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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Gamma ray irradiated AgFeO{sub 2} nanoparticles with enhanced gas sensor properties

AgFeO{sub 2} nanoparticles were synthesized via a facile hydrothermal method and irradiated by various doses of gamma ray. The products were characterized with X-ray powder diffraction, UV–vis absorption spectrum and transmission electron microscope. The results revealed that the crystal structure, morphology and size of the samples remained unchanged after irradiation, while the intensity of UV–Vis spectra increased with irradiation dose increasing. In addition, gamma ray irradiation improved the performance of gas sensor based on the AgFeO{sub 2} nanoparticles including the optimum operating temperature and sensitivity, which might be ascribed to the generation of defects. - Graphical abstract: Gamma ray irradiation improved the performance of gas sensor based on the AgFeO{sub 2} nanoparticles including sensitivity and optimum operating temperature, which might be ascribed to the generation of defects. - Highlights: • AgFeO{sub 2} nanoparticles were synthesized and irradiated with gamma ray. • AgFeO{sub 2} nanoparticles were employed to fabricate gas sensors to detect ethanol. • Gamma ray irradiation improved the sensitivity and optimum operating temperature.

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

Synthesis and characterisation of In-doped MnWO{sub 4}-type solid-solutions: Mn{sub 1−3x}In{sub 2x}□{sub x}WO{sub 4} (x=0–0.11)

Substitution of In{sup 3+} for Mn{sup 2+} in MnWO{sub 4}, which is one of the most studied multiferroics, was conducted systematically by solid-state reactions at 1050 °C to obtain a series of Mn{sub (1−3x)}In{sub 2x}□{sub x}WO{sub 4} solid solutions (x=0–0.11; the box indicates vacancy). The successful In-doping could be proven by electron microprobe, and statically disordered structures of this solid solution series were elucidated by Rietveld analyses with X-Ray powder diffraction (XPD) data. Its average structure maintains the space group P2/c at least up to the replacement of 33 at% Mn. The tendency of their unit cells proportionally enlarging with In-doping is an unexpected observation because In{sup 3+} is smaller than Mn{sup 2+}. This could not be explained alone by average atomic bonding distances and angles evaluated from XPD data analyses. Complimentarily, micro-Raman spectra of Mn{sub (1−3x)}In{sub 2x}□{sub x}WO{sub 4} materials feature a hardening of Raman modes due to stronger atomic bonds in W{sub 2}O{sub 4} and WO{sub 2} units with increasing In-doping. This is considered as an inevitable consequence of broken bonding in directly neighbouring Mn–O bonds as the presence of In{sup 3+} in MnWO{sub 4} accompanies the creation of defects at Mn sites. The current study using XRD and micro-Raman suggests the enlarging local space around the bridging oxygen as the reason for the unexpected cell expansion when smaller In{sup 3+} along with defects replace Mn{sup 2+} in MnWO{sub 4}. - Graphical abstract: Despite of substitution of smaller In{sup 3+} for larger Mn{sup 2+}, the In-rich solid solution Mn{sub 0.71(2)}In{sub 0.19(1)}□{sub 0.10}WO{sub 4} undergoes a volume expansion of 0.4% with respect to MnWO{sub 4}. This could be explained by a local space expansion of 0.13% around bridging oxygen at O2 sites, as illustrated by dashed lines for clarity. - Highlights: • Investigation of Mn{sub (1−3x)}In{sub 2x}□{sub x}WO{sub 4} solid solutions (x=0–0.11). • An unexpected lattice expansion by In-doping. • Strong change in local environment around bridging oxygens. • Enhancement of atomic bonds in W{sub 2}O{sub 4} and WO{sub 2} units with increasing In-doping.

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

Synthesis, crystal structure and properties of alluaudite-like triple molybdate Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24}

A new triple molybdate Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} were obtained and its structure was solved (the space group P1{sup ¯}, a=12.5814(5), b=13.8989(5), c=28.4386(9) Å, α=90.108(2), β=90.064(2), γ=90.020(2)°, V=4973.0(3) Å{sup 3}, Z=2, R=0.0440). Characteristic features of the structure are polyhedral layers composed of pairs of edge-shared FeO{sub 6} and (Fe, Na)O{sub 6} octahedra, which are connected by bridging MoO{sub 4} tetrahedra. The layers share common vertices with bridging MoO{sub 4} tetrahedra to form an open 3D framework with the cavities occupied by the Cs{sup +} and Na{sup +} cations. The compound undergoes first-order phase transformation at 642 K and above this phase transition, electrical conductivity reaches 10{sup −3}–10{sup −2} S cm{sup −1}. Thus, Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} may be considered as a promising compound for developing new materials with high ionic conductivity. - Graphical abstract: A new triple molybdate Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} was synthesized and structurally characterized, its physicochemical properties were studied. - Highlights: • New compound Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} was synthesized. • Physicochemical properties of the compound were studied. • The first-order phase transformation is observed. • Electrical conductivity above 642 K is (10{sup −2}–10{sup −3}) S cm{sup −1}. • New compound may be considered as promising object with high ionic conductivity.

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

Monoclinic distortion and magnetic coupling in the double perovskite Sr{sub 2−x}Ca{sub x}YRuO{sub 6}

Abstracts: This work investigates in the insulating double perovskites Sr{sub 2−x}Ca{sub x}YRuO{sub 6}. We address the angular dependence of the strength of the magnetic coupling due to the deviation from planarity of the basal layers of the monoclinic structure, characterized by the in-plane angle α<180°, in order to probe the impact of the structural distortions in the magnetic properties of the compounds. High resolution x-ray powder diffraction, susceptibility, and specific heat measurements were performed. The deviation from planarity significantly increases (α=144° for x=1) while the bond distances vary in a complex way as a consequence of the strong monoclinic distortion. We found that the magnetic transition temperature, T{sub M}, shows a linear dependence on cos [(π−α)/2]. This result is discussed in terms of t{sub 2g}(π)–e{sub g}(σ) mixing of the magnetic orbitals of the Ru{sup 5+} ions and unbalanced competitive super-exchange interactions. The deleterious effect of Ca doping for the magnetic coupling is confirmed by the reduction in the short-range antiferromagnetic correlations characteristic of the parent compound at T>>T{sub M} and the enhancement of magnetic frustration for T<T{sub M}. - Graphical abstract: Tilting of the oxygen octahedra in Sr{sub 2−x}Ca{sub x}YRuO{sub 6} due to strong monoclinic distortions. - Highlights: • Neel temperatures in SrCaYRuO were correlated quantitatively with lattice distortions. • Bending of Ru–O–Y planes plays a major role in the magnetic properties of SrCaYRuO. • The structural–magnetic correlation is due to π–σ mixing of the magnetic orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural and magnetic properties of the La{sub 2−x}Ca{sub x}CoIrO{sub 6} double perovskite series

Polycrystalline samples of the series La{sub 2−x}Ca{sub x}CoIrO{sub 6} (0≤x≤1.2) have been synthesized and its structural and magnetic properties were investigated using experiments of X-ray powder diffraction, temperature dependent magnetic susceptibility and magnetization as a function of applied magnetic field. All grown polycrystalline compounds form in a monoclinic structure (space group P2{sub 1}/n) with a partially ordered distribution of transition metal cations Co/Ir over the six-coordinate sites. Our results indicate variation of the magnetic interactions between Co and Ir magnetic sublattices possibly due to valence changes of the transition metals, induced by doping. The undoped La{sub 2}CoIrO{sub 6} presents magnetic ordering at ∼97K, while for Ca-doped compounds a decrease of net magnetization and ordering temperatures was observed. For x=0.2 and 0.5 the emergence of a second magnetic interaction, due to the presence of high spin Co{sup 3+}, becomes evident. Interestingly, for x=0.8 the large effective magnetic moment indicates strong orbital contribution and spin-orbit coupling and/or the presence of Co{sup 4+} in high spin state. - Graphical abstract: Field cooling M vs.T curves for La{sub 2−x}Ca{sub x}CoIrO{sub 6} shows the suppression of magnetism with increasing La content. Zero field cooled curves indicate a second magnetic phase induced by the appearance of Co{sup 3+}. - Highlights: • Novel double perovskite series La{sub 2−x}Ca{sub x}CoIrO{sub 6} were synthesized by solid state reaction. • La{sup 3+} to Ca{sup 2+} substitution leads to Co valence and possibly spin state changes. • For some doped compounds, the emergence of a second magnetic phase, due to the presence of high spin Co{sup 3+}, becomes evident. • Physical properties of each compound can be well correlated to the electronic and magnetic evolution of the system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural and magnetic study of Yb{sup 3+} in the perovskites Sr{sub 2}YbMO{sub 6} (M=Nb, Ta, Sb)

The compounds Sr{sub 2}YbNbO{sub 6}, Sr{sub 2}YbTaO{sub 6} and Sr{sub 2}YbSbO{sub 6} have been prepared using solid state methods by heating pelleted reagents in air at temperatures up to 1400 °C. Rietveld refinement against room temperature neutron powder diffraction data show that all three compounds crystallise with a cation-ordered variant of the perovskite structure in the P2{sub 1}/n space group. Complete cation ordering occurs between M{sup 5+} and Yb{sup 3+} over two octahedrally-coordinated sites in the structure and all compounds are stoichiometric in oxygen. The Sb–O bond lengths are similar to related perovskite compounds but differ slightly from those indicated by bond valence sums. Magnetic susceptibility data resemble Curie–Weiss paramagnetic behaviour, but can be better understood as arising from the effect of the octahedral crystal field on the {sup 2}F{sub 5/2} ground state of Yb{sup 3+} leading to a temperature dependent magnetic moment on this ion below 100 K. - Graphical abstract: The magnetic susceptibility of the face-centred cubic Yb{sup 3+} lattice is dominated by the temperature dependent single-ion moment below 100 K. - Highlights: • Cation-ordered perovskites are studied using neutron diffraction and magnetometry. • Yb{sup 3+} cations form a pseudo face centred cubic lattice in a distorted structure. • Sb{sup 5+} cation is slightly overbonded as observed in related perovskites. • Crystal field splitting of 4f{sup 13} Yb{sup 3+} giving a temperature dependent moment. • Magnetic susceptibility reproduces theoretical predictions below 100 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Magnetic order and crystal structure study of YNi{sub 4}Si-type NdNi{sub 4}Si

Magnetic measurements and neutron powder diffraction investigation of the magnetic structure of the orthorhombic YNi{sub 4}Si-type (space group Cmmm) NdNi{sub 4}Si compound are presented. The magnetocaloric effect of NdNi{sub 4}Si is calculated in terms of the isothermal magnetic entropy change and it reaches the maximum value of –3.3 J/kg K for a field change of 50 kOe near T{sub C}=12 K. Below ∼12 K, NdNi{sub 4}Si exhibits a commensurate b-axis collinear ferromagnetic ordering with the Cmm′m magnetic space group in a zero magnetic field. At 1.5 K, the neodymium atoms have the magnetic moment of 2.37(5) μ{sub B}. The orthorhombic crystal structure and its thermal evolution are discussed in comparison with the CaCu{sub 5}-type compound. - Graphical abstract: The NdNi{sub 4}Si supplement the series of the orthorhombic derivative of the CaCu{sub 5}-type, namely the YNi{sub 4}Si-type, RNi{sub 4}Si compounds (R=Y, La, Ce, Sm, Gd–Ho). Below ∼12 K in a zero applied magnetic field, NdNi{sub 4}Si exhibits a commensurate b-axis collinear ferromagnetic ordering with the Cmm′m magnetic space group. Compared to the CaCu{sub 5}-type NdNi{sub 4}Si compound, the YNi{sub 4}Si-type counterpart has the relatively high ferromagnetic ordering temperature (9.2 K vs. 12 K), the small magnetocaloric effect (–7.3 J/kg K vs. –3.3 J/kg K for ∆H=50 kOe), and the large magnetic anisotropy at low temperatures. In contrast with CaCu{sub 5}-type NdNi{sub 4}Si, YNi{sub 4}Si-type NdNi{sub 4}Si shows distinct hysteresis loop at 2 K.We suggest that orthorhombic distortion may be used as a prospective route for optimization of permanent magnetic properties in the family of CaCu{sub 5}-type rare earth materials. - Highlights: • Below ∼12 K the YNi{sub 4}Si-type NdNi{sub 4}Si shows a ferromagnetic ordering. • MCE of NdNi{sub 4}Si reaches value of –3.3 J/kg K in 0–50 kOe near Curie point. • NdNi{sub 4}Si exhibits b-axis ferromagnetic order with the Cmm′m magnetic space group. • Contrary to CaCu{sub 5}-type, YNi{sub 4}Si-type NdNi{sub 4}Si shows hysteresis loop at 2 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Preparation and properties of a new ternary phase Mg{sub 3+x}Ni{sub 7−x}B{sub 2} (0.17≤x≤0.66) and its Cu-doping effect

In recent years, the materials in the B–Mg–Ni system have been intensively studied due to their excellent properties of hydrogen storage and superconductivity. Solving the crystal structure of phases in this system will facilitate an understanding of the mechanism of their physical properties. In this study, we report the preparation, crystal structure and physical properties of a new ternary phase Mg{sub 3+x}Ni{sub 7−x}B{sub 2} in the B–Mg–Ni system. The Mg{sub 3+x}Ni{sub 7−x}B{sub 2} phase was prepared by solid-state reactions at 1073 K and its crystal structure was determined and refined using X-ray powder diffraction data. The Mg{sub 3+x}Ni{sub 7−x}B{sub 2} phase crystallizes in the Ca{sub 3}Ni{sub 7}B{sub 2} structure type (space group R-3m, no. 166) with a=4.9496(3)–5.0105(6) Å, c=20.480(1)–20.581(1) Å depending on the x value, where x varies from 0.17 to 0.66. Two samples with nominal compositions Mg{sub 10}Ni{sub 20}B{sub 6} and Mg{sub 12}Ni{sub 18}B{sub 6} were characterized by magnetization and electric resistivity measurements in the temperature range from 5 K to room temperature. Both samples exhibited metallic behavior and showed spin-glass-like behavior with a spin freezing temperature (T{sub f}) around 33 K. A study of the Cu-doping effect showed that limited Cu content can be doped into the Mg{sub 3+x}Ni{sub 7−x}B{sub 2} compound and T{sub f} decreases as the Cu content increases. - Graphical abstract: The crystal structure of the Mg{sub 3+x}Ni{sub 7−x}B{sub 2} phase. - Highlights: • The crystal structure and solid solution range of Mg{sub 3+x}Ni{sub 7−x}B{sub 2} were revealed. • The magnetization and electrical resistivity of Mg{sub 3+x}Ni{sub 7−x}B{sub 2} were studied. • The Cu-doping effect of Mg{sub 3+x}Ni{sub 7−x}B{sub 2} was investigated.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Structural and magnetic properties of RTiNO{sub 2} (R=Ce, Pr, Nd) perovskite nitride oxides

Neutron powder diffraction indicates that CeTiNO{sub 2} and PrTiNO{sub 2} crystallize with orthorhombic Pnma symmetry (Ce: a=5.5580(5), b=7.8369(7), and c=5.5830(4) Å; Pr: a=5.5468(5), b=7.8142(5), and c=5.5514(5) Å) as a result of a{sup –}b{sup +}a{sup –} tilting of the titanium-centered octahedra. Careful examination of the NPD data, confirms the absence of long range anion order in both compounds, while apparent superstructure reflections seen in electron diffraction patterns provide evidence for short range anion order. Inverse magnetic susceptibility plots reveal that the RTiNO{sub 2} (R=Ce, Pr, Nd) compounds are paramagnetic with Weiss constants that vary from −28 to −42 K. Effective magnetic moments for RTiNO{sub 2} (R=Ce, Pr, Nd) are 2.43 μ{sub B}, 3.63 μ{sub B}, and 3.47 μ{sub B}, respectively, in line with values expected for free rare-earth ions. Deviations from Curie–Weiss behavior that occur below 150 K for CeTiNO{sub 2} and below 30 K for NdTiNO{sub 2} are driven by magnetic anisotropy, spin–orbit coupling, and crystal field effects. - Graphical abstract: The structure and magnetism of the oxide nitride perovskites RTiNO{sub 2} (R=Ce, Pr, Nd) have been explored. The average symmetry is shown to be Pnma with a random distribution of oxide and nitride ions and a{sup −}b{sup +}a{sup −} tilting of the titanium-centered octahedra, but electron diffraction shows evidence for short range anion order. All three compounds are paramagnetic but deviations from the Curie Weiss law are seen below 150 K for R=Ce and below 30 K for R=Nd. - Highlights: • The oxide nitride perovskites RTiNO{sub 2} (R=Ce, Pr) have been prepared and their structures determined. • Diffraction measurements indicate short range cis-order of O and N, but no long range order. • Compounds are paramagnetic with Weiss constants that vary from −28 to −42 K. • CeTiO{sub 2}N and NdTiO{sub 2}N deviate from Curie–Weiss behavior below 150 and 30 K, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

How the guest molecules in nanoporous Zn(II) metal-organic framework can prevent agglomeration of ZnO nanoparticles

The host and the apohost framework of [Zn{sub 2}(BDC){sub 2}(H{sub 2}O){sub 2}·(DMF){sub 2}]{sub n} (1·2H{sub 2}O·2DMF), (BDC{sup 2−}=benzene-1,4-dicarboxylate and DMF=N,N-Dimethylformamide), were synthesized and subsequently used for preparation of ZnO nanomaterials. With calcination of the host framework of 1·2H{sub 2}O·2DMF, ZnO nanoparticles were obtained. By the same process on the apohost framework of 1, agglomerated nanoparticles of ZnO were formed. These nano-structures were characterized by X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). These results indicate that with removal of the guest DMF and coordinated H{sub 2}O molecules from the one-dimensional channels of 1·2H{sub 2}O·2DMF, the tendency of nanoparticles to agglomerate increases and the role of this MOF in preparation of ZnO nanoparticles from this precursor was reduced. - Graphical abstract: Nano-porous zinc(II) MOF with guest DMF and coordinated H{sub 2}O molecules has been synthesized and characterized. The host and the apohost framework of it were used for preparation of ZnO nanomaterials. The role of these species in preparation of ZnO nanoparticles from the host framework is probably similar to the role of polymeric stabilizers in formation of nanoparticles. - Highlights: • Nanoparticles of ZnO were fabricated from nanoporous metal-organic framework. • The effect of guest DMF and coordinated H{sub 2}O molecules on this process was studied. • The effect of them in formation nanoparticle is similar to polymeric stabilizers.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Crystal chemistry of the orthorhombic Ln{sub 2}TiO{sub 5} compounds with Ln=La, Pr, Nd, Sm, Gd, Tb and Dy

The crystal structures of seven samples of orthorhombic (Pnma) Ln{sub 2}TiO{sub 5} compounds with Ln=La, Pr, Nd, Sm, Gd, Tb and Dy were refined by Rietveld analysis of synchrotron X-ray powder diffraction (S-XRD) data. With increasing size of the lanthanide cation, the lattice parameters increase systematically: c by only ~1.5% whereas both a and b by ~6% from Dy{sub 2}TiO{sub 5} to La{sub 2}TiO{sub 5}. The mean Ti–O bond length only increases by ~1% with increasing radius of the Ln cation from Gd to La, primarily due to expansion of the pair of Ti–O{sub 3} bonds to opposite corners of the Ti–O{sub 5} square based pyramid polyhedra. For Dy{sub 2}TiO{sub 5} and Tb{sub 2}TiO{sub 5}, a significant variation in Ti–O{sub 1} and Ti–O{sub 4} bond lengths results in an increased deformation of the Ti–O{sub 5} base. The particular configuration consists of large rhombic shaped tunnels and smaller triangular tunnels along the b axis, which have implications for defect formation and migration caused by radiation damage or the ionic conductivity. - Graphical abstract: Figure: The crystallographic study of a systematic series of compounds with nominal stoichiometry Ln{sub 2}TiO{sub 5} (with Ln representing La, Pr, Nd, Sm, Gd, Tb and Dy) and orthorhombic, Pnma, symmetry shows changes in cell parameters which fit a linear trend. However, bond lengths are shown to deviate from trend with compounds containing the smaller, heavier lanthanides. - Highlights: • First fabrication and crystallographic refinement of compound Pr{sub 2}TiO{sub 5}. • First systematic study of the crystallography, using S-XRD, for Ln{sub 2}TiO{sub 5} series. • Cation to anion bonding trends and valence states are investigated. • The densities and band-gaps of the series are experimentally determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Thermoelectric properties of Fe and Al double substituted MnSi{sub γ} (γ~1.73)

Two series of Fe and Al double substituted MnSi{sub γ} chimney ladders with a nominal valence electron count, VEC=14 per transition metal were prepared (γ=1.75). Simultaneous replacement of Mn with Fe and Si with Al yielded the Mn{sub 1−x}Fe{sub x}Si{sub 1.75−x}Al{sub x} series while the second Mn{sub 1−x}Fe{sub x}Si{sub 1.75–1.75x}Al{sub 2x} series follows the pseudo-binary between MnSi{sub 1.75} and FeAl{sub 2}. Scanning electron microscopy and elemental mapping revealed that ~60% of the nominal Al content ends up in the product with the remainder lost to sublimation, and that up to 7% Al can be substituted in the main group sublattice. Profile analysis of X-ray powder diffraction data revealed gradual changes in the cell metrics, consistent with the simultaneous substitution of Fe and Al in a fixed ratio. All samples are p-type with VEC≈13.95 from the structural data and ~1×10{sup 21} holes cm{sup −3} from variable temperature Seebeck measurements. The substituted samples have lower electrical resistivities (ρ{sub 300} {sub K}=2–5 mΩ cm) due to an improved microstructure. This leads to increased thermoelectric power factors (largest S{sup 2}/ρ=1.95 mW m{sup −1} K{sup −2}) compared to MnSi{sub γ}. The thermal conductivity for the Mn{sub 0.95}Fe{sub 0.05}Si{sub 1.66}Al{sub 0.1} sample is 2.7 W m{sup −1} K{sup −1} between 300 and 800 K, and is comparable to literature data for the parent material. - Graphical abstract: The crystal structure, microstructure and thermoelectric properties of Fe and Al double substituted MnSi{sub γ} (γ~1.73) have been investigated. - Highlights: • Up to 7% Al can be substituted in MnSi{sub γ} when co-doped with Fe. • Improved microstructure and reduced electrical resistivities for Al substituted samples. • Largest power factor 1.95 mW m{sup −1} K{sup −2} and best estimated ZT=0.5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Crystal structure and high-temperature properties of the Ruddlesden–Popper phases Sr{sub 3−x}Y{sub x}(Fe{sub 1.25}Ni{sub 0.75})O{sub 7−δ} (0≤x≤0.75)

Ruddlesden–Popper n=2 member phases Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been investigated by X-ray and neutron powder diffraction, thermogravimetry and Mössbauer spectroscopy. Both samples as-prepared at 1300 °C under N{sub 2}(g) flow and samples subsequently air-annealed at 900 °C were studied. The as-prepared x=0.75 phase is highly oxygen deficient with δ=1, the O1 atom site being vacant, and the Fe{sup 3+}/Ni{sup 2+} ions having a square pyramidal coordination. For as-prepared phases with lower x values, the Mössbauer spectral data are in good agreement with the presence of both 5- and 4-coordinated Fe{sup 3+} ions, implying in addition a partial occupancy of the O3 atom sites that form the basal plane of the square pyramid. The air-annealed x=0.75 sample has a δ value of 0.61(1) and the structure has Fe/Ni ions in both square pyramids and octahedra. Mössbauer spectroscopy shows the phase to contain only Fe{sup 3+}, implying that all Ni is present as Ni{sup 3+}. Air-annealed phases with lower x values are found to contain both Fe{sup 3+} and Fe{sup 4+}. For both the as-prepared and the air-annealed samples, the Y{sup 3+} cations are found to be mainly located in the perovskite block. The high-temperature thermal expansion of as-prepared and air-annealed x=0.75 phases were investigated by high-temperature X-ray diffraction and dilatometry and the linear thermal expansion coefficient determined to be 14.4 ppm K{sup −1}. Electrical conductivity measurements showed that the air-annealed samples have higher conductivity than the as-prepared ones. - Highlights: • Ruddlesden–Popper, n=2, Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been synthesised. • The crystal structures of the phases have been determined. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6}, made in N{sub 2}(g) has Fe{sup 3+}/Ni{sup 2+} in square pyramides. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6.4}, made in air has Fe{sup 3+}/Ni{sup 3+} in square pyramides and octahedra. • Air annealed samples have higher electrical conductivity than N{sub 2}(g) annealed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structure and magnetism of Sr{sub 3}NiSb{sub 2}O{sub 9}

The crystal structure of the perovskite-related oxide Sr{sub 3}NiSb{sub 2}O{sub 9} has been refined from X-ray and neutron powder diffraction data; space group P2{sub 1}/n, a=5.64381(2), b=5.62299(2), c=7.95687(3) Å, β=90.014(2)°. The structure has two crystallographically-distinct six-coordinate cation sites with occupancies Sb 0.97(1), Ni 0.03 and Sb 0.36, Ni 0.64. The magnetic susceptibility has been measured over the temperature range 2≤T/K≤300. Fitting data recorded in the temperature range 150<T/K<300 to the Curie–Weiss law resulted in µ{sub eff}=3.49(1) µ{sub B} per Ni{sup 2+}, θ=−138(1) K. Ferrimagnetic coupling in the vicinity of the antisite defects is suggested to be responsible for the enhanced susceptibility observed below ~90 K. The zero-field cooled susceptibility shows a maximum at 8.7 K that is not observed in the field-cooled susceptibility. Hysteresis is observed in M(H) at 2 K but not at 7.5 K. - Graphical abstract: Antisite defects on the B sites of perovskite-related Sr{sub 3}NiSb{sub 2}O{sub 9} lead to complex magnetic behaviour. - Highlights: • Sr{sub 3}NiSb{sub 2}O{sub 9} is a monoclinic perovskite. • The magnetic behaviour of Sr{sub 3}NiSb{sub 2}O{sub 9} at around 90 K can be attributed to antisite defects. • The magnetic behaviour of Sr{sub 3}NiSb{sub 2}O{sub 9} can be related to that of the relaxor ferromagnet La{sub 3}Ni{sub 2}SbO{sub 9}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

A solid solution series of atacamite type Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3}

For the first time a complete solid solution series Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these two metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 2−2x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes. • Substitution of Ni{sup 2+} by Mg{sup 2+} results in systematic Raman and IR band shifts. • α-Polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+}, … as described in literature do not exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis and characterization of montmorillonite clay intercalated with molecular magnetic compounds

In this work montmorillonite (MMT) clay, whose matrix was modified with an ammonium salt (hexadecyltrimethylammonium bromide – CTAB), was employed as an inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange: a nitronyl nitroxide derivative 2-[4-(N-ethyl)-pyridinium]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (p-EtRad{sup +}) and two binuclear coordination compounds, [Ni(valpn)Ln]{sup 3+}, where H{sub 2}valpn stands for 1,3-propanediyl-bis(2-iminomethylene-6-methoxy-phenol), and Ln=Gd{sup III}; Dy{sup III}. The pristine MMT and the intercalated materials were characterized by X-ray powder diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and magnetic measurements. The X-ray diffraction data analysis showed an increase of the interlamellar space of the intercalated MMT, indicating the intercalation of the magnetic compounds. Furthermore, the magnetic properties of the hybrid compounds were investigated, showing similar behavior as the pure magnetic guest species. - Graphical abstract: Montmorillonite clay was employed as inorganic host for the intercalation of three different molecular magnetic compounds through ion exchange - Highlights: • Montmorillonite was employed as a host material. • Three molecular magnetic compounds were intercalated through ion exchange. • The compounds were successful intercalated maintaining the layered structure. • The hybrid materials exhibited similar magnetic behavior as the pure magnetic guest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

(Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5}, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt{sub 1−x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.33) forms a B-filled β-Mn-type structure (space group P4{sub 1}32; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt{sub 9}Cu{sub 3}B{sub 5} (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt{sub 6}] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt{sub 6}] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt{sub 6}] and [Pt{sub 6}] trigonal prisms, rotated perpendicularly to the central one. There is no B–B contact as well as Cu–B contact in the structure. The relationships of Pt{sub 9}Cu{sub 3}B{sub 5} structure with the structure of Ti{sub 1+x}Os{sub 2−x}RuB{sub 2} as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ{sub 0}H{sub C2}(0){sup WHH} of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt{sub 9}Cu{sub 3}B{sub 5} (Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure) from electrical resistivity measurements. - Highlights: • First two copper platinum borides, (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5} were obtained. • (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B forms a B-filled β-Mn-type structure. • Pt{sub 9}Cu{sub 3}B{sub 5} adopts a Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure. • Boron atoms exhibit octahedral and trigonal prismatic coordination. • (Pt{sub 1–x}Cu{sub x})3Cu{sub 2}B (x=0.3) is a bulk superconductor with T{sub c} 2.06 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Growth, structure, defects and polarized absorption spectral properties of Er:Yb:YCa{sub 4}O(BO{sub 3}){sub 3} crystals

YCa{sub 4}O(BO{sub 3}){sub 3} (YCOB) crystals co-doped with 3 at% Er{sup 3+} and 20 at% Yb{sup 3+} were successfully grown by the Czochralski method. X-ray powder diffraction (XRPD) results show that the as-grown Er:Yb:YCOB crystal belongs to the monoclinic system with space group Cm. And the lattice parameters are a=8.076(8) Å, b=16.023(7) Å, c=3.528(4) Å and β=101.15(4)°. Crystal defects were revealed by chemical etching experiments. The density of etch pits, attributed to dislocations and observed on (010) planes, was found to be not uniform along the crystal diameter. The detailed polarized absorption spectra were measured. The polarized absorption cross sections at 977 nm are 1.01×10{sup −20}, 1.22×10{sup −20} and 1.05×10{sup −20} cm{sup 2} for E//X, E//Y and E//Z, respectively. And the polarized absorption cross sections at 1538 nm is about 1.86×10{sup −20} cm{sup 2} for both E//X and E//Z, but for E//Y the result is 1.03×10{sup −20} cm{sup 2}, which is much smaller. The relationship between the crystal structure and absorption spectra was discussed. - Graphical abstract: The as-grown bulk Er:Yb:YCOB crystal (the long axis is along the b-axis) and LeBail fit to the XRPD pattern of Er:Yb:YCOB (top) compared to the diffraction pattern of YCOB from the JCPDS data bank (bottom). Reflection markers indicate the calculated reflection positions. The middle trace gives the difference between observed and calculated intensity. Reflection indices corresponding to the strongest diffraction peaks are marked on the experimental pattern. - Highlights: • Er:Yb:YCOB crystal with a new composition was grown. • XRPD and FT-IR showed a certain degree of deformation in the crystal structure. • Detailed polarized absorption cross sections at 977 nm and 1538 nm were calculated. • Crystal defects were clearly revealed by chemical etching experiments.

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