2}(N{sub 3}){sub 3}(L)]{sub n} (1, HL=pyrazine-2-carboxylic acid), has been synthesized by hydrothermal reaction with 'Non-innocent' reagent in the aqueous solution. In the reaction system, Cu{sup II} ions are avoided to reduce to Cu{sup I} ions due to the existence of Nd{sup III}. It is found that the complex is a 3D structure based on two double EO azido bridged trimmers and octahedron Cu{sup II} ions, in which the azide ligands take on EO and {mu}{sub 1,1,3} mode to form Cu{sup II}-azido 2D layers, furthermore L ligands pillar 2D layers into an infinite 3D framework with the Schlaefli symbol of {l_brace}4;6{sup 2}{r_brace}4{l_brace}4{sup 2};6{sup 12};8{sup 10};10{sup 4}{r_brace}{l_brace}4{sup 2};6{sup 4}{r_brace}. Magnetic studies revealed that the interactions between the Cu{sup II} ions in the trimmer are ferromagnetic for the Cu-N-Cu angle nearly 98 Degree-Sign , while the interactions between the trimmer and octahedron Cu{sup II} ion are antiferromgantic and result in an antiferromagnetic state. - Graphical abstract: A 3D complex containing novel 2D Cu{sup II}-azido layers, [Cu{sub 2}(N{sub 3}){sub 3}(L)]{sub n} (HL=pyrazine-2-carboxylic acid), was synthesized by hydrothermal reaction and exhibit interesting structure and magnetic properties. Highlights: Black-Right-Pointing-Pointer 'Non-innocent' reagents plays a key role in the process of formation of this complex. Black-Right-Pointing-Pointer 2D layer is formed only by Cu{sup II} ions and azido ligands. Black-Right-Pointing-Pointer Pyrazine-2-carboxylate ligands reinforce 2D layers and pillar them into an infinite 3D framework. Black-Right-Pointing-Pointer Magnetic study indicates that alternating FM-AF coupling exists in the complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Rare-earth chromium gallides RE{sub 4}CrGa{sub 12} (RE=Tb-Tm)

The ternary rare-earth-metal chromium gallides RE{sub 4}CrGa{sub 12} (RE=Tb-Tm) have been prepared by reactions of the elements at 1000 Degree-Sign C in the presence of excess gallium used as a self-flux. Their structures are derived by inserting Cr atoms into a quarter of the empty Ga{sub 6} octahedral clusters found in the parent binary gallides REGa{sub 3} (AuCu{sub 3}-type), although single-crystal X-ray diffraction studies suggest that complex superstructures may be adopted. An ideal ordered Y{sub 4}PdGa{sub 12}-type structure was successfully refined for a crystal of Dy{sub 4}CrGa{sub 12} (Pearson symbol cI34, space group Im3{sup Macron }m, Z=2, a=8.572(1) A). Magnetic measurements on single-crystal samples reveal ferromagnetic or possibly ferrimagnetic ordering for the Tb, Dy, and Er members (T{sub C}=22, 15, and 2.8 K, respectively) and antiferromagnetic ordering for the Ho member (T{sub N}=7.5 K). Band structure calculations on a hypothetical 'Y{sub 4}CrGa{sub 12}' model suggest that the Cr atoms carry no local magnetic moment. - Graphical abstract: RE{sub 4}CrGa{sub 12} is derived by inserting Cr atoms into empty Ga{sub 6} octahedral clusters present in the parent binary gallides REGa{sub 3}. Highlights: Black-Right-Pointing-Pointer RE{sub 4}MGa{sub 12} (previously known for M=Fe, Ni, Pd, Pt, Ag) has been extended to M=Cr. Black-Right-Pointing-Pointer RE{sub 4}CrGa{sub 12} compounds show predominantly ferromagnetic ordering. Black-Right-Pointing-Pointer Band structure calculations suggest that Cr atoms carry no local magnetic moment.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Crystal structure and chemical bonding of novel Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16}

A novel Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16} has been synthesized using the high-temperature reaction method and characterized by both powder and single-crystal X-ray diffractions. The title compound crystallized in the orthorhombic crystal system (space group Immm, Z=2, Pearson symbol oI78) with fifteen crystallographically unique atomic positions in the asymmetric unit, and the lattice parameters are refined as a=4.5244(4) A, b=6.9932(6) A, and c=53.043(5) A. The complex crystal structure of the title compound can be described as a 2:1 intergrowth of two closely related compounds: La{sub 2}Li{sub 2}Ge{sub 3} (Ce{sub 2}Li{sub 2}Ge{sub 3}-type) and La{sub 3}Li{sub 4}Ge{sub 4} (Zr{sub 3}Cu{sub 4}Si{sub 4}-type) acting like 'building-blocks' along the c-axis. Six La sites are categorized into three distinct types based on the local coordination environment showing the coordination numbers of 12-14. Three unique Li sites are placed in the centers of local tetrahedra formed by four Ge atoms which eventually construct Ge{sub 2} dimers or 1-dimensional cis-/trans-Ge chains. Theoretical investigations using the tight-binding linear muffin-tin orbital (LMTO) method provide rationales for an improved structural stability and for unique local coordination geometries established by anionic elements including [LiGe{sub 4}] tetrahedra, cis-/trans-Ge chain and Ge{sub 2} dimers. - Graphical abstract: Reported is a novel ternary Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16}. The complex crystal structure can be viewed as a simple combination of two closely related known compounds acting as 'building-blocks', La{sub 2}Li{sub 2}G{sub 3} and La{sub 3}Li{sub 4}Ge{sub 4}, in a 2:1 stoichiometric ratio. Highlights: Black-Right-Pointing-Pointer A novel Li-containing polar intermetallic compound La{sub 11}Li{sub 12}Ge{sub 16} was synthesized. Black-Right-Pointing-Pointer The complex crystal structure was easily explained as a combination of two known compounds. Black-Right-Pointing-Pointer Theoretical calculations indicated that the Fermi level was located near the pseudogap.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Spin reorientation and magnetization reversal in the perovskite oxides, YFe{sub 1-x}Mn{sub x}O{sub 3} (0{<=}x{<=}0.45): A neutron diffraction study

Members of the YFe{sub 1-x}Mn{sub x}O{sub 3} (0{<=}x{<=}0.45) family crystallize in the GdFeO{sub 3} type orthorhombic perovskite structure (space group Pnma) where the Fe and Mn ions are disordered at the 4b crystallographic site. Upon substitution of Mn at the Fe-site in the canted antiferromagnetic YFeO{sub 3} (T{sub N}=640 K), a first-order spin-reorientation transition occurs at a temperature, T{sub SR}, where the magnetic structure changes from the canted to a collinear state. With increasing Mn-concentration, T{sub SR} increases whereas T{sub N} decreases. Neutron diffraction studies on the x=0.4 sample reveal that the spin structure changes from {Gamma}{sub 4} to {Gamma}{sub 1} below T{sub SR}. Intriguingly, when x=0.4 and 0.45, a temperature-induced magnetization reversal is observed below a compensation temperature T{sup Low-Asterisk} (T{sup Low-Asterisk }<T{sub SR}<T{sub N}). The reversal is explained on the basis of a ferrimagnetic ground state resulting from antiferromagnetic coupling of the canted moments of Fe-O-Fe and Mn-O-Mn with that of Fe-O-Mn ordering. - Graphical abstract: Neutron diffraction study on YFe{sub 1-x}Mn{sub x}O{sub 3} demonstrates a spin-reorientation transition from canted {Gamma}{sub 4} to collinear symbol {Gamma}{sub 1} spin structure. A temperature-induced magnetization reversal is observed for x=0.4 and 0.45. Highlights: Black-Right-Pointing-Pointer Neutron diffraction study on YFe{sub 1-x}Mn{sub x}O{sub 3}. Black-Right-Pointing-Pointer Spin-reorientation from spin structure {Gamma}{sub 4} to {Gamma}{sub 1}. Black-Right-Pointing-Pointer Magnetization reversal phenomenon in disordered perovskite oxides, YFe{sub 1-x}Mn{sub x}O{sub 3} and YCr{sub 1-x}Mn{sub x}O{sub 3}. Black-Right-Pointing-Pointer Presence of tunable positive and negative magnetocaloric effects in YFe{sub 1-x}Mn{sub x}O{sub 3}.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Magnetic behavior of the Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7} pyrochlore solid solution

The temperature dependence of magnetic susceptibility of the Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7} system was studied from 2 to 300 K. According to these measurements, the solid solution (0≤y≤0.9) does not show any magnetic transition; however, a noticeable deviation from the Curie–Weiss law occurs and the magnetic behavior of this system can be ascribed to short-range magnetic order that is also present in several geometrically frustrated systems. The Pauli magnetic susceptibility decreases as the Sr content increases, this can be associated with a shift towards Ir{sup 5+} in samples; also the Ir effective magnetic moment decreases. The estimated Wilson-ratio indicates the presence of strong electron–electron correlations. - Graphical abstract: Temperature dependence of the magnetic susceptibility of Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7}. The samples of this system showed no magnetic transition down to 2 K. Analyzing magnetic data (symbols for experimental data, continuous line for the Curie–Weiss (CW) equation and black dots for a modified CW equation), it is found that this system departures from a CW-like equation and the magnetic parameters C and θ notably deviate from the expected values for Ir. Better fittings with a modified CW equation are shown in the A and B insets. Highlights: ► The magnetic susceptibility of the Bi{sub 2−x}Sr{sub x}Ir{sub 2}O{sub 7} system is discussed. ► No magnetic transition is observed. ► Magnetic measurements on the Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7} indicate the existence of Ir{sup 5+}. ► The magnetic susceptibility does not follow a Curie–Weiss law. ► A modified Curie–Weiss equation describes correctly the magnetic susceptibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Crystal and magnetic structure of (1−x)BiFeO{sub 3}–xSrTiO{sub 3} (x=0.2, 0.3, 0.4 and 0.8)

The effect of doping SrTiO{sub 3} into BiFeO{sub 3} on the magnetic and crystal structure has been explored using powder neutron diffraction for (1−x)BiFeO{sub 3}–xSrTiO{sub 3} where x=0.2, 0.3, 0.4, 0.6 and 0.8. While the data are not sensitive to the cycloidal component of the magnetic ordering, the evolution of the collinear antiferromagnetic moment of the G-type antiferromagnetic component with T and x has been explored, as have structural parameters. It is found that for x≤0.4 pure phase samples form in the R3c cell, and for x=0.8 a non-magnetic Pm3{sup ¯}m phase is obtained. The x=0.6 sample gives a mixed phase. Through the R3c phase the magnetic structure does not change appreciably apart from the reduction of magnetic moment magnitude with the increasing T and/or x. - Graphical abstract: A simple phase diagram for (1−x)BiFeO{sub 3}–xSrTiO{sub 3} , where hexagons indicate the rhombohedral R3c phase and boxes the cubic phase. Filled symbols indicate magnetic ordering. The black arrow indicates T{sub N} for BiFeO{sub 3}. Display Omitted - Highlights: • We have established part of the phase diagram for doping SrTiO{sub 3} into BiFeO{sub 3}. • (1−x)BiFeO{sub 3}–xSrTiO{sub 3} is isostructural with BiFeO{sub 3} up to x<0.4, and cubic for x>0.85. • We have examined the evolution of ordered magnetic moment with T and x.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Synthesis, structures and properties of a family of four two-dimensional coordination polymers constructed from 5-hydroxyisophthalate

Four 2D coordination polymers (CPs) with different structures containing the multifunctional ligand 5-hydroxyisophthalate (5-OH-BDC{sup 2−}), [Zn(5-OH-BDC)(btb)]·2H{sub 2}O (1), [Cd(5-OH-BDC)(btp)(H{sub 2}O)]·3H{sub 2}O (2), [Cd(5-OH-BDC)(bth){sub 2}(H{sub 2}O)]·H{sub 2}O (3) and [Pb(5-OH-BDC)]·H{sub 2}O (4) [btp=1, 3-bis(1,2,4-triazol-1-yl)propane, btb=1,4-bis(1,2,4-triazol-1-yl)butane, bth=1, 6-bis(1,2,4-triazol-1-yl)hexane] were obtained. 1–3 were synthesised hydrothermally, while 4 was obtained under ambient condition. The adjacent (2D→2D) polycatenated 2D layers of 1 polythread in a parallel manner to form an unusual 2D→3D polythreaded framework. 2 contains an undulated 2D (4, 4) network and further extends into an “embracing” double-layer structure through the C–H···π and π···π stacking interactions. 3 exhibits a non-interpenetrating 2D (4, 4)-network. 4 exhibits a 2D double-layered binodal (4, 4)-net containing oblong nanochannels with symbol (4{sup 3}6{sup 3}){sub 2}. Reversible dehydration–rehydration is observed in 1, 2 and 4, which fall within the category of “recoverable collapsing” and “guest-induced re-formation” frameworks, while 3 exhibits irreversible dehydration–rehydration behaviour. The solid state fluorescent properties of 1–4 have been investigated. -- Graphical abstract: Among four 2D CPs reported, 1 is an unusual 2D→3D polythreaded framework. 4 exhibits 2D double-layered binodal (4, 4)-net containing nanochannels. Reversible dehydration–rehydration is observed in 1, 2 and 4. Highlights: • Four 2D CPs based on 5-hydroxyisophthalate with d{sup 10} and Pb(II) ions were reported. • 1 is an unusual 2D→3D polythreaded framework. • 4 shows a binodal (4, 4)-connected 2D double-layer network with nanochannels. • The materials 1, 2 and 4 show reversible dehydration–rehydration behaviours. • Solid state fluorescent properties were investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A new 3D Co(II)–organic framework with acylamide-containing tetracarboxylate ligand: Solvothermal synthesis, crystal structure, gas adsorption and magnetic property

A new cobalt(II)–organic framework, [Co{sub 2}(L)(py){sub 2}(DMSO)]{sub n}• 0.5nDMF• 2nDMSO (1) [H{sub 4}L=5,5'-((naphthalene-2,6-dicarbonyl)bis(azanediyl))diisophthalic acid, py=pyridine, DMSO=dimethyl sulfoxide, DMF=N,N-dimethylformamide], has been solvothermally synthesized and characterized by elemental analysis, IR, TGA, PXRD and single-crystal X-ray crystallography. The structural analysis reveals that complex 1 is a 3D framework built from nanosized acylamide-containing tetracarboxylate ligands (L{sup 4−}) and dinuclear [Co{sub 2}(CO{sub 2}){sub 4}] secondary building units (SBUs), exhibiting a uninodal (4,4)-connected crb topology with the Schläfli symbol of (4• 6{sup 5}). The desolvated complex (1a) displays higher adsorption capability for CO{sub 2} than N{sub 2}, which may be due to the relatively strong binding affinity between the CO{sub 2} molecules and acylamide groups in the framework. The magnetic investigation shows that the dominant antiferromagnetic interaction is observed in complex 1. - Graphical abstract: A new 3D Co(II)–organic framework with nanosized acylamide-containing tetracarboxylate ligand was solvothermally synthesized and structurally characterized, its thermal stability, gas adsorption and magnetic property were studied. - Highlights: • A new 3D Co(II)–organic framework with nanosized acylamide-containing tetracarboxylate ligand has been solvothermally synthesized and characterized. • Complex 1 exhibits a uninodal (4,4)-connected crb topology. • The thermal stability, gas adsorption and magnetic property were studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Calcium substitution in rare-earth metal germanides with the hexagonal Mn{sub 5}Si{sub 3} structure type. structural characterization of the extended series RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Rare-earth metal)

Reported are the synthesis and the structural characterization of an extended family of rare-earth metal–germanides with a general formula RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu; x<2). All twelve phases are isotypic, crystallizing with the Mn{sub 5}Si{sub 3} structure type (Pearson index hP16, hexagonal space group P6{sub 3}/mcm); they are the Ca-substituted variants of the corresponding RE{sub 5}Ge{sub 3} binaries. Across the series, despite some small variations in the Ca-uptake, the unit cell volumes decrease monotonically, following the lanthanide contraction. Temperature dependent DC magnetization measurements reveal paramagnetic behavior in the high temperature range, and the obtained effective moments are consistent with free-ion RE{sup 3+} ground state, as expected from prior studies of the binary RE{sub 5}Ge{sub 3} phases. The onset of magnetic ordering is observed in the low temperature range, and complex magnetic interactions (ferromagnetic/ferrimagnetic) can be inferred, different from the binary phases RE{sub 5}Ge{sub 3}, which are known as antiferromagnetic. In order to understand the role of Ca in the bonding, the electronic structures of the La{sub 5}Ge{sub 3} and the hypothetical compounds La{sub 2}Ca{sub 3}Ge{sub 3} and La{sub 3}Ca{sub 2}Ge{sub 3} with ordered metal atoms are compared and discussed. - Graphical abstract: The family of rare-earth metal–calcium–germanides with the general formula RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu) crystallize in the hexagonal space group P6{sub 3}/mcm (No. 193, Pearson symbol hP16) with a structure that is a variant of the Mn{sub 5}Si{sub 3} structure type. - Highlights: • The newly synthesized RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu) constitute an extended family. • The structure is a substitution variant of the hexagonal Mn{sub 5}Si{sub 3} structure type. • Ca-uptake is the highest in the early members, and decreases for the late rare-earth metal analogs. • Experimental and theoretical work suggest limiting solubility range RE{sub ≈3}Ca{sub ≈2}Ge{sub 3}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗