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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

High Resolution Electron Microscopy Of Dislocation Ribbons In A CMSX-4 Superalloy single crystal

High-resolution scanning transmission electron microscopy (HR STEM) has been used to study the structure of dislocations in single crystal superalloy samples that have been subjected to conditions that favour the primary creep regime. The study has revealed the detailed structure of extended a 2 h112i dislocations as they shear the 0 precipitates during creep. These dislocations dissociate in a manner that is consistent with the PFMD predictions made and also suggests the importance of the reordering process during their movement. The shearing done by the ah112i dislocationswas also found to distort the/ 0 interface, changing its appearance from linear to a 'saw tooth' pattern. Another important observation was the segregation of alloying element with high atomic mass to the stacking faults to reduce their energies during shear. Numerous a 2 h110i dissociated dislocations were also observed in the channels of the superalloy. The high resolution provided by the STEM imaging enables one to study the high energy faults that are usually di*cult to observe in conventional weak-beam TEM, such as CISF and CESF-1 in the 0 andthe ISF in the, and to make estimates of their energies. Key

36 MATERIALS SCIENCE↗
DOE OSTI2011

Infrared Protein Crystallography

We consider the application of infrared spectroscopy to protein crystals, with particular emphasis on exploiting molecular orientation through polarization measurements on oriented single crystals. Infrared microscopes enable transmission measurements on individual crystals using either thermal or nonthermal sources, and can accommodate flow cells, used to measure spectral changes induced by exposure to soluble ligands, and cryostreams, used for measurements of flash-cooled crystals. Comparison of unpolarized infrared measurements on crystals and solutions probes the effects of crystallization and can enhance the value of the structural models refined from X-ray diffraction data by establishing solution conditions under which they are most relevant. Results on several proteins are consistent with similar equilibrium conformational distributions in crystal and solutions. However, the rates of conformational change are often perturbed. Infrared measurements also detect products generated by X-ray exposure, including CO{sub 2}. Crystals with favorable symmetry exhibit infrared dichroism that enhances the synergy with X-ray crystallography. Polarized infrared measurements on crystals can distinguish spectral contributions from chemically similar sites, identify hydrogen bonding partners, and, in opportune situations, determine three-dimensional orientations of molecular groups. This article is part of a Special Issue entitled: Protein Structure and Function in the Crystalline State.

08 HYDROGEN↗
DOE OSTI2014

Experimental and computational study of thaumasite structure

The structure of thaumasite has been studied experimentally by means of a single crystal X-ray diffraction and FTIR methods, and theoretically using density functional theory (DFT) method. Very good agreement was achieved between calculated and experimental structural parameters. In addition, calculations offered the refinement of the positions of the hydrogen atoms. The detailed analysis of the hydrogen bonds existing in the thaumasite structure has been performed. Several types of hydrogen bonds have been classified. The water molecules coordinating Ca{sup 2+} cation act as proton donors in moderate O-H···O hydrogen bonds formed with CO₃⁻²and SO₄⁻² anions. The multiple O-H···O hydrogen bonds exist among water molecules themselves. Finally, relatively weak hydrogen bonds form water molecules with the OH groups from the coordination sphere of the Si(OH)₆⁻² anion. Further, calculated vibrational spectrum allowed complete assignment of all vibrational modes which are not available from the experimental spectrum that has a complex structure with overlapped bands, especially below 1500 cm⁻¹. Highlights: • The thaumasite structure was studied experimentally and using DFT method. • We used DFT method for the refinement of the positions of hydrogen atoms. • A detailed analysis of the hydrogen bonds was done. • A complete assignment of all bands to particular types of vibrations was done.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Synthesis of monocrystalline Ca{sub 3}SiO{sub 5} using the optical floating zone method

Alite (Ca{sub 3}SiO{sub 5}/C{sub 3}S with low concentrations of foreign ions) is the main constituent of Ordinary Portland Cement. Normally it forms during sintering but with quite low crystal sizes (ca. 30 μm). For experiments on alite hydration behavior monocrystalline grains are required. Due to its incongruent melting behavior and its thermodynamic instability below 1250 °C it is very challenging to obtain large alite single crystals. In the present study, the floating zone method was used for annealing polycrystalline rods of monoclinic and triclinic C{sub 3}S just below the melting point of the phase. Large monocrystalline grains (> 500 μm) of the monoclinic (Al, Mg-doped) and triclinic polymorphs could successfully be obtained. Monocrystallinity was demonstrated by electron backscatter diffraction (EBSD). The chemical composition regarding incorporation of foreign ions and thus the resulting crystallographic modification of the C{sub 3}S can easily be adjusted. Chemical homogeneity of the synthesized monocrystalline grains was proven by electron probe microanalysis (EPMA).

36 MATERIALS SCIENCE↗
DOE OSTI2021

The crystal structure of a new calcium aluminate phase containing formate

A new calcium aluminate phase containing formate ions was synthesized and its crystal structure determined. This new phase is indicated as M-phase and was firstly observed in Portland cement pastes hydrated in presence of Ca-formate and in excess of water. The crystal structure of the M-phase was successfully solved in the R-3 space group of the trigonal system on the basis of synchrotron X-ray single crystal diffraction data. The structural model was confirmed by Rietveld refinement of the powder diffraction data acquired on the synthesized pure sample. The crystal structure of the M-phase is similar to that of ettringite, being characterized by columns of AlO{sub 6} octahedra alternating with groups of three edge-sharing CaO{sub 7} polyhedra. The formate ions (HCOO){sup −} share two oxygens with Ca polyhedra and are located in the interspace between the columns. The crystal structure of the M-phase testifies the strong interaction occurring between small organic molecules as formate and the calcium aluminate components of Portland cement.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nanostructural evolution of Al(OH)3 gel formed by the cubic and orthorhombic ye'elimite clinkers of calcium sulfoaluminate cements in an ultra-wide hydration temperature range

This paper investigated the influence of hydration temperature on the nanostructure of the AH{sub 3} phase formed in calcium sulfoaluminate cements. Orthorhombic ye'elimite (st-ye'elimite) and cubic ye'elimite (ss-ye'elimite) were hydrated in an ultra-wide temperature range (5–220 °C). Results showed that the AH{sub 3} phase formed by ss-ye'elimite was always microcrystalline in nature at various curing temperatures (5–130 °C), and transformed into the AlOOH phase at 150 °C and above. However, the AH{sub 3} phase formed by st-ye'elimite grew from a microcrystal to a favorable crystal as the temperature increased, and transformed into the AlOOH phase at 170 °C and above. The nanostructure of hydration products was further investigated using TEM/SAED analysis together with FE-SEM images, directly evidencing that the formed AFm-12 phase was single-crystal in nature, and the formed AH{sub 3} phase was microcrystalline at low temperatures and grew into single-crystal hexagonal prisms with the preferred growth direction along [001] direction at high temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Heterogeneous Reduction of U6+ by Structural Fe2+ From Theory and Experiment

Computational and experimental studies were performed to explore heterogeneous reduction of U6+ by structural Fe2+ at magnetite (Fe3O4) surfaces. Molecular Fe-Fe-U models representing a uranyl species adsorbed in a biatomic bidentate fashion to an iron surface group were constructed. Various possible charge distributions in this model surface complex were evaluated in terms of their relative stabilities and electron exchange rates using ab initio molecular orbital methods. Freshly-cleaved, single crystals of magnetite with different initial Fe2+/Fe3+ ratios were exposed to uranyl-nitrate solution (pH ~ 4) for 90 hours. X ray photoelectron spectroscopy and electron microscopy indicated the presence of a mixed U6+/U5+ precipitate heterogeneously nucleated and grown on stoichiometric magnetite surfaces, but only the presence of sorbed U6+ and no precipitate on sub-stoichiometric magnetite surfaces. Calculated electron transfer rates indicate that sequential multi-electron uranium reduction is not kinetically limited by conductive electron resupply to the adsorption site. Both theory and experiment point to local structural Fe2+ density and sterically accessible uranium coordination environments as key controls on uranium reduction extent and rate. Uranium incorporation in solid phases where its coordination is constrained to the 6-fold uranate type should widen the stability field of U5+ relative to U6+. If uranium cannot acquire 8 fold coordination then reduction may proceed to U5+ but not necessarily U4+.

58 GEOSCIENCES↗
DOE OSTI2011

Structure Stability of Methane Hydrate at High Pressures

The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil cells. The diffraction data for types II (sII) and H (sH) were refined to the known structures with space groups Fd3m and P6{sub 3}/mmc, respectively. Upon compression, sI methanehydrate transforms to the sII phase at 120 MPa, and then to the sH phase at 600 MPa. The sII methanehydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methanehydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3mstructure and ice VII (Pn3m). The results highlight the role of guest (CH{sub 4})-host (H{sub 2}O) interactions in the stabilization of the hydratestructures under pressure.

03 NATURAL GAS↗
DOE OSTI2012

Mineralogy under extreme conditions

We have performed measurements of minerals based on the synchrotron source for single crystal and powder X-ray diffraction, inelastic scattering, spectroscopy and radiography by using diamond anvil cells. We investigated the properties of iron (Fe), iron-magnesium oxides (Fe, Mg)O, silica(SiO{sub 2}), iron-magnesium silicates (Fe, Mg)SiO{sub 3} under simulated high pressure-high temperature extreme conditions of the Earth's crust, upper mantle, low mantle, core-mantle boundary, outer core, and inner core. The results provide a new window on the investigation of the mineral properties at Earth's conditions.

58 GEOSCIENCES↗
DOE OSTI2012

Reactivity studies of a pseudo three-coordinate vanadium(II) complex: Synthesis of terminal oxo and sulfido complexes of vanadium(IV) and S-S and Se-Se reductive bond cleavage reactions

Terminal oxo and sulfido complexes in the form of (nacnac)V=E(Ntol 2 ) (nacnac = [ArNC(CH 3 )] 2 CH - , Ar = 2,6-(CHMe 2 ) 2 C 6 H 3 , Ntol 2 = - N(C 6 H 4 -4-Me), E = O (1), S (2)) were isolated from treatment of the masked three-coordinate vanadium(II) complex, (nacnac)V(Ntol 2 ), with C 5 H 5 NO and S 8 , respectively. Both vanadium(IV) species, 1 and 2, have been characterized by room temperature X-band EPR spectroscopic studies, and in the case of complex 1, a single crystal molecular structure confirmed the presence of a terminal oxo moiety. Moreover, reaction of (nacnac)V(Ntol 2 ) with diphenyl-disulfide and diphenyl-diselenide results in the reductive cleavage of these compounds to produce the vanadium(III) complexes (nacnac)V(XPh)(Ntol 2 ) (X = S, (3), Se (4)). A molecular structure of the phenylsulfide complex, 3, confirmed formation of the d 2 complex resulting from reductive cleavage of the S-S bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Single crystal growth of Ga[subscript 2](Se[subscript x]Te[subscript 1;#8722;x])[subscript 3] semiconductors and defect studies via positron annihilation spectroscopy

Small single crystals of Ga{sub 2}(Se{sub x}Te{sub 1-x}){sub 3} semiconductors, for x = 0.1, 0.2, 0.3, were obtained via modified Bridgman growth techniques. High resolution powder x-ray diffractometry confirms a zincblende cubic structure, with additional satellite peaks observed near the (111) Bragg line. This suggests the presence of ordered vacancy planes along the [111] direction that have been previously observed in Ga{sub 2}Te{sub 3}. Defect studies via positron annihilation spectroscopy show an average positron lifetime of {approx} 400 ps in bulk as-grown specimens. Such a large lifetime suggests that the positron annihilation sites in these materials are dominated by defects. Moreover, analyzing the electron momenta via coincidence Doppler broadening measurements suggests a strong presence of large open-volume defects, likely to be vacancy clusters or voids.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

Visualizing Active-Site Dynamics in Single Crystals of HePTP: Opening of the WPD Loop Involves Coordinated Movement of the E Loop

Phosphotyrosine hydrolysis by protein tyrosine phosphatases (PTPs) involves substrate binding by the PTP loop and closure over the active site by the WPD loop. The E loop, located immediately adjacent to the PTP and WPD loops, is conserved among human PTPs in both sequence and structure, yet the role of this loop in substrate binding and catalysis is comparatively unexplored. Hematopoietic PTP (HePTP) is a member of the kinase interaction motif (KIM) PTP family. Compared to other PTPs, KIM-PTPs have E loops that are unique in both sequence and structure. In order to understand the role of the E loop in the transition between the closed state and the open state of HePTP, we identified a novel crystal form of HePTP that allowed the closed-state-to-open-state transition to be observed within a single crystal form. These structures, which include the first structure of the HePTP open state, show that the WPD loop adopts an 'atypically open' conformation and, importantly, that ligands can be exchanged at the active site, which is critical for HePTP inhibitor development. These structures also show that tetrahedral oxyanions bind at a novel secondary site and function to coordinate the PTP, WPD, and E loops. Finally, using both structural and kinetic data, we reveal a novel role for E-loop residue Lys182 in enhancing HePTP catalytic activity through its interaction with Asp236 of the WPD loop, providing the first evidence for the coordinated dynamics of the WPD and E loops in the catalytic cycle, which, as we show, is relevant to multiple PTP families.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Thermodynamic and transport properties of single crystalline RCo2Ge2 (R=Y, La–Nd, Sm–Tm)

Single crystals of RCo2Ge2 (R=Y, La–Nd, Sm–Tm) were grown using a self-flux method and were characterized by room-temperature powder X-ray diffraction; anisotropic, temperature and field dependent magnetization; temperature and field dependent, in-plane resistivity; and specific heat measurements. In this series, the majority of the moment-bearing members order antiferromagnetically; YCo2Ge2 and LaCo2Ge2 are non-moment-bearing. Ce is trivalent in CeCo2Ge2 at high temperatures, and exhibits an enhanced electronic specific heat coefficient due to the Kondo effect at low temperatures. In addition, CeCo2Ge2 shows two low-temperature anomalies in temperature-dependent magnetization and specific heat measurements. Three members (R=Tb–Ho) have multiple phase transitions above 1.8 K. Eu appears to be divalent with total angular momentum L =0. Both EuCo2Ge2 and GdCo2Ge2 manifest essentially isotropic paramagnetic properties consistent with J =S =7/2. Clear magnetic anisotropy for rare-earth members with finite L was observed, with ErCo2Ge2 and TmCo2Ge2 manifesting planar anisotropy and the rest members manifesting axial anisotropy. The experimentally estimated crystal electric field (CEF) parameters B 20 were calculated from the anisotropic paramagnetic θ ab and θ c values and follow a trend that agrees well with theoretical predictions. The ordering temperatures, TNTN, as well as the polycrystalline averaged paramagnetic Curie–Weiss temperature, Θavg, for the heavy rare-earth members deviate from the de Gennes scaling, as the magnitude of both is the highest for Tb, which is sometimes seen for extremely axial systems. Except for SmCo2Ge2, metamagnetic transitions were observed at 1.8 K for all members that ordered antiferromagnetically.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Na27Ru14O48: A New Mixed-valence Sodium Ruthenate with Magnetic Heptameric Plaquettes

Na{sub 27}Ru{sub 14}O{sub 48} has been synthesized in air at 700 C. The composition and crystal structure of the phase were determined by single crystal X-ray diffraction. The triclinic crystal structure contains isolated planar Ru{sub 7}O{sub 24} plaquettes made from seven edge-sharing RuO{sub 6} octahedra. The complex Na:Ru ratio is a result of tilting of the plaquettes to disrupt the packing of nominally hexagonal close packed planes made of Na ions and RuO{sub 6} octrahedra. Resistivity measurements show that the material is semiconducting with an activation energy of 0.53 eV. The observed magnetic moment of 3.11 {micro}{sub B} per Ru is lower than the expected spin only value, but is within the range seen in other compounds and is too large to indicate that the fundamental magnetic entities are the isolated Ru{sub 7}O{sub 24} plaquettes. Small, reproducible deviations in the Curie-Weiss behavior occur below 200 K and the onset of a broad magnetic transition is seen between 40 and 32 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Neutron diffraction study of La[subscript 4]LiAuO[subscript 8]: Understanding Au[superscript 3+] in an oxide environment

Owing to gold's oxophobicity, its oxide chemistry is rather limited, and elevated oxygen pressures are usually required to prepare ternary and quaternary oxide compounds with gold ions. The Au{sup 3+} oxide, La{sub 4}LiAuO{sub 8}, is remarkable both because it can be prepared at ambient pressure in air, and because of its unusual stability toward thermal decomposition and reduction. The structure of La{sub 4}LiAuO{sub 8} was established by Pietzuch et al. using single crystal X-ray diffraction [1]. The compound adopts an ordered modification of the Nd{sub 2}CuO{sub 4} structure, containing two-dimensional sheets in which AuO{sub 4} square planes are separated from one another by LiO{sub 4} square planes. In light of the meager X-ray scattering factors of Li and O, relative to La and Au, we report here a neutron powder diffraction study of La{sub 4}LiAuO{sub 8}, definitively confirming the structure. To our knowledge, this is the first reported neutron diffraction study of any stoichiometric oxide compound of gold. X-N maps, which make use of nuclear positions obtained from Rietveld refinement of time-of-flight neutron diffraction data and electron densities obtained from synchrotron X-ray powder diffraction data, point to the highly covalent nature of the Au-O bonding in La{sub 4}LiAuO{sub 8}. This is in good agreement with charge densities and Bader charges obtained from full density functional relaxation of the structure.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

Phase-controlled solvothermal synthesis and characterization of nickel sulfides with good single crystalline nature

Dispersed rhombohedral NiS rods with high aspect ratios and rhombic dodecahedron-like cubic NiS{sub 2} crystals were prepared by solvothermal routes using NiCl{sub 2}.6H{sub 2}O and Na{sub 2}S{sub 2}O{sub 3}.5H{sub 2}O as reagents and ethylenediamine as a solvent, and 3D blossoming flower-like rhombohedral NiS microstructures were synthesized using different sulfur sources of thiourea. The products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, energy dispersion spectrometry and selected area electronic diffraction. All the products were pure and had good single crystalline nature. The synthesis parameters were of great importance on the purity and morphology of the products. The possible growth mechanisms have been discussed based on the analyses of the effects of sulfur sources and solvent on the crystal structures and detailed configurations of the products. The present work is likely to help the phase-controlled synthesis of other metal chalcogenides. - Graphical abstract: Rhombohedral NiS dispersed rods and 3D flower-like microstructures are evolved from dispersed nucleus and aggregate of nucleus, respectively, and the cross-sections of such rods are in equilateral triangle-like shape. Highlights: > 3D blossoming flower-like r-NiS microstructures are obtained. > Equilateral triangle-like cross-sections of r-NiS rods are observed. > Approach based on XRD analysis to phase-controlled synthesis is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Magnetostructural correlations in the antiferromagnetic Co{sub 2-x} Cu{sub x}(OH)AsO{sub 4} (x=0 and 0.3) phases

The Co{sub 2-x}Cu{sub x}(OH)AsO{sub 4} (x=0 and 0.3) compounds have been synthesized under mild hydrothermal conditions and characterized by X-ray single-crystal diffraction and spectroscopic data. The hydroxi-arsenate phases crystallize in the Pnnm orthorhombic space group with Z=4 and the unit-cell parameters are a=8.277(2) A, b=8.559(2) A, c=6.039(1) A and a=8.316(1) A, b=8.523(2) A, c=6.047(1) A for x=0 and 0.3, respectively. The crystal structure consists of a three-dimensional framework in which M(1)O{sub 5}-trigonal bipyramid dimers and M(2)O{sub 6}-octahedral chains (M=Co and Cu) are present. Co{sub 2}(OH)AsO{sub 4} shows an anomalous three-dimensional antiferromagnetic ordering influenced by the magnetic field below 21 K within the presence of a ferromagnetic component below the ordering temperature. When Co{sup 2+} is partially substituted by Cu{sup 2+}ions, Co{sub 1.7}Cu{sub 0.3}(OH)AsO{sub 4}, the ferromagnetic component observed in Co{sub 2}(OH)AsO{sub 4} disappears and the antiferromagnetic order is maintained in the entire temperature range. Heat capacity measurements show an unusual magnetic field dependence of the antiferromagnetic transitions. This {lambda}-type anomaly associated to the three-dimensional antiferromagnetic ordering grows with the magnetic field and becomes better defined as observed in the non-substituted phase. These results are attributed to the presence of the unpaired electron in the dx{sup 2}-y{sup 2} orbital and the absence of overlap between neighbour ions. - Graphical abstract: Schematic drawing of the Co{sub 2-x}Cu{sub x}(OH)AsO{sub 4} (x=0 and 0.3) crystal structure view along the |0 1 0| direction. Polyhedra are occupied by the M(II) ions (M=Co and Cu) and the AsO{sub 4} groups are represented by tetrahedra. Open circles correspond to the oxygen atoms, and small circles show the hydrogen atoms. Highlights: > Synthesis of a new adamite-type compound, Co{sub 1.7}Cu{sub 0.3}(OH)AsO{sub 4}. > Single crystal structure, spectroscopic characterization and magnetic properties. > Unusual dependence on the magnetic field for antiferromagnetic transitions. > Incommensurate magnetic structure at low temperature. > Magnetostructural correlations in cobalt-based M{sub 2}(OH)XO{sub 4} (M=Co and Cu) insulation compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗