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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.

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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Synthesis, crystal structures, and physical properties of the new Zintl phases A{sub 21}Zn{sub 4}Pn{sub 18} (A=Ca, Eu; Pn=As, Sb)—Versatile arrangements of [ZnPn{sub 4}] tetrahedra

Four new Zintl phases, Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18} and Eu{sub 21}Zn{sub 4}Sb{sub 18} have been synthesized by metal flux reactions. Their structures have been established from single-crystal X-ray diffraction. Despite the similar chemical makeup and the identical formulae, the structures of the four compounds are not the same—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18} and Eu{sub 21}Zn{sub 4}As{sub 18} crystallize in the monoclinic space group C2/m (No. 12, Z=4) with the β-Ca{sub 21}Mn{sub 4}Sb{sub 18} structure type, while Eu{sub 21}Zn{sub 4}Sb{sub 18} adopts the Ba{sub 21}Cd{sub 4}Sb{sub 18} structure type with the orthorhombic space group Cmce (No. 64, Z=8). Both structures are based on ZnAs{sub 4} or ZnSb{sub 4} tetrahedra, linked in slightly different ways, and Ca{sup 2+} and Eu{sup 2+} cations that fill the space between them. The structural relationships between the title compounds and other known ternary phases with intricate structures are discussed. Electrical resistivity measurement on single-crystalline Eu{sub 21}Zn{sub 4}Sb{sub 18} suggests an intrinsic semiconductor behavior with a band gap of ca. 0.2 eV. The temperature dependent DC magnetization measurement on the same material indicates Curie–Weiss paramagnetism in the high-temperature regime, and a spontaneous antiferromagnetic ordering below 8 K. The calculated effective moments of Eu confirm the divalent Eu{sup 2+} ground state, as expected from the Zintl–Klemm concept. - Graphical abstract: The four new Zintl phases—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18}—crystallize in two structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. - Highlights: • Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18} are new compounds in the respective ternary phase diagrams. • They form with structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. • For both structures, the valence electron count follows the Zintl–Klemm rules.

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

Synthesis, crystal structure, optical, and electronic study of the new ternary thorium selenide Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2}

The compound Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} has been synthesized by solid-state methods at 1173 K. Its crystal structure features one-dimensional chains of {sup 1}{sub ∞}[Th(Se){sub 3}(Se{sub 2}){sub 2}{sup 6−}] separated by Ba{sup 2+} cations. Each Th atom in these chains is coordinated to two Se–Se single-bonded pairs and four Se atoms to give rise to a pseudooctahedral geometry around Th. The Th–Se distances are consistent with Th{sup 4+} and hence charge balance of Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is achieved as 3×Ba{sup 2+}, 1×Th{sup 4+}, 3×Se{sup 2−}, and 2×Se{sub 2}{sup 2−}. From optical measurements the band gap of Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is 1.96(2) eV. DFT calculations indicate that the compound is a semiconductor. - Graphical abstract: Local coordination environment of Th atoms in the Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} structure. - Highlights: • Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} has been synthesized by solid-state methods at 1173 K. • The structure features chains of {sup 1}{sub ∞}[Th(Se){sub 3}(Se{sub 2}){sub 2}{sup 6−}] separated by Ba{sup 2+} cations. • Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is a semiconductor with a band gap of 1.96(2) eV.

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

Synthesis, structure, and magnetic characterization of Cr{sub 4}US{sub 8}

The compound Cr{sub 4}US{sub 8} has been synthesized at 1073 K and its crystal structure has been determined at 100 K. The structure is modulated with a two-fold commensurate supercell. The subcell may be indexed in an orthorhombic cell but weak supercell reflections lead to the monoclinic superspace group P2{sub 1}/c(α0γ)0s with two Cr sites, one U site, and four S sites. The structure comprises a three-dimensional framework of CrS{sub 6} octahedra with channels that are partially occupied by U atoms. Each U atom in these channels is coordinated by eight S atoms in a bicapped trigonal-prismatic arrangement. The magnetic behavior of Cr{sub 4}US{sub 8} is complex. At temperatures above ~120 K at all measured fields, there is little difference between field-cooled and zero field-cooled data and χ(T) decreases monotonously with temperature, which is reminiscent of the Curie–Weiss law. At lower temperatures, the temperature dependence of χ(T) is complex and strongly dependent on the magnetic field strength. - Graphical abstract: Structure of Cr{sub 4}US{sub 8} viewed down the a axis. - Highlights: • At 1073 K Cr{sub 4}US{sub 8} was synthesized and at 100 K its crystal structure was determined. • The 3D structure comprises CrS{sub 6} octahedra with channels partially occupied by U. • The magnetic behavior of Cr{sub 4}US{sub 8} is complex.

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

Synthesis, crystal structure, and magnetic properties of quaternary iron selenides: Ba{sub 2}FePnSe{sub 5} (Pn=Sb, Bi)

Two new barium iron pnictide–selenides, Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, were synthesized by a high-temperature solid-state route and their crystal structures were determined using single crystal X-ray diffraction. Both compounds are isomorphic to the high pressure phase Ba{sub 3}FeS{sub 5} and crystallize in the orthorhombic space group Pnma (No. 62) with cell parameters of a=12.603(2)/12.619(2) Å, b=9.106(1)/9.183(1) Å, c=9.145(1)/9.123(1) Å and Z=4 for Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, respectively. According to differential scanning calorimetry, Ba{sub 2}FePnSe{sub 5} compounds exhibit high thermal stability and melt congruently at 1055(5) K (Pn=Sb) and 1105(5) K (Pn=Bi). Magnetic characterizations reveal strong antiferromagnetic nearest-neighbor interactions in both compounds resulting in an antiferromagnetic ordering at 58(1) K for Ba{sub 2}FeSbSe{sub 5} and 79(2) K for Ba{sub 2}FeBiSe{sub 5}. The magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Graphical abstract: In Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} the magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Highlights: • New compounds Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} have been synthesized. • The crystal structure was determined by single crystal X-ray diffraction. • Both compounds melt congruently at temperatures above 1000 K. • Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} exhibit AFM ordering at 58 K (Sb) and 70 K (Bi). • Magnetic exchange between Fe{sup 3+} is mediated by either Se–Sb(Bi)–Se or Se–Ba–Se bridges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Synthesis and characterization of metastable, 20 nm-sized Pna2{sub 1}-LiCoPO{sub 4} nanospheres

The majority of research activities on LiCoPO{sub 4} are focused on the phospho-olivine (space group Pnma), which is a promising high-voltage cathode material for Li-ion batteries. In contrast, comparably little is known about its metastable Pna2{sub 1} modification. Herein, we present a comprehensive study on the structure–property relationships of 15–20 nm Pna2{sub 1}-LiCoPO{sub 4} nanospheres prepared by a simple microwave-assisted solvothermal process. Unlike previous reports, the results indicate that the compound is non-stoichiometric and shows cation-mixing with Co ions on the Li sites, which provides an explanation for the poor electrochemical performance. Co L{sub 2,3}-edge X-ray absorption spectroscopic data confirm the local tetrahedral symmetry of Co{sup 2+}. Comprehensive studies on the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and in situ powder X-ray diffraction show an exothermic phase transition to olivine Pnma-LiCoPO{sub 4} at 527 °C. The influence of the atmosphere and the particle size on the thermal stability is also investigated. - Graphical abstract: Blue nano-sized Pna2{sub 1}-LiCoPO{sub 4,} featuring tetrahedrally-coordinated Co{sup 2+}, was synthesized in a rapid one-step microwave-assisted solvothermal process. The phase relation between this metastable and the stable polymorph was analyzed and electrochemical properties are discussed. - Highlights: • Preparation of uniform 15–20 nm nanospheres of metastable Pna2{sub 1}-LiCoPO{sub 4} polymorph. • Structure redetermination shows cation-mixing (Co blocking Li sites). • In situ investigation of phase transformation to olivine Pnma-LiCoPO{sub 4} at 527 °C. • Pna2{sub 1}-LiCoPO{sub 4} reemerges as a stable high-temperature phase above 800 °C. • X-ray absorption spectroscopy confirms local tetrahedral symmetry (T{sub d} Co{sup 2+}).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Facile, One-Step Synthesis for Core–Shell Perovskite Materials via Molten Salt

Core–shell La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF)–La 0.8 Sr 0.2 MnO 3 (LSM) heterostructure crystalline materials have been synthesized in a simple, one-step feeding method via a KNO 3 molten salt solvent. Two-phase perovskite composites can be synthesized in times as short as 10 minutes and is demonstrated for the first time in a molten salt. Further, a combination of X-ray diffraction and S/TEM energy dispersive X-ray spectroscopy has been utilized to confirm the formation of an LSM shell on LSCF cores in all samples when adjusting dwell time, core size, weight ratio between core and shell precursors, and weight ratio of powder to salt. Specifically, decreasing the LSCF core size increases core–shell yield. Smaller cores introduce a greater density of facets on the crystal surface and provide more favorable sites for LSM heterogeneous nucleation.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Graphene and nano-diamond synthesis in expansions of molten liquid carbon

Despite their widespread use in high-pressure experiments, little is known about the physical and chemical properties of carbon-containing materials as they expand and cool to ambient conditions. As a result, interpretation of experiments can rely on use of unconstrained models with poor accuracy for the ensuing equation of state properties and final chemical products. To this end, we use quantum simulations to study the free expansion and cooling of carbon from metallic liquid states achieved during shock compression. Expansions from three different sets of shock conditions yielded of a variety of chain and ring structures. We then quantify the relative amounts of graphite-like and diamond-like particles formed during cooling and equilibration. Here, we observe that for all cases, graphene sheets are the majority product formed with more extreme initial conditions producing increasingly larger amounts of diamond particles. Our results can address key needs for future meso-scale models of experiments, where knowledge of material properties and chemical end products can have a pronounced effect on interpreting experimental observables.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Enhanced power factor of higher manganese silicide via melt spin synthesis method

We report on the thermoelectric properties of the Higher Manganese Silicide MnSi₁.₇₅ (HMS) synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describe the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5x10²⁰ cm⁻³ at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper; the maximum value is superior to those reported in the literatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

High pressure synthesis of amorphous TiO{sub 2} nanotubes

Amorphous TiO{sub 2} nanotubes with diameters of 8-10 nm and length of several nanometers were synthesized by high pressure treatment of anatase TiO{sub 2} nanotubes. The structural phase transitions of anatase TiO{sub 2} nanotubes were investigated by using in-situ high-pressure synchrotron X-ray diffraction (XRD) method. The starting anatase structure is stable up to ∼20GPa, and transforms into a high-density amorphous (HDA) form at higher pressure. Pressure-modified high- to low-density transition was observed in the amorphous form upon decompression. The pressure-induced amorphization and polyamorphism are in good agreement with the previous results in ultrafine TiO{sub 2} nanoparticles and nanoribbons. The relationship between the LDA form and α-PbO{sub 2} phase was revealed by high-resolution transmission electron microscopy (HRTEM) study. In addition, the bulk modulus (B{sub 0} = 158 GPa) of the anatase TiO{sub 2} nanotubes is smaller than those of the corresponding bulks and nanoparticles (180-240 GPa). We suggest that the unique open-ended nanotube morphology and nanosize play important roles in the high pressure phase transition of TiO{sub 2} nanotubes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Controlled synthesis of Eu{sup 2+} and Eu{sup 3+} doped ZnS quantum dots and their photovoltaic and magnetic properties

Eu-doped ZnS quantum dots (QDs) have been synthesized by wet-chemical method and found to form in zinc blende (cubic) structure. Both Eu{sup 2+} and Eu{sup 3+} doped ZnS can be controllably synthesized. The Eu{sup 2+} doped ZnS QDs show broad photoluminescence emission peak around 512 nm, which is from the Eu{sup 2+} intra-ion transition of 4f{sup 6}d{sup 1} – 4f{sup 7}, while the Eu{sup 3+} doped samples exhibit narrow emission lines characteristic of transitions between the 4f levels. The investigation of the magnetic properties shows that the Eu{sup 3+} doped samples exhibit signs of ferromagnetism, on the other hand, Eu{sup 2+} doped samples are paramagnetic of Curie-Weiss type. The incident photon to electron conversion efficiency is increased with the Eu doping, which suggests the QD solar cell efficiency can be enhanced by Eu doping due to widened absorption windows. This is an attractive approach to utilize benign and environmentally friendly wide band gap ZnS QDs in solar cell technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

GAS PHASE SYNTHESIS OF (ISO)QUINOLINE AND ITS ROLE IN THE FORMATION OF NUCLEOBASES IN THE INTERSTELLAR MEDIUM

Nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) have been proposed to play a key role in the astrochemical evolution of the interstellar medium, yet the formation mechanisms of even their simplest prototypes—quinoline and isoquinoline—remain elusive. Here, we reveal a novel concept that under high temperature conditions representing circumstellar envelopes of carbon stars, (iso)quinoline can be synthesized via the reaction of pyridyl radicals with two acetylene molecules. The facile gas phase formation of (iso)quinoline in circumstellar envelopes defines a hitherto elusive reaction class synthesizing aromatic structures with embedded nitrogen atoms that are essential building blocks in contemporary biological-structural motifs. Once ejected from circumstellar shells and incorporated into icy interstellar grains in cold molecular clouds, these NPAHs can be functionalized by photo processing forming nucleobase-type structures as sampled in the Murchison meteorite.

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

Synthesis of NaTi 2 ( PO 4 ) 3 by the Inorganic–Organic Steric Entrapment Method and Its Thermal Expansion Behavior

Crystalline pure NaTi 2 ( PO 4 ) 3 ( NTP ) powder was synthesized at 700°C using a simple and low energy, hybrid inorganic–organic, steric entrapment method. Sodium nitrite (Na NO 2 ) and ammonium phosphate dibasic (( NH 4 ) 2 HPO 4 ) dissolved in water, whereas titanium ( IV ) isopropoxide (Ti[ OCH ( CH 3 ) 2 ] 4 ) hydrolyzed in water. Ethylene glycol ( HOCH 2 CH 2 OH ) was used as a polymeric entrapper and hydrolysis of the Ti source was hindered by its dissolution in isopropyl alcohol. The resulting NTP powder was characterized by thermogravimetric analysis/differential thermal analysis, X‐ray diffractometry, scanning electron microscopy, specific surface area by Brunauer–Emmett–Teller nitrogen absorption, and particle size analysis. Furthermore, C, H, N were measured by the classical Pregl‐Dumas method. The thermal expansion behavior in all { hkl } pole directions was also determined by in situ high‐temperature X‐ray diffraction using synchrotron radiation and was found to be in agreement with other published studies.

Ribero, Daniel↗