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At least 1,279 records · Page 71
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

In situ measurements of reactions in a glass-forming batch by X-ray and neutron diffraction

We report the batch materials used in glass production are often too coarse to allow phase evolution measurements by in situ high-temperature x-ray diffraction (HTXRD). Reducing the particle sizes to accommodate these measurements changes the reaction kinetics and can alter the reaction pathway. Unlike conventional laboratory XRD, which operates in reflection mode and analyzes the surface region of finely ground powder, neutron diffraction can be used to characterize as-received batch materials by means of an intense beam which penetrates through a bulk sample. In this study, the phase evolution in a glass-forming batch made with fine batch materials was probed in situ by both HTXRD and time-of-flight neutron diffraction to determine the similarities and differences between measurements by the two techniques. Therefore, the same composition, prepared using the coarser, as-received size distributions of the same batch materials, was studied by both techniques, demonstrating the unique capability of neutron diffraction to analyze material which is too coarse for the HTXRD, and to reveal the effect of the particle size distribution on the reaction kinetics.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Antiferromagnetic Ordering in Quasi-One-Dimensional FeBi 4 S 7

Here, we report a detailed study of the synthesis, composition, magnetic structure, and transport properties of a quasi-one-dimensional antiferromagnet FeBi 4 S 7 that contains chains of edge-sharing FeS 6 octahedra. High-resolution powder X-ray diffraction (PXRD) analysis, aided by variation of synthetic conditions, suggests that the true formula of the material is Fe 1.2 Bi 3.8 S 7 , due to the minor substitution of Fe into Bi sites. This finding is in agreement with crystal structure refinement from neutron powder diffraction data as well as with the small band gap of 0.23 eV determined from electrical transport measurements. Analysis of the neutron diffraction pattern collected below the antiferromagnetic ordering temperature of 64 K revealed ferromagnetic coupling between the Fe moments in the chains of FeS 6 octahedra. The overall ordering, however, is antiferromagnetic due to the antiparallel arrangement of moments on neighboring chains. The collinear spin arrangement is described by a k-vector (1, 0, 1/2), which indicates doubling of the unit cell in the c direction and the loss of the C-centering translation as compared to the nuclear cell. The ferromagnetic nature of the sulfide-bridged chains of Fe 2+ ions in FeBi 4 S 7 , in contrast to the antiferromagnetic coupling between Fe moments in compounds with similar structural fragments, can be justified by the analysis of metric parameters that characterize the Fe–S bonding in these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Thermal stability of titanate nanorods and titania nanowires formed from titanate nanotubes by heating

The structure of titanate nanowires was studied by a combination of powder X-ray diffraction (XRD) and 3D precession electron diffraction. Titania nanowires and titanate nanorods were prepared by heating of titanate nanotubes. The structure of final product depended on heating conditions. Titanium nanotubes heated in air at a temperature of 850 °C decomposed into three phases — Na{sub 2}Ti{sub 6}O{sub 13} (nanorods) and two phases of TiO{sub 2} — anatase and rutile. At higher temperatures the anatase form of TiO{sub 2} transforms into rutile and the nanorods change into rutile nanoparticles. By contrast, in the vacuum only anatase phases of TiO{sub 2} were obtained by heating at 900 °C. The anatase transformation into rutile began only after a longer time of heating at 1000 °C. For the description of anisotropic XRD line broadening in the total powder pattern fitting by the program MSTRUCT a model of nanorods with elliptical base was included in the software. The model parameters — rod length, axis size of the elliptical base, the ellipse flattening parameter and twist of the base could be refined. Variation of particle shapes with temperature was found. - Highlights: • Titanate nanotubes changed to particles of TiO{sub 2} and nanorods of Na{sub 2}Ti{sub 6}O{sub 13} at 850 °C. • With heating time and temperature nanorods transformed to rutile nanoparticles. • X-ray diffraction powder pattern fitting indicated an elliptical shape of nanorod base. • No transition of titanate nanotubes to Na{sub 2}Ti{sub 6}O{sub 13} was found after heating in vacuum. • Heating of titanate nanotubes in vacuum leads to appearance of anatase nanowires.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Synthesis and structural studies on (1−x)Bi(Mg{sub 1/2}Ti{sub 1/2})O{sub 3}−xPbTiO{sub 3} piezoceramics

We present here the structural studies on (1−x)Bi(Mg{sub 1/2}Ti{sub 1/2})O{sub 3}−xPbTiO{sub 3} (BMT-xPT) piezoceramics with x=0.28, 0.37 and 0.45 using powder x-ray diffraction data. Rietveld refinement of powder x-ray diffraction data reveals the tetragonal structure (space group P4mm) for the compositions with x>0.40 and rhombohedral (space group R3m) for the compositions with x<0.30 of BMT-xPT ceramics. The morphotropic phase boundary is found for the intermediate composition with 0.30<x<0.40, where the coexistence of two phases are observed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

d -Electron Heavy Fermion Behavior in a Near-Room-Temperature Polar Metallic Ferrimagnet: A Case of Mn 5 SiC

Polycrystalline Mn 5 SiC was synthesized by using a high-temperature solid-state method. Mn 5 SiC adopts a polar space group (Cmc2 1 ) with six crystallographic Mn sites confirmed by X-ray and neutron diffraction, transmission electron microscopy, and second harmonic generation experiments. The complex crystal structure features edge-sharing trigonal prisms and icosahedra, as well as face/edge-sharing pentagonal prisms. Magnetic measurements indicate ferrimagnetic ordering with a transition temperature of 284 K. The ferrimagnetic structure (magnetic space group Cm’c’2 1 ) was further identified by powder neutron diffraction, where collinear Mn spins align along the crystallographic c-axis. The refined magnetic moment for each crystallographic Mn site at 4 K is 1.8(2), −2.42(9), −1.72(8), 0.51(6), 0.50(4), and 1.7(2) μ B . Density functional theory calculations confirm both the metallic behavior and the ferrimagnetic structure observed experimentally and further provide insight into the observed Mn moment dependence across crystallographic sites. The resistivity and specific heat measurements and density functional theory calculations reveal a substantially large Kadowaki–Woods ratio of 5 × 10 –5 μΩ·cm/(mJ/mol) 2 and a many-body renormalization factor of 5.5, indicating the unusual heavy Fermion behavior in such an itinerant magnetic metal.

Messegee, Zachary T. [George Mason University, Fai↗
DOE OSTI2025

Experimental determination of the magnetic anisotropy in five-coordinated Co( II ) field-induced single molecule magnets

Magnetic anisotropy of the central metal atom is a crucial property of single molecule magnets (SMMs). Small structural changes can alter the magnetic properties, and accurate experimental methods to investigate magnetic anisotropy are therefore critical. Here, we investigate two five-coordinated Co( II ) SMMs, [CoCl 2 Cltpy] (1) and [CoBr 2 Cltpy] (2) (Cltpy = 4′-chloro-2,2′:6′,2′′-terpyridine), through multiple techniques. Ab initio theoretical calculations performed on the two compounds show that both possess axial magnetic anisotropy with the magnetic easy axis pointing towards one of the terminal halogen atoms. Theoretical calculations on SMMs are typically done on isolated molecular species, and to validate this approximation the magnetic anisotropy was further studied through experimental techniques. EPR measurements confirm an axial anisotropy of 1, and magnetic measurements provide experimental Zero-Field Splitting (ZFS) parameters, showing that the values from theoretical calculations are slightly overestimated. The X-ray electron density determined from 20 K single-crystal synchrotron X-ray diffraction data provides estimated d-orbital populations also suggesting axial magnetic anisotropy in both systems, and furthermore suggesting a more pronounced axiality in 1 compared to 2. This is in good agreement with the results obtained from both magnetic measurements and theoretical calculations. The magnetic anisotropy of 1 is quantified experimentally through polarized powder neutron diffraction via the site susceptibility method, confirming an axial magnetic anisotropy of the compound. A slight deviation in the easy axis direction is observed between experimental and theoretical results. This, together with the overestimation of the ZFS parameters from theoretical calculations, shows that experimental investigation of the magnetic anisotropy of SMMs is of high relevance. Magnetic anisotropy of the central metal atom is a crucial property of single molecule magnets (SMMs).

Slavensky, Hannah H. [Aarhus Univ. (Denmark)] (ORC↗
DOE OSTI2023

Temperature-Dependent Optical and Structural Properties of Chiral Two-Dimensional Hybrid Lead-Iodide Perovskites

Layered hybrid halide perovskites gain chirality via the incorporation of chiral organic cations in the spacer layer. These so-called chiral two-dimensional (2D) halide perovskites have attracted considerable interest recently for chiral optoelectronic, spintronic, and ferroelectric applications. However, the effect of temperature on these materials, especially how the structure changes with temperature and its impact on the chiral optoelectronic properties, remains an open question. Here, we study the effect of temperature change on chiral optoelectronic and structural properties through temperature-dependent circularly polarized photoluminescence (CPPL) microscopy and synchrotron powder X-ray diffraction as well as pair distribution function analysis to elucidate the intrinsic chiral optoelectronic and structural variations for R-, S-, and racemic-methylbenzylamine lead iodide. Here our results show that the temperature-induced band gap changes indicate a strong electron–phonon coupling compared to the thermal-induced lattice expansion in chiral 2D perovskites. From powder diffraction measurements, a monotonic lattice expansion is observed on heating with no structural phase transitions over 90–360 K detected for the three samples studied herein. Locally, a strongly anisotropic and even negative expansion in some components of the instantaneous Pb–I pair-distance distribution is suggestive of coupling between dynamical intralayer distortions and lattice expansion. This work provides insights into the fundamental understanding of the temperature effect on chiral optoelectronic and structural properties of chiral 2D perovskites, which can lead to new chiral materials design strategies for future chiral optoelectronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}]

The compounds Ba[H{sub 4}TeO{sub 6}] (I), Ba[H{sub 2}TeO{sub 5}] (II), Ba[Te{sub 2}O{sub 6}(OH){sub 2}] (III) and Ba[TeO{sub 4}] (IV) were prepared by application of a diffusion method (I), under hydrothermal conditions (II and III) and from solid state reactions (IV), respectively. Structure analysis on the basis of single crystal X-ray diffraction data revealed novel structure types for (I), (II) and (III) and isotypism of (IV) with PrSbO{sub 4} and LaSbO{sub 4}. Common feature of the four oxotellurate(VI) structures are [TeO{sub 6}] octahedra. Whereas in the crystal structure of (I) the octahedral units are isolated, they are condensed into chains via corner-sharing in (II) and via edge-sharing in (III) and (IV). The coordination numbers of the barium cations in the four structures range from seven to ten. Although hydrogen atom positions could not be located for the structures of (I) and (II), short interpolyhedral O···O contacts are evident for strong hydrogen bonding. The temperature behaviour of (I), (II) and (IV) was monitored by simultaneous thermal analysis (STA) measurements and in situ powder X-ray diffraction, revealing the decomposition sequence Ba[H{sub 4}TeO{sub 6}] → Ba[H{sub 2}TeO{sub 5}] → Ba[TeO{sub 4}]→ Ba[TeO{sub 3}] upon heating to temperatures up to 900 °C. - Graphical abstract: The crystal structures of the four oxotellurates(VI) were determined from single crystal data. The thermal decomposition of Ba[H{sub 4}TeO{sub 6}], monitored by temperature-dependent X-ray powder diffraction and simultaneous thermal analysis measurements, involves two condensation reactions according to Ba[H{sub 4}TeO{sub 6}]→Ba[H{sub 2}TeO{sub 5}]+H{sub 2}O(↑)→Ba[TeO{sub 4}]+ H{sub 2}O(↑). Display Omitted.

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

Neutron Diffraction and Magnetic Susceptibility Studies on a High-Voltage Li 1.2 Mn 0.55 Ni 0.15 Co 0.10 O 2 Lithium Ion Battery Cathode: Insight into the Crystal Structure

Lithium- and manganese-rich oxides undergo structural transformation and/or atomic rearrangements during the delithiation/lithiation process and ultimately suffer from several issues such as first cycle irreversible capacity and voltage fade. In order to understand the mechanism of these issues, perception of a detailed crystal structure of pristine material is obviously demanding. In this study, combined powder neutron diffraction (ND) and temperature-dependent magnetic susceptibility techniques were employed to investigate the structure of a pristine lithium- and manganese-rich Li1.2Mn0.55Ni0.15Co0.10O2 cathode oxide. Rietveld refinement on the experimental ND pattern yields good fits by considering either Li2MO3 (M = Co, Mn, Ni) type monoclinic (C2/m space group) phase with 1% of Ni residing in the 4h lithium site or a composite structure consisting of 50% of Li2MnO3 type monoclinic (C2/m space group) and 50% LiMO2 (M = Co, Mn, Ni) type trigonal (R$\bar{3}$m space group) structure. In the composite structure, 3% Li/Ni site exchange in the trigonal phase is also proposed. Further, temperature-dependent dc magnetic susceptibility shows Curie–Weiss paramagnetic behavior at T ≥ 100 K, and no ordering/deviation of the field cooling (FC) curve in the temperature range 2–320 K indicates the random distribution of metal ions in the transition metal (TM) layer in the trigonal phase. Bifurcation of the zero-field cooling (ZFC) curve from the FC curve showing a magnetic ordering at TN 50 K reveals the presence of cation ordering in the TM layers arising from a distinct Li2MnO3-like phase. These results suggest that the lithium- and manganese-rich oxide with a composition Li1.2Mn0.55Ni0.15Co0.10O2 is more likely a composite of monoclinic and trigonal phases. The report also highlights the unique materials diagnostic capability of combined ND and magnetic susceptibility techniques to obtain detailed structural information of complex oxide systems.

Mohanty, Debasish↗
DOE OSTI2017

Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO 4 [Accommodation of High Transformation Strain in Battery Electrodes via Formation of Nanoscale Intermediate Phases: Operando Structure Investigation of Olivine Sodium Iron Phosphate]

Virtually all intercalation compounds used as battery electrodes exhibit significant changes in unit cell volume during use. Na x FePO 4 (0 < x < 1, NFP) olivine, of interest as a cathode for sodium-ion batteries, is a model for topotactic, high strain systems as it exhibits one of the largest discontinuous volume changes (~17% by volume) during its first-order transition between two otherwise isostructural phases. Using synchrotron radiation powder X-ray diffraction (PXD) and pair distribution function (PDF) analysis, we discover a new strain-accommodation mechanism wherein a third, <10 nm scale nanocrystalline phase forms to buffer the large lattice mismatch between primary phases. The new phase has a and b lattice parameters matching one crystalline endmember phase and c lattice parameter matching the other, and is not detectable by powder diffraction alone. Finally, we suggest that this strain-accommodation mechanism may apply to systems with large transformation strains but in which true “amorphization” does not occur.

25 ENERGY STORAGE↗
DOE OSTI2014

Investigation of some new hydro(solvo)thermal synthesis routes to nanostructured mixed-metal oxides

We present a study of two new solvothermal synthesis approaches to mixed-metal oxide materials and structural characterisation of the products formed. The solvothermal oxidation of metallic gallium by a diethanolamine solution of iron(II) chloride at 240 °C produces a crystalline sample of a spinel-structured material, made up of nano-scale particles typically 20 nm in dimension. XANES spectroscopy at the K-edge shows that the material contains predominantly Fe{sup 2+} in an octahedral environment, but that a small amount of Fe{sup 3+} is also present. Careful analysis using transmission electron microscopy and powder neutron diffraction shows that the sample is actually a mixture of two spinel materials: predominantly (>97%) an Fe{sup 2+} phase Ga{sub 1.8}Fe{sub 1.2}O{sub 3.9}, but with a minor impurity phase that is iron-rich. In contrast, the hydrothermal reaction of titanium bis(ammonium lactato)dihydroxide in water with increasing amounts of Sn(IV) acetate allows nanocrystalline samples of the SnO{sub 2}–TiO{sub 2} solid solution to be prepared directly, as proved by powder XRD and Raman spectroscopy. - Graphical abstract: New solvothermal synthesis approaches to spinel and rutile mixed-metal oxides are reported. - Highlights: • Solvothermal oxidation of gallium metal in organic iron(II) solution gives a novel iron gallate spinel. • Hydrothermal reaction of titanium(IV) complex and tin(IV) acetate produces the complete SnO{sub 2}–TiO{sub 2} solid solution. • Nanostructured mixed-metal oxide phases are produced directly from solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Venturing into Unexplored Phase Space: Synthesis, Structure, and Properties of MgCo 3 B 2 Featuring a Rumpled Kagomé Network

MgCo 3 B 2 , a novel ternary boride in a previously unexplored phase space, was synthesized using the hydride route. In situ powder X-ray diffraction and DFT calculations aided in the discovery of this compound, whose structure was then determined by single-crystal X-ray diffraction. Like the closely related CeCo 3 B 2 , MgCo 3 B 2 crystallizes in centrosymmetric space group P6/mmm (a = 4.883(2) Å, c = 2.926(2) Å at 210 K, Z = 1). Unlike CeCo 3 B 2 , however, it adopts a disordered structure that features a rumpled Kagomé network of Co atoms, and Mg atoms fill the channels of a Co–B framework. Although the structural disorder leads to motifs that are similar to those observed in MgNi 3 B 2 and other related ternary borides, no evidence of an ordered superstructure was found by single-crystal X-ray diffraction or high-resolution powder X-ray diffraction. In the case of CeCo 3 B 2 , boron atoms occupy the center of regular Co 6 trigonal prisms; in MgCo 3 B 2 , boron atoms are shifted from the center of the prism to form B–B dimers with roughly the same length as those found in MgNi 3 B 2 . Magnetic susceptibility data exhibit an unusual temperature dependence that cannot be convincingly modeled by the modified Curie–Weiss equation, consistent with DFT calculations predicting a nonmagnetic ground state. Intrinsic susceptibility at 300 K is 1.42 × 10 –3 emu/mol Oe, which is comparable to that of paramagnetic YCo 3 B 2 and CeCo 3 B 2 with a similar structure and composition. Here, this study showcases the efficacy of combining several methodologies to discover new solids in unexplored phase spaces. This approach includes in situ PXRD data to monitor reactions of precursors upon heating, a diffusion-enhanced synthesis method, and DFT assessment of compound stability.

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

Structure and properties of Na{sub x}M{sub 2}SbO{sub 6}·yH{sub 2}O, M=Co(III), Ni(III) honeycomb oxyhydrates

The oxyhydrates Na{sub 0.85}Co{sub 2}SbO{sub 6}·1.7H{sub 2}O and Na{sub 0.95}Ni{sub 2}SbO{sub 6}·1.5H{sub 2}O were prepared by Br{sub 2} oxidation of Na{sub 3}Co{sub 2}SbO{sub 6} and Na{sub 3}Ni{sub 2}SbO{sub 6} and exposure to ambient air. Their composition and structure are characterized by thermogravimetric analysis, elemental analysis and powder X-ray diffraction. Both form monolayer hydrates with metal cations (Co or Ni) near the 3+ oxidation state. In the parent materials, MO{sub 6} octahedra surround SbO{sub 6} units, forming a honeycomb geometry; Rietveld refinement of the hydrate phases indicate that this motif is retained. Magnetic susceptibility plots display paramagnetic behavior and Curie–Weiss fits support the 3+ oxidation state (low spin d{sup 6}s=0 for Co and low spin d{sup 7}s=1/2 for Ni). Close inspection of the Ni hydrate’s susceptibility reveals a feature at 6.2 K and a non-linear magnetization at 2 K with no saturation up to 9 T. Heat capacity measurements show a large amount of excess entropy in the Ni hydrate in the 2–20 K temperature range, while the heat capacity of the Co hydrate can be described by a simple lattice contribution. The Ni hydrate sample is easily dehydrated by heating above 100 °C and forms a new Na-deficient phase, Na{sub 0.95}Ni{sub 2}SbO{sub 6}, which is stable at room temperature. Magnetic susceptibility of this phase is consistent with the Ni atom remaining in the 3+ oxidation state after dehydration. - Graphical abstract: Powder diffraction patterns of Na{sub 3}Ni{sub 2}SbO{sub 6}, Na{sub 0.95}Ni{sub 2}SbO{sub 6}·1.5H{sub 2}O and Na{sub 0.95}Ni{sub 2}SbO{sub 6}. Each pattern has been normalized in intensity. Cartoons depict the change in layer separation with hydration and give the approximate distances between layers and Ni atoms. Highlights: • New oxyhydrate phases with honeycomb lattices are formed. • Curie–Weiss fits indicate Ni{sup 3+} (s=1/2). • Heat capacity shows a large release of entropy for Ni phase, likely due to a complex magneto-structural phase transition.

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

Scaffolds of magnetically active 3d metals in the valence electron controlled borides Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8} (M=Cr–Ni; x=0.5–1): Structutral, electronic and magnetic properties

Polycrystalline samples of the boride series Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8} (M=Cr, Co, Mn, Ni) including single crystals of Ti{sub 8}Co{sub 3}Ru{sub 18}B{sub 8} have been prepared by arc-melting the elements. The phases were characterized by powder X-ray diffraction (Rietveld refinement), single-crystal X-ray diffraction (for M=Co), and energy-dispersive X-ray (EDX) analysis. They are substitutional variants of the Zn{sub 11}Rh{sub 18}B{sub 8} structure type, space group P4/mbm (No. 127) and contain a “scaffold” structural unit (M-ladders interacting with M/Ti-chains) as well as isolated M/Ti-chains. According to DFT calculations, the Ru–X (X=B, Ti, Ti/M) bonding interactions are nearly constant throughout the series and responsible for the structural stability of these phases, whereas the M–M and Ru–M interactions vary significantly with varying valence electron count. Furthermore, density of states (DOS) analyses predict the phases with M=Mn and Ni to develop a total magnetic moment but not the M=Co phase. Susceptibility measurements confirm the Co phase to be paramagnetic and the Mn Phase orders ferrimagnetically below 120 K and thus develops a magnetic moment, as predicted. - Graphical abstract: The crystal structures of the new phases (M=Cr, Mn, Co, Ni) are confirmed by Rietveld refinement of powder diffraction data and single crystal X-ray diffraction (for M=Co) to contain beside the M-ladder also M/Ti-chains. Similar to the series Ti{sub 9}M{sub 2}Ru{sub 18}B{sub 8}, the crystal structure of the new phases are mainly stabilized by the heteroatomic Ru–B and Ru–Ti bonds that remain nearly constant throughout the series, whereas the M-containing bonds vary significantly with varying valence electron count. An experimental finding confirmed and even extended by COHP bonding analyses. In addition, the DOS analyses of the M-elements reveal the development of magnetic moments for the M=Mn, Ni cases but not for M=Co. Indeed, Ti{sub 8}Co{sub 3}Ru{sub 18}B{sub 8} was found experimentally to be a paramagnet and ferrimagnetic ordering below 120 K is found for M=Mn. Highlights: • Synthesis of the valence electron controlled borides Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8} (M=Cr–Ni). • Prediction of magnetic properties of Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8}. • Ferrimagnetic ordering found in Ti{sub 8}M{sub 3}Ru{sub 18}B{sub 8}. • Chemical bonding studied by density functional theory.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Low Temperature Phases of Na 2 Ti 3 Cl 8 Revisited

Here, the low temperature phases of Na 2 Ti 3 Cl 8 and their phase transitions were investigated by powder neutron diffraction, heat capacity, and magnetic susceptibility measurements between 1.6 K and room temperature. Aside from the previously known high temperature α-phase ( R 3m) and low temperature γ-phase ( R 3m), a new intermediate temperature β-phase was detected. It has a k = (1/4,1/4,0) superstructure and its molar volume and χT product are half way between the α- and γ-phases. The β-phase is observed between 210 K and 190 K on cooling in powder samples. Its formation is kinetically hindered in crystals. Upon heating the β→α transition occurs at 227 K. From the γ-phase, a γ→α transitions is observed on heating. Only in heat capacity measurements, a shoulder of the peak indicates an intermediate formation of the β-phase. Strong antiferromagnetic interactions between the Ti 2+ ions result in the formation of triangular trimers (Ti 3 clusters). In the γ-phase all Ti 2+ ions are part of trimers. For the β-phase a structural model is proposed, where half of the Ti 2+ ions form trimers. No long-range magnetic order was observed in Na 2 Ti 3 Cl 8 down to 1.6 K.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Single crystal growth of Sr{sub 2}TiMnO{sub 6} by optical floating zone technique

Single crystals of Sr{sub 2}TiMnO{sub 6} were grown by optical floating zone technique. Powder X-ray diffraction studies confirmed the single phase nature of the grown crystal. Laue diffraction studies proved the quality of the grown crystal. Neutron diffraction showed no magnetic ordering down to 6 K. Impedance studies showed temperature dependant relaxation which is due to the presence of oxygen vacancies in the grown crystal.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

A new strontium antimonate{sup III} Sr{sub 5}Sb{sub 22}O{sub 38}: Synthesis, crystal structure and characterizations

A new strontium antimonate{sup III}, Sr{sub 5}Sb{sub 22}O{sub 38}, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. It crystallizes in the P2{sub 1}/n space group of the monoclinic system with a=11.739(9) Å, b=12.014(10) Å, c=16.412(13) Å, β=91.460(8)°, V=2314.0(3) Å{sup 3}. The crystal structure is built of seven trigonal–pyramidal SbO{sub 3} and four sphenoid SbO{sub 4} polyhedra which are connected through sharing corner-oxygen atoms to form the complex three-dimensional {sub ∞}{sup 3}[Sb{sub 22}O{sub 38}]{sup 10−} anionic network with two different intersectant tunnels along the [111-bar ] and [11-bar 1-bar ] directions accommodating the electric charge balanced Sr{sup 2+} cations. First-principles electronic structure calculations based on the density functional theory (DFT) and the UV–vis diffuse reflectance spectroscopy measurements both indicate that the compound belongs to a direct band insulator with an optical gap value of 3.3 eV. - Graphical abstract: The 2D Sb–O slabs are stacked through sharing oxygen atoms to form the 3D network structure of the new strontium antimonate{sup III} Sr{sub 5}Sb{sub 22}O{sub 38}. - Highlights: • A new strontium antimonate{sup III}, Sr{sub 5}Sb{sub 22}O{sub 38}, has been hydrothermally synthesized. • The single crystal structure was determined by X-ray diffraction. • The powder XRD and UV–vis absorption spectroscopy were studied. • Theoretical studies interpret the relationships between optical absorption and crystal structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗