Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “OMIT”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Synthesis, structure and electrochemical properties of layered La{sub 2}Li{sub 2x}(CO{sub 3}){sub 1−x}O{sub 2+2x}

An oxide ion conductor, La{sub 2}Li{sub 2x}(CO{sub 3}){sub 1−x}O{sub 2+x} (x=0.15), was synthesized using a solid-state reaction, and its structure was subsequently determined by Rietveld refinement analyses of synchrotron X-ray and high-resolution powder neutron diffraction data. These analyses determined that carbonate groups are situated between (La{sub 2}O{sub 2}{sup 2+}){sub n} layers in an ordered arrangement and that both oxygen vacancies and interstitial oxygen ions exist within the carbonate layers, resulting in a composition of La{sub 2}Li{sub 0.3}(CO{sub 3}){sub 0.85}O{sub 2.3}. This material is structurally stable up to 500 °C and exhibits a conductivity of 5.5×10{sup −5} S cm{sup −1} at 450 °C. Oxide vacancies associated with carbonate anions appear to be responsible for the ionic conduction observed in this material. - Graphical abstract: Thermal ellipsoid projection of the carbonate layer viewed from the c-axis, showing oxygen migration paths: (A, blue line) interstitial hopping and (B, green line) co-operative rotation. Display Omitted - Highlights: • Lithium insertion in the structure causes the structural changes in carbonate layer. • These structural changes create oxygen vacancies within the flexible carbonate layers and introduce interstitial oxygen. • These interstitial oxygen atoms and oxygen vacancies are involved in oxide ion diffusion through the carbonate layer.

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

Magnetocrystalline interactions and oxidation state determination of Mn{sub (2−x)}V{sub (1+x)}O{sub 4} (x=0, 1/3 and 1) magnetorresistive spinel family

Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn{sub (2−x)}V{sub (1+x)}O{sub 4} (x=0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn{sub (2−x)}V{sub (1+x)}O{sub 4} (x=0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution Kβ X-ray fluorescence spectra. The ionic models found are Mn{sup 2+}{sub 2}V{sup 4+}O{sub 4}, Mn{sup 2+}{sub 5/3}V{sup 3.5+}{sub 4/3}O{sub 4} and Mn{sup 2+}V{sup 3+}{sub 2}O{sub 4}. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn{sup 2+}. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V{sup 3+} ion instead of the weak Mn{sup 2+} (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques. - Graphical abstract: View of the crystallographic structure of a spinel. It shows as an example one of the models of ion distribution determined for the spinels Mn{sub (2−x)}V{sub (1+x)}O{sub 4} (x=0, 1/3,1). Display Omitted - Highlights: • Determination of oxidation state of the metallic ions in Mn{sub (2−x)}V{sub (1+x)}O{sub 4} (x=0,1/3,1) by XAS and XES techniques. • The ionic models found are Mn{sup 2+}{sub 2}V{sup 4+}O{sub 4}, Mn{sup 2+}{sub 5/3}V{sup 3.5+}{sub 4/3}O{sub 4} and Mn{sup 2+}V{sup 3+}O{sub 4}. • EPR spectra correspond almost exclusively to a resonance of Mn{sup 2+}.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Corrosion behavior of mesoporous transition metal nitrides

Transition metal nitrides (TMN) have many desirable characteristics such as high hardness and good thermal stability under reducing conditions. This work reports an initial survey of the chemical stability of mesoporous TMNs (TM=Nb, V, Cr and Ti) in water at 80 °C at neutral, acidic and alkaline pH. The mesoporous TMNs had specific surface areas of 25–60 m{sup 2}/g with average pore sizes ranging from 10 to 50 nm. The high surface areas of these materials enhance the rate of corrosion per unit mass over that of a bulk material, making detection of corrosion much easier. The products were characterized by Rietveld refinement of powder X-ray diffraction (PXRD) patterns and by scanning electron microscopy (SEM). Several nitrides have corrosion rates that are, within error, not distinguishable from zero (±1 Å/day). Of the nitrides examined, CrN appears to be the most corrosion resistant under acidic conditions. None of the nitrides studied are corrosion resistant under alkaline conditions. - Graphical abstract: Corrosion behavior of mesoporous transition metal nitrides (TM=Nb, V, Cr and Ti) in acidic and alkaline solutions at 80 °C for 2 weeks. Display Omitted - highlights: • Corrosion rates of mesoporous transition metal nitrides in aqueous solution is reported. • The mesoporous TMNs had surface areas of 25–60 m{sup 2}/g. • CrN is the most corrosion resistant under the conditions studied.

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

Combined effect of chemical pressure and valence electron concentration through the electron-deficient Li substitution on the RE{sub 4}LiGe{sub 4} (RE=La, Ce, Pr, and Sm) system

Four members of the RE{sub 4}LiGe{sub 4} (RE=La, Ce, Pr, and Sm) system have been prepared by high-temperature reaction method and characterized by X-ray diffractions. All compounds crystallize in the orthorhombic Gd{sub 5}Si{sub 4}-type structure (space group Pnma, Pearson code oP16) with bonding interactions for interslab Ge{sub 2} dimers. The Li substitution for rare-earth elements in the RE{sub 4}LiGe{sub 4} system leads to a combined effect of the increased chemical pressure and the decreased valance electron concentration (VEC), which eventually results in the structure transformation from the Sm{sub 5}Ge{sub 4}-type with all broken interslab Ge–Ge bond for the parental RE{sub 5}Ge{sub 4} to the Gd{sub 5}Si{sub 4}-type structure for the ternary RE{sub 4}LiGe{sub 4} (RE=La, Ce, Pr, and Sm) system. Site-preference between rare-earth metals and Li is proven to generate energetically the most favorable atomic arrangements according to coloring-problem, and the rationale is provided using both the size-factor and the electronic-factor related, respectively, to site-volume and electronegativity as well as QVAL values. Tight-binding, linear-muffin-tin-orbital (TB-LMTO) calculations are performed to investigate electronic densities of states (DOS) and crystal orbital Hamilton population (COHP) curves. The influence of reduced VEC for chemical bonding including the formation of interslab Ge{sub 2} dimers is also discussed. The magnetic property measurements prove that the non-magnetic Li substitution leads to the ferromagnetic (FM)-like ground state for Ce{sub 4}LiGe{sub 4} and the co-existence of antiferromagntic (AFM) and FM ground states for Sm{sub 4}LiGe{sub 4}. - Graphical abstract: Reported is a combined effect of the chemical pressure and the reduced VEC caused by the smaller monovalent non-magnetic Li substitution for the larger trivalent magnetic rare-earth metals in the RE{sub 4}LiGe{sub 4} (RE=La, Ce, Pr, and Sm) system. This results in the structure transformation from the Sm{sub 5}Ge{sub 4}-type to the Gd{sub 5}Si{sub 4}-type structure and the changes in magnetic properties. Display Omitted - Highlights: • Four Li-containing intermetallic compounds RE{sub 4}LiGe{sub 4} (RE=La, Ce, Pr and Sm) were synthesized. • The combined effect of the chemical pressure and the reduced VEC caused by Li substitution for a rare-earth metal results in the structure transformation. • Electronic structures and magnetic properties of title compounds were thoroughly investigated.

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

Synthesis, characterization and magnetic behavior of Co/MCM-41 nano-composites

Synthesis, structure and magnetic properties of Co/MCM-41 as magnetic nano-composites have been investigated. Mesoporous materials with different degrees of metal loading were prepared by wet impregnation and characterized by ICP, XRD, N{sub 2} adsorption, UV–vis DRS, TPR and EPMA-EDS. Cobalt oxide clusters and Co{sub 3}O{sub 4} nano-particles could be confined inside the mesopores of MCM-41, being this fact favored by the Co loading increasing. In addition, larger crystals of Co{sub 3}O{sub 4} detectable by XRD also grow on the surface when the Co loading is enhanced. The magnetic characterization was performed in a SQUID magnetometer using a maximum magnetic applied field µ{sub 0}Ha=1 T. While the samples with the higher Co loadings showed a behavior typically paramagnetic, a superparamagnetic contribution is more notorious for lower loadings, suggesting high Co species dispersion. - Graphical abstract: Room temperature hysteresis loops as a function of the Co content. Display Omitted - Highlights: • Co species as isolated Co{sup 2+}, oxide clusters and Co{sub 3}O{sub 4} nano-particles were detected. • For higher Co loads were detected, by XRD, Co{sub 3}O{sub 4} particles on the external surface. • The confining of Co species inside the mesopores was achieved by increasing Co load. • Paramagnetism from oxide clusters/nano-particles becomes dominant for higher Co loads. • Superparamagnetism can be assigned to Co species of small size and finely dispersed.

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

New ternary phosphides and arsenides. Syntheses, crystal structures, physical properties of Eu{sub 2}ZnP{sub 2}, Eu{sub 2}Zn{sub 2}P{sub 3} and Eu{sub 2}Cd{sub 2}As{sub 3}

Three new europium pnictides Eu{sub 2}ZnP{sub 2}, Eu{sub 2}Zn{sub 2}P{sub 3} and Eu{sub 2}Cd{sub 2}As{sub 3} have been synthesized and their structures were determined by single-crystal X-ray diffraction. Eu{sub 2}ZnP{sub 2} is isotypic with Yb{sub 2}CdSb{sub 2} (Cmc2{sub 1} (No. 36); cell parameters a=4.1777(7) Å, b=15.925(3) Å, c=7.3008(12) Å), while the latter two compounds crystallize with the Ba{sub 2}Cd{sub 2}Sb{sub 3} structure type (C2/m (No. 12); cell parameters a=15.653(5)/16.402(1) Å, b=4.127(1)/4.445(4) Å, c=11.552(4)/12.311(1) Å and β=126.647(4)/126.515(7)° for Eu{sub 2}Zn{sub 2}P{sub 3} and Eu{sub 2}Cd{sub 2}As{sub 3}, respectively). Magnetic susceptibility measurements in the interval 5–300 K confirm paramagnetic behavior and effective magnetic moments characteristic of Eu{sup 2+} ([Xe] 4f{sup 7}) ground states. Temperature-dependent electrical conductivity measurements also prove that Eu{sub 2}Cd{sub 2}As{sub 3} is a semiconducting compound with a narrow band gap of 0.059 eV below 100 K. According to TG/DSC analyses, Eu{sub 2}Cd{sub 2}As{sub 3} starts to decompose at about 950 K. - Graphical abstract: A polyhedral view of the crystal structure of new pnictides Eu{sub 2}T{sub 2}Pn{sub 3} (T=Zn or Cd; Pn=P or As). Display Omitted - Highlights: • Three new ternary pnictide Zintl compounds, Eu{sub 2}ZnP{sub 2}, Eu{sub 2}Zn{sub 2}P{sub 3} and Eu{sub 2}Cd{sub 2}As{sub 3}, have been synthesized and characterized. • The europium cations are divalent and ferromagnetically coupled in both Eu{sub 2}Zn{sub 2}P{sub 3} and Eu{sub 2}Cd{sub 2}As{sub 3}. • Eu{sub 2}Cd{sub 2}As{sub 3} has a very small band gap of 0.06 eV and starts to decompose over 950 K.

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

Magnetic structure of Sr{sub 2}Fe{sub 2}O{sub 5} brownmillerite by single-crystal Mössbauer spectroscopy

In order to determine orientation of the Fe{sup 3+} magnetic moments and electric field gradient (efg) axes in the brownmillerite-type strontium ferrite structure for both iron sublattices where the efg tensor is not axially symmetric, the Mössbauer spectra of powdered and oriented single-crystal Sr{sub 2}Fe{sub 2}O{sub 5} were analyzed by solving the complete Hamiltonian for hyperfine interactions in the excited and ground states of the {sup 57}Fe nuclei. The magnetic moments of both octahedrally and tetrahedrally coordinated iron cations lie on the ac-plane of the orthorhombic unit cell and are parallel to the shortest c-axis, whilst the main efg axes are parallel to the longest crystallographic axis, b. This orientation is similar to that in Ca{sub 2}Fe{sub 2}O{sub 5}, in spite of the structural differences of strontium and calcium ferrite brownmillerites at low temperatures. - Graphical abstract: Mössbauer spectra of powdered and oriented single-crystal Sr{sub 2}Fe{sub 2}O{sub 5}, analyzed by solving the complete Hamiltonian for hyperfine interactions in the excited and ground states of the {sup 57}Fe nuclei, show that the magnetic moments of both octahedrally and tetrahedrally coordinated iron cations are parallel to the shortest c-axis of the orthorhombic brownmillerite unit cell . Display Omitted - Highlights: • Single-crystal Mössbauer spectroscopy is used to study magnetic structure of Sr{sub 2}Fe{sub 2}O{sub 5}. • Complete Hamiltonian for hyperfine interactions in excited and ground states was solved. • Fe{sup 3+} magnetic moments are parallel to the shortest crystallographic axis c. • The orientation of nuclear electric field gradient is similar to that in Ca{sub 2}Fe{sub 2}O{sub 5}.

36 MATERIALS SCIENCE↗
DOE OSTI2013

The synthesis, single-crystal structure, optical absorption, and resistivity of Th{sub 2}GeSe{sub 5}

The compound Th{sub 2}GeSe{sub 5} has been synthesized by the reaction of the elements at 1273 K. From a single-crystal study Th{sub 2}GeSe{sub 5} crystallizes in the Ba{sub 5}Si{sub 3} structure type with four formula units in the space group D{sup 8}{sub 4h}−P4/ncc of the tetragonal system in a cell with dimensions a=7.4968(4) Å and c=13.6302(9) Å at 100(2) K. From optical absorption measurements Th{sub 2}GeSe{sub 5} is found to have an optical band gap of 1.92 eV (indirect) or 1.98 eV (direct), consistent with its red color. Th{sub 2}GeSe{sub 5} is a wide gap semiconductor, as indicated by its electrical resistivity at 298 K of 4.37(2)×10{sup 9} Ω cm measured on a single crystal. - Graphical abstract: The structure of Th{sub 2}GeSe{sub 5}. Display Omitted - Highlights: • The new compound Th{sub 2}GeSe{sub 5} was synthesized from the elements and recrystallized from Sb{sub 2}Se{sub 3}. • Th{sub 2}GeSe{sub 5} crystallizes in the Ba{sub 5}Si{sub 3} structure type. • The band gap of Th{sub 2}GeSe{sub 5} is1.92 eV and its resistivity shows it to be a wide gap semiconductor.

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

From fluorite to pyrochlore: Characterisation of local and average structure of neodymium zirconate, Nd{sub 2}Zr{sub 2}O{sub 7}

The structural characterisation of Nd{sub 2}Zr{sub 2}O{sub 7} prepared via a precursor route was performed using a combination of local and average structure probes (neutron total scattering, X-ray and neutron diffraction). We present the first total scattering and reverse Monte Carlo (RMC) modelling study of Nd{sub 2}Zr{sub 2}O{sub 7}, which provides compelling evidence for the adoption of a disordered fluorite-type structure by Nd{sub 2}Zr{sub 2}O{sub 7} prepared by a low-temperature precursor route. Annealing the material at high temperatures leads to a transformation to a pyrochlore-type structure; however, Rietveld refinement using powder neutron diffraction data shows that the oxygen sublattice retains a degree of disorder. - Graphical abstract: Display Omitted - Highlights: • The first total scattering and RMC modelling study of Nd{sub 2}Zr{sub 2}O{sub 7}. • Demonstration that the synthetic route influences the crystal structure adopted. • Insight into the importance of total scattering in studies of complex superstructures, especially for nano-sized materials.

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

Pressure-induced volume collapse and structural phase transitions in SrRuO{sub 3}

We report on the low temperature (6 K) structural properties of SrRuO{sub 3} under quasi-hydrostatic pressure studied by synchrotron X-ray powder diffraction in a diamond anvil cell. First principle calculations predict a first-order perovskite (Pv) to post-perovskite (pPv) phase transition at ∼40 GPa accompanied by a 1.9% volume collapse. Our results rule out the occurrence of a pPv phase to 54 GPa. Instead, we find a Pv to monoclinic to triclinic sequence of phase transitions. The monoclinic to triclinic phase transition at ∼38 GPa is accompanied by a 3.5% volume collapse. X-ray absorption spectroscopy indicates that this volume collapse is not accompanied by a change in Ru valence state. Our results should help guide improvements to theoretical treatments of this and other correlated d-electron systems based on density functional theory. - Graphical abstract: Unit cell volume as a function of pressure (T=6 K). Black squares and red circles correspond to Ne and He pressure media, respectively. Blue dashed lines are fit to the data before the volume collapse using a second-order Birch–Murnaghan equation of state excluding (lower curve) and including (upper curve) neutron diffraction data for the low temperature, ambient pressure volume. Dashed lines denote structural phase boundaries. Display Omitted - Highlights: • Crystal structure of SrRuO3 was studied under high pressure up to 54 GPa. • Pv to monoclinic to triclinic sequence of phase transitions was observed. • Transition to triclinic phase at ∼38 GPa is accompanied by a 3.5% volume collapse. • Volume collapse in SrRuO3 is not driven by a change in Ru valence state. • Pv-to-pPv phase transition predicted by DFT at 40 Gpa is not observed up to 54 GPa.

36 MATERIALS SCIENCE↗
DOE OSTI2013

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↗
DOE OSTI2013

Designing new n=2 Sillen–Aurivillius phases by lattice-matched substitutions in the halide and [Bi{sub 2}O{sub 2}]{sup 2+} layers

A new n=2 Sillen–Aurivillius compound Bi{sub 3}Sr{sub 2}Nb{sub 2}O{sub 11}Br has been synthesised based on Bi{sub 3}Pb{sub 2}Nb{sub 2}O{sub 11}Cl by simultaneously replacing Pb{sup 2+} with Sr{sup 2+} and Cl{sup −} with Br{sup −}. Rietveld refinements against X-ray and neutron powder diffraction data revealed a significant relative compression in the stacking axis (c-axis) of the new compound. Sr{sup 2+} doping reduces the impact of the stereochemically active 6s{sup 2} lone pair found on Pb{sup 2+} and Bi{sup 3+}, resulting in a contraction of the c-axis by 1.22% and an expansion of the ab plane by 0.25%. This improves the inter-layer compatibility with the larger halide Br{sup −}. Analysis of X-ray absorption near-edge spectroscopy data show that the ferroelectric distortion of the B-site cation is less apparent in Bi{sub 3}Sr{sub 2}Nb{sub 2}O{sub 11}Br compared to Bi{sub 3}Pb{sub 2}Nb{sub 2}O{sub 11}Cl, and variable-temperature neutron diffraction data show no evidence for a ferroelectric distortion. - Graphical abstract: The structural expansion and contractions in the stacking axis of co-doped Sillen–Aurivillius phases. Display Omitted - Highlights: • A new Sillen–Aurivillius phase Bi{sub 3}Sr{sub 2}Nb{sub 2}O{sub 11}Br is synthesised based on Bi{sub 3}Pb{sub 2}Nb{sub 2}O{sub 11}Cl. • The stacking axis contracts although local expansion accommodates the larger halide Br. • Majority of the contraction is observed in the [Bi{sub 2}O{sub 2}]{sup 2+} layers where we replaced Pb{sup 2+} for Sr{sup 2+}. • Removing the Pb{sup 2+} lowers the lone pair effect and improves inter-layer compatibility. • XANES and NPD suggest that the ferroelectric properties are minimised or suppressed.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Bismuth alloying properties in GaAs nanowires

First-principles calculations have been performed to investigate the structural, electronic and optical properties of bismuth alloying in GaAs nanowires. A typical model of Ga{sub 31}As{sub 31} nanowires is introduced for its reasonable band gap. The band gap of GaAs{sub 1−x}Bi{sub x} shrinks clearly with the increasing Bi concentration and the band edge shifts when spin–orbit coupling (SOC) is considered. The insertion of Bi atom leads to hybridization of Ga/As/Bi p states which contributes a lot around Fermi level. Scissor effect is involved. The optical properties are presented, including dielectric function, optical absorption spectra and reflectivity, which are also varied with the increasing of Bi concentrations. - Graphical abstract: Top view of Bi-doped GaAs nanowires. Ga, As, and Bi atoms are denoted with grey, purple and red balls, respectively. Display Omitted - Highlights: • A typical model of Ga{sub 31}As{sub 31} nanowires is introduced for its reasonable band gap. • The band gap of GaAs{sub 1−x}Bi{sub x} shrinks clearly with the increasing Bi concentration. • The band edge shifts when spin–orbit coupling (SOC) is considered. • The insertion of Bi atom leads to hybridization of Ga/As/Bi p states.

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

Physical properties of zircon and scheelite lutetium orthovanadate: Experiment and first-principles calculation

Pure zircon and scheelite LuVO{sub 4} were prepared by solid state reaction and high-pressure route, respectively. Structure, elastic constants, lattice dynamics and thermodynamics of LuVO{sub 4} polymorphs were studied by experiments and first principles calculation. Calculations here are in good agreement with the experimental results. The phonon dispersions of LuVO{sub 4} polymorphs were studied by the linear response method. The calculated phonon dispersions show that zircon and scheelite LuVO{sub 4} phases are dynamically stable. Raman-active frequencies were measured and assigned to different modes according to the calculations. The internal frequencies shift downward after phase transition from zircon to scheelite. Born effective charge tensors elements for both phases are analyzed. The finite temperature thermodynamic properties of LuVO{sub 4} polymorphs were calculated from the obtained phonon density of states by quasi-harmonic approach. - Graphical abstract: Lutetium orthovanadate polymorphs were synthesized by SSR and HP methods and their physical and chemical properties, including lattice dynamical properties, were determined by DFT calculations and experiments. Display Omitted - Highlights: • Pure zircon and scheelite LuVO{sub 4} polymorphs were synthesized by solid state reaction and high-pressure route. • Chemical and physical properties of LuVO4 polymorphs were studied by experiments and first principles calculation. • Raman-active frequencies were measured and assigned to different modes according to the calculations. • Lattice dynamics of polymorphs were discussed in details.

36 MATERIALS SCIENCE↗
DOE OSTI2013

New double molybdate Na{sub 9}Fe(MoO{sub 4}){sub 6}: Synthesis, structure, properties

A new double molybdate Na{sub 9}Fe(MoO{sub 4}){sub 6} was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, X-ray fluorescence analysis, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na{sub 9}Fe(MoO{sub 4}){sub 6} were obtained and its structure was solved (the space group R3{sup ¯}, a=14.8264(2), c=19.2402(3) Å, V=3662.79(9) Å{sup 3}, Z=6, R=0.0132). The structure is related to that of sodium ion conductor II-Na{sub 3}Fe{sub 2}(AsO{sub 4}){sub 3}. The basic structure units are polyhedral clusters composed of central FeO{sub 6} octahedron sharing edges with three Na(1)O{sub 6} octahedra. The clusters share common vertices with bridging MoO{sub 4} tetrahedra to form an open 3D framework where the cavities are occupied by Na(2) and Na(3) atoms. The compound melts incongruently at 904.7±0.2 K. Arrhenius type temperature dependence of electric conductivity σ has been registered in solid state (σ=6.8×10{sup −2} S cm{sup −1} at 800 K), thus allowing considering Na{sub 9}Fe(MoO{sub 4}){sub 6} as a new sodium ion conductor. - Graphical abstract: A new double molybdate Na{sub 9}Fe(MoO{sub 4}){sub 6} was synthesized and structurally characterized, its physicochemical properties were studied. Display Omitted - Highlights: • A new compound Na{sub 9}Fe(MoO{sub 4}){sub 6} was synthesized as ceramics and single crystals. • Na{sub 9}Fe(MoO{sub 4}){sub 6} structure is related to that of sodium-ion conductor II-Na{sub 3}Fe{sub 2}(AsO{sub 4}){sub 3}. • Physicochemical properties of the compound were studied. • Arrhenius plot for conductivity showed 6.8×10{sup −2} S cm{sup −1} at 800 K, E{sub a}∼0.8 eV. • Thus, Na{sub 9}Fe(MoO{sub 4}){sub 6} may be considered as a new sodium ion conductor.

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

Hall mobility in tin iodide perovskite CH{sub 3}NH{sub 3}SnI{sub 3}: Evidence for a doped semiconductor

CH{sub 3}NH{sub 3}SnI{sub 3} is a metal halide perovskite that shows metallic conductivity over a wide temperature range, although ab initio calculations and optical absorption indicate that its band structure is consistent with that of an intrinsic semiconductor. Hall effect measurements of as-grown crystals give a hole concentration of about 9×10{sup 17} cm{sup −3} with rather high Hall mobility of about 200 cm{sup 2} V{sup −1} s{sup −1} at 250 K. Artificial hole doping enhances the electrical conductivity of the crystals without influencing mobility. These observations indicate that the electronic structure in stoichiometric CH{sub 3}NH{sub 3}SnI{sub 3} can be described as that of an intrinsic semiconductor with a wide valence band. This situation leads to metal-like conduction with even a trace amount of spontaneous hole doping in the as-grown crystal. - Graphical abstract: Hall effect measurements of as-grown CH{sub 3}NH{sub 3}SnI{sub 3} crystals give a hole concentration of about 9×10{sup 17} cm{sup −3}. Artificial hole doping enhances the electrical conductivity of the crystals without influencing mobility, indicating that the electronic structure of CH{sub 3}NH{sub 3}SnI{sub 3} can be described as that of an intrinsic semiconductor with a wide valence band. Display Omitted - Highlights: • Hole concentration in highly conducting CH{sub 3}NH{sub 3}SnI{sub 3} was determined. • Hall mobility was not affected by artificial hole doping. • The electronic structure can be described as that of an intrinsic semiconductor.

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

Synthesis, characterization, magnetic and electrochemical properties of a new 3D hexa-copper-substituted germanotungstate

An inorganic–organic hybrid hexa-copper-substituted germanotungstate Na{sub 2}[Cu(dap){sub 2}]{sub 2}[Cu(dap){sub 2}] ([Cu{sub 6}(H{sub 2}O){sub 2}(dap){sub 2}][B-α-GeW{sub 9}O{sub 34}]{sub 2})·4H{sub 2}O (1) (dap=1,2-diaminopropane) has been hydrothermally prepared and characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 displays the six-connected 3D network with the long topological (O′Keefe) vertex symbol is 4·4·6{sub 4}·4·4·4·4·6{sub 4}·4·4·4·6{sub 4}·4·4·4 and the short vertex (Schläfli) symbol of 4{sup 12}6{sup 3}. Magnetic measurements indicate that there are the overall ferromagnetic exchange interactions in the belt-like hexa-Cu{sup II} cluster in 1. Furthermore, the electrochemical behavior and electrocatalysis of 1 modified carbon paste electrode (1-CPE) have been studied. The reductions of nitrite, bromate and hydrogen peroxide are principally mediated by the W{sup VI}-based wave. - Graphical abstract: A hexa-Cu{sup II} sandwiched germanotungstate has been synthesized and structurally characterized. The magnetic, solid-state electrochemical and electrocatalytic properties have been investigated. Display Omitted - Highlights: • Transition-metal substituted polyoxometalates. • Hexa-copper-substituted germanotungstate. • Six-connected 3D network. • Electrocatalytic reduction of nitrite, bromate and hydrogen peroxide.

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

Structure analysis of BaCe{sub 0.8}Y{sub 0.2}O{sub 3−δ} in dry and wet atmospheres by high-temperature X-ray diffraction measurement

High temperature X-ray diffraction measurements were performed under dry and wet atmospheres to investigate phase behavior of BaCe{sub 0.8}Y{sub 0.2}O{sub 3−δ} (BCY20). In the temperature range of 30–400 °C, BCY20 was identified to be rhombohedral and monoclinic structures in dry and wet atmospheres, respectively. Larger lattice volumes were obtained in a wet atmosphere due to a chemical expansion induced by water incorporation. A gradual change in diffraction peak shape due to a phase transformation from rhombohedral to monoclinic was observed at 300 °C when moisture was introduced into the atmosphere. These results indicated clearly the dependence of phase behavior of BCY20 on partial pressure of water vapor in atmosphere. - Graphical abstract: A BaCe{sub 0.8}Y{sub 0.2}O{sub 3−δ} rhombohedral phase transited to a monoclinic phase at 300 °C when moisture was introduced into the atmosphere. Display Omitted - Highlights: • Different structures for hydrated and dehydrated BaCe{sub 0.8}Y{sub 0.2}O{sub 3−δ} (BCY20). • Slow phase transition from rhombohedral to monoclinic at 300 °C in wet atmosphere. • Chemical expansion of BCY20 in wet atmosphere. • Importance of considering moisture when discussing phase behavior of BCY20.

36 MATERIALS SCIENCE↗