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Phase transformations and thermal expansion coefficients of unirradiated U-X wt.% Zr (X = 6, 10, 20, 30) measured via neutron diffraction

This work characterizes the crystallographic evolution of unirradiated U-X wt.% Zr (X = 6, 10, 20, 30) while cooling from equilibration, single phase γ-U-Zr, at 900 °C to ambient temperature using time-of-flight neutron diffraction. The β-U phase was unobserved during cooling at 1 °C/min in all alloys. All alloys followed the phase transformation pathway of γ-U-Zr→γ-U-Zr+α-U→α-U +δ-UZr2 with an observed miscibility gap in γ-U-Zr. The α-U and δ-UZr2 transformation took place simultaneously in the U-30 wt.% Zr sample. These findings strengthen the need to re-approach the U-Zr phase diagram in entirety. Bulk volumetric CTEs agree well with published data, strengthening the quantification of lattice-specific CTEs reported in this study. A compositionally dependent discontinuity in thermal expansion, increasing in magnitude with decreasing U content, occurs during the γ-U-Zr→α-U+δ-UZr2 transformation. The γ-U-Zr lattice parameter was measured to have a compositional dependency.

36 MATERIALS SCIENCE↗

Heat capacity and neutron diffraction studies on the frustrated magnetic Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1] solid solution

The Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1] solid solution exhibits a complex magnetic behaviour due to the bond-frustration in its magnetic structure. Heat capacity measurements of the (x=0.1-0.5) phases show a three-dimensional magnetic ordering ({lambda} anomaly) that shifts to lower temperatures and becomes broader as the AsO{sub 4}{sup 3-} content increases. For x=0.75, no significant feature was observed whereas for higher arsenate ion content, x=0.9 and 1, a small maximum was detected. The magnetic structures of solid solution are consistent with the existence of predominant antiferromagnetic superexchange interactions through the |OH| and |XO{sub 4}| (X=P and As) groups between the Co{sup +2} ions. The substitution of PO{sub 4}{sup 3-} by AsO{sub 4}{sup 3-} anions by more than 90% substantially modifies the magnetic exchange pathways in the solid solution, leading to an incommensurate antiferromagnetic structure in Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [x=0.9 and 1] phases. - Graphical abstract: Magnetic structures of Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1]. The ordering of the magnetic moments of Co{sup 2+} is in c direction for the two crystallographic positions (dimers and chains) in all compounds. The unit cell is surrounded by a red line. Highlights: Black-Right-Pointing-Pointer Synthesis of a new adamite-type compounds, Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} (0.1, 0.25, 0.5, 0.75, 0.9) phases. Black-Right-Pointing-Pointer Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} (0-1) solid solution; magnetic frustrated system. Black-Right-Pointing-Pointer High resolution neutron powder diffraction to determine the crystal structures. Black-Right-Pointing-Pointer Incommensurate magnetic structures at low temperature. Black-Right-Pointing-Pointer Magnetostructural correlations in cobalt-based Co{sub 2}(OH)XO{sub 4} (X=P and As) insulation compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural characterization of the CeO{sub 2}/Gd{sub 2}O{sub 3} mixed system by synchrotron X-ray diffraction

The structural determination of the CeO{sub 2}/Gd{sub 2}O{sub 3} mixed system is a non-trivial problem because of the close resemblance between the ionic sizes of Ce{sup 4+} and Gd{sup 3+} and between the crystal structures of CeO{sub 2} and Gd{sub 2}O{sub 3}. (Ce{sub 1-x}Gd{sub x})O{sub 2-x/2} powder samples with x ranging between 0 and 1 have been synthesized by coprecipitation of mixed oxalates and subsequent thermal decomposition in air at 1200 Degree-Sign C followed by slow cooling. Synchrotron powder X-ray diffraction data were collected and refined by the Rietveld method. Lattice parameters do not follow Vegard's law and no peak splitting has been observed for any composition, meaning that no biphasic regions exist over the whole compositional range. The same hybrid structural model - a proper mixture of the structures of the two pure oxides - was used for the refinements, allowing to account for the data observed. - graphical abstract: Substituting Ce{sup 4+} by Gd{sup 3+}, a gradual transition from the F structure (typical of CeO{sub 2}) to the C structure (typical of Gd{sub 2}O{sub 3}) takes place. The lattice parameters do not follow Vegard's law. Highlights: Black-Right-Pointing-Pointer A structural study of Ce-Gd mixed oxides has been performed. Black-Right-Pointing-Pointer In (Ce{sub 1-x}Gd{sub x})O{sub 2-x/2} a solid solution forms for 0{<=}x{<=}0.3. Black-Right-Pointing-Pointer For x>0.3 a gradual transition from the C to the F structure is observed. Black-Right-Pointing-Pointer Lattice parameters do not follow Vegard's law.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The T2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

The solid solution based on Nb{sub 5}Si{sub 3} (Cr{sub 5}B{sub 3} structure type, D8{sub l}, tI32, I4/mcm, No140, a=6.5767 A, c=11.8967 A) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. - Graphial abstract: Valence-charge electron localization function in the z=0 plane of the D8{sub l} structure for the ordered compound Nb{sub 5}SiB{sub 2}. Highlights: Black-Right-Pointing-Pointer Coupling between ab initio data and experimental results from synchrotron powder diffraction. Black-Right-Pointing-Pointer Excellent agreement between the two techniques for the site occupancies and internal coordinates. Black-Right-Pointing-Pointer Explanation of the phase stability up to Nb{sub 5}SiB{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High pressure structural study of {beta}-Ti{sub 3}O{sub 5}: X-ray diffraction and Raman spectroscopy

The structural stability of {beta}-Ti{sub 3}O{sub 5} (C2/m) has been investigated by X-ray diffraction and Raman spectroscopy with diamond anvil cells. {beta}-Ti{sub 3}O{sub 5} is stable up to about 26 GPa at room temperature. Isothermal pressure-volume relationship of {beta}-Ti{sub 3}O{sub 5} is well presented by the third-order Birch-Murnaghan equation of state with V{sub 0}=348.6(8) A{sup 3} and B{sub 0}=216(9) GPa. Axial compressibility presents obvious anisotropy. The a-axis and c-axis are more compressible than b-axis due to the different crystal structure arrangement of {beta}-Ti{sub 3}O{sub 5} along b-axis and perpendicular to b-axis direction. The Grueneisen parameters of thirteen observed Raman modes are 0.79-1.74, whose mean is 1.32. - Graphical abstract: The crystal structure of {beta}-Ti{sub 3}O{sub 5}: the projection of {beta}-Ti{sub 3}O{sub 5} along b-axis (Left) and the projection of {beta}-Ti{sub 3}O{sub 5} along c-axis (Right). Highlights: Black-Right-Pointing-Pointer High pressure structural stability of {beta}-Ti{sub 3}O{sub 5} was investigated. Black-Right-Pointing-Pointer {beta}-Ti{sub 3}O{sub 5} is stable up to about 26 GPa. Black-Right-Pointing-Pointer Axial compressibility presents obvious anisotropy. Black-Right-Pointing-Pointer Pressure-volume relationship is well presented by Birch-Murnaghan equation of state. Black-Right-Pointing-Pointer The Grueneisen parameters are 0.79-1.74.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by charge flipping method

Samples with five different zirconium carbide compositions (C/Zr molar ratio=0.84, 0.89, 0.95, 1.05, and 1.17) have been fabricated and studied using a variety of experimental techniques. Each sample was zone refined to ensure that the end product was polycrystalline with a grain size of 10-100 {mu}m. It was found that the lattice parameter was largest for the x=0.89 composition and smallest for the x=1.17 total C/Zr composition, but was not linear; this nonlinearity is possibly explained using electron densities calculated using charge flipping technique. Among the five samples, the unit cell of the ZrC{sub 0.89} sample showed the highest electron density, corresponding to the highest carbon incorporation and the largest lattice parameter. The ZrC{sub 0.84} sample showed the lowest carbon incorporation, resulting in a larger number of carbon vacancies and resultant strain. Samples with larger carbon ratios (x=0.95, 1.05, and 1.17) showed a slight decrease in lattice parameter, due to a decrease in electron density. Optical anisotropy measurements suggest that these three samples contained significant amounts of a graphitic carbon phase, not bonded to the Zr atoms. - Graphical abstract: Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by the charge flipping method. Highlights: Black-Right-Pointing-Pointer The lattice parameter variation: ZrC{sub 0.89}>ZrC{sub 0.84}>ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}. Black-Right-Pointing-Pointer Surface oxygen with no correlation to the lattice parameter variation. Black-Right-Pointing-Pointer ZrC{sub 0.89} had highest electron densities correspond to highest carbon incorporation. Black-Right-Pointing-Pointer Second highest lattice parameter in ZrC{sub 0.84} due to strain. Black-Right-Pointing-Pointer Unit cell electron density order: ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-linear thermal evolution of the crystal structure and phase transitions of LaFeO{sub 3} investigated by high temperature X-ray diffraction

The crystal structure, anisotropic thermal expansion and structural phase transition of the perovskite LaFeO{sub 3} has been studied by high-temperature X-ray diffraction from room temperature to 1533 K. The structural evolution of the orthorhombic phase with space group Pbnm and the rhombohedral phase with R3{sup Macron }c structure of LaFeO{sub 3} is reported in terms of lattice parameters, thermal expansion coefficients, atomic positions, octahedral rotations and polyhedral volumes. Non-linear lattice expansion across the antiferromagnetic to paramagnetic transition of LaFeO{sub 3} at T{sub N}=735 K was compared to the corresponding behavior of the ferroelectric antiferromagnet BiFeO{sub 3} to gain insight to the magnetoelectric coupling in BiFeO{sub 3}, which is also multiferroic. The first order phase transition of LaFeO{sub 3} from Pbnm to R3{sup Macron }c was observed at 1228{+-}9 K, and a subsequent transition to Pm3{sup Macron }m was extrapolated to occur at 2140{+-}30 K. The stability of the Pbnm and R3{sup Macron }c polymorphs of LaFeO{sub 3} is discussed in terms of the competing enthalpy and entropy of the two crystal polymorphs and the thermal evolution of the polyhedral volume ratio V{sub A}/V{sub B}. - Graphical abstract: Aniostropic thermal evolution of the lattice parameters and phase transition of LaFeO{sub 3}. Highlights: Black-Right-Pointing-Pointer The crystal structure of LaFeO{sub 3} is studied by HTXRD from RT to 1533 K. Black-Right-Pointing-Pointer A non-linear expansion across the Neel temperature is observed for LaFeO{sub 3}. Black-Right-Pointing-Pointer The ratio V{sub A}/V{sub B} is used to rationalize the thermal evolution of the structure.

36 MATERIALS SCIENCE↗

On the crystal energy and structure of A{sub 2}Ti{sub n}O{sub 2n+1} (A=Li, Na, K) titanates by DFT calculations and neutron diffraction

First-principles quantum-mechanical calculations (CRYSTAL09 code, B3LYP functional) were performed on alkali titanates A{sub 2}Ti{sub n}O{sub 2n+1} with layered structure (n=3,4,6). Monoclinic structural types with unshifted (P2{sub 1}/m) and with shifted (C2/m) layers were considered. Crystal energies and full structural details were obtained for all Li, Na, and K phases. Neutron diffraction data were collected on powder samples of P2{sub 1}/m-Li{sub 2}Ti{sub 3}O{sub 7} (a=9.3146(3), b=3.7522(1), c=7.5447(3) Å, β=97.611(4)°) and C2/m-K{sub 2}Ti{sub 4}O{sub 9} (a=18.2578(8), b=3.79160(9), c=12.0242(4) Å, β=106.459(4)°) and their structures were Rietveld-refined. Computed energies show the P2{sub 1}/m arrangement as favoured over the C2/m one for n=3, and the opposite holds for n=6. In the n=4 case the P2{sub 1}/m configuration is predicted to be more stable for Li and Na, and the C2/m one for K titanates. Analysis of Li–O and K–O crystal-chemical environments from experiment and theory shows that the alkali atom bonding is stabilized/destabilized in the different phases consistently with the energy trend. - Graphical abstract: Display Omitted - Highlights: • The P2{sub 1}/m structure-type is found to be more stable for A{sub 2}Ti{sub 3}O{sub 7} layer titanates. • The C2/m structure-type is found to be more stable for A{sub 2}Ti{sub 6}O{sub 13} layer titanates. • Tetratitanates are predicted to prefer the P2{sub 1}/m (Li and Na) or C2/m (K) structure. • Li–O and K–O bond distances follow a trend consistent with computed phase energies.

36 MATERIALS SCIENCE↗

Investigation of phase evolution of CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) by in situ synchrotron high-temperature powder diffraction

In situ synchrotron X-ray powder diffraction was used to study the high-temperature phase evolution of CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) precursors prepared via solid-state and sol–gel methods. After the precursors are heated to 1225 °C, the CCTO phase is the main phase observed in the calcined powder, with the presence of some minor impurities. Comparing the two precursors, we found that the onset temperature for the CCTO phase formation is 800 °C in the sol–gel precursor, lower than that in the solid-state precursor (875 °C). Intermediate phases were only observed in the sol–gel precursor. Both precursors are able to be calcined to sub-micrometric sized powders. Based on the synchrotron data along with differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), the phase formation sequence and mechanism during calcination are proposed in this study. -- Graphical abstract: The in situ synchrotron HT-XRD patterns of CCTO sol–gel and solid-state precursor. Highlights: • Phase formation sequence/mechanism in two CCTO precursors has been established. • Formation temperature of CCTO via sol–gel method is lower than solid-state method. • Intermediate phases are only observed in the sol–gel precursor. • Both precursors are able to be calcined into sub-micrometric sized powders.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calcination products of gibbsite studied by X-ray diffraction, XPS and solid-state NMR

The changes caused by heat treatment of gibbsite powder at 300–1473 K were studied using the X-ray diffraction (XRD), X-ray photoemission (XPS) spectra and {sup 27}Al magic angle spinning nuclear magnetic resonance spectroscopy ({sup 27}Al MAS NMR). XRD analysis indicates that the transformation sequence involves the formation of κ-Al{sub 2}O{sub 3} as an intermediate phase between χ- and α-Al{sub 2}O{sub 3}. The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. XPS analysis indicates that the ratio of aluminium atoms to oxygen atoms in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3} increases, whereas the expected ratio is observed in α-Al{sub 2}O{sub 3}. The percentage of AlO{sub 4} units in the transition aluminas follows the same behaviour as the ratio of Al/O. - Graphical abstract: The percentage of AlO{sub 4} units in transition aluminas follows the same behaviour as the ratio of Al/O. - Highlights: • Calcination products of gibbsite studied by XRD, XPS and solid-state NMR. • The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. • The Al/O atomic ratio determined by XPS is larger than 2/3 in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3}. • The percentage of AlO{sub 4} in the aluminas follows the same behaviour as the Al/O atomic ratio.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic ordering in the pyrochlore Ho{sub 2}CrSbO{sub 7} determined from neutron diffraction, and the magnetic properties of other RE{sub 2}CrSbO{sub 7} phases (RE=Y, Tb, Dy, Er)

The magnetic structure of the pyrochlore Ho{sub 2}CrSbO{sub 7}, which orders magnetically below 13 K, has been studied using neutron powder diffraction. Ho{sub 2}CrSbO{sub 7} is found to form an “ordered spin-ice structure” where the magnetic moments are constrained along the 111 axes, but with a ferromagnetic moment in one direction. The Cr{sup 3+} ions order ferromagnetically and this is thought to lift the degeneracy of the x, y and z directions in the cubic structure causing the ferromagnetic component from the Ho{sup 3+} ions to align. The pyrochlores RE{sub 2}CrSbO{sub 7} where RE=Y, Tb, Dy and Er have also been prepared and studied using SQUID magnetometry. - Graphical abstract: The Ho magnetic moments align to provide an overall ferromagnetic moment along [001]. - Highlights: • Despite having inherent frustration on the Ho sublattice, Ho{sub 2}CrSbO{sub 7} orders ferromagnetically below 13 K. • Ordering on the Cr/Sb sublattice appears to remove the degenerate ground state for the Ho order. • The Ho{sup 3+} magnetic moments are aligned along <111> directions by crystal field effects. • Y{sub 2}CrSbO{sub 7} with diamagnetic Y{sup 3+} ions also has a ferromagnetic ground state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-temperature X-ray diffraction measurements of fluorite-related rare earth antimonates Ln{sub 3}SbO{sub 7} (Ln=Nd, Tb) and their magnetic properties

Ternary rare-earth antimonates Ln{sub 3}SbO{sub 7} (Ln=rare earths) were prepared, and their structures were determined by X-ray diffraction measurements. They crystallize in an orthorhombic superstructure of cubic fluorite (space group Cmcm for Ln=La, Pr; Ccmm for Ln=Sm–Dy), in which Ln{sup 3+} ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated). For Ln=Nd, two phases with the Cmcm and Ccmm space groups coexist at room temperature. When the temperature was increased, the Nd{sub 3}SbO{sub 7} compound transformed into a single phase with the space group Cmcm. Through magnetic susceptibility measurements, an antiferromagnetic transition was observed at 3.0 K (Ln=Nd) and 7.8 K (Ln=Tb). Analysis of the magnetic specific heat for Tb{sub 3}SbO{sub 7} indicates that the 8-coordinated Tb ions magnetically orders at 7.8 K, and with furthermore decreasing temperature, the 7-coordinated Tb ions shows antiferromagnetic ordering at 3.0 K. - Graphical abstract: Temperature dependence of the specific heat divided by temperature (C{sub p}/T) and the magnetic entropy (S{sub mag}) for Tb{sub 3}SbO{sub 7}. Two-step magnetic transition has been observed. - Highlights: • The phase transition of Nd{sub 3}SbO{sub 7} is from the Ccmm space group to the Cmcm one. • Nd{sub 3}SbO{sub 7} shows an antiferromagnetic transition at 3.0 K. • For Tb{sub 3}SbO{sub 7}, two-step magnetic transition has been observed at 7.8 and 3.0 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pressure induced phase transformations in NaZr{sub 2}(PO{sub 4}){sub 3} studied by X-ray diffraction and Raman spectroscopy

Raman spectroscopic and x-ray diffraction measurements on NaZr{sub 2}(PO{sub 4}){sub 3} were carried out up to 30 GPa at close intervals of pressure, revealing two structural phase transformations around 5 and 6.6 GPa. The second phase at 5.4 GPa is indexed to R3 space group similar to that of RbTi{sub 2}(PO{sub 4}){sub 3}. Bulk modulus decreases abruptly from 53 GPa (B′=4) to 36 GPa (B′=4) in the second phase above 5 GPa. The structure of the phase III at 8.2 GPa is indexed as orthorhombic similar to the case of high temperature phase of monoclinic LiZr{sub 2}(PO{sub 4}){sub 3}. Bulk modulus of this phase III is found to be 65 GPa (B′=4), which is higher than that of the ambient phase. In high pressure Raman studies, modes corresponding to 72 and 112 cm{sup −1} soften in the ambient phase whereas around 5 GPa, the ones at 60, 105, 125 and 190 cm{sup −1} soften with pressure contributing negatively to overall thermal expansion. - Graphical abstract: High pressure study of NaZr{sub 2}(PO{sub 4}){sub 3} shows a reversible phase transition from R-3c to R3 structure at 5 GPa accompanied by an increase in compressibility signaling a polyhedral tilt transition. - Highlights: • NaZr{sub 2}(PO{sub 4}){sub 3} undergoes two reversible phase transitions at 5 and 6.7 GPa. • The transition at 5 is from rhombohedral R-3c to R3 structure. • Bulk modulus of NaZr{sub 2}(PO{sub 4}){sub 3} is lower than that for the isostructural RbTi{sub 2}(PO{sub 4}){sub 3.} • Compressibility increases with substitution of a smaller cation (Na). • Zr-translational and PO{sub 4} librational modes contribute to phase transition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal expansion of mullite-type Bi{sub 2}Al{sub 4}O{sub 9}: A study by X-ray diffraction, vibrational spectroscopy and density functional theory

Polycrystalline Bi{sub 2}Al{sub 4}O{sub 9} powder samples were synthesized using the glycerine method. Single crystals were produced from the powder product in a Bi{sub 2}O{sub 3} melt. The lattice thermal expansion of the mullite-type compound was studied using X-ray diffraction, Raman spectroscopy and density functional theory (DFT). The metric parameters were modeled using Grüneisen approximation for the zero pressure equation of state, where the temperature-dependent vibrational internal energy was calculated from the Debye characteristic frequency. Both the first-order and second-order Grüneisen approximations were applied for modeling the volumetric expansion, and the second-order approach provided physically meaningful axial parameters. The phonon density of states as well as phonon dispersion guided to set the characteristic frequency for simulation. The experimental infrared and Raman phonon bands were compared with those calculate from the DFT calculations. Selective Raman modes were analyzed for the thermal anharmonic behaviors using simplified Klemens model. The respective mode Grüneisen parameters were calculated from the pressure-dependent Raman spectra. - Graphical abstract: Crystal structure of mullite-type Bi{sub 2}Al{sub 4}O{sub 9} showing the edge-sharing AlO{sub 6} octahedra running parallel to the c-axis. - Highlights: • Thermal expansion of Bi{sub 2}Al{sub 4}O{sub 9} was studied using XRD, FTIR, Raman and DFT. • Metric parameters were modeled using Grüneisen approximation. • Phonon DOS and phonon dispersion helped to set the Debye frequency. • Mode Grüneisen parameters were calculated from the pressure-dependent Raman spectra. • Anharmonicity was analyzed for some selective Raman modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithium insertion properties of Li{sub x}TiNb{sub 2}O{sub 7} investigated by neutron diffraction and first-principles modelling

TiNb{sub 2}O{sub 7}, a good candidate as anode in lithium batteries, was treated with n-butyllithium to synthesize Li{sub x}TiNb{sub 2}O{sub 7} phases similar to those formed during electrochemical reactions. The Li{sub 2.67}TiNb{sub 2}O{sub 7} and Li{sub 3.33}TiNb{sub 2}O{sub 7} compounds, monoclinic C2/m, were studied by time-of-flight powder neutron diffraction. Their crystal structures, containing 3×3 blocks of (Ti,Nb)O{sub 6} octahedra, were Rietveld refined including Li positions. The Li atoms are distributed in similar amounts over sites with (Li–O) Coordination Numbers 5 and 4, although CN=5 should be preferred for having lower energy. Quantum-mechanical calculations were also performed, determining the average charge–discharge voltages to be 1.415 and 1.571 V for Li{sub 3.33}TiNb{sub 2}O{sub 7} and Li{sub 2.67}TiNb{sub 2}O{sub 7}, respectively, in good agreement with experimental results. An analysis of the theoretical charge distribution shows that, on lithiation, the chemical reduction of Ti and Nb atoms concentrates in the more condensed peripheral octahedra of the 3×3 block. This corresponds to electrons moving into a partly spin-polarized small band which gives rise to semi-metallic conductivity. - Graphical abstract: Structure of monoclinic Li{sub 3.33}TiNb{sub 2}O{sub 7}, and corresponding electron density of states. - Highlights: • Lithium was chemically inserted into the battery anode material TiNb{sub 2}O{sub 7}. • Li atoms are distributed over four- and fivefold oxygen coordinated sites. • On lithiation Nb and Ti atoms are reduced according to a peculiar structural pattern. • Theoretically predicted charge–discharge voltages fit experiments very well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unusual thermal expansion of Sr{sub 2}IrO{sub 4}: A variable temperature synchrotron X-ray diffraction study

The structure of Sr{sub 2}IrO{sub 4} has been studied between 20 and 1273 K using synchrotron X-ray diffraction. Sr{sub 2}IrO{sub 4} undergoes an apparently continuous transition from I4{sub 1}/acd to I4/mmm near 1123 K. The cooperative tilting of the corner sharing IrO{sub 6} octahedra in I4{sub 1}/acd results in highly anisotropic and unusual thermal expansion behavior with negative thermal expansion along the c-axis. - Graphical abstract: The progressive reduction in the magnitude of the tilting of the corner sharing IrO{sub 6} octahedra in Sr{sub 2}IrO{sub 4} results in negative thermal expansion along the c-axis before undergoing an apparently continuous transition from I4{sub 1}/acd to I4/mmm near 1123 K. - Highlights: • Thermal expansion of Sr{sub 2}IrO{sub 4} was studied using Synchrotron-XRD. • Unusual negative thermal expansion along c-axis observed. • I4{sub 1}/acd→I4/mmm phase transition detected near 1120 K. • Tilting of the corner sharing IrO{sub 6} octahedra related to the observed NTE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interplay between crystal and magnetic structures in YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} compounds studied by neutron diffraction

We report a detailed magnetic structure investigation of YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} (α=0, 0.64, 1) compounds presenting a strong (H,D) isotope effect by neutron diffraction and Mössbauer spectroscopy analysis. They crystallize in the same monoclinic structure (Pc space group) with 8 inequivalent Fe sites having different H(D) environment. At low temperature, the compounds are ferromagnetic (FM) and show an easy magnetization axis perpendicular to the b axis and only slightly tilted away from the c axis. Upon heating, they display a first order transition from a ferromagnetic towards an antiferromagnetic (AFM) structure at T{sub M0} which is sensitive to the H/D isotope nature. The AFM cell is described by doubling the crystal cell along the monoclinic b axis. It presents an unusual coexistence of non magnetic Fe layer sandwiched by two thicker ferromagnetic Fe layers which are antiparallel to each other. This FM-AFM transition is driven by the loss of ordered moment on one Fe site (Fe7) through an itinerant electron metamagnetic (IEM) behaviour. The key role of the Fe7 position is assigned to both its hydrogen rich atomic environment and its geometric position. Above T{sub M0} a field induced metamagnetic transition is observed from the AFM towards the FM structure accompanied by a cell volume increase. Both thermal and magnetic field dependence of the magnetic structure are found strongly related to the anisotropic cell distortion induced by (H,D) order in interstitial sites. - Graphical abstract: Representation of the FM-AFM magnetic structures of YFe{sub 2}D{sub 4.2} deuteride. - Highlights: • YFe{sub 2}(H,D){sub 4.2} compounds undergoes a isotope sensitive FM-AFM transition at T{sub M0}. • The FM structure is formed of Fe moments perpendicular to the monoclinic b axis. • AFM structure is formed by antiparallel Fe layers separated by non-magnetic Fe layer. • One Fe site among eight loses its moment at T{sub M0} due to larger Fe–H bonding. • Magnetic properties are driven by the monoclinic distortion induced by D order.

36 MATERIALS SCIENCE↗

Coherent 3D nanostructure of γ-Al{sub 2}O{sub 3}: Simulation of whole X-ray powder diffraction pattern

The structure and nanostructure features of nanocrystalline γ-Al{sub 2}O{sub 3} obtained by dehydration of boehmite with anisotropic platelet-shaped particles were investigated. The original models of 3D coherent nanostructure of γ-Al{sub 2}O{sub 3} were constructed. The models of nanostructured γ-Al{sub 2}O{sub 3} particles were first confirmed by a direct simulation of powder X–Ray diffraction (XRD) patterns using the Debye Scattering Equation (DSE) with assistance of high-resolution transmission electron microscopy (HRTEM) study. The average crystal structure of γ-Al{sub 2}O{sub 3} was shown to be tetragonally distorted. The experimental results revealed that thin γ-Al{sub 2}O{sub 3} platelets were heterogeneous on a nanometer scale and nanometer-sized building blocks were separated by partially coherent interfaces. The XRD simulation results showed that a specific packing of the primary crystalline blocks in the nanostructured γ-Al{sub 2}O{sub 3} particles with formation of planar defects on (001), (100), and (101) planes nicely accounted for pronounced diffuse scattering, anisotropic peak broadening and peak shifts in the experimental XRD pattern. The identified planar defects in cation sublattice seem to be described as filling cation non-spinel sites in existing crystallographic models of γ-Al{sub 2}O{sub 3} structure. The overall findings provided an insight into the complex nanostructure, which is intrinsic to the metastable γ-Al{sub 2}O{sub 3} oxide. - Highlights: • Thin plate-like crystallites of γ-Al{sub 2}O{sub 3} were obtained. • Models of 3D coherent nanostructure of γ-Al{sub 2}O{sub 3} were constructed. • Models were verified by simulating XRD patterns using the Debye Scattering Equation. • Specific broadening of XRD peaks was explained in terms of planar defects. • Primary crystalline blocks in γ-Al{sub 2}O{sub 3} are separated by partially coherent interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗