Development of dielectrophoresis MEMS device for PC12 cell patterning to elucidate nerve-network generation

NASA Astrophysics Data System (ADS)

Nakamachi, Eiji; Koga, Hirotaka; Morita, Yusuke; Yamamoto, Koji; Sakamoto, Hidetoshi

2018-01-01

We developed a PC12 cell trapping and patterning device by combining the dielectrophoresis (DEP) methodology and the micro electro mechanical systems (MEMS) technology for time-lapse observation of morphological change of nerve network to elucidate the generation mechanism of neural network. We succeeded a neural network generation, which consisted of cell body, axon and dendrites by using tetragonal and hexagonal cell patterning. Further, the time laps observations was carried out to evaluate the axonal extension rate. The axon extended in the channel and reached to the target cell body. We found that the shorter the PC12 cell distance, the less the axonal connection time in both tetragonal and hexagonal structures. After 48 hours culture, a maximum success rate of network formation was 85% in the case of 40 μm distance tetragonal structure.

Ba0.06(Na,Bi)0.94Ti1-x(Ni1/3Nb2/3)xO3 ceramics: X-ray diffraction and infrared spectroscopy studies

NASA Astrophysics Data System (ADS)

Mishra, R. K.; Prasad, Ashutosh; Chandra, K. P.; Prasad, K.

2018-05-01

Non-lead ceramic samples of Ba0.06(Na0.5Bi0.5)0.94Ti1-x(Ni1/3Nb2/3)xO3; 0 ≤ x ≤ 1.0 were prepared by standard high temperature ceramic synthesis method. Rietveld refinements of X-ray diffraction data of these ceramics were carried out using FullProf software and determined their crystal symmetry, space group and unit cell dimensions. Rietveld refinement revealed that Ba0.06(Na0.5Bi0.5)0.94TiO3 has a monoclinic structure with space group P4/m while B0.06(Na0.5Bi0.5)0.94(Ni1/3Nb2/3)O3 has tetragonal (pseudo-cubic) structure with space group P4/mmm. Partial replacement of Ti4+ ion by pseudo-cation (Ni1/33 +Nb2/3 5 +) 4 + resulted in the change of unit cell structure from monoclinic to tetragonal. SEM studies were carried out in order to access the quality of the prepared ceramics which showed a change in grain sizes with the increase of (Ni1/33 +Nb2/3 5 +) 4 + content. FTIR spectra confirmed the formation of perovskite type solid solutions.

Structural stability and electronic properties of β-tetragonal boron: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayami, Wataru, E-mail: hayami.wataru@nims.go.jp

2015-01-15

It is known that elemental boron has five polymorphs: α- and β-rhombohedral, α- and β-tetragonal, and the high-pressure γ phase. β-tetragonal (β-t) boron was first discovered in 1960, but there have been only a few studies since then. We have thoroughly investigated, using first-principles calculations, the atomic and electronic structures of β-t boron, the details of which were not known previously. The difficulty of calculation arises from the fact that β-t boron has a large unit cell that contains between 184 and 196 atoms, with 12 partially-occupied interstitial sites. This makes the number of configurations of interstitial atoms too greatmore » to calculate them all. By introducing assumptions based on symmetry and preliminary calculations, the number of configurations to calculate can be greatly reduced. It was eventually found that β-t boron has the lowest total energy, with 192 atoms (8 interstitial atoms) in an orthorhombic lattice. The total energy per atom was between those of α- and β-rhombohedral boron. Another tetragonal structure with 192 atoms was found to have a very close energy. The valence bands were fully filled and the gaps were about 1.16 to 1.54 eV, making it comparable to that of β-rhombohedral boron. - Graphical abstract: Electronic density distribution for the lowest-energy configuration (N=192) viewed from the 〈1 0 0〉 direction. Left: isosurface (yellow) at d=0.09 electrons/a.u.{sup 3} Right: isosurface (orange) at d=0.12 electrons/a.u.{sup 3}. - Highlights: • β-tetragonal boron was thoroughly investigated using first-principles calculations. • The lowest energy structure contains 192 atoms in an orthorhombic lattice. • Another tetragonal structure with 192 atoms has a very close energy. • The total energy per atom is between those of α- and β-rhombohedral boron. • The band gap of the lowest energy structure is about 1.16 to 1.54 eV.« less

AFM Studies of Salt Concentration Effects on the (110) Surface Structure of Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Pusey, Marc Lee; Gorti, Sridhar; Forsythe, Elizabeth; Konnert, John

2002-01-01

Previous high resolution AFM studies of the (110) surface of tetragonal chicken egg white lysozyme crystals had shown that only one of two possible molecular surfaces is present, those constituting the completed 43 helices. These suggested that the crystal growth process was by the solution-phase assembly of the growth units, which then attach to the surface. However, the best fit for the imaged surfaces, vs. those predicted based upon the bulk crystallographic coordinates, were obtained when the packing about the 43 helices was "tightened up", while maintaining the underlying crystallographic unit cell spacing. This results in a widening of the gap between adjacent helices, and the top- most layer(s) may no longer be in contact. We postulated that the tightened packing about the helices is a result of the high salt concentrations in the bulk solution, used to crystallize the protein, driving hydrophobic interactions. Once the crystal surface is sufficiently buried by subsequent growth layers the ratio of salt to protein molecules decreases and the helices relax to their bulk crystallographic coordinates. The crystal surface helix structure is thus a reflection of the solution structure, and the tightness of the packing about the 43 helices would be a function of the bulk salt concentration. AFM images of the (110) surface of tetragonal lysozyme crystals grown under low (2%) and high (5%) NaCl concentrations reveal differences in the packing about the 43 helices consistent with the above proposal.

Tetragonal Almandine, (Fe,Mg,Ca,Na)3(Al,Si,Mg)2Si3O12, a New High-Pressure Mineral from the Shergotty Impact on Mars: an Integrated FESEM-EPMA-Synchrotron Diffraction Investigation

NASA Astrophysics Data System (ADS)

Ma, C.; Tschauner, O. D.

2016-12-01

The combination of FESEM-EDS-EBSD, EPMA, and synchrotron microdiffraction is developing into a powerful tool for identification of micron-scale minerals in rocks such as high-pressure phases in shocked meteorites. During a nanomineralogy investigation of the Shergotty meteorite using this approach, we have identified a new shock-induced high-pressure silicate, majoritic almandine with a tetragonal I41/a structure, in an impact melt pocket. The Shergotty meteorite, which fell in the Gaya district, Bihar, India in 1865, is a Martian basaltic shergottite with shock features. Tetragonal almandine in Shergotty occurs as aggregates of subhedral crystals, 0.8 - 2.5 µm in diameter, along with stishovite in the central region of a shock melt pocket, showing an empirical formula of (Fe1.16Ca0.75Mg0.61Na0.42Mn0.03K0.01)(Al1.16Si0.63Mg0.19Ti0.02)Si3O12. Its general formula is (Fe,Mg,Ca,Na)3(Al,Si,Mg)2Si3O12. EBSD indicated this phase has a garnet-related structure. Synchrotron X-ray diffraction revealed that this garnet has actually a tetragonal structure (I41/a) with unit cell dimensions: a = 11.585(9) Å, c = 11.63(4) Å, V = 1561(7) Å3, and Z = 8. Tetragonal almandine is the polymorph of cubic almandine, a new high-pressure garnet mineral, formed by shock metamorphism via the Shergotty impact event on Mars. It apparently crystallized from Fe-rich shock-induced melt under high-pressure and high-temperature conditions.

Automatic procedure for stable tetragonal or hexagonal structures: application to tetragonal Y and Cd

NASA Astrophysics Data System (ADS)

Marcus, P. M.; Jona, F.

2005-05-01

A simple effective procedure (MNP) for finding equilibrium tetragonal and hexagonal states under pressure is described and applied. The MNP procedure finds a path to minima of the Gibbs free energy G at T=0 K (G=E+pV, E=energy per atom, p=pressure, V=volume per atom) for tetragonal and hexagonal structures by using the approximate expansion of G in linear and quadratic strains at an arbitrary initial structure to find a change in the strains which moves toward a minimum of G. Iteration automatically proceeds to a minimum within preset convergence criteria on the calculation of the minimum. Comparison is made with experimental results for the ground states of seven metallic elements in hexagonal close-packed (hcp), face- and body-centered cubic structures, and with a previous procedure for finding minima based on tracing G along the epitaxial Bain path (EBP) to a minimum; the MNP is more easily generalized than the EBP procedure to lower symmetry and more atoms in the unit cell. Comparison is also made with a molecular-dynamics program for crystal equilibrium structures under pressure and with CRYSTAL, a program for crystal equilibrium structures at zero pressure. Application of MNP to the elements Y and Cd, which have hcp ground states at zero pressure, finds minima of E at face-centered cubic (fcc) structure for both Y and Cd. Evaluation of all the elastic constants shows that fcc Y is stable, hence a metastable phase, but fcc Cd is unstable.

Twin and habit plane microstructures due to the tetragonal to monoclinic transformation of zirconia

NASA Astrophysics Data System (ADS)

Simha, N. K.

1997-02-01

We first construct Bain strains for the tetragonal to monoclinic ( t → m) transformation of zirconia (ZrO 2), and then examine the resulting twin and habit plane microstructures. The ( t → m) transformation in zirconia occurs via two paths; transformation along path I has two Bain strains that involve shearing of a rectangular face of the tetragonal unit cell, and shearing of the square base corresponds to path II. The monoclinic variants resulting from each of the three Bain strains can form 12 twins, and four of the twins corresponding to path II are neither of type I nor of type II. Habit planes do not exist for the transformation along path I, whereas transformation along path II has: (± 0.8139, ± 0.3898, - 0.4309) t, (± 0.6489, ± 0.6271, - 0.4309) t, (± 0.7804, ± 0.4530, - 0.4309) t. We predict the exact twin planes observed by Bailey [(1964) Phase transformation at high temperatures in hafnia and zirconia. Proc. Roy. Soc.279A, 395-412], Bansal and Heuer [(1972) On a martensitic phase transformation in Zirconia ZrO 2—I. Metallographic evidence. Acta Metall.20, 1281-1289] and Buljan et al. [(1976) Optical and X-ray single crystal studies of the monoclinic ↔ tetragonal transition in ZrO 2. J. Am. Ceram. Soc.59, 351-354]; additional twins and habit planes that we predict have not yet been observed.

Superconductivity in YTE2Ge2 compounds (TE = d-electron transition metal)

NASA Astrophysics Data System (ADS)

Chajewski, G.; Samsel-Czekała, M.; Hackemer, A.; Wiśniewski, P.; Pikul, A. P.; Kaczorowski, D.

2018-05-01

Polycrystalline samples of YTE2Ge2 with TE = Co, Ni, Ru, Rh, Pd and Pt were synthesized and characterized by means of X-ray powder diffraction and low-temperature electrical resistivity and specific heat measurements, supplemented by fully relativistic full-potential local-orbital band structure calculations. We confirm that most of the compounds studied crystallize in a body-centered tetragonal ThCr2S2 -type structure (space group I 4 / mmm) and have three-dimensional Fermi surfaces, while only one of them (YPt2Ge2) forms with a primitive tetragonal CaBe2Ge2 -type unit cell (space group P 4 / nmm) and possesses quasi-two-dimensional Fermi surface sheets with some nesting. Physical properties data show conventional superconductivity in the phases with TE = Co, Pd and Pt, i.e. independently of the structure type (and hence the dimensionality of the Fermi surface).

Strain Phase Diagram of SrTiO3 Thin Films

NASA Astrophysics Data System (ADS)

He, Feizhou; Shapiro, S. M.

2005-03-01

SrTiO3 thin films were used as a model system to study the effects of strain and epitaxial constraint on structural phase transitions of oxide films. The basic phenomena revealed will apply to a variety of important structural transitions including the ferroelectric transition. Highly strained, epitaxial films of SrTiO3 were grown on different substrates. The structural phase transition temperature Tc increases from 105 K in bulk STO to 167 K for films under tensile strain and 330 K for films with compressive strain. The measured temperature-strain phase diagram is qualitatively consistent with theory [1], however the increase in Tc is much larger than predicted in all cases. The symmetry of the phases involved in the transition is different from the corresponding bulk structures largely because of epitaxial constraint, the clamping effect. Thus the shape of the STO unit cell is tetragonal at all temperatures. The possibility exists of a very unique low temperature phase with orthorhombic symmetry (Cmcm) but tetragonal unit cell shape. More generally, we have characterized at least three different manifestations of the clamping effect, showing it is much more subtle than usually recognized. This work is supported through NSF DMR-0239667, DMR-0132918, by the Research Corp, and at BNL by the US DOE DE-AC02-98CH10886. [1] N. A. Pertsev, A. K. Tagantsev and N. Setter, Phys. Rev. B61, R825 (2000).

Thermal stability and phase transformation in fully indium oxide (InO{sub 1.5}) stabilized zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piva, R.H., E-mail: honorato.piva@ua.pt; Piva, D.H

2017-01-15

Indium oxide (InO{sub 1.5}) stabilized zirconia (InSZ) is an attractive material as electrolyte, or electrode, in solid oxide fuel cells (SOFCs), and as corrosion resistant top coat in thermal barrier coatings. However, little is known about the phase stability of cubic InSZ at temperatures that simulate the conditions in an operating SOFC or turbine. This article provides an investigation of the phase stability and phase transformations in cubic InSZ after heat treatments at 800, 1000, and 1200 °C for periods up to 2000 h. The results revealed that cubic InSZ is not stable during annealing at 1000 and 1200 °C,more » owing to a fast destabilization of the initial cubic phase to tetragonal, and eventually to monoclinic (c → t → m). The c → t → m transition in InSZ is intimately associated with the indium volatilization. On the other hand, cubic InSZ remained stable for 2000 h at 800 °C, although the partial formation of the tetragonal phase was observed along with a 0.25% contraction in the unit cell volume of the cubic phase, caused by short-range ordering. These results demonstrate that technological applications of cubic InSZ are restricted to temperatures at which the volatilization of the InO{sub 1.5} stabilizer does not occur. - Highlights: •Phase stability of fully InO{sub 1.5} stabilized zirconia (cubic InSZ) was evaluated. •Cubic InSZ is instable at temperatures ≥ 1000 °C, owing to the cubic-to-tetragonal-to-monoclinic destabilization. •Cubic InSZ undergoes the cubic-to-tetragonal transformation at ~ 800 °C. •Owing to the low phase stability, applications of cubic InSZ in TBCs or SOFCs are restricted.« less

Formation of collapsed tetragonal phase in EuCo₂As₂ under high pressure.

PubMed

Bishop, Matthew; Uhoya, Walter; Tsoi, Georgiy; Vohra, Yogesh K; Sefat, Athena S; Sales, Brian C

2010-10-27

The structural properties of EuCo₂As₂ have been studied up to 35 GPa, through the use of x-ray diffraction in a diamond anvil cell at a synchrotron source. At ambient conditions, EuCo₂As₂ ) (I4/mmm) has a tetragonal lattice structure with a bulk modulus of 48 ± 4 GPa. With the application of pressure, the a axis exhibits negative compressibility with a concurrent sharp decrease in c-axis length. The anomalous compressibility of the a axis continues until 4.7 GPa, at which point the structure undergoes a second-order phase transition to a collapsed tetragonal (CT) state with a bulk modulus of 111 ± 2 GPa. We found a strong correlation between the ambient pressure volume of 122 parents of superconductors and the corresponding tetragonal to collapsed tetragonal phase transition pressures.

High-pressure behavior of cuprospinel CuFe 2O 4: Influence of the Jahn-Teller effect on the spinel structure

DOE PAGES

Kyono, Atsushi; Gramsch, Stephen A.; Nakamoto, Yuki; ...

2015-08-14

The Jahn-Teller-effect at Cu 2+ in cuprospinel CuFe 2O 4 was investigated using high-pressure, single crystal synchrotron x-ray diffraction (XRD) techniques at beamline BL10A at the Photon Factory, KEK, Japan. Six data sets were collected in the pressure range from ambient to 5.9 GPa at room temperature. Structural refinements based on the data were performed at 0.0, 1.8, 2.7, and 4.6 GPa. The unit cell volume of cuprospinel decreases continuously from 590.8 (6) Å 3 to 579.5 (8) Å 3 up to 3.8 GPa. Leastsquares fitting to a third-order Birch-Murnaghan equation of state yields zero-pressure volume V 0 = 590.7more » (1) Å 3 and bulk modulus K 0 = 188.1 (4.4) GPa with K’ fixed at 4.0. The crystal chemical composition determined by electron-probe analysis and x-ray site-occupancy refinement is represented as [Cu 0.526Fe 0.474] [6][Cu 0.074Fe 1.926]O 4. Most of the Cu 2+ are preferentially distributed onto the tetrahedral (T) site of the spinel structure. At 4.6 GPa, a cubic-tetragonal phase transition is indicated by a splitting of the a axis of the cubic structure into a smaller a axis and a longer c axis, with unit cell parameters a = 5.882 (1) Å and c = 8.337 (1) Å. The tetragonal crystal structure with space group I4 1/amd was refined to R1 = 0.0182 and wR2 = 0.0134 using observed 35 x-ray reflections. At the T site, the tetrahedral O-T-O bond angles along the c-axis direction of the unit cell decreases slightly from 109.47 ° to 108.7 (4) °, which generates a stretched tetrahedral geometry along the c-axis. The cubic-totetragonal transition induced by the Jahn-Teller effect at Cu 2+ is attributable to the angular distortion at the tetrahedral site. At the octahedral (M) site, on the other hand, the two M-O bonds parallel to the caxis are shortened with respect to the four M-O bonds parallel to the ab-plane, which are lengthened as a result of the phase transition, leading to a compressed octahedral geometry along the c-axis. With the competing distortions between the stretched tetrahedron and the compressed octahedron along the c-axis, the a unit cell parameter is shortened with respect to the c unit cell parameter, giving a c/a ratio slightly greater than unity as referred to cubic lattice (c/a = 1.002). The c/a value increases to 1.007 with pressure, suggesting a further evolution of the stretched tetrahedron and the compressed octahedron. The variation of c/a ratio of the cuprospinel is similar to that observed in the tetragonally distorted cuprospinel with Cu 2+ fully occupying the octahedral site of the structure.« less

Purification, crystallization and preliminary crystallographic studies of plant S-adenosyl-l-homocysteine hydrolase (Lupinus luteus)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brzezinski, Krzysztof; Department of Crystallography, Faculty of Chemistry, A. Mickiewicz University, Poznan; Bujacz, Grzegorz

2008-07-01

Single crystals of recombinant S-adenosyl-l-homocysteine hydrolase from L. luteus in complex with adenosine diffract X-rays to 1.17 Å resolution at 100 K. The crystals are tetragonal, space group P4{sub 3}2{sub 1}2, and contain one copy of the dimeric enzyme in the asymmetric unit. By degrading S-adenosyl-l-homocysteine, which is a byproduct of S-adenosyl-l-methionine-dependent methylation reactions, S-adenosyl-l-homocysteine hydrolase (SAHase) acts as a regulator of cellular methylation processes. S-Adenosyl-l-homocysteine hydrolase from the leguminose plant yellow lupin (Lupinus luteus), LlSAHase, which is composed of 485 amino acids and has a molecular weight of 55 kDa, has been cloned, expressed in Escherichia coli and purified.more » Crystals of LlSAHase in complex with adenosine were obtained by the hanging-drop vapour-diffusion method using 20%(w/v) PEG 4000 and 10%(v/v) 2-propanol as precipitants in 0.1 M Tris–HCl buffer pH 8.0. The crystals were tetragonal, space group P4{sub 3}2{sub 1}2, with unit-cell parameters a = 122.4, c = 126.5 Å and contained two protein molecules in the asymmetric unit, corresponding to the functional dimeric form of the enzyme. Atomic resolution (1.17 Å) X-ray diffraction data have been collected using synchrotron radiation.« less

Purification, crystallization and preliminary X-ray diffraction analysis of the kinase domain of human tousled-like kinase 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garrote, Ana M.; Redondo, Pilar; Montoya, Guillermo, E-mail: gmontoya@cnio.es

2014-02-19

The C-terminal kinase domain of TLK2 (a human tousled-like kinase) has been cloned and overexpressed in Escherichia coli followed by purification to homogeneity. Crystallization experiments in the presence of ATP-γ-S yielded crystals suitable for X-ray diffraction analysis belonging to two different space groups: tetragonal I4{sub 1}22 and cubic P2{sub 1}3. Tousled-like kinases (TLKs) are an evolutionarily conserved family of serine/threonine protein kinases involved in chromatin dynamics, including DNA replication and repair, transcription and chromosome segregation. The two members of the family reported in humans, namely TLK1 and TLK2, localize to the cell nucleus and are capable of forming homo- ormore » hetero-oligomers by themselves. To characterize the role of TLK2, its C-terminal kinase domain was cloned and overexpressed in Escherichia coli followed by purification to homogeneity. Crystallization experiments in the presence of ATP-γ-S yielded crystals suitable for X-ray diffraction analysis belonging to two different space groups: tetragonal I4{sub 1}22 and cubic P2{sub 1}3. The latter produced the best diffracting crystal (3.4 Å resolution using synchrotron radiation), with unit-cell parameters a = b = c = 126.05 Å, α = β = γ = 90°. The asymmetric unit contained one protein molecule, with a Matthews coefficient of 4.59 Å{sup 3} Da{sup −1} and a solvent content of 73.23%.« less

Crystallization and preliminary crystallographic analysis of a family 43 β-d-xylosidase from Geobacillus stearothermophilus T-6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brüx, Christian; Niefind, Karsten; Ben-David, Alon

2005-12-01

The crystallization and preliminary X-ray analysis of a β-d-xylosidase from G. stearothermophilus T-6, a family 43 glycoside hydrolase, is described. Native and catalytic inactive mutants of the enzymes were crystallized in two different space groups, orthorhombic P2{sub 1}2{sub 1}2 and tetragonal P4{sub 1}2{sub 1}2 (or the enantiomorphic space group P4{sub 3}2{sub 1}2), using a sensitive cryoprotocol. The latter crystal form diffracted X-rays to a resolution of 2.2 Å. β-d-Xylosidases (EC 3.2.1.37) are hemicellulases that cleave single xylose units from the nonreducing end of xylooligomers. In this study, the crystallization and preliminary X-ray analysis of a β-d-xylosidase from Geobacillus stearothermophilus T-6more » (XynB3), a family 43 glycoside hydrolase, is described. XynB3 is a 535-amino-acid protein with a calculated molecular weight of 61 891 Da. Purified recombinant native and catalytic inactive mutant proteins were crystallized and cocrystallized with xylobiose in two different space groups, P2{sub 1}2{sub 1}2 (unit-cell parameters a = 98.32, b = 99.36, c = 258.64 Å) and P4{sub 1}2{sub 1}2 (or the enantiomorphic space group P4{sub 3}2{sub 1}2; unit-cell parameters a = b = 140.15, c = 233.11 Å), depending on the detergent. Transferring crystals to cryoconditions required a very careful protocol. Orthorhombic crystals diffract to 2.5 Å and tetragonal crystals to 2.2 Å.« less

Crystallization of the Fab from a human monoclonal antibody against gp 41 of human immunodeficiency virus type I

NASA Technical Reports Server (NTRS)

Casale, Elena; He, Xiao-Min; Snyder, Robert S.; Carter, Daniel C.; Wenisch, Elisabeth; Jungbauer, Alois; Tauer, Christa; Ruker, Florian; Righetti, Pier Giorgio

1990-01-01

A monoclonal IgG antibody directed against gp 41 from the human immunodeficiency virus (HIV-1) has been crystallized in both intact and Fab forms. Crystals of the intact antibody grow as tetragonal-like prisms too small for conventional X-ray analysis. However, the Fab portion of the antibody produces suitable platelike crystals which belong to the space group P2(1)2(1)2(1) with unit cell constants of a = 66.5 A, b = 74.3 A, and c = 105.3 A. There is one molecule of Fab in the asymmetric unit. The Fab crystals show diffraction to d-spacings less than 3.0 A.

Effects of vacancies on atom displacement threshold energy calculations through Molecular Dynamics Methods in BaTiO3

NASA Astrophysics Data System (ADS)

Gonzalez Lazo, Eduardo; Cruz Inclán, Carlos M.; Rodríguez Rodríguez, Arturo; Guzmán Martínez, Fernando; Abreu Alfonso, Yamiel; Piñera Hernández, Ibrahin; Leyva Fabelo, Antonio

2017-09-01

A primary approach for evaluating the influence of point defects like vacancies on atom displacement threshold energies values Td in BaTiO3 is attempted. For this purpose Molecular Dynamics Methods, MD, were applied based on previous Td calculations on an ideal tetragonal crystalline structure. It is an important issue in achieving more realistic simulations of radiation damage effects in BaTiO3 ceramic materials. It also involves irradiated samples under severe radiation damage effects due to high fluency expositions. In addition to the above mentioned atom displacement events supported by a single primary knock-on atom, PKA, a new mechanism was introduced. It corresponds to the simultaneous excitation of two close primary knock-on atoms in BaTiO3, which might take place under a high flux irradiation. Therefore, two different BaTiO3 Td MD calculation trials were accomplished. Firstly, single PKA excitations in a defective BaTiO3 tetragonal crystalline structure, consisting in a 2×2×2 BaTiO3 perovskite like super cell, were considered. It contains vacancies on Ba and O atomic positions under the requirements of electrical charge balance. Alternatively, double PKA excitations in a perfect BaTiO3 tetragonal unit cell were also simulated. On this basis, the corresponding primary knock-on atom (PKA) defect formation probability functions were calculated at principal crystal directions, and compared with the previous one we calculated and reported at an ideal BaTiO3 tetrahedral crystal structure. As a general result, a diminution of Td values arises in present calculations in comparison with those calculated for single PKA excitation in an ideal BaTiO3 crystal structure.

Combinatorial compatibility as habit-controlling factor in lysozyme crystallization I. Monomeric and tetrameric F faces derived graph-theoretically

NASA Astrophysics Data System (ADS)

Strom, C. S.; Bennema, P.

1997-03-01

A series of two articles discusses possible morphological evidence for oligomerization of growth units in the crystallization of tetragonal lysozyme, based on a rigorous graph-theoretic derivation of the F faces. In the first study (Part I), the growth layers are derived as valid networks satisfying the conditions of F slices in the context of the PBC theory using the graph-theoretic method implemented in program FFACE [C.S. Strom, Z. Krist. 172 (1985) 11]. The analysis is performed in monomeric and alternative tetrameric and octameric formulations of the unit cell, assuming tetramer formation according to the strongest bonds. F (flat) slices with thickness Rdhkl ( {1}/{2} < R ≤ 1 ) are predicted theoretically in the forms 1 1 0, 0 1 1, 1 1 1. The relevant energies are established in the broken bond model. The relation between possible oligomeric specifications of the unit cell and combinatorially feasible F slice compositions in these orientations is explored.

Interplay between structural and magnetic-electronic responses of FeA l2O4 to a megabar: Site inversion and spin crossover

NASA Astrophysics Data System (ADS)

Xu, W. M.; Hearne, G. R.; Layek, S.; Levy, D.; Pasternak, M. P.; Rozenberg, G. Kh.; Greenberg, E.

2018-02-01

X-ray diffraction pressure studies at room temperature demonstrate that the spinel FeA l2O4 transforms to a tetragonal phase at ˜18 GPa. This tetragonal phase has a highly irregular unit-cell volume versus pressure dependence up to ˜45 GPa, after which a transformation to a Cmcm postspinel phase is onset. This is attributable to pressure driven Fe↔Al site inversion at room temperature, corroborated by signatures in the 57Fe Mössbauer spectroscopy pressure data. At the tetragonal→postspinel transition, onset in the range 45-50 GPa, there is a concurrent emergence of a nonmagnetic spectral component in the Mössbauer data at variable cryogenic temperatures. This is interpreted as spin crossover at sixfold coordinated Fe locations emanated from site inversion. Spin crossover commences at the end of the pressure range of the tetragonal phase and progresses in the postspinel structure. There is also a much steeper volume change ΔV /V ˜ 10% in the range 45-50 GPa compared to the preceding pressure regime, from the combined effects of the structural transition and spin crossover electronic change. At the highest pressure attained, ˜106 GPa, the Mössbauer data evidence a diamagnetic Fe low-spin abundance of ˜50%. The rest of the high-spin Fe in eightfold coordinated sites continue to experience a relatively small internal magnetic field of ˜33 T. This is indicative of a magnetic ground state associated with strong covalency, as well as substantive disorder from site inversion and the mixed spin-state configuration. Intriguingly, magnetism survives in such a spin-diluted postspinel lattice at high densities. The R (300 K) data decrease by only two orders of magnitude from ambient pressure to the vicinity of ˜100 GPa. Despite a ˜26% unit-cell volume densification from the lattice compressibility, structural transitions, and spin crossover, FeA l2O4 is definitively nonmetallic with an estimated gap of ˜400 meV at ˜100 GPa. At such high densification appreciable bandwidth broadening and gap closure would be anticipated. Reasons for the resilient nonmetallic behavior are briefly discussed.

Surface structure of Bi2Sr2CaCu2O(8+delta) high-temperature superconductors studied using low-energy electron diffraction

NASA Astrophysics Data System (ADS)

Lindberg, P. A. P.; Shen, Z.-X.; Wells, B. O.; Mitzi, D. B.; Lindau, I.

1988-12-01

The surface structure of Bi2Sr2CaCu2O(8+delta) has been studied using low-energy electron diffraction (LEED). Sharp diffraction spots indicative of a well-ordered surface are observed. The LEED patterns unequivocally show that this type of material preferentially cleaves along the a-b planes of the nearly tetragonal unit cell. A superstructure extending along one of the axes in the a-b plane (b) is found to have a periodicity of 27 + or - 0.5 A, in good agreement with earlier studies of the three-dimensional crystal structure. The superstructure at the surface is nonlocal in character and reflects the long-range superlattice of the bulk along the b axis. Intensity modulations of the diffraction spots oriented along the b axis are also reported and discussed in terms of the cell dimension of the unit cell along the b axis.

Crystallization and preliminary crystallographic analysis of an Enterococcus faecalis repressor protein, CylR2, involved in regulating cytolysin production through quorum-sensing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ni, Shuisong; McAteer, Kathleen; Bussiere, Dirksen E.

2004-06-01

CylR2 is one of the two regulatory proteins associated with the quorum-sensing-dependent synthesis of cytolysin for the common pathogen Enterococcus faecalis. The protein was expressed with a C-terminal 6-histidine tag and purified to homogeneity with a cobalt affinity column followed by another size exclusion column. Both native and SeMet proteins were crystallized. A complete X-ray diffraction data set from the native crystal was collected to 2.3 resolution. The crystal was tetragonal, belonging to space group P41/43, with unit-cell dimensions a=b=66.2 , c=40.9 and a=b=g=90. The asymmetric unit contained two molecules of CylR2.

Purification, crystallization and preliminary X-ray structural studies of a 7.2 kDa cytotoxin isolated from the venom of Daboia russelli russelli of the Viperidae family

PubMed Central

Roy Choudhury, Subhasree; Gomes, Aparna; Gomes, Antony; Dattagupta, Jiban K.; Sen, Udayaditya

2006-01-01

A cytotoxin (MW 7.2 kDa) from Indian Russell’s viper (Daboia russelli russelli) venom possessing antiproliferative activity, cardiotoxicity, neurotoxicity and myotoxicity has been purified, characterized and crystallized. The crystals belong to the tetragonal space group P41, with unit-cell parameters a = b = 47.94, c = 50.2 Å. Larger crystals, which diffracted to 1.5 Å, were found to be twinned; diffraction data were therefore collected to 2.93 Å resolution using a smaller crystal. Molecular-replacement calculations identified two molecules of the protein in the asymmetric unit, which is in accordance with the calculated V M value. PMID:16511326

Ab initio prediction of superdense tetragonal and monoclinic polymorphs of carbon

DOE PAGES

Li, Zhen -Zhen; Wang, Jian -Tao; Xu, Li -Fang; ...

2016-11-02

The design and synthesis of three-dimensional denser carbons are one of the hot issues in condensed matter physics because of their fascinating properties. Here we identify by ab initio calculations several tetragonal and monoclinic polymorphs of carbon that adopt the t32, t32*, m32, and m32* structures in P4¯2 1c, P4 32 12, P2 1/c, and C2 symmetry, respectively. These carbon polymorphs have large 32-atom unit cells in all-sp 3 bonding networks comprising five- and six-membered rings that are dynamically stable, as verified by a phonon mode analysis. Electronic band structure calculations show that they are insulators with band gaps inmore » the range of 5.19–5.41 eV, close to the calculated band gap of 5.34 eV for diamond. Remarkably, these carbon phases possess an extremely high atom number density exceeding that of diamond. Lastly, the present results establish different types of carbon phases and offer insights into their outstanding structural and electronic properties.« less

Colossal Negative Thermal Expansion in Electron-Doped PbVO3 Perovskites.

PubMed

Yamamoto, Hajime; Imai, Takashi; Sakai, Yuki; Azuma, Masaki

2018-07-02

Colossal negative thermal expansion (NTE) with a volume contraction of about 8 %, the largest value reported so far for NTE materials, was observed in an electron-doped giant tetragonal perovskite compound Pb 1-x Bi x VO 3 (x=0.2 and 0.3). A polar tetragonal (P4mm) to non-polar cubic structural transition took place upon heating. The coefficient of thermal expansion (CTE) and the working temperature could be tuned by changing the Bi content, and La substitution decreased the transition temperature to room temperature. Pb 0.76 La 0.04 Bi 0.20 VO 3 exhibited a unit cell volume contraction of 6.7 % from 200 K to 420 K. Interestingly, further gigantic NTE of about 8.5 % was observed in a dilametric measurement of a Pb 0.76 La 0.04 Bi 0.20 VO 3 polycrystalline sample. The pronounced NTE in the sintered body should be attributed to an anisotropic lattice parameter change. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Symmetry of Epitaxial BiFeO3 Films in the Ultrathin Regime

NASA Astrophysics Data System (ADS)

Yang, Yongsoo; Schlep&üTz, Christian; Adamo, Carolina; Schlom, Darrell; Clarke, Roy

2013-03-01

BiFeO3 (BFO) films grown on SrTiO3 (STO) with a SrRuO3 buffer layer exhibit a monoclinic structure at thicknesses greater than 40 nm, but higher structural symmetry can be observed for thinner films [Phys. Rev. B 81, 144115 (2010)]. We report a structural phase transition from monoclinic to tetragonal in ultra-thin BFO films grown directly on (100)-oriented STO. X-ray diffraction measurements of 3-dimensional reciprocal space maps reveal half-integer order peaks due to oxygen octahedral tilting. When the film thickness is decreased below 20 unit cells, the integer-order Bragg peak splitting associated with the presence of multiple domains of the monoclinic phase disappears. Instead, a single peak that is commensurate with the STO substrate lattice appears. The diffraction pattern has four-fold symmetry, ruling out the presence of a single monoclinic domain in favor of a tetragonal film structure. The evolution of the oxygen octahedra tilt pattern inferred from the intensities of half-order peaks suggests that this transition originates from the corner-connectivity of oxygen atoms at the interface between BFO and STO, and also strongly supports this monoclinic to tetragonal transition. Supported in part by the U.S. Department of Energy (DE-FG02-06ER46273). Measurements performed at Sectors 13-BMC, 33-IDD, 33-BMC of the Advanced Photon Source, Argonne National Laboratory, USA (DOE contract No. DE-AC02-06CH11357).

Crystallization of SHARPIN using an automated two-dimensional grid screen for optimization.

PubMed

Stieglitz, Benjamin; Rittinger, Katrin; Haire, Lesley F

2012-07-01

An N-terminal fragment of human SHARPIN was recombinantly expressed in Escherichia coli, purified and crystallized. Crystals suitable for X-ray diffraction were obtained by a one-step optimization of seed dilution and protein concentration using a two-dimensional grid screen. The crystals belonged to the primitive tetragonal space group P4(3)2(1)2, with unit-cell parameters a = b = 61.55, c = 222.81 Å. Complete data sets were collected from native and selenomethionine-substituted protein crystals at 100 K to 2.6 and 2.0 Å resolution, respectively.

Purification, crystallization and preliminary crystallographic analysis of biotin protein ligase from Staphylococcus aureus.

PubMed

Pendini, Nicole R; Polyak, Steve W; Booker, Grant W; Wallace, John C; Wilce, Matthew C J

2008-06-01

Biotin protein ligase from Staphylococcus aureus catalyses the biotinylation of acetyl-CoA carboxylase and pyruvate carboxylase. Recombinant biotin protein ligase from S. aureus has been cloned, expressed and purified. Crystals were grown using the hanging-drop vapour-diffusion method using PEG 8000 as the precipitant at 295 K. X-ray diffraction data were collected to 2.3 A resolution from crystals using synchrotron X-ray radiation at 100 K. The diffraction was consistent with the tetragonal space group P4(2)2(1)2, with unit-cell parameters a = b = 93.665, c = 131.95.

Effect of epitaxial strain on ferroelectric polarization in multiferroic BiFeO3 films

NASA Astrophysics Data System (ADS)

Kim, Dae Ho; Lee, Ho Nyung; Biegalski, Michael D.; Christen, Hans M.

2008-01-01

Multiferroic BiFeO3 epitaxial films with thicknesses ranging from 40to960nm were grown by pulsed laser deposition on SrTiO3 (001) substrates with SrRuO3 bottom electrodes. X-ray characterization shows that the structure evolves from angularly distorted tetragonal with c /a≈1.04 to more bulklike distorted rhombohedral (c/a≈1.01) as the strain relaxes with increasing thickness. Despite this significant structural evolution, the ferroelectric polarization along the body diagonal of the distorted pseudocubic unit cells, as calculated from measurements along the normal direction, barely changes.

Phase transition in a tetragonal In90Pb10 alloy under high pressure: a switch from c/a > 1 to c/a < 1

NASA Astrophysics Data System (ADS)

Degtyareva, V. F.; Bdikin, I. K.; Porsch, F.; Novokhatskaya, N. I.

2003-03-01

The effect of pressure on tetragonal In-Pb alloys with 10, 15, and 22 at.% Pb has been studied up to pressure 30 GPa with diamond anvil cells using synchrotron radiation. The In-type face-centred tetragonal phase of the In alloy with 10 at.% Pb undergoes under pressure a phase transition with a discontinuous jump of the axial ratio from c/a > 1 to c/a < 1 via a two-phase region from 7 to 20 GPa. The tetragonal phases of the In alloys with 15 and 22 at.% Pb with c/a < 1 at ambient pressure show only a slight decrease in c/a with pressure increase. The correlation of the axial ratio with the alloy content and its change with pressure in In alloys and In itself are attributed to Brillouin-zone-Fermi-sphere interactions.

Crystallization of Chicken Egg White Lysozyme from Sulfate Salts

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth; Pusey, Marc

1998-01-01

It has been "known" that chicken egg white lysozyme does not crystallize from sulfate, particularly ammonium sulfate, salts, but instead gives amorphous precipitates. This has been the basis of several studies using lysozyme comparing macromolecule crystal nucleation and amorphous precipitation. Recently Ries-Kautt et al (Acta Cryst D50, (1994) 366) have shown that purified isoionic CEWL could be crystallized from low concentrations of sulfate at basic pH, and we subsequently showed that in fact CEWL could be purified in both the tetragonal and orthorhombic forms using ammonium sulfate over the pH range 4.0 to 7.8 (Acta Cryst D53, (1997) 795). We have now extended these observations to include a range of common sulfate salts, specifically sodium, potassium, rubidium, magnesium, and manganese sulfates. In all cases but the manganese sulfates both the familiar tetragonal and orthorhombic forms were obtained, with unit cell dimensions close to those known for the "classic" sodium chloride crystallized forms. Manganese sulfate has only yielded orthorhombic crystals to date. All crystallizations were carried out using low (typically less than or equal to 6 M) salt and high (greater than approximately 90 mg/ml) protein concentrations. As with ammonium sulfate, the tetragonal - orthorhombic phase shift appears to be a function of both the temperature and the protein concentration, with higher temperatures and concentrations favoring the orthorhombic and lower the tetragonal form. The phase change range is somewhat reduced for the sulfate salts, depending upon conditions being typically between approximately 15 - 20 C. Both the magnesium and manganese sulfates gave crystals at salt concentrations over 0.6 M as well, with magnesium sulfate giving a very slowly nucleating and growing hexagonal form. A triclinic crystal form, characterized by aggressively small crystals (typically 0.1 mm in size) has been occasionally obtained from ammonium sulfate. Finally, preliminary spot solubility determinations have suggested that in some cases the solubility increases with increasing salt concentrations.

Cross-Linking Studies of Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth; Pusey, Marc

2000-01-01

Tetragonal chicken egg white crystals consist of 4(sub 3) helices running in alternating directions, the helix rows having a two fold symmetry with each other. The unit cell consists of one complete tetrameric turn from each of two adjacent helices (an octamer). PBC analysis indicates that the helix intermolecular bonds are the strongest in the crystal, therefore likely formed first. AFM analysis of the (110) surface shows only complete helices, no half steps or bisected helices being found, while AFM line scans to measure the growth step increments show that they are multiples of the 4(sub 3) helix tetramer dimensions. This supports our thesis that the growth units are in fact multiples of the four molecule 4(sub 3) helix unit, the "average" growth unit size for the (110) face being an octamer (two turns about the helix) and the (101) growth unit averaging about the size of a hexamer. In an effort to better understand the species involved in the crystal nucleation and growth process, we have initiated an experimental program to study the species formed in solution compared to what is found in the crystal through covalent cross-linking studies. These experiments use the heterobifunctional cross-linking agent aminoethyl-4-azidonitroanaline (AEANA). An aliphatic amine at one end is covalently attached to the protein by a carbodiimide-mediated reaction, and a photo reactive group at the other can be used to initiate crosslinking. Modifications to the parent structure can be used to alter the distance between the two reactive groups and thus the cross-linking agents "reach". In practice, the cross-linking agent is first coupled to the asp101 side chain through the amine group. Asp101 lies within the active site cleft, and previous work with fluorescent probes had shown that derivatives at this site still crystallize in the tetragonal space group. This was also found to be the case with the AEANA derivative, which gave red tetragonal crystals. The protein now has a reactive group that can be photoactivated at a specific point in the nucleation or crystal growth process to "capture" protein molecules bound within reach of the crosslinking agent. If those bound protein molecules have a defined geometric relationship with the capturing molecule, such as would be found in a crystal, then the photoreacted cross-linking site should be consistent. Random protein interactions, typical of an amorphous precipitate or interaction, would show a random cross-linking reaction. The results of these and other experiments will be presented.

Construction of the Seven Basic Crystallographic Units.

ERIC Educational Resources Information Center

Li, Thomas; Worrell, Jay H.

1989-01-01

Presents an exercise to get students more intimately involved in the three dimensional nature of basic units by constructing models. Uses balsa wood, glue, sandpaper, and a square. Studies seven crystals: cubic, hexagonal, monoclinic, orthorhombic, rhombohedral, tetragonal, and triclinic. Plans are available for a Macintosh computer. (MVL)

Structural features of single crystals of LuB{sub 12} upon a transition to the cage-glass phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolotina, N. B., E-mail: nb-bolotina@mail.ru; Verin, I. A.; Shitsevalova, N. Yu.

2016-03-15

The unit-cell parameters of dodecaboride LuB{sub 12}, which undergoes a transition to the cage-glass phase, have been determined for the first time in the temperature range of 50–75 K by X-ray diffraction, and the single-crystal structure of this compound is established at 50 K. Nonlinear changes in the unit-cell parameters correspond to anomalies in the physical properties near the glass-transition temperature T* ~ 50–70 K. This compound has cubic symmetry at room temperature, and it is reduced to tetragonal symmetry at lower temperatures. Based on the X-ray diffraction data and relying on the physical properties of the crystals, the structuremore » model, in which a small part (~15%) of Lu atoms are displaced from the 2a sites at the centers of the B{sub 24} cuboctahedra to the 16n sites of sp. gr. I4/mmm, seems preferable.« less

Preparation and crystal structure of U3Fe2C5: An original uranium-iron carbide

NASA Astrophysics Data System (ADS)

Henriques, M. S.; Paixão, J. A.; Henriques, M. S. C.; Gonçalves, A. P.

2015-09-01

The U3Fe2C5 compound was prepared from the elements by arc-melting, followed by an heat-treatment in an induction furnace, at 1250 °C for 1 h and 1300 °C for 2 h. The crystal structure of this phase was determined by direct methods from single crystal X-ray diffraction data. U3Fe2C5 crystallizes in an original tetragonal crystal structure, with space group I4/mmm, a = 3.4980(3) Å and c = 19.8380(15) Å as lattice constants and two formula units per cell. This new type structure is characterized by the simultaneous presence of isolated and pairs of carbon atoms, the interatomic distances in the pairs being similar to a typical carbon-carbon double bond length found in a molecule. U3Fe2C5 is closely related to UC and UFeC2, and can be seen as build from two (distorted) UFeC2 unit cells and a UC layer.

Purification, crystallization and preliminary crystallographic analysis of biotin protein ligase from Staphylococcus aureus

PubMed Central

Pendini, Nicole R.; Polyak, Steve W.; Booker, Grant W.; Wallace, John C.; Wilce, Matthew C. J.

2008-01-01

Biotin protein ligase from Staphylococcus aureus catalyses the biotinylation of acetyl-CoA carboxylase and pyruvate carboxylase. Recombinant biotin protein ligase from S. aureus has been cloned, expressed and purified. Crystals were grown using the hanging-drop vapour-diffusion method using PEG 8000 as the precipitant at 295 K. X-ray diffraction data were collected to 2.3 Å resolution from crystals using synchrotron X-ray radiation at 100 K. The diffraction was consistent with the tetragonal space group P42212, with unit-cell parameters a = b = 93.665, c = 131.95. PMID:18540065

Synthesis and structural analysis of Fe doped TiO2 nanoparticles using Williamson Hall and Scherer Model

NASA Astrophysics Data System (ADS)

Patle, L. B.; Labhane, P. K.; Huse, V. R.; Gaikwad, K. D.; Chaudhari, A. L.

2018-05-01

The nanoparticles of Pure and doped Ti1-xFexO were synthesized by modified co-precipitation method successfully with nominal composite of x=0.0, 0.01, 0.03 and 0.05 at room temperature. The precursors were further calcined at 500°C for 6hrs in muffle furnace which results in the formation of different TiO2 phase compositions. The structural analysis carried out by XRD (Bruker D8 Cu-Kα1). X-ray peak broadening analysis was used to evaluate the crystalline sizes, the lattice parameters, atomic packing fraction, c/a ratio, X-ray density and Volume of unit cell. The Williamson Hall analysis is used to find grain size and Strain of prepared TiO2 nano particles. Crystalline TiO2 with a Tetragonal Anatase phase is confirmed by XRD results. The grain size of pure and Fe doped samples were found in the range of 10nm to 18nm. All the physical parameters of anatase tetragonal TiO2 nanoparticles were calculated more precisely using modified W-H plot a uniform deformation model (UDM). The results calculated from both the techniques were approximately similar.

Study of the transformation sequence on a high temperature martensitic transformation Ni-Mn-Ga-Co shape memory alloy

NASA Astrophysics Data System (ADS)

Recarte, V.; Pérez-Landazábal, J. I.; Sánchez-Alarcos, V.; Rodríguez-Velamazán, J. A.

2014-11-01

Ni-Mn-Ga alloys show the highest magnetic-field-induced strain among ferromagnetic shape memory alloys. A great effort is being done in this alloy system to increase the application temperature range. In this sense, the addition of small amounts of Cobalt to NiMnGa alloys has been proved to increase the MT temperatures through the increase of the electron per atom relation (e/a). In this work, the analysis of the crystal structure of the present phases and the phase transformations has been performed on a Ni-Mn-Ga-Co alloy by neutron diffraction measurements from 10 K to 673 K. The study has been completed by means of calorimetric and magnetic measurements. On cooling the alloy undergoes a martensitic transformation from a face centered cubic structure to a nonmodulated tetragonal martensite. The appearance of intermartensite transformations can be disregarded in the whole temperature range below the martensitic transformation. However, a jump in the unit-cell volume of the tetragonal martensite has been observed at 325 K. Since this temperature is close to the Curie temperature of the alloy both, the structural and magnetic contributions are taken into account to explain the results.

Competition between magnetism and superconductivity in Eu-based intermetallic compounds

NASA Astrophysics Data System (ADS)

Stavinoha, Macy; Green, Lance; Chan, Julia; Morosan, Emilia

Eu-based intermetallic compounds present a path to discover new correlated electronic behavior in quantum materials. Reports of superconductivity, intermediate valence behavior, and heavy fermions indicate that Eu-based compounds are promising routes to study the relationship between crystallography and electronic properties. The present work is focused on EuGa4, an antiferromagnet with TN = 16 K isostructural with the tetragonal RT2M2 (R = rare earth, T = transition metal, M = metal or metalloid) family that exhibits heavy fermion behavior and unconventional superconductivity. Single crystals of the doped series (Eu1-xLax)Ga4, (Eu1-xCax)Ga4, and Eu(Ga1-xAlx)4 have been grown using the self-flux method and tested for change in unit cell volume and magnetic susceptibility. Results show that doping with Ca (isoelectronic doping) and La (hole doping) reduce TN to 12.4 K and 2.3 K, respectively, for Ca doping up to x = 0.11 and La doping up to x = 0.74 without an associated change in unit cell volume. The series Eu(Ga1-xAlx)4 has shown incommensurate-to-commensurate magnetic transitions. Future studies will aim to further decrease TN and the unit cell volume using physical pressure and chemical pressure through doping. ICAM, Gordon and Betty Moore Foundation.

Sigma-phase packing of icosahedral clusters in 780-atom tetragonal crystals of Cr5Ni3Si2 and V15Ni10Si that by twinning achieve 8-fold rotational point-group symmetry

PubMed Central

Pauling, Linus

1988-01-01

A 780-atom primitive tetragonal unit with edges 27.3, 27.3, and 12.6 Å is assigned to rapidly solidified Cu5Ni3Si2 and V15Ni10Si by analysis of electron diffraction photographs with the assumption that the crystals contain icosahedral clusters. There are thirty 26-atom clusters at the sigma-phase positions. Apparent 8-fold symmetry results from 45° twinning on the basal plane. PMID:16593915

Sigma-phase packing of icosahedral clusters in 780-atom tetragonal crystals of Cr(5)Ni(3)Si(2) and V(15)Ni(10)Si that by twinning achieve 8-fold rotational point-group symmetry.

PubMed

Pauling, L

1988-04-01

A 780-atom primitive tetragonal unit with edges 27.3, 27.3, and 12.6 A is assigned to rapidly solidified Cu(5)Ni(3)Si(2) and V(15)Ni(10)Si by analysis of electron diffraction photographs with the assumption that the crystals contain icosahedral clusters. There are thirty 26-atom clusters at the sigma-phase positions. Apparent 8-fold symmetry results from 45 degrees twinning on the basal plane.

Kinetic Roughening Transition and Energetics of Tetragonal Lysozyme Crystal Growth

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2004-01-01

Interpretation of lysozyme crystal growth rates using well-established physical theories enabled the discovery of a phenomenon possibly indicative of kinetic roughening. For example, lysozyme crystals grown above a critical supersaturation sigma, (where supersaturation sigma = ln c/c(sub eq), c = the protein concentration and c(sub eq) = the solubility concentration) exhibit microscopically rough surfaces due to the continuous addition of growth units anywhere on the surface of a crystal. The rate of crystal growth, V(sub c), for the continuous growth process is determined by the continuous flux of macromolecules onto a unit area of the crystal surface, a, from a distance, xi, per unit time due to diffusion, and a probability of attachment onto the crystal surface, expressed. Based upon models applied, the energetics of lysozyme crystal growth was determined. The magnitudes of the energy barriers of crystal growth for both the (110) and (101) faces of tetragonal lysozyme crystals are compared. Finally, evidence supportive of the kinetic roughening hypothesis is presented.

Monitoring a Silent Phase Transition in CH 3NH 3PbI 3 Solar Cells via Operando X-ray Diffraction

DOE PAGES

Schelhas, Laura T.; Christians, Jeffrey A.; Berry, Joseph J.; ...

2016-10-13

The relatively modest temperature of the tetragonal-to-cubic phase transition in CH 3NH 3PbI 3 perovskite is likely to occur during real world operation of CH 3NH 3PbI 3 solar cells. In this work, we simultaneously monitor the structural phase transition of the active layer along with solar cell performance as a function of the device operating temperature. The tetragonal to cubic phase transition is observed in the working device to occur reversibly at temperatures between 60.5 and 65.4 degrees C. In these operando measurements, no discontinuity in the device performance is observed, indicating electronic behavior that is insensitive to themore » structural phase transition. Here, this decoupling of device performance from the change in long-range order across the phase transition suggests that the optoelectronic properties are primarily determined by the local structure in CH 3NH 3PbI 3. That is, while the average crystal structure as probed by X-ray diffraction shows a transition from tetragonal to cubic, the local structure generally remains well characterized by uncorrelated, dynamic octahedral rotations that order at elevated temperatures but are unchanged locally.« less

Monitoring a Silent Phase Transition in CH 3NH 3PbI 3 Solar Cells via Operando X-ray Diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schelhas, Laura T.; Christians, Jeffrey A.; Berry, Joseph J.

The relatively modest temperature of the tetragonal-to-cubic phase transition in CH 3NH 3PbI 3 perovskite is likely to occur during real world operation of CH 3NH 3PbI 3 solar cells. In this work, we simultaneously monitor the structural phase transition of the active layer along with solar cell performance as a function of the device operating temperature. The tetragonal to cubic phase transition is observed in the working device to occur reversibly at temperatures between 60.5 and 65.4 degrees C. In these operando measurements, no discontinuity in the device performance is observed, indicating electronic behavior that is insensitive to themore » structural phase transition. Here, this decoupling of device performance from the change in long-range order across the phase transition suggests that the optoelectronic properties are primarily determined by the local structure in CH 3NH 3PbI 3. That is, while the average crystal structure as probed by X-ray diffraction shows a transition from tetragonal to cubic, the local structure generally remains well characterized by uncorrelated, dynamic octahedral rotations that order at elevated temperatures but are unchanged locally.« less

Effect of Biaxial Strain on the Phase Transitions of Ca (Fe1 -xCox)2As2

NASA Astrophysics Data System (ADS)

Böhmer, A. E.; Sapkota, A.; Kreyssig, A.; Bud'ko, S. L.; Drachuck, G.; Saunders, S. M.; Goldman, A. I.; Canfield, P. C.

2017-03-01

We study the effect of applied strain as a physical control parameter for the phase transitions of Ca (Fe1 -xCox)2As2 using resistivity, magnetization, x-ray diffraction, and Fe 57 Mössbauer spectroscopy. Biaxial strain, namely, compression of the basal plane of the tetragonal unit cell, is created through firm bonding of samples to a rigid substrate via differential thermal expansion. This strain is shown to induce a magnetostructural phase transition in originally paramagnetic samples, and superconductivity in previously nonsuperconducting ones. The magnetostructural transition is gradual as a consequence of using strain instead of pressure or stress as a tuning parameter.

Effect of biaxial strain on the phase transitions of Ca ( Fe 1 – x Co x ) 2 As 2

DOE PAGES

Bohmer, A. E.; Sapkota, A.; Kreyssig, A.; ...

2017-03-10

We study the effect of applied strain as a physical control parameter for the phase transitions of Ca(Fe 1–xCo x) 2As 2 using resistivity, magnetization, x-ray diffraction, and 57Fe Mossbauer spectroscopy. Biaxial strain, namely, compression of the basal plane of the tetragonal unit cell, is created through firm bonding of samples to a rigid substrate via differential thermal expansion. This strain is shown to induce a magnetostructural phase transition in originally paramagnetic samples, and superconductivity in previously nonsuperconducting ones. Lastly, the magnetostructural transition is gradual as a consequence of using strain instead of pressure or stress as a tuning parameter.

Intercalation of the layered solid acid HCa/sub 2/Nb/sub 3/O/sub 10/ by organic amines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobson, A.J.; Johnson, J.W.; Lewandowski, J.T.

1987-01-01

Layered compounds of formula C/sub n/H/sub 2n+1/NH/sub 3/Ca/sub 2/Nb/sub 3/O/sub 10/ are formed by reaction of n-alkylamines with the solid acid HCa/sub 2/Nb/sub 3/O/sub 10/. Other organic bases such as pyridine can also be intercalated. The lattice constants of the new compounds have been determined by powder X-ray diffraction. The unit cells are tetragonal with a axes that are unchanged with variation of the intercalated amine. The c axes lengths (layer spacings) vary systematically with the hydrocarbon chain length of the alkylamine.

Structural investigation of cooperite (PtS) crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rozhdestvina, V. I., E-mail: veronika@ascnet.ru; Udovenko, A. A.; Rubanov, S. V.

2016-03-15

The single-crystal structure of cooperite, a natural platinum sulfide PtS, is studied by X-ray diffraction supported by high-resolution scanning transmission electron microscopy and X-ray spectrum microanalysis. It is found that, in addition to the main reflections corresponding to the known tetragonal cell (a = 3.47 and c = 6.11 Å; space group P4{sub 2}/mmc), many weak reflections with intensities I ≤ 60σ(I) are clearly observed. These reflections fit the tetragonal cell (space group I4/mmm) with doubled parameters. In structures with small (P4{sub 2}/mmc) and large (I4/mmm) cells, the S atoms occupy statistically two special positions. It is shown that themore » chemical composition of the cooperite crystals deviates from the stoichiometric composition: sulfur-deficient specimens predominate.« less

Hybridization gap in the semiconducting compound SrIr 4In 2Ge 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Calta, Nicholas P.; Im, Jino; Fang, Lei

Here, large single crystals of SrIr 4In 2Ge 4 were synthesized using the In flux method. This compound is a hybridization gap semiconductor with an experimental optical band gap of E g = 0.25(3) eV. It crystallizes in the tetragonal EuIr 4In 2Ge 4 structure type with space group 1more » $$\\overline{4}$$2m and unit cell parameters a = 6.9004(5) Å and c = 8.7120(9) Å. The electronic structure is very similar to both EuIr 4In 2Ge 4 and the parent structure Ca 3Ir 4Ge 4, suggesting that these compounds comprise a new family of hybridization gap materials that exhibit indirect gap, semiconducting behavior at a valence electron count of 60 per formula unit, similar to the Heusler alloys.« less

Crystallization and preliminary X-ray analysis of CTP:phosphoethanolamine cytidylyltransferase (ECT) from Saccharomyces cerevisiae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohtsuka, Jun; Nagata, Koji; Lee, Woo Cheol

2006-10-01

CTP:phosphoethanolamine cytidylyltransferase from S. cerevisiae has been expressed, purified and crystallized. CTP:phosphoethanolamine cytidylyltransferase (ECT) is the enzyme that catalyzes the conversion of phosphoethanolamine to CDP-ethanolamine in the phosphatidylethanolamine-biosynthetic pathway (Kennedy pathway). ECT from Saccharomyces cerevisiae was crystallized by the sitting-drop vapour-diffusion method using PEG 4000 as precipitant. The crystals diffracted X-rays from a synchrotron-radiation source to 1.88 Å resolution. The space group was assigned as primitive tetragonal, P4{sub 1}2{sub 1}2 or P4{sub 3}2{sub 1}2, with unit-cell parameters a = b = 66.3, c = 150.8 Å. The crystals contain one ECT molecule in the asymmetric unit (V{sub M} = 2.2more » Å{sup 3} Da{sup −1}), with a solvent content of 43%.« less

Hybridization gap in the semiconducting compound SrIr 4In 2Ge 4

DOE PAGES

Calta, Nicholas P.; Im, Jino; Fang, Lei; ...

2016-11-18

Here, large single crystals of SrIr 4In 2Ge 4 were synthesized using the In flux method. This compound is a hybridization gap semiconductor with an experimental optical band gap of E g = 0.25(3) eV. It crystallizes in the tetragonal EuIr 4In 2Ge 4 structure type with space group 1more » $$\\overline{4}$$2m and unit cell parameters a = 6.9004(5) Å and c = 8.7120(9) Å. The electronic structure is very similar to both EuIr 4In 2Ge 4 and the parent structure Ca 3Ir 4Ge 4, suggesting that these compounds comprise a new family of hybridization gap materials that exhibit indirect gap, semiconducting behavior at a valence electron count of 60 per formula unit, similar to the Heusler alloys.« less

Crystallization and preliminary X-ray diffraction studies of hyperthermophilic archaeal Rieske-type ferredoxin (ARF) from Sulfolobus solfataricus P1

PubMed Central

Kounosu, Asako; Hasegawa, Kazuya; Iwasaki, Toshio; Kumasaka, Takashi

2010-01-01

The hyperthermophilic archaeal Rieske-type [2Fe–2S] ferredoxin (ARF) from Sulfolobus solfataricus P1 contains a low-potential Rieske-type [2Fe–2S] cluster that has served as a tractable model for ligand-substitution studies on this protein family. Recombinant ARF harbouring a pET30a vector-derived N-­terminal extension region plus a hexahistidine tag has been heterologously overproduced in Escherichia coli, purified and crystallized by the hanging-drop vapour-diffusion method using 0.05 M sodium acetate, 0.05 M HEPES, 2 M ammonium sulfate pH 5.5. The crystals diffracted to 1.85 Å resolution and belonged to the tetragonal space group P43212, with unit-cell parameters a = 60.72, c = 83.31 Å. The asymmetric unit contains one protein molecule. PMID:20606288

Crystallization and preliminary X-ray diffraction studies of hyperthermophilic archaeal Rieske-type ferredoxin (ARF) from Sulfolobus solfataricus P1.

PubMed

Kounosu, Asako; Hasegawa, Kazuya; Iwasaki, Toshio; Kumasaka, Takashi

2010-07-01

The hyperthermophilic archaeal Rieske-type [2Fe-2S] ferredoxin (ARF) from Sulfolobus solfataricus P1 contains a low-potential Rieske-type [2Fe-2S] cluster that has served as a tractable model for ligand-substitution studies on this protein family. Recombinant ARF harbouring a pET30a vector-derived N-terminal extension region plus a hexahistidine tag has been heterologously overproduced in Escherichia coli, purified and crystallized by the hanging-drop vapour-diffusion method using 0.05 M sodium acetate, 0.05 M HEPES, 2 M ammonium sulfate pH 5.5. The crystals diffracted to 1.85 A resolution and belonged to the tetragonal space group P4(3)2(1)2, with unit-cell parameters a = 60.72, c = 83.31 A. The asymmetric unit contains one protein molecule.

First principles investigation of half-metallicity and spin gapless semiconductor in CH3NH3Cr x Pb1- x I3 mixed perovskites

NASA Astrophysics Data System (ADS)

Huang, H. M.; Zhu, Z. W.; Zhang, C. K.; He, Z. D.; Luo, S. J.

2018-04-01

The structural, electronic and magnetic properties of organic-inorganic hybrid mixed perovskites CH3NH3Cr x Pb1- x I3 ( x = 0.25, 0.50, 0.75, 1.00) in cubic, tetragonal and orthorhombic phases have been investigated by first-principles calculation. The results indicate that the tetragonal CH3NH3Cr0.75Pb0.25I3 is a spin gapless semiconductor with Curie temperature of 663 K estimated using mean field approximation. All other CH3NH3Cr x Pb1- x I3 mixed perovskites are half-metallic ferromagnets together with 100% spin polarization, and their total magnetic moment are 4.00, 8.00, 12.00 and 16.00 µB per unit cell for x = 0.25, 0.50, 0.75 and 1.00, respectively. The effect of <100>, <110> and <111> orientation of organic cation CH3NH3 + on the electronic properties of CH3NH3Cr0.50Pb0.50I3 was investigated. The results show that the CH3NH3 + in different orientations have a slight effect on the lattice constants, the energy gap in minority-spin states, half-metallic gap, local magnetic moment, and Curie temperature.

Variation in superconducting transition temperature due to tetragonal domains in two-dimensionally doped SrTiO 3

DOE PAGES

Noad, Hilary; Spanton, Eric M.; Nowack, Katja C.; ...

2016-11-28

Strontium titanate is a low-temperature, non–Bardeen-Cooper-Schrieffer superconductor that superconducts to carrier concentrations lower than in any other system and exhibits avoided ferroelectricity at low temperatures. Neither the mechanism of superconductivity in strontium titanate nor the importance of the structure and dielectric properties for the superconductivity are well understood. We studied the effects of twin structure on superconductivity in a 5.5-nm-thick layer of niobium-doped SrTiO 3 embedded in undoped SrTiO 3. We used a scanning superconducting quantum interference device susceptometer to image the local diamagnetic response of the sample as a function of temperature. We observed regions that exhibited a superconductingmore » transition temperature T c ≳ 10% higher than the temperature at which the sample was fully superconducting. The pattern of these regions varied spatially in a manner characteristic of structural twin domains. Some regions are too wide to originate on twin boundaries; therefore, we propose that the orientation of the tetragonal unit cell with respect to the doped plane affects T c. Finally, our results suggest that the anisotropic dielectric properties of SrTiO 3 are important for its superconductivity and need to be considered in any theory of the mechanism of the superconductivity.« less

Tensile Strain Effects on the Magneto-transport in Calcium Manganese Oxide Thin Films: Comparison with its Hole-doped Counterpart

NASA Astrophysics Data System (ADS)

Lawson, Bridget; Neubauer, Samuel; Chaudhry, Adeel; Hart, Cacie; Ferrone, Natalie; Houston, David; Yong, Grace; Kolagani, Rajeswari

Magnetoresistance properties of the epitaxial thin films of doped rare earth manganites are known to be influenced by the effect of bi-axial strain induced by lattice mismatch with the substrate. In hole-doped manganites, the effect of both compressive and tensile strain is qualitatively consistent with the expected changes in unit cell symmetry from cubic to tetragonal, leading to Jahn-Teller strain fields that affect the energy levels of Mn3 + energy levels. Recent work in our laboratory on CaMnO3 thin films has pointed out that tetragonal distortions introduced by tensile lattice mismatch strain may also have the effect of modulating the oxygen content of the films in agreement with theoretical models that propose such coupling between strain and oxygen content. Our research focuses on comparing the magneto-transport properties of hole-doped manganite LaCaMnO3 thin films with that of its electron doped counter parts, in an effort to delineate the effects of oxygen stoichiometry changes on magneto-transport from the effects of Jahn-Teller type strain. Towson University Office of Undergraduate Research, Fisher Endowment Grant and Undergraduate Research Grant from the Fisher College of Science and Mathematics, Seed Funding Grant from the School of Emerging technologies and the NSF Grant ECCS 112856.

Pseudomorphic to orthomorphic growth of Fe films on Cu3Au(001)

NASA Astrophysics Data System (ADS)

Bruno, F.; Terreni, S.; Floreano, L.; Cossaro, A.; Cvetko, D.; Luches, P.; Mattera, L.; Morgante, A.; Moroni, R.; Repetto, M.; Verdini, A.; Canepa, M.

2002-06-01

The structure of Fe films grown on the (001) surface of a Cu3Au single crystal at room temperature has been investigated by means of grazing incidence x-ray diffraction (GIXRD) and photo/Auger-electron diffraction (ED) as a function of thickness in the (3-36)-Å range. The combination of GIXRD and ED allows one to obtain quantitative information on the in-plane spacing a from the former technique, and the ratio between the vertical spacing c and a, from the latter one. At low coverage the film grows pseudomorphic to the face-centered-cubic substrate. The experimental results obtained on a film of 8 Å thickness clearly indicate the overcoming of the limit for pseudomorphic growth. Above this limit the film is characterized by the coexistence of the pseudomorphic phase with another tetragonally strained phase γ, which falls on the epitaxial line of ferromagnetic face-centered cubic Fe. Finally, the development of a body-centered phase α, whose unit cell is rotated by 45° with respect to the substrate one, has been clearly observed at ~17 Å. α is the dominating phase for film thickness above ~25 Å and its lattice constant evolves towards the orthomorphic phase in strict quantitative agreement with epitaxial curves calculated for body-centered tetragonal iron phases.

X-ray diffraction and infrared spectroscopy studies of Ba(Fe1/2Nb1/2)O3-(Na1/2Bi1/2)TiO3 ceramics

NASA Astrophysics Data System (ADS)

Chandra, K. P.; Yadav, Anjana; Prasad, K.

2018-05-01

Ceramics (1-x)Ba(Fe1/2Nb1/2)O3-x(Na1/2Bi1/2)TiO3; 0≤x≤1.0 were prepared by conventional ceramic synthesis technique. Rietveld refinements of X-ray diffraction data of these ceramics were carried out using FullProf software and determined their crystal symmetry, space group and unit cell dimensions. Rietveld refinement revealed that Ba(Fe1/2Nb1/2)O3 has cubic structure with space group Pm 3 ¯ m and Na1/2Bi1/2)TiO3 has rhombohedral structure with space group R3c. Addition of (Na1/2Bi1/2)TiO3 to Ba(Fe1/2Nb1/2)O3 resulted in the change of unit cell structure from cubic to tetragonal (P4/mmm) for x = 0.75 and the X-Ray diffraction peaks slightly shift towards higher Bragg's angle, suggesting slight decrease in unit cell volume. SEM studies were carried out in order to access the quality of the prepared ceramics which showed a change in grain shapes with the increase of (Na1/2Bi1/2)TiO3 content. FTIR spectra confirmed the formation of perovskite type solid solutions.

Fabrication of luminescent SrWO{sub 4} thin films by a novel electrochemical method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen Lianping; Gao Yuanhong

2007-10-02

Highly crystallized SrWO{sub 4} thin films with single scheelite structure were prepared within 60 min by a cell electrochemical method. X-ray diffraction analysis shows that SrWO{sub 4} thin films have a tetragonal structure. Scanning electron microscopy examinations reveal that SrWO{sub 4} grains grow well in tetragonal tapers and grains like flowers or bunches, which can usually form by using the electrolysis electrochemical method, have disappeared under cell electrochemical conditions. X-ray photoelectron spectra and energy dispersive X-ray microanalysis examinations demonstrate that the composition of the film is consistent with its stoichiometry. These SrWO{sub 4} films show a single blue emission peakmore » (located at 460 nm) using an excitation wave of 230 nm. The speed of cell electrochemical method can be controlled by changing temperature. The optimum treatment temperature is about 50-60 deg. C.« less

Determining the Molecular Growth Mechanisms of Protein Crystal Faces by Atomic Force Microscopy

NASA Technical Reports Server (NTRS)

Nadarajah, Arunan; Li, Huayu; Pusey, Marc L.

1999-01-01

A high resolution atomic force microscopy (AFM) study had shown that the molecular packing on the tetragonal lysozyme (110) face corresponded to only one of two possible packing arrangements, suggesting that growth layers on this face were of bimolecular height. Theoretical analyses of the packing also indicated that growth of this face should proceed by the addition of growth units of at least tetramer size corresponding to the 43 helices in the crystal. In this study an AFM linescan technique was devised to measure the dimensions of individual growth units on protein crystal faces as they were being incorporated into the lattice. Images of individual growth events on the (110) face of tetragonal lysozyme crystals were observed, shown by jump discontinuities in the growth step in the linescan images as shown in the figure. The growth unit dimension in the scanned direction was obtained from these images. A large number of scans in two directions on the (110) face were performed and the distribution of lysozyme growth unit sizes were obtained. A variety of unit sizes corresponding to 43 helices, were shown to participate in the growth process, with the 43 tetramer being the minimum observed size. This technique represents a new application for AFM allowing time resolved studies of molecular process to be carried out.

Tetragonal Chicken Egg White Lysozyme Solubility in Sodium Chloride Solutions

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth L.; Judge, Russell A.; Pusey, Marc L.

1998-01-01

The solubility of chicken egg white lysozyme, crystallized in the tetragonal form was measured in sodium chloride solutions from 1.6 to 30.7 C, using a miniature column solubility apparatus. Sodium chloride solution concentrations ranged from 1 to 7% (w/v). The solutions were buffered with 0.1 M sodium acetate buffer with the solubility being measured at pH values in 0.2 pH unit increments in the range pH 4.0 to 5.4, with data also included at pH 4.5. Lysozyme solubility was found to increase with increases in temperature and decreasing salt concentration. Solution pH has a varied and unpredictable effect on solubility.

Crystallization and preliminary X-ray diffraction analysis of mouse galectin-4 N-terminal carbohydrate recognition domain in complex with lactose

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krejčiříková, Veronika; Fábry, Milan; Marková, Vladimíra

2008-07-01

Mouse galectin-4 carbohydrate binding domain was overexpressed in E. coli and crystallized in the presence of lactose. The crystals belong to tetragonal space group P42{sub 1}2 and diffraction data were collected to 2.1 Å resolution. Galectin-4 is thought to play a role in the process of tumour conversion of cells of the alimentary tract and the breast tissue; however, its exact function remains unknown. With the aim of elucidating the structural basis of mouse galectin-4 (mGal-4) binding specificity, we have undertaken X-ray analysis of the N-terminal domain, CRD1, of mGal-4 in complex with lactose (the basic building block of knownmore » galectin-4 carbohydrate ligands). Crystals of CRD1 in complex with lactose were obtained using vapour-diffusion techniques. The crystals belong to tetragonal space group P42{sub 1}2 with unit-cell parameters a = 91.1, b = 91.16, c = 57.10 Å and preliminary X-ray diffraction data were collected to 3.2 Å resolution. An optimized crystallization procedure and cryocooling protocol allowed us to extend resolution to 2.1 Å. Structure refinement is currently under way; the initial electron-density maps clearly show non-protein electron density in the vicinity of the carbohydrate binding site, indicating the presence of one lactose molecule. The structure will help to improve understanding of the binding specificity and function of the potential colon cancer marker galectin-4.« less

Impedance spectroscopy studies on lead free Ba1-xMgx(Ti0.9Zr0.1)O3 ceramics

NASA Astrophysics Data System (ADS)

Ben Moumen, S.; Neqali, A.; Asbani, B.; Mezzane, D.; Amjoud, M.; Choukri, E.; Gagou, Y.; El Marssi, M.; Luk'yanchuk, Igor A.

2018-06-01

Ba1-xMgx(Ti0.9Zr0.1)O3 (x = 0.01 and 0.02) ceramics were prepared using the conventional solid state reaction. Rietveld refinement performed on X-ray diffraction patterns indicates that the samples are tetragonal crystal structure with P4mm space group. By increasing Mg content from 1 to 2% the unit cell volume decreased. Likewise, the grains size is greatly reduced from 10 μm to 4 μm. The temperature dependence of dielectric constants at different frequencies exhibited typical relaxor ferroelectric characteristic, with sensitive dependence in frequency and temperature for ac conductivity. The obtained activation energy values were correlated to the proposed conduction mechanisms.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bischoff, A. J., E-mail: alina.bischoff@iom-leipzig.de; Arabi-Hashemi, A.; Ehrhardt, M.

Combining experimental methods and classical molecular dynamics (MD) computer simulations, we explore the martensitic transformation in Fe{sub 70}Pd{sub 30} ferromagnetic shape memory alloy thin films induced by laser shock peening. X-ray diffraction and scanning electron microscope measurements at shock wave pressures of up to 2.5 GPa reveal formation of martensitic variants with preferred orientation of the shorter c-axis of the tetragonal unit cell perpendicular to the surface plane. Moreover, consequential merging of growth islands on the film surface is observed. MD simulations unveil the underlying physics that are characterized by an austenite-martensite transformation with a preferential alignment of the c-axis alongmore » the propagation direction of the shock wave, resulting in flattening and in-plane expansion of surface features.« less

Four crystal forms of a Bence-Jones protein

PubMed Central

Makino, Debora L.; Henschen-Edman, Agnes H.; McPherson, Alexander

2005-01-01

Four crystal forms have been grown and characterized by X-ray diffraction of a Bence-Jones protein collected from the urine of a multiple myeloma patient more than 40 years ago. Closely related tetragonal and orthorhombic forms belonging to space groups P43212 and P212121, with unit-cell parameters a = b = 68.7, c = 182.1 and a = 67.7, b = 69.4, c = 87.3 Å, diffract to 1.5 and 1.9 Å, respectively. Two closely related trigonal forms, both belonging to space group P3121 with unit-cell parameters a = b = 154.3 Å but differing by a doubling of the c axis, one 46.9 Å and the other 94.0 Å, diffract to 2.9 and 2.6 Å resolution, respectively. The trigonal crystal of short c-axis length shows a positive indication of twinning. The trigonal crystal of longer c axis, which appeared only after eight months of incubation at room temperature, is likely to be composed of proteolytically degraded molecules and unlike the other crystal forms contains two entire Bence-Jones dimers in the asymmetric unit. This latter crystal form may shed some light on the formation of fibrils common to certain storage diseases. PMID:16508097

Atomistic simulation of cubic and tetragonal phases of U-Mo alloy: Structure and thermodynamic properties

NASA Astrophysics Data System (ADS)

Starikov, S. V.; Kolotova, L. N.; Kuksin, A. Yu.; Smirnova, D. E.; Tseplyaev, V. I.

2018-02-01

We studied structure and thermodynamic properties of cubic and tetragonal phases of pure uranium and U-Mo alloys using atomistic simulations: molecular dynamics and density functional theory. The main attention was paid to the metastable γ0 -phase that is formed in U-Mo alloys at low temperature. Structure of γ0 -phase is similar to body-centered tetragonal (bct) lattice with displacement of a central atom in the basic cell along [ 001 ] direction. Such displacements have opposite orientations for part of the neighbouring basic cells. In this case, such ordering of the displacements can be designated as antiferro-displacement. Formation of such complex structure may be interpreted through forming of short U-U bonds. At heating, the tetragonal structure transforms into cubic γs -phase, still showing ordering of central atom displacements. With rise in temperature, γs -phase transforms to γ-phase with a quasi body-centered cubic (q-bcc) lattice. The local positions of uranium atoms in γ-phase correspond to γs -phase, however, orientations of the central atom displacements become disordered. Transition from γ0 to γ can be considered as antiferro-to paraelastic transition of order-disorder type. This approach to the structure description of uranium alloy allows to explain a number of unusual features found in the experiments: anisotropy of lattice at low temperature; remarkably high self-diffusion mobility in γ-phase; decreasing of electrical resistivity at heating for some alloys. In addition, important part of this work is the development of new interatomic potential for U-Mo system made with taking into account details of studied structures.

First determination of the valence band dispersion of CH3NH3PbI3 hybrid organic-inorganic perovskite

NASA Astrophysics Data System (ADS)

Lee, Min-I.; Barragán, Ana; Nair, Maya N.; Jacques, Vincent L. R.; Le Bolloc'h, David; Fertey, Pierre; Jemli, Khaoula; Lédée, Ferdinand; Trippé-Allard, Gaëlle; Deleporte, Emmanuelle; Taleb-Ibrahimi, Amina; Tejeda, Antonio

2017-07-01

The family of hybrid organic-inorganic halide perovskites is in the limelight because of their recently discovered high photovoltaic efficiency. These materials combine photovoltaic energy conversion efficiencies exceeding 22% and low-temperature and low-cost processing in solution; a breakthrough in the panorama of renewable energy. Solar cell operation relies on the excitation of the valence band electrons to the conduction band by solar photons. One factor strongly impacting the absorption efficiency is the band dispersion. The band dispersion has been extensively studied theoretically, but no experimental information was available. Herein, we present the first experimental determination of the valence band dispersion of methylammonium lead halide in the tetragonal phase. Our results pave the way for contrasting the electronic hopping or the electron effective masses in different theories by comparing to our experimental bands. We also show a significant broadening of the electronic states, promoting relaxed conditions for photon absorption, and demonstrate that the tetragonal structure associated to the octahedra network distortion below 50 °C induces only a minor modification of the electronic bands, with respect to the cubic phase at high temperature, thus minimizing the impact of the cubic-tetragonal transition on solar cell efficiencies.

High pressure low temperature studies on 1-2-2 iron-based superconductors using designer diamond cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uhoya, Walter O.; Tsoi, Georgiy M.; Vohra, Yogesh K.

In this study, high pressure low temperature electrical resistance measurements were carried out on a series of 122 iron-based superconductors using a designer diamond anvil cell. These studies were complemented by image plate x-ray diffraction measurements under high pressures and low temperatures at beamline 16-BM-D, HPCAT, Advanced Photon Source. A common feature of the 1-2-2 iron-based materials is the observation of anomalous compressibility effects under pressure and a Tetragonal (T) to Collapsed Tetragonal (CT) phase transition under high pressures. Specific studies on antiferromagnetic spin-density-wave Ba 0.5Sr 0.5Fe 2As 2 and Ba(Fe 0.9Ru 0.1) 2As 2 samples are presented to 10more » K and 41 GPa. The collapsed tetragonal phase was observed at a pressure of 14 GPa in Ba 0.5Sr 0.5Fe 2As 2 at ambient temperature. The highest superconducting transition temperature in Ba 0.5Sr 0.5Fe 2As 2 was observed to be at 32 K at a pressure of 4.7 GPa. The superconductivity was observed to be suppressed on transformation to the CT phase in 122 materials.« less

Purification, crystallization and preliminary X-ray analysis of a thermostable glycoside hydrolase family 43 β-xylosidase from Geobacillus thermoleovorans IT-08

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rohman, Ali; Oosterwijk, Niels van; Kralj, Slavko

2007-11-01

The β-xylosidase was crystallized using PEG 6000 as precipitant. 5% PEG 6000 yielded bipyramid-shaped tetragonal crystals diffracting to 1.55 Å resolution, and 13% PEG 6000 gave rectangular monoclinic crystals diffracting to 1.80 Å resolution. The main enzymes involved in xylan-backbone hydrolysis are endo-1,4-β-xylanase and β-xylosidase. β-Xylosidase converts the xylo-oligosaccharides produced by endo-1,4-β-xylanase into xylose monomers. The β-xylosidase from the thermophilic Geobacillus thermoleovorans IT-08, a member of glycoside hydrolase family 43, was crystallized at room temperature using the hanging-drop vapour-diffusion method. Two crystal forms were observed. Bipyramid-shaped crystals belonging to space group P4{sub 3}2{sub 1}2, with unit-cell parameters a = bmore » = 62.53, c = 277.4 Å diffracted to 1.55 Å resolution. The rectangular crystals belonged to space group P2{sub 1}, with unit-cell parameters a = 57.94, b = 142.1, c = 153.9 Å, β = 90.5°, and diffracted to 1.80 Å resolution.« less

Study of the electronic structure and half-metallicity of CaMnO3/BaTiO3 superlattice

NASA Astrophysics Data System (ADS)

Wang, Kai; Jiang, Wei; Chen, Jun-Nan; Huang, Jian-Qi

2016-09-01

In this paper, the electronic structure, magnetic properties and half-metallicity of the CaMnO3/BaTiO3 superlattice are investigated by employing the first-principle calculation based on density functional theory within the GGA or GGA + U exchange-correlation functional. The CaMnO3/BaTiO3 superlattice is constructed by the cubic CaMnO3 and the tetragonal ferroelectric BaTiO3 growing alternately along (0 0 1) direction. The cubic CaMnO3 presents a robust half-metallicity and a metastable ferromagnetic phase. Its magnetic moment is an integral number of 3.000 μB per unit cell. However, the CaMnO3/BaTiO3 superlattice has a stable ferromagnetic phase, for which the magnetic moment is 12.000 μB per unit cell. It also retains the robust half-metallicity which mainly results from the strong hybridization between Mn and O atoms. The results show that the constructed CaMnO3/BaTiO3 superlattice exhibits superior magnetoelectric properties. It may provide a theoretical reference for the design and preparation of new multiferroic materials.

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

PubMed Central

Li, Dehui; Wang, Gongming; Cheng, Hung-Chieh; Chen, Chih-Yen; Wu, Hao; Liu, Yuan; Huang, Yu; Duan, Xiangfeng

2016-01-01

Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Our findings offer significant fundamental insight on the temperature- and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials. PMID:27098114

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

DOE PAGES

Li, Dehui; Wang, Gongming; Cheng, Hung -Chieh; ...

2016-04-21

Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirmmore » that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Lastly, our findings offer significant fundamental insight on the temperature-and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.« less

Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal-Cubic Structural Phase Transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoque, Md Nadim Ferdous; Islam, Nazifah; Li, Zhen

Practical hybrid perovskite solar cells (PSCs) must endure temperatures above the tetragonal-cubic structural phase transition of methylammonium lead iodide (MAPbI3). However, the ionic and optical properties of MAPbI3 in such a temperature range, and particularly, dramatic changes in these properties resulting from a structural phase transition, are not well studied. Herein, we report a striking contrast at approximately 45 degrees C in the ionic/electrical properties of MAPbl3 owing to a change of the ion activation energy from 0.7 to 0.5 eV, whereas the optical properties exhibit no particular transition except for the steady increase of the bandgap with temperature. Thesemore » observations can be explained by the 'continuous' nature of perovskite phase transition. We speculate that the critical temperature at which the ionic/electrical properties change, although related to crystal symmetry variation, is not necessarily the same temperature as when tetragonal-cubic structural phase transition occurs.« less

Manipulation of polar order in the "empty" tetragonal tungsten bronzes: Ba4-xSrxDy0.67□1.33Nb10O30, x = 0, 0.25, 0.5, 1, 2, 3

NASA Astrophysics Data System (ADS)

Gardner, Jonathan; Morrison, Finlay D.

2016-08-01

A series of "empty" tetragonal tungsten bronze (TTB) ferroelectrics, Ba4-xSrxDy0.67□1.33Nb10O30 (x = 0, 0.25, 0.5, 1, 2, 3; □ = vacancy), is reported. With increasing x the unit cell contracts in both the ab plane and c-axis; x ≤ 1 compounds are normal ferroelectrics (FE) with decreasing TC as x increases, while x ≥ 2 are relaxor ferroelectrics (RFE) with associated frequency dependent permittivity peaks and with similar Tm and Tf (Vogel-Fulcher freezing temperatures) values. This observation is rationalised by differing cation occupancies: for x ≤ 1, Sr2+ principally occupies the A2-site (co-occupied by Ba2+ with the A1-site occupied by Dy3+ and vacancies); for x ≥ 2 significant Sr A1-site occupation leads to the observed RFE characteristics. This FE to RFE crossover is consistent with a previously proposed TTB crystal chemical framework where both a decrease in average A-site size and concurrent increase in A1-site tolerance factor (tA1) favour destabilization of long range polar order and relaxor behaviour. The effect of increasing tA1 as a result of Sr occupancy at the A1 site is dominant in the compounds reported here.

Photoluminescent emission of Pr 3+ ions in different zirconia crystalline forms

NASA Astrophysics Data System (ADS)

Ramos-Brito, F.; Alejo-Armenta, C.; García-Hipólito, M.; Camarillo, E.; Hernández A, J.; Murrieta S, H.; Falcony, C.

2008-08-01

Polycrystalline praseodymium doped-zirconia powders were synthesized by crystallization of a saturated solution and annealed in air at T a = 950 °C. Monoclinic, tetragonal and cubic crystalline phases of zirconia were obtained. EDS studies showed homogeneous chemical composition over all the powders particles and chemical elemental contents in good agreement with the incorporation of Pr 3+ ion in Zr 4+ sites. XRD patterns showed stabilization of tetragonal and cubic phases at 1.28 and 2.87 at.% of Pr 3+ doping concentrations, respectively. Both unit cells expand when Pr 3+ content increases. All samples showed a crystallite size lower than 27 nm. Diffuse reflectance studies exhibited the presence of the 4f5d absorption band of Pr 3+, and absorption peaks in 440-610 nm region associated with 4f inter-level electronic transitions in Pr 3+ ion. Low temperature (20 K) photo-luminescent spectroscopic measurements over excitation of 488 nm for praseodymium doped zirconia, showed multiple emission peaks in the 520-900 nm range of the electromagnetic spectrum, associated with typical 4f inter-level electronic transition in Pr 3+. Incorporation of Pr 3+ in more than one zirconia crystalline phase and the incorporation in cubic C 2 sites, were observed. Zirconia powders presented significant differences in its emission spectra as a function of the type of crystalline phase compounds.

Overexpression, purification and crystallization of a choline-binding protein CbpI from Streptococcus pneumoniae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paterson, Neil G., E-mail: neison@chem.gla.ac.uk; Riboldi-Tunicliffe, Alan; Mitchell, Timothy J.

2006-07-01

The choline-binding protein CbpI from S. pneumoniae has been purified and crystallized and diffraction data have been collected to 3.5 Å resolution. The choline-binding protein CbpI from Streptococcus pneumoniae is a 23.4 kDa protein with no known function. The protein has been successfully purified initially using Ni–NTA chromatography and to homogeneity using Q-Sepharose ion-exchange resin as an affinity column. CbpI was crystallized using PEG 3350 as a precipitant and X-ray crystallographic analysis showed that the crystals belonged to the tetragonal space group P4, with unit-cell parameters a = b = 83.31, c = 80.29 Å, α = β = γmore » = 90°. The crystal contains two molecules in the asymmetric unit with a solvent content of 55.7% (V{sub M} = 2.77 Å{sup 3} Da{sup −1}) and shows a diffraction limit of 3.5 Å.« less

Crystallization and preliminary X-ray crystallographic analysis of the tRNA-specific adenosine deaminase from Streptococcus pyogenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ku, Min-Je; Lee, Won-Ho; Biotechnology and Genetic Engineering, Korea University, Seoul 136-701

2005-04-01

The tRNA-specific adenosine deaminase from the pathogenic bacteria S. pyogenes has been overexpressed and crystallized. The tRNA-specific adenosine deaminase from the pathogenic bacteria Streptococcus pyogenes (spTAD) has been overexpressed in Escherichia coli and crystallized in the presence of Zn{sup 2+} ion at 295 K using ammonium sulfate as a precipitant. Flash-cooled crystals of spTAD diffracted to 2.0 Å using 30%(v/v) glycerol as a cryoprotectant. X-ray diffraction data have been collected to 2.0 Å using synchrotron radiation. The crystal belongs to the tetragonal space group P4{sub 2}2{sub 1}2, with unit-cell parameters a = b = 81.042, c = 81.270 Å. Themore » asymmetric unit contains one subunit of spTAD, with a corresponding crystal volume per protein weight (V{sub M}) of 3.3 Å{sup 3} Da{sup −1} and a solvent content of 62.7%.« less

Crystallization and preliminary crystallographic analysis of a flavoprotein NADH oxidase from Lactobacillus brevis

PubMed Central

Kuzu, Mutlu; Niefind, Karsten; Hummel, Werner; Schomburg, Dietmar

2005-01-01

NADH oxidase (NOX) from Lactobacillus brevis is a homotetrameric flavoenzyme composed of 450 amino acids per subunit. The molecular weight of each monomer is 48.8 kDa. The enzyme catalyzes the oxidation of two equivalents of NADH and reduces one equivalent of oxygen to yield two equivalents of water, without releasing hydrogen peroxide after the reduction of the first equivalent of NADH. Crystals of this protein were grown in the presence of 34% polyethylene glycol monomethyl ether 2000, 0.1 M sodium acetate and 0.2 M ammonium sulfate at pH 5.4. They belong to the tetragonal space group P43212, with unit-cell parameters a = 74.8, b = 95.7, c = 116.9 Å, α = γ = 90, β = 103.8°. The current diffraction limit is 4.0 Å. The self-rotation function of the native data set is consistent with a NOX tetramer in the asymmetric unit. PMID:16511087

Crystallization and preliminary X-ray diffraction studies of NP24-I, an isoform of a thaumatin-like protein from ripe tomato fruits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Raka; Chakrabarti, Chandana, E-mail: chandana.chakrabarti@saha.ac.in

2005-08-01

A thaumatin-like antifungal protein, NP24-I, has been isolated from ripe tomato fruits. It was crystallized by the vapour-diffusion method and data were collected to 2.45 Å. The structure was solved by molecular replacement. NP24 is a 24 kDa (207-amino-acid) antifungal thaumatin-like protein (TLP) found in tomato fruits. An isoform of the protein, NP24-I, is reported to play a possible role in ripening of the fruit in addition to its antifungal properties. The protein has been isolated and purified and crystallized by the hanging-drop vapour-diffusion method. The crystals belong to the tetragonal space group P4{sub 3}, with unit-cell parameters a =more » b = 61.01, c = 62.90 Å and one molecule per asymmetric unit. X-ray diffraction data were processed to a resolution of 2.45 Å and the structure was solved by molecular replacement.« less

Synthesis, molecular structure and physicochemical properties of bis(3‧-azido-3‧-deoxythymidin-5‧-yl) carbonate

NASA Astrophysics Data System (ADS)

Raviolo, Mónica A.; Williams, Patricia A. M.; Etcheverry, Susana B.; Piro, Oscar E.; Castellano, Eduardo E.; Gualdesi, Maria S.; Briñón, Margarita C.

2010-04-01

3'-Azido-3'-deoxythymidine (zidovudine, AZT), a synthetic analog of natural nucleoside thymidine, has been used extensively in AIDS treatments. We report here the synthesis, X-ray crystal and molecular structure, NMR, IR and Raman spectra and the thermal behavior of a novel carbonate of AZT [(AZT-O) 2C dbnd O], prepared by the reaction of zidovudine with carbonyldiimidazole. The carbonate compound, C 21H 24N 10O 9, crystallizes in the tetragonal space group P4 12 12 with a = b = 15.284(1), c = 21.695(1) Å, and Z = 8 molecules per unit cell. It consists of two AZT moieties of closely related conformations which are bridged by a carbonyl group to adopt a folded Z-like shape.

Monodomain to polydomain transition in ferroelectric PbTiO3 thin films with La0.67Sr0.33MnO3 electrodes

NASA Astrophysics Data System (ADS)

Lichtensteiger, Céline; Dawber, Matthew; Stucki, Nicolas; Triscone, Jean-Marc; Hoffman, Jason; Yau, Jeng-Bang; Ahn, Charles H.; Despont, Laurent; Aebi, Philipp

2007-01-01

Finite size effects in ferroelectric thin films have been probed in a series of epitaxial perovskite c-axis oriented PbTiO3 films grown on thin La0.67Sr0.33MnO3 epitaxial electrodes. The film thickness ranges from 480 down to 28Å (seven unit cells). The evolution of the film tetragonality c /a, studied using high resolution x-ray diffraction measurements, shows first a decrease of c /a with decreasing film thickness followed by a recovery of c /a at small thicknesses. This recovery is accompanied by a change from a monodomain to a polydomain configuration of the polarization, as directly demonstrated by piezoresponse atomic force microscopy measurements.

Crystallization and preliminary X-ray diffraction analysis of the small laccase from Streptomyces coelicolor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skálová, Tereza, E-mail: skalova@imc.cas.cz; Dohnálek, Jan; Institute of Physics, Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 162 53 Praha 6

2007-12-01

The expression, purification and crystallization of the small laccase from S. coelicolor are reported. Diffraction data were collected to 3 Å resolution. The small bacterial laccase from the actinobacterium Streptomyces coelicolor which lacks the second of the three domains of the laccases structurally characterized to date was crystallized. This multi-copper phenol oxidase crystallizes in a primitive tetragonal lattice, with unit-cell parameters a = b = 179.8, c = 175.3 Å. The crystals belong to either space group P4{sub 1}2{sub 1}2 or P4{sub 3}2{sub 1}2. The self-rotation function shows the presence of a noncrystallographic threefold axis in the structure. Phases willmore » be determined from the anomalous signal of the natively present copper ions.« less

TEM study on a new Zr-(Fe, Cu) phase in furnace-cooled Zr-1.0Sn-0.3Nb-0.3Fe-0.1Cu alloy

NASA Astrophysics Data System (ADS)

Liu, Yushun; Qiu, Risheng; Luan, Baifeng; Hao, Longlong; Tan, Xinu; Tao, Boran; Zhao, Yifan; Li, Feitao; Liu, Qing

2018-06-01

A new Zr-(Fe, Cu) phase was found in furnace-cooled Zr-1.0Sn-0.3Nb-0.3Fe- 0.1Cu alloy and alloys aged at 580 °C for 10min, 2 h and 10 h. Electron diffraction experiment shows the crystal structure of this phase to be body-centered tetragonal with unit cell dimensions determined to be a = b = 6.49 Å, c = 5.37 Å. Its possible space groups have been discussed and the reason accounting for its formation is believed to be the addition of Cu according to the atom-level images. In addition, no crystal structural or chemical composition changes were observed throughout the aging process.

Synthesis and properties of the compound: LiNi 3/5Cu 2/5VO 4

NASA Astrophysics Data System (ADS)

Ram, Moti

2009-12-01

The LiNi 3/5Cu 2/5VO 4 is synthesized by solution-based chemical method and its formation has been checked by X-ray diffraction (XRD) study. XRD study shows a tetragonal unit cell structure with lattice parameters of a = 11.6475 (18) Å, c = 2.4855 (18) Å and c/ a = 0.2134 Å. Electrical properties are verified using complex impedance spectroscopy (CIS) technique. Complex impedance analysis reveals following points: (i) the bulk contribution to electrical properties up to 200 °C, (ii) the bulk and grain boundary contribution at T ≥ 225 °C, (iii) the presence of temperature dependent electrical relaxation phenomena in the material. D.c. conductivity study indicates that electrical conduction in the material is a thermally activated process.

Structure, stability, and thermomechanical properties of Ca-substituted Pr2NiO4 + δ

NASA Astrophysics Data System (ADS)

Pikalova, E. Yu.; Medvedev, D. A.; Khasanov, A. F.

2017-04-01

Ca-substituted layered nickelates with a general Pr2- x Ca x NiO4 + δ composition ( x = 0-0.7, Δ x = 0.1) were prepared in the present work and their structural and physic-chemical properties were investigated in order to select the most optimal materials, which can be used as cathodes for solid oxide fuel cells. With an increase in Ca content in Pr2- x Ca x NiO4 + δ the following tendencies were observed: (i) a decrease in the concentration of nonstoichiometric oxygen (δ), (ii) a decrease in the unit cell parameters and volume, (iii) stabilization of the tetragonal structure, (iv) a decrease of the thermal expansion coefficients, and (v) enchancement of thermodynamic stability and compatibility with selected oxygen- and proton-conducting electrolytes. The Pr1.9Ca0.1NiO4 + δ material, having highest δ value, departs from the general "properties-composition" dependences ascertained. This indicates that oxygen non-stoichiometry has determining influence on the functional properties of layered nickelates.

On the metal-insulator-transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Jovaini, Azita; Fujita, Shigeji; Godoy, Salvador; Suzuki, Akira

2012-02-01

Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity σ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop.

Determining the Molecular Growth Mechanisms of Protein Crystal faces by Atomic Force Microscopy

NASA Technical Reports Server (NTRS)

Li, Huayu; Nadarajah, Arunan; Pusey, Marc L.

1998-01-01

A high resolution atomic force microscopy (AFM) study had shown that the molecular packing on the tetragonal lysozyme (110) face corresponded to only one of two possible packing arrangements, suggesting that growth layers on this face were of bimolecular height (Li et al., 1998). Theoretical analyses of the packing had also indicated that growth of this face should proceed by the addition of growth units of at least tetramer size corresponding to the 43 helices in the crystal. In this study an AFM linescan technique was devised to measure the dimensions of individual growth units on protein crystal faces. The growth process of tetragonal lysozyme crystals was slowed down by employing very low supersaturations. As a result images of individual growth events on the (110) face were observed, shown by jump discontinuities in the growth step in the linescan images. The growth unit dimension in the scanned direction was obtained by suitably averaging these images. A large number of scans in two directions on the (110) face were performed and the distribution of lysozyme aggregate sizes were obtained. A variety of growth units, all of which were 43 helical lysozyme aggregates, were shown to participate in the growth process with a 43 tetramer being the minimum observed size. This technique represents a new application for AFM allowing time resolved studies of molecular process to be carried out.

Low temperature structural transformation in T[Ni(CN){sub 4}].xpyz with x=1,2; T=Mn,Co,Ni,Zn,Cd; pyz=pyrazine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez-Hernandez, J.; Instituto de Ciencia y Tecnologia de Materiales, Universidad de La Habana; Lemus-Santana, A.A.

2010-01-15

The materials under study are pillared solids T[Ni(CN){sub 4}].xpyz with one and two (x=1,2) pyrazine (pyz) molecules and where T=Mn, Co, Ni, Zn, Cd. Stimulated by their structural features and potential role as prototype of porous solids for hydrogen storage, the structural stability under cryogenic conditions for this series of pillared solids was studied. At low temperature, in the 100-200 K range, the occurrence of a reversible structural transformation was found. For T=Mn, Co, Zn, Cd, with x=2, the structural transformation was observed to occur around 185 K, and the low temperature phase crystallizes with a monoclinic unit cell (spacemore » group Pc). This structure change results from certain charge redistribution on cooling within the involved ligands. For T=Ni with x=1, both the low and high temperature phases crystallize with unit cells of tetragonal symmetry, within the same space group but with a different unit cell volume. In this case the structure change is observed around 120 K. Above that temperature the rotational states for the pyrazine molecule are thermally excited and all the pyrazine molecules in the structure become equivalent. Under this condition the material structure is described using a smaller structural unit. The structural study using X-ray powder diffraction data was complemented with calorimetric and Raman spectroscopy measurements. For the low temperature phases the crystal structures were solved from Patterson methods and then refined using the Rietveld method. - Graphical abstract: Low temperature ordered structure for pyrazine in T[Ni(CN){sub 4}].pyz.« less

Transition to collapsed tetragonal phase in CaFe2As2 single crystals as seen by 57Fe Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Bud'ko, Sergey L.; Ma, Xiaoming; Tomić, Milan; Ran, Sheng; Valentí, Roser; Canfield, Paul C.

2016-01-01

Temperature dependent measurements of 57Fe Mössbauer spectra on CaFe2As2 single crystals in the tetragonal and collapsed tetragonal phases are reported. Clear features in the temperature dependencies of the isomer shift, relative spectra area, and quadrupole splitting are observed at the transition from the tetragonal to the collapsed tetragonal phase. From the temperature dependent isomer shift and spectral area data, an average stiffening of the phonon modes in the collapsed tetragonal phase is inferred. The quadrupole splitting increases by ˜25 % on cooling from room temperature to ˜100 K in the tetragonal phase and is only weakly temperature dependent at low temperatures in the collapsed tetragonal phase, in agreement with the anisotropic thermal expansion in this material. In order to gain microscopic insight about these measurements, we perform ab initio density functional theory calculations of the electric field gradient and the electron density of CaFe2As2 in both phases. By comparing the experimental data with the calculations we are able to fully characterize the crystal structure of the samples in the collapsed-tetragonal phase through determination of the As z coordinate. Based on the obtained temperature dependent structural data we are able to propose charge saturation of the Fe-As bond region as the mechanism behind the stabilization of the collapsed-tetragonal phase at ambient pressure.

Rotational Rehybridization and the High Temperature Phase of UC2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wen, Xiaodong; Rudin, Sven P.; Batista, Enrique R.

2012-12-03

The screened hybrid approximation (HSE) of density functional theory (DFT) is used to examine the structural, optical, and electronic properties of the high temperature phase, cubic UC(2). This phase contains C(2) units with a computed C-C distance of 1.443 Å which is in the range of a CC double bond; U is formally 4+, C(2) 4-. The closed shell paramagnetic state (NM) was found to lie lowest. Cubic UC(2) is found to be a semiconductor with a narrow gap, 0.4 eV. Interestingly, the C(2) units connecting two uranium sites can rotate freely up to an angle of 30°, indicating amore » hindered rotational solid. Ab-initio molecular dynamic simulations (HSE) show that the rotation of C(2) units in the low temperature phase (tetragonal UC(2)) occurs above 2000 K, in good agreement with experiment. The computed energy barrier for the phase transition from tetragonal UC(2) to cubic UC(2) is around 1.30 eV per UC(2). What is fascinating about this system is that at high temperature, the phase transformation to the cubic phase is associated with a rehybridization of the C atoms from sp to sp(3).« less

Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide

DOE PAGES

Whitfield, P. S.; Herron, N.; Guise, W. E.; ...

2016-10-21

Here, we examine the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbI 3) using time-of-flight neutron and synchrotron X-ray powder diffraction. Near 330 K the high temperature cubic phases transformed to a body-centered tetragonal phase. The variation of the order parameter Q for this transition scaled with temperature T as Q (T c-T) , where T c is the critical temperature and the exponent was close to , as predicted for a tricritical phase transition. We also observed coexistence of the cubic and tetragonal phases over amore » range of temperature in all cases, demonstrating that the phase transition was in fact first-order, although still very close to tricritical. Upon cooling further, all the tetragonal phases transformed into a low temperature orthorhombic phase around 160 K, again via a first-order phase transition. Finally, based upon these results, we discuss the impact of the structural phase transitions upon photovoltaic performance of MAPbI 3 based solar cells.« less

Discovery of a Frank-Kasper [sigma] Phase in Sphere-Forming Block Copolymer Melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Sangwoo; Bluemle, Michael J.; Bates, Frank S.

Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma ({sigma}) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the {sigma} phase in undiluted linear block copolymers (and certain branchedmore » dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mueller, M. H.; Brun, T. O.; Hitterman, R. L.

Recent resistivity and neutron diffraction measurements have provided evidence for ordering of D(H) atoms on the octahedral interstitial sites of PdD/sub 1-x/. This order--disorder transition is responsible for the 50 K anomaly which has been reported in many of the physical properties. Neutron diffraction measurements on a PdD/sub 0/ /sub 76/ single crystal revealed satellite reflection at (4/5,2/5,0) and equivalent positions. These satellites can be accounted for by a multi-domained tetragonal unit cell with a/sub t/ = a/sub c/ root 5/2 and c/sub t/ = c/sub a/. This ordered state can be described as a deuteron density wave along amore » < 420 > cubic direction. This density is modulated such that four fully occupied planes (Pd and D) are followed by a vacant plane (Pd only).« less

Solvothermal synthesis of a new 3-D mixed-metal sulfide framework, (H1.33tren)[In2.67Sb1.33S8]·tren

NASA Astrophysics Data System (ADS)

Lampkin, John D.; Powell, Anthony V.; Chippindale, Ann M.

2016-11-01

A new indium(III) antimony(V) sulfide, (H1.33tren)[In2.67Sb1.33S8]·tren, has been prepared solvothermally at 433 K. The compound crystallises in the tetragonal space group I-42d (lattice parameters, a=12.6248(5) and c=19.4387(18) Å at 150 K) and contains adamantane-like T2 supertetrahedral units comprised of corner-sharing InS45- and SbS43- tetrahedra. The adamantane-like units are then linked through sulfur vertices to generate an open, 3-D framework structure containing large pores in which neutral, protonated tren (tris(2-aminoethylene)amine) molecules reside. The presence of the organic components was confirmed by solid-state 13C NMR (10 kHz), combustion and thermogravimetric analysis. The band gap, obtained from UV-vis diffuse reflectance measurements, is 2.7(2) eV. Stirring with either water or alkali-metal salt solution leads to removal of the neutral tren molecules and an 9% reduction in unit-cell volume on formation of (H1.33tren)[In2.67Sb1.33S8]·(H2O)4.

Transition to collapsed tetragonal phase in CaFe 2As 2 single crystals as seen by 57Fe Mössbauer spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bud'ko, Sergey L.; Ma, Xiaoming; Tomić, Milan

Temperature dependent measurements of 57Fe Mössbauer spectra on CaFe 2As 2 single crystals in the tetragonal and collapsed tetragonal phases are reported. Clear features in the temperature dependencies of the isomer shift, relative spectra area, and quadrupole splitting are observed at the transition from the tetragonal to the collapsed tetragonal phase. From the temperature dependent isomer shift and spectral area data, an average stiffening of the phonon modes in the collapsed tetragonal phase is inferred. The quadrupole splitting increases by ~25% on cooling from room temperature to ~100 K in the tetragonal phase and is only weakly temperature dependent atmore » low temperatures in the collapsed tetragonal phase, in agreement with the anisotropic thermal expansion in this material. In order to gain microscopic insight about these measurements, we perform ab initio density functional theory calculations of the electric field gradient and the electron density of CaFe 2As 2 in both phases. By comparing the experimental data with the calculations we are able to fully characterize the crystal structure of the samples in the collapsed-tetragonal phase through determination of the As z coordinate. Furthermore, based on the obtained temperature dependent structural data we are able to propose charge saturation of the Fe-As bond region as the mechanism behind the stabilization of the collapsed-tetragonal phase at ambient pressure.« less

Interfacial Stability of Li Metal-Solid Electrolyte Elucidated via in Situ Electron Microscopy.

PubMed

Ma, Cheng; Cheng, Yongqiang; Yin, Kuibo; Luo, Jian; Sharafi, Asma; Sakamoto, Jeff; Li, Juchuan; More, Karren L; Dudney, Nancy J; Chi, Miaofang

2016-11-09

Despite their different chemistries, novel energy-storage systems, e.g., Li-air, Li-S, all-solid-state Li batteries, etc., face one critical challenge of forming a conductive and stable interface between Li metal and a solid electrolyte. An accurate understanding of the formation mechanism and the exact structure and chemistry of the rarely existing benign interfaces, such as the Li-cubic-Li 7-3x Al x La 3 Zr 2 O 12 (c-LLZO) interface, is crucial for enabling the use of Li metal anodes. Due to spatial confinement and structural and chemical complications, current investigations are largely limited to theoretical calculations. Here, through an in situ formation of Li-c-LLZO interfaces inside an aberration-corrected scanning transmission electron microscope, we successfully reveal the interfacial chemical and structural progression. Upon contact with Li metal, the LLZO surface is reduced, which is accompanied by the simultaneous implantation of Li + , resulting in a tetragonal-like LLZO interphase that stabilizes at an extremely small thickness of around five unit cells. This interphase effectively prevented further interfacial reactions without compromising the ionic conductivity. Although the cubic-to-tetragonal transition is typically undesired during LLZO synthesis, the similar structural change was found to be the likely key to the observed benign interface. These insights provide a new perspective for designing Li-solid electrolyte interfaces that can enable the use of Li metal anodes in next-generation batteries.

Tuning the metal-insulator transition of VO2 by introducing W dopants via a combinatorial approach

NASA Astrophysics Data System (ADS)

Liang, Yangang; Lee, Seunghun; Zhang, Xiaohang; Takeuchi, Ichiro

We have systematically studied the structural phase transition and the electronic properties of composition spread V1-xWxO2 (0 <= x <= 0.037) thin films fabricated on silicon (001) and c-cut sapphire substrates through combinatorial pulsed laser deposition of a V2O5 target and a WO3 target. Our in-situ temperature-dependent x-ray diffraction measurements reveal a gradual change in the film structure from a monoclinic phase to a tetragonal phase via an intermediate mixture of the two as the concentration of tungsten increases from 0% to 3.7% at 300 K. At 358 K, the film is found to be in a tetragonal phase for the entire composition range we studied. The results also suggest that the volume of the unit cell increases as the concentration of tungsten increases. Electrical transport results further show that both the phase transition temperature and the width of the hysteresis loop decrease with the increasing of the concentration of tungsten. Especially, epitaxial V1-xWxO2 films fabricated on c-cut sapphire substrates show narrower hysteresis loop compared to textured V1-xWxO2 films fabricated on Si (100) substrates. In addition, the Hall effect measurements on the epitaxial V1-xWxO2 thin films at various temperature points provide important information for the change in the electronic structure upon increasing the concentration of tungsten. This work was supported by CNAM.

Potassium doped methylammonium lead iodide (MAPbI3) thin films as a potential absorber for perovskite solar cells; structural, morphological, electronic and optoelectric properties

NASA Astrophysics Data System (ADS)

Muzammal uz Zaman, Muhammad; Imran, Muhammad; Saleem, Abida; Kamboh, Afzal Hussain; Arshad, Muhammad; Khan, Nawazish Ali; Akhter, Parvez

2017-10-01

In this article, we have demonstrated the doping of K in the light absorbing CH3NH3PbI3 perovskite i.e. (M = CH3, A = NH3; x = 0-1). One of the major merits of methylammonium lead iodide (CH3NH3PbI3) perovskites is that they act as efficient absorbing material of light in photovoltaic cell imparting long carrier lifetime and optimum band gap. The structural, morphological, electronic and optoelectric properties of potassium (K) doped light absorber methylammonium lead iodide (CH3NH3PbI3) perovskites are reported here i.e. Kx(MA)1-xPbI3 (M = CH3, A =NH3; x = 0-1). The thin films of perovskites (x = 0-1) were deposited by spin coating on cleaned FTO substrates and characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), current-voltage (IV), X-ray photoelectron spectroscopy (XPS) and Diffused reflectance spectroscopy (DRS) analysis. The organic constituents i.e. MA = CH3NH3, in perovskites solar cells induce instability even at the room temperature. To overcome such instabilities we have replaced the organic constituents by K because both of them have electropositive nature. Potassium successfully replaces the CH3NH3. Initially, this compound grows in a tetragonal crystal structure, however, beyond 30% doping of potassium orthorhombic distortions are induced in the parent tetragonal unit cell. Such phase transformation is microscopically visible in the electron micrographs of doped samples; cubic grains for MAPbI3 begin to transform into strip like structures in K-doped samples. The resistance of the samples is decreased for partial K-doping, which we suggested to be arising due to the electropositive nature of K. It is observed that the binding energy difference between Pb4f and I3d core levels are very similar in all the investigated systems and show formal oxidation states. Also, the partially doped samples showed increased absorption and bandgaps around 1.5 eV which is an optimum value for solar absorption.

Tetragonal CH3NH3PbI3 is ferroelectric

PubMed Central

Bar-Elli, Omri; Meirzadeh, Elena; Kaslasi, Hadar; Peleg, Yagel; Hodes, Gary; Lubomirsky, Igor; Oron, Dan; Ehre, David; Cahen, David

2017-01-01

Halide perovskite (HaP) semiconductors are revolutionizing photovoltaic (PV) solar energy conversion by showing remarkable performance of solar cells made with HaPs, especially tetragonal methylammonium lead triiodide (MAPbI3). In particular, the low voltage loss of these cells implies a remarkably low recombination rate of photogenerated carriers. It was suggested that low recombination can be due to the spatial separation of electrons and holes, a possibility if MAPbI3 is a semiconducting ferroelectric, which, however, requires clear experimental evidence. As a first step, we show that, in operando, MAPbI3 (unlike MAPbBr3) is pyroelectric, which implies it can be ferroelectric. The next step, proving it is (not) ferroelectric, is challenging, because of the material’s relatively high electrical conductance (a consequence of an optical band gap suitable for PV conversion) and low stability under high applied bias voltage. This excludes normal measurements of a ferroelectric hysteresis loop, to prove ferroelectricity’s hallmark switchable polarization. By adopting an approach suitable for electrically leaky materials as MAPbI3, we show here ferroelectric hysteresis from well-characterized single crystals at low temperature (still within the tetragonal phase, which is stable at room temperature). By chemical etching, we also can image the structural fingerprint for ferroelectricity, polar domains, periodically stacked along the polar axis of the crystal, which, as predicted by theory, scale with the overall crystal size. We also succeeded in detecting clear second harmonic generation, direct evidence for the material’s noncentrosymmetry. We note that the material’s ferroelectric nature, can, but need not be important in a PV cell at room temperature. PMID:28588141

Nematic fluctuations and phase transitions in LaFeAsO: A Raman scattering study

DOE PAGES

Kaneko, U. F.; Gomes, P. F.; Garcia-Flores, A. F.; ...

2017-07-10

Raman scattering experiments on LaFeAsO with distinct antiferromagnetic ( T AFM=140 K) and tetragonal-orthorhombic ( T S=155 K) transitions show a quasielastic peak (QEP) in B 2g symmetry (2 Fe tetragonal cell) that fades away below ~ T AFM and is ascribed to electronic nematic fluctuations. A scaling of the reported shear modulus with the T dependence of the QEP height rather than the QEP area indicates that magnetic degrees of freedom drive the structural transition. As a result, the large separation between T S and T AFM in LaFeAsO compared to BaFe 2As 2 manifests itself in slower dynamicsmore » of nematic fluctuations in the former.« less

The structure and optical properties of Sr{sub 1−x}Ca{sub x}MoO{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hopper, H.A.; Macphee, D.E.; Mclaughlin, A.C., E-mail: a.c.mclaughlin@abdn.ac.uk

2016-10-15

The solid solution Sr{sub 1−x}Ca{sub x}MoO{sub 3} (x=0.00, 0.05, 0.10, 0.13, 0.15 and 0.17) has successfully been synthesised and X-ray Powder diffraction has revealed the occurrence of structural phase transitions, from cubic Pm−3m to tetragonal I4/mcm, and then to orthorhombic Imma as the value of x increased. Discontinuities were observed in the cell parameters and bond lengths and angles at the transition from tetragonal to orthorhombic symmetry as a result of the switching of the octahedral rotation axis at the tetragonal to orthorhombic transition. The increased octahedral tilting could also be linked to the decrease in the band gap frommore » 2.20 eV to 2.10 eV as x increased from 0 to 0.17. - Graphical abstract: Table of Contents Figure Caption: Ultraviolet-visible absorbance spectra for Sr{sub 1−x}Ca{sub x}MoO{sub 3} showing a reduction in band gap upon increasing x as a result of increased octahedral tilting. - Highlights: • The solid solution Sr{sub 1−x}Ca{sub x}MoO{sub 3} has been synthesised. • Structural phase transitions are observed. • Discontinuities were observed in the cell parameters and bond lengths and angles. • Upon increasing x from 0 to 0.17 the band gap reduces from 2.20 eV to 2.10 eV.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavira, José A.; Jesus, Walleska de; Camara-Artigas, Ana

The haemoglobin II from the clam L. pectinata has been crystallized using counter-diffusion in single capillary in the presence of agarose to improve crystal quality. Initial phases have been obtained by molecular replacement. Haemoglobin II is one of three haemoglobins present in the cytoplasm of the Lucina pectinata mollusc that inhabits the Caribbean coast. Using HBII purified from its natural source, crystallization screening was performed using the counter-diffusion method with capillaries of 0.2 mm inner diameter. Crystals of HbII suitable for data collection and structure determination were grown in the presence of agarose at 0.1%(w/v) in order to improve theirmore » quality. The crystals belong to the tetragonal space group P4{sub 2}2{sub 1}2, with unit-cell parameters a = b = 73.92, c = 152.35 Å, and diffracted X-rays to a resolution of better than 2.0 Å. The asymmetric unit is a homodimer with a corresponding Matthews coefficient (V{sub M}) of 3.15 Å{sup 3} Da{sup −1} and a solvent content of 61% by volume.« less

Expression, purification, crystallization and preliminary X-ray crystallographic analysis of human histidine triad nucleotide-binding protein 2 (hHINT2)

PubMed Central

Dolot, Rafał; Włodarczyk, Artur; Bujacz, Grzegorz D.; Nawrot, Barbara

2013-01-01

Histidine triad nucleotide-binding protein 2 (HINT2) is a mitochondrial adenosine phosphoramidase mainly expressed in the pancreas, liver and adrenal gland. HINT2 possibly plays a role in apoptosis, as well as being involved in steroid biosynthesis, hepatic lipid metabolism and regulation of hepatic mitochondria function. The expression level of HINT2 is significantly down-regulated in hepatocellular carcinoma patients. To date, endogenous substrates for this enzyme, as well as the three-dimensional structure of human HINT2, are unknown. In this study, human HINT2 was cloned, overexpressed in Escherichia coli and purified. Crystallization was performed at 278 K using PEG 4000 as the main precipitant; the crystals, which belonged to the tetragonal space group P41212 with unit-cell parameters a = b = 76.38, c = 133.25 Å, diffracted to 2.83 Å resolution. Assuming two molecules in the asymmetric unit, the Matthews coefficient and the solvent content were calculated to be 2.63 Å3 Da−1 and 53.27%, respectively. PMID:23832208

Purification, crystallization and preliminary X-ray structural studies of a 7.2 kDa cytotoxin isolated from the venom of Daboia russelli russelli of the Viperidae family

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roy Choudhury, Subhasree; Gomes, Aparna; Gomes, Antony

2006-03-01

A cytotoxin from Indian Russell’s viper (D. russelli russelli) venom having multifunctional activity has been crystallized in space group P4{sub 1}. Larger crystals diffracted to 1.5 Å but were found to be twinned; preliminary data were therefore collected (2.93 Å) from a smaller crystal. A cytotoxin (MW 7.2 kDa) from Indian Russell’s viper (Daboia russelli russelli) venom possessing antiproliferative activity, cardiotoxicity, neurotoxicity and myotoxicity has been purified, characterized and crystallized. The crystals belong to the tetragonal space group P4{sub 1}, with unit-cell parameters a = b = 47.94, c = 50.2 Å. Larger crystals, which diffracted to 1.5 Å, weremore » found to be twinned; diffraction data were therefore collected to 2.93 Å resolution using a smaller crystal. Molecular-replacement calculations identified two molecules of the protein in the asymmetric unit, which is in accordance with the calculated V{sub M} value.« less

Half-metallicity and tetragonal distortion in semi-Heusler alloy FeCrSe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, H. M., E-mail: smilehhm@163.com; Luo, S. J.; Yao, K. L.

2014-01-28

Full-potential linearized augmented plane wave methods are carried out to investigate the electronic structures and magnetic properties in semi-Heusler alloy FeCrSe. Results show that FeCrSe is half-metallic ferromagnet with the half-metallic gap 0.31 eV at equilibrium lattice constant. Calculated total magnetic moment of 2.00μ{sub B} per formula unit follows the Slater-Pauling rule quite well. Two kinds of structural changes are used to investigate the sensitivity of half-metallicity. It is found that the half-metallicity can be retained when lattice constant is changed by −4.56% to 3.52%, and the results of tetragonal distortion indicate the half-metallicity can be kept at the range ofmore » c/a ratio from 0.85 to 1.20. The Curie temperature, cohesive energy, and heat of formations of FeCrSe are also discussed.« less

Phase Transition and Structure of Silver Azide at High Pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

D Hou; F Zhang; C Ji

2011-12-31

Silver azide (AgN{sub 3}) was compressed up to 51.3 GPa. The results reveal a reversible second-order orthorhombic-to-tetragonal phase transformation starting from ambient pressure and completing at 2.7 GPa. The phase transition is accompanied by a proximity of cell parameters a and b, a 3{sup o} rotation of azide anions, and a change of coordination number from 4-4 (four short, four long) to eight fold. The crystal structure of the high pressure phase is determined to be in I4/mcm space group, with Ag at 4a, N{sub 1} at 4d, and N{sub 2} at 8h Wyckoff positions. Both of the two phasesmore » have anisotropic compressibility: the orthorhombic phase exhibits an anomalous expansion under compression along a-axis and is more compressive along b-axis than c-axis; the tetragonal phase is more compressive along the interlayer direction than the intralayer directions. The bulk moduli of the orthorhombic and tetragonal phases are determined to be K{sub OT} = 39{+-}5 GPa with K{sub OT'} = 10{+-}7 and K{sub OT} = 57 {+-}2 GPa with K{sub OT'} = 6.6{+-}0.2, respectively.« less

Structure symmetry determination and magnetic evolution in Sr 2Ir 1–xRh xO 4

DOE PAGES

Ye, Feng; Wang, Xiaoping; Hoffmann, Christina; ...

2015-11-23

We use single-crystal neutron diffraction to determine the crystal structure symmetry and to study the magnetic evolution in the rhodium doped iridates Sr 2Ir 1–xRh xO 4 (0 ≤ x ≤ 0.16). Throughout this doping range, the crystal structure retains a tetragonal symmetry (space group I4 1/a) with two distinct magnetic Ir sites in the unit cell forming staggered IrO 6 rotation. Upon Rh doping, the magnetic order is suppressed and the magnetic moment of Ir4+ is reduced from 0.21 μ B/Ir for x = 0 to 0.18 μ B/Ir for x = 0.12. As a result, the magnetic structuremore » at x = 0.12 is different from that of the parent compound while the moments remain in the basal plane.« less

The Fe{sup 2+}/Fe{sup 3+} ratio in natural and heat-treated iron-rich eudialytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rastsvetaeva, R. K., E-mail: rast@ns.crys.ras.ru; Aksenov, S. M.; Rozenberg, K. A.

2011-03-15

The structures of natural iron-rich eudialyte (specimen 3458 from the Khibiny massif, the Kola Peninsula) and two heat-treated samples of this mineral calcined at 700 and 800 Degree-Sign C were determined by X-ray diffraction. The trigonal unit-cell parameters (sp. gr. R3m) are as follows: a = 14.2645(1) Angstrom-Sign , c = 29.9635(5) Angstrom-Sign ; a = 14.1307(1) Angstrom-Sign , c = 30.1229(3) Angstrom-Sign ; a = 14.1921(2) Angstrom-Sign , c = 30.2417(5) Angstrom-Sign , respectively. It was found that Fe{sup 3+} ions in the calcined eudialytes, as well as impurities in the starting specimen, occupy the square-pyramidal Fe{sup 3+}(V) sites,more » whereas Fe{sup 2+} ions are in the planar-tetragonal Fe{sup 2+}(IV) sites.« less

Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun

We report the discovery of an ionic small molecule surfactant that undergoes water-drive self- assembly into quasispherical micelles, which pack into the first lyotropic liquid crystalline Frank–Kasper σ phase. Small-angle X-ray scattering studies indicate that this unexpected, low-symmetry phase is characterized by a tetragonal unit cell, in which 30 sub-2 nm micelles of five discrete types are arranged into a tetrahedral close packing with exceptional translational order. Varying the relative amounts of surfactant and water in these lyotropic phases enables formation of a Frank–Kasper A15 sphere packing and a more common body-centered cubic structure. MD simulations reveal that the symmetrymore » breaking that drives the selection of the σ and A15 phases arises from a delicate interplay between the drive to maintain local spherical particle symmetry and the maximization of electrostatic cohesion between the soft micellar particles.« less

Local atomic and magnetic structure of dilute magnetic semiconductor (Ba ,K ) (Zn,Mn ) 2As2

NASA Astrophysics Data System (ADS)

Frandsen, Benjamin A.; Gong, Zizhou; Terban, Maxwell W.; Banerjee, Soham; Chen, Bijuan; Jin, Changqing; Feygenson, Mikhail; Uemura, Yasutomo J.; Billinge, Simon J. L.

2016-09-01

We have studied the atomic and magnetic structure of the dilute ferromagnetic semiconductor system (Ba ,K )(Zn ,Mn )2As2 through atomic and magnetic pair distribution function analysis of temperature-dependent x-ray and neutron total scattering data. We detected a change in curvature of the temperature-dependent unit cell volume of the average tetragonal crystallographic structure at a temperature coinciding with the onset of ferromagnetic order. We also observed the existence of a well-defined local orthorhombic structure on a short length scale of ≲5 Å , resulting in a rather asymmetrical local environment of the Mn and As ions. Finally, the magnetic PDF revealed ferromagnetic alignment of Mn spins along the crystallographic c axis, with robust nearest-neighbor ferromagnetic correlations that exist even above the ferromagnetic ordering temperature. We discuss these results in the context of other experiments and theoretical studies on this system.

Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity

DOE PAGES

Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun; ...

2017-04-03

We report the discovery of an ionic small molecule surfactant that undergoes water-drive self- assembly into quasispherical micelles, which pack into the first lyotropic liquid crystalline Frank–Kasper σ phase. Small-angle X-ray scattering studies indicate that this unexpected, low-symmetry phase is characterized by a tetragonal unit cell, in which 30 sub-2 nm micelles of five discrete types are arranged into a tetrahedral close packing with exceptional translational order. Varying the relative amounts of surfactant and water in these lyotropic phases enables formation of a Frank–Kasper A15 sphere packing and a more common body-centered cubic structure. MD simulations reveal that the symmetrymore » breaking that drives the selection of the σ and A15 phases arises from a delicate interplay between the drive to maintain local spherical particle symmetry and the maximization of electrostatic cohesion between the soft micellar particles.« less

Electric-field-induced phase transformation at a lead-free morphotropic phase boundary: Case study in a 93%(Bi0.5Na0.5)TiO3-7% BaTiO3 piezoelectric ceramic

NASA Astrophysics Data System (ADS)

Daniels, John E.; Jo, Wook; Rödel, Jürgen; Jones, Jacob L.

2009-07-01

The electric-field-induced strain in 93%(Bi0.5Na0.5)TiO3-7%BaTiO3 polycrystalline ceramic is shown to be the result of an electric-field-induced phase transformation from a pseudocubic to tetragonal symmetry. High-energy x-ray diffraction is used to illustrate the microstructural nature of the transformation. A combination of induced unit cell volumetric changes, domain texture, and anisotropic lattice strains are responsible for the observed macroscopic strain. This strain mechanism is not analogous to the high electric-field-induced strains observed in lead-based morphotropic phase boundary systems. Thus, systems which appear cubic under zero field should not be excluded from the search for lead-free piezoelectric compositions.

Observation of shift in band gap with annealing in hydrothermally synthesized TiO2-thin films

NASA Astrophysics Data System (ADS)

Pawar, Vani; Jha, Pardeep K.; Singh, Prabhakar

2018-05-01

Anatase TiO2 thin films were synthesized by hydrothermal method. The films were fabricated on a glass substrate by spin coating unit and annealed at 500 °C for 2 hours in ambient atmosphere. The effect of annealing on microstructure and optical properties of TiO2 thin films namely, just deposited and annealed thin film were investigated. The XRD data confirms the tetragonal crystalline structure of the films with space group I41/amd. The surface morphology suggests that TiO2 particles are almost homogeneous in size and annealing of the film affect the grain growth of the particles. The band gap energy increases from 2.81 to 3.34 eV. On the basis of our observation, it can be concluded that the annealing of TiO2 thin films enhances the absorption range and it may find potential application in the field of solar cells.

Preparation and transport properties of superconducting layers in the Ca-Sr-Bi-Cu-O system

NASA Astrophysics Data System (ADS)

Klee, M.; Stollman, G. M.; Stotz, S.; de Vries, J. W. C.

1988-08-01

Superconducting layers in the CaSrBiCuO system are prepared by thermal decomposition of metal carboxylates using a spin-coating and a dip-coating method onto ceramic MgO substrates. The samples consist of a tetragonal calcium-strontium-bismuth-cuprate and two bismuth-free calcium-strontium-cuprates. A step in the resistance versus temperature curve is observed which, together with the influence of magnetic fields, is interpreted as typical for a granular superconductor. The analysis shows that the critical current density is determined by domains of the order of some unit cells. The strong dependence of the superconducting transition on the orientation of an applied magnetic field is probably caused by the anisotropic layer structure. The coherence length perpendicular to the c-axis of the material is estimated to be ξab(0) = 4.0 nm and parallel to the c-axis ξc(0) = 0.6 nm.

Spiral chain structure of high pressure selenium-II{sup '} and sulfur-II from powder x-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujihisa, Hiroshi; Yamawaki, Hiroshi; Sakashita, Mami

2004-10-01

The structure of high pressure phases, selenium-II{sup '} (Se-II{sup '}) and sulfur-II (S-II), for {alpha}-Se{sub 8} (monoclinic Se-I) and {alpha}-S{sub 8} (orthorhombic S-I) was studied by powder x-ray diffraction experiments. Se-II{sup '} and S-II were found to be isostructural and to belong to the tetragonal space group I4{sub 1}/acd, which is made up of 16 atoms in the unit cell. The structure consisted of unique spiral chains with both 4{sub 1} and 4{sub 3} screws. The results confirmed that the structure sequence of the pressure-induced phase transitions for the group VIb elements depended on the initial molecular form. The chemicalmore » bonds of the phases are also discussed from the interatomic distances that were obtained.« less

Observation of Superconductivity in Tetragonal FeS.

PubMed

Lai, Xiaofang; Zhang, Hui; Wang, Yingqi; Wang, Xin; Zhang, Xian; Lin, Jianhua; Huang, Fuqiang

2015-08-19

The possibility of superconductivity in tetragonal FeS has attracted considerable interest because of its similarities to the FeSe superconductor. However, all efforts made to pursue superconductivity in tetragonal FeS have failed so far, and it remains controversial whether tetragonal FeS is metallic or semiconducting. Here we report the observation of superconductivity at 5 K in tetragonal FeS that is synthesized by the hydrothermal reaction of iron powder with sulfide solution. The obtained samples are highly crystalline and less air-sensitive, in contrast to those reported in the literature, which are meta-stable and air-sensitive. Magnetic and electrical properties measurements show that the samples behave as a paramagnetic metal in the normal state and exhibit superconductivity below 5 K. The high crystallinity and the stoichiometry of the samples play important roles in the observation of superconductivity. The present results demonstrate that tetragonal FeS is a promising new platform to realize high-temperature superconductors.

In situ study of the growth and degradation processes in tetragonal lysozyme crystals on a silicon substrate by high-resolution X-ray diffractometry

NASA Astrophysics Data System (ADS)

Kovalchuk, M. V.; Prosekov, P. A.; Marchenkova, M. A.; Blagov, A. E.; D'yakova, Yu. A.; Tereshchenko, E. Yu.; Pisarevskii, Yu. V.; Kondratev, O. A.

2014-09-01

The results of an in situ study of the growth of tetragonal lysozyme crystals by high-resolution X-ray diffractometry are considered. The crystals are grown by the sitting-drop method on crystalline silicon substrates of different types: both on smooth substrates and substrates with artificial surface-relief structures using graphoepitaxy. The crystals are grown in a special hermetically closed crystallization cell, which enables one to obtain images with an optical microscope and perform in situ X-ray diffraction studies in the course of crystal growth. Measurements for lysozyme crystals were carried out in different stages of the crystallization process, including crystal nucleation and growth, developed crystals, the degradation of the crystal structure, and complete destruction.

Phase Transitions and Domain Structure in Mixed Tetragonal-Rhombohedral BiFeO3 thin films using Raman Spectroscopy and Nonlinear Optics

NASA Astrophysics Data System (ADS)

Vlahos, E.; Kumar, A.; Denev, S.; Melville, A.; Adamo, C.; Ihlefeld, J. F.; Sheng, G.; Zeches, R. J.; Zhang, J. X.; He, Q.; Yang, C. H.; Erni, R.; Rossell, M. D.; J, A.; Hatt; Chu, Y.-H.; Wang, C. H.; Ederer, C.; Gopalan, V.; Chen, L. Q.; Schlom, D. G.; Spaldin, N. A.; Martin, L. W.; Ramesh, R.; Tenne, Dmitri

2010-03-01

We have shown that biaxially strained BiFeO3 thin films can undergo an isosymmetric phase transition from a rhombohedral-like to a tetragonal-like phase. This talk discusses the evolution of the tetragonal and the mixed phases in BiFeO3/YAlO3 thin films with varying film thickness using optical second harmonic generation (SHG) and Raman spectroscopy. 25nm, 75nm, and 225 nm thick films were studied; thinner films are dominated by the tetragonal phase, whereas thicker films exhibit both tetragonal and rhombohedral phases. The evolution of these phases as function of film thickness and temperature was experimentally determined.

Tetragonal and collapsed-tetragonal phases of CaFe2As2 : A view from angle-resolved photoemission and dynamical mean-field theory

NASA Astrophysics Data System (ADS)

van Roekeghem, Ambroise; Richard, Pierre; Shi, Xun; Wu, Shangfei; Zeng, Lingkun; Saparov, Bayrammurad; Ohtsubo, Yoshiyuki; Qian, Tian; Sefat, Athena S.; Biermann, Silke; Ding, Hong

2016-06-01

We present a study of the tetragonal to collapsed-tetragonal transition of CaFe2As2 using angle-resolved photoemission spectroscopy and dynamical mean field theory-based electronic structure calculations. We observe that the collapsed-tetragonal phase exhibits reduced correlations and a higher coherence temperature due to the stronger Fe-As hybridization. Furthermore, a comparison of measured photoemission spectra and theoretical spectral functions shows that momentum-dependent corrections to the density functional band structure are essential for the description of low-energy quasiparticle dispersions. We introduce those using the recently proposed combined "screened exchange + dynamical mean field theory" scheme.

Structural phase transition and phonon instability in Cu 12Sb 4S 13

DOE PAGES

May, Andrew F.; Delaire, Olivier A.; Niedziela, Jennifer L.; ...

2016-02-08

In this study, a structural phase transition has been discovered in the synthetic tetrahedrite Cu 12Sb 4S 13 at approximately 88 K. Upon cooling, the material transforms from its known cubic symmetry to a tetragonal unit cell that is characterized by an in-plane ordering that leads to a doubling of the unit cell volume. Specific heat capacity measurements demonstrate a hysteresis of more than two degrees in the associated anomaly. A similar hysteresis was observed in powder x-ray diffraction measurements, which also indicate a coexistence of the two phases, and together these results suggest a first-order transition. This structural transitionmore » coincides with a recently-reported metal-insulator transition, and the structural instability is related to the very low thermal conductivity κ in these materials. Inelastic neutron scattering was used to measure the phonon density of states in Cu 12Sb 4S 13 and Cu 10Zn 2Sb 4S 13, both of which possess a localized, low-energy phonon mode associated with strongly anharmonic copper displacements that suppress κ. In Cu 12Sb 4S 13, signatures of the phase transition are observed in the temperature dependence of the localized mode, which disappears at the structural transition. In contrast, in the cubic Zn-doped material, the mode is at slightly higher-energy but observable for all temperatures, though it softens upon cooling.« less

Effect of pressure on the tetragonal distortion in TiH2: a first-principles study

NASA Astrophysics Data System (ADS)

de Coss, R.; Quijano, R.; Singh, D. J.

2009-03-01

The transition metal dihydride TiH2 present the fluorite structure (CaF2) at high temperature but undergoes a tetragonal distortion with c/a<1 at low temperature. Early electronic band structure calculations have shown that TiH2 in the cubic phase display a nearly flat double degenerated band at the Fermi level. Thus the low temperature tetragonal distortion has been associated to a Jahn-Teller effect. Nevertheless, recently we have show that the instability of fcc-TiH2 is likely to be related with a van Hove singularity. In the present work, we have performed ab-initio calculations of the electronic structure and the tetragonal distortion for TiH2 under pressure (0-30 GPa). We found that the fcc-fct energy barrier and the tetragonal distortion increases with pressure. The evolution of the tetragonal distortion is analyzed in terms of the electronic band structure. This research was supported by Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grant No. 49985.

Crystallization and initial X-ray diffraction studies of scaffolding protein (gp7) of bacteriophage ϕ29

DOE Office of Scientific and Technical Information (OSTI.GOV)

Badasso, Mohammed O., E-mail: badas001@umn.edu; Anderson, Dwight L.; Department of Oral Science, University of Minnesota, Minneapolis, MN 55455

2005-04-01

ϕ29 bacteriophage scaffolding protein (gp7) has been overproduced in E. coli, purified, crystallized and characterized by X-ray diffraction. Two distinct crystal forms were obtained and a diffraction data set was collected to 1.8 Å resolution. The Bacillus subtilis bacteriophage ϕ29 scaffolding protein (gp7) has been crystallized by the hanging-drop vapour-diffusion method at 293 K. Two new distinct crystal forms that both differed from a previously crystallized and solved scaffolding protein were grown under the same conditions. Form I belongs to the primitive tetragonal space group P4{sub 1}2{sub 1}2, with unit-cell parameters a = b = 77.13, c = 37.12 Å.more » Form II crystals exhibit an orthorhombic crystal form, with space group C222 and unit-cell parameters a = 107.50, b = 107. 80, c = 37.34 Å. Complete data sets have been collected to 1.78 and 1.80 Å for forms I and II, respectively, at 100 K using Cu Kα X-rays from a rotating-anode generator. Calculation of a V{sub M} value of 2.46 Å{sup 3} Da{sup −1} for form I suggests the presence of one molecule in the asymmetric unit, corresponding to a solvent content of 50.90%, whereas form II has a V{sub M} of 4.80 Å{sup 3} Da{sup −1} with a solvent content of 48.76% and two molecules in the asymmetric unit. The structures of both crystal forms are being determined by the molecular-replacement method using the coordinates of the published crystal structure of gp7.« less

Enhancement of tetragonal anisotropy and stabilisation of the tetragonal phase by Bi/Mn-double-doping in BaTiO3 ferroelectric ceramics

PubMed Central

Yabuta, Hisato; Tanaka, Hidenori; Furuta, Tatsuo; Watanabe, Takayuki; Kubota, Makoto; Matsuda, Takanori; Ifuku, Toshihiro; Yoneda, Yasuhiro

2017-01-01

To stabilise ferroelectric-tetragonal phase of BaTiO3, the double-doping of Bi and Mn up to 0.5 mol% was studied. Upon increasing the Bi content in BaTiO3:Mn:Bi, the tetragonal crystal-lattice-constants a and c shrank and elongated, respectively, resulting in an enhancement of tetragonal anisotropy, and the temperature-range of the ferroelectric tetragonal phase expanded. X-ray absorption fine structure measurements confirmed that Bi and Mn were located at the A(Ba)-site and B(Ti)-site, respectively, and Bi was markedly displaced from the centrosymmetric position in the BiO12 cluster. This A-site substitution of Bi also caused fluctuations of B-site atoms. Magnetic susceptibility measurements revealed a change in the Mn valence from +4 to +3 upon addition of the same molar amount of Bi as Mn, probably resulting from a compensating behaviour of the Mn at Ti4+ sites for donor doping of Bi3+ into the Ba2+ site. Because addition of La3+ instead of Bi3+ showed neither the enhancement of the tetragonal anisotropy nor the stabilisation of the tetragonal phase, these phenomena in BaTiO3:Mn:Bi were not caused by the Jahn-Teller effect of Mn3+ in the MnO6 octahedron, but caused by the Bi-displacement, probably resulting from the effect of the 6 s lone-pair electrons in Bi3+. PMID:28367973

Bone-Inspired Spatially Specific Piezoelectricity Induces Bone Regeneration

PubMed Central

Yu, Peng; Ning, Chengyun; Zhang, Yu; Tan, Guoxin; Lin, Zefeng; Liu, Shaoxiang; Wang, Xiaolan; Yang, Haoqi; Li, Kang; Yi, Xin; Zhu, Ye; Mao, Chuanbin

2017-01-01

The extracellular matrix of bone can be pictured as a material made of parallel interspersed domains of fibrous piezoelectric collagenous materials and non-piezoelectric non-collagenous materials. To mimic this feature for enhanced bone regeneration, a material made of two parallel interspersed domains, with higher and lower piezoelectricity, respectively, is constructed to form microscale piezoelectric zones (MPZs). The MPZs are produced using a versatile and effective laser-irradiation technique in which K0.5Na0.5NbO3 (KNN) ceramics are selectively irradiated to achieve microzone phase transitions. The phase structure of the laser-irradiated microzones is changed from a mixture of orthorhombic and tetragonal phases (with higher piezoelectricity) to a tetragonal dominant phase (with lower piezoelectricity). The microzoned piezoelectricity distribution results in spatially specific surface charge distribution, enabling the MPZs to bear bone-like microscale electric cues. Hence, the MPZs induce osteogenic differentiation of stem cells in vitro and bone regeneration in vivo even without being seeded with stem cells. The concept of mimicking the spatially specific piezoelectricity in bone will facilitate future research on the rational design of tissue regenerative materials. PMID:28900517

CFA-2 and CFA-3 (Coordination Framework Augsburg University-2 and -3); novel MOFs assembled from trinuclear Cu(I)/Ag(I) secondary building units and 3,3',5,5'-tetraphenyl-bipyrazolate ligands.

PubMed

Grzywa, Maciej; Geßner, Christof; Denysenko, Dmytro; Bredenkötter, Björn; Gschwind, Fabienne; Fromm, Katharina M; Nitek, Wojciech; Klemm, Elias; Volkmer, Dirk

2013-05-21

The syntheses of H2-phbpz, [Cu2(phbpz)]·2DEF·MeOH (CFA-2) and [Ag2(phbpz)] (CFA-3) (H2-phbpz = 3,3',5,5'-tetraphenyl-1H,1'H-4,4'-bipyrazole) compounds and their crystal structures are described. The Cu(I) containing metal-organic framework CFA-2 crystallizes in the tetragonal crystal system, within space group I4(1)/a (no. 88) and the following unit cell parameters: a = 30.835(14), c = 29.306(7) Å, V = 27 865(19) Å(3). CFA-2 features a flexible 3-D three-connected two-fold interpenetrated porous structure constructed of triangular Cu(I) subunits. Upon exposure to different kinds of liquids (MeOH, EtOH, DMF, DEF) CFA-2 shows pronounced breathing effects. CFA-3 crystallizes in the monoclinic crystal system, within space group P2(1)/c (no. 14) and the following unit cell parameters: a = 16.3399(3), b = 32.7506(4), c = 16.2624(3) Å, β = 107.382(2)°, V = 8305.3(2) Å(3). In contrast to the former compound, CFA-3 features a layered 2-D three-connected structure constructed from triangular Ag(i) subunits. Both compounds are characterized by elemental and thermogravimetric analyses, single crystal structure analysis and X-ray powder diffraction, FTIR- and fluorescence spectroscopy. Preliminary results on oxygen activation in CFA-2 are presented and potential improvements in terms of framework robustness and catalytic efficiency are discussed.

Collapsed tetragonal phase transition in LaRu 2 P 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drachuck, Gil; Sapkota, Aashish; Jayasekara, Wageesha T.

Here, the structural properties of LaRu 2P 2 under external pressure have been studied up to 14 GPa, employing high-energy x-ray diffraction in a diamond-anvil pressure cell. At ambient conditions, LaRu 2P 2 (I4/ mmm) has a tetragonal structure with a bulk modulus of B = 105(2) GPa and exhibits superconductivity at T c = 4.1 K. With the application of pressure, LaRu 2P 2 undergoes a phase transition to a collapsed tetragonal (cT) state with a bulk modulus of B = 175(5) GPa. At the transition, the c-lattice parameter exhibits a sharp decrease with a concurrent increase of themore » a-lattice parameter. The cT phase transition in LaRu 2P 2 is consistent with a second-order transition, and was found to be temperature dependent, increasing from P = 3.9(3) GPa at 160 K to P = 4.6(3) GPa at 300 K. In total, our data are consistent with the cT transition being near, but slightly above 2 GPa at 5 K where superconductivity is suppressed. Finally, we compare the effect of physical and chemical pressure in the RRu 2P 2 ( R = Y, La–Er, Yb) isostructural series of compounds and find them to be analogous.« less

Collapsed tetragonal phase transition in LaRu2P2

NASA Astrophysics Data System (ADS)

Drachuck, Gil; Sapkota, Aashish; Jayasekara, Wageesha T.; Kothapalli, Karunakar; Bud'ko, Sergey L.; Goldman, Alan I.; Kreyssig, Andreas; Canfield, Paul C.

2017-11-01

The structural properties of LaRu2P2 under external pressure have been studied up to 14 GPa, employing high-energy x-ray diffraction in a diamond-anvil pressure cell. At ambient conditions, LaRu2P2 (I4/mmm) has a tetragonal structure with a bulk modulus of B =105 (2 ) GPa and exhibits superconductivity at Tc=4.1 K. With the application of pressure, LaRu2P2 undergoes a phase transition to a collapsed tetragonal (cT) state with a bulk modulus of B =175 (5 ) GPa. At the transition, the c -lattice parameter exhibits a sharp decrease with a concurrent increase of the a -lattice parameter. The cT phase transition in LaRu2P2 is consistent with a second-order transition, and was found to be temperature dependent, increasing from P =3.9 (3 ) GPa at 160 K to P =4.6 (3 ) GPa at 300 K. In total, our data are consistent with the cT transition being near, but slightly above 2 GPa at 5 K where superconductivity is suppressed. Finally, we compare the effect of physical and chemical pressure in the RRu2P2 (R = Y, La -Er , Yb) isostructural series of compounds and find them to be analogous.

Collapsed tetragonal phase transition in LaRu 2 P 2

DOE PAGES

Drachuck, Gil; Sapkota, Aashish; Jayasekara, Wageesha T.; ...

2017-11-10

Here, the structural properties of LaRu 2P 2 under external pressure have been studied up to 14 GPa, employing high-energy x-ray diffraction in a diamond-anvil pressure cell. At ambient conditions, LaRu 2P 2 (I4/ mmm) has a tetragonal structure with a bulk modulus of B = 105(2) GPa and exhibits superconductivity at T c = 4.1 K. With the application of pressure, LaRu 2P 2 undergoes a phase transition to a collapsed tetragonal (cT) state with a bulk modulus of B = 175(5) GPa. At the transition, the c-lattice parameter exhibits a sharp decrease with a concurrent increase of themore » a-lattice parameter. The cT phase transition in LaRu 2P 2 is consistent with a second-order transition, and was found to be temperature dependent, increasing from P = 3.9(3) GPa at 160 K to P = 4.6(3) GPa at 300 K. In total, our data are consistent with the cT transition being near, but slightly above 2 GPa at 5 K where superconductivity is suppressed. Finally, we compare the effect of physical and chemical pressure in the RRu 2P 2 ( R = Y, La–Er, Yb) isostructural series of compounds and find them to be analogous.« less

Overexpression, crystallization and preliminary X-ray crystallographic analysis of phosphopantetheine adenylyltransferase from Enterococcus faecalis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Ji Yong; Lee, Hyung Ho; Yoon, Hye Jin

2006-11-01

Phosphopantetheine adenylyltransferase from En. faecalis was crystallized and X-ray diffraction data were collected to 2.70 Å resolution. Phosphopantetheine adenylyltransferase, an essential enzyme in the coenzyme A biosynthetic pathway, catalyzes the reversible transfer of an adenylyl group from ATP to 4′-phosphopantetheine, yielding 3′-dephospho-CoA and pyrophosphate. Enterococcus faecalis PPAT has been overexpressed in Escherichia coli as a fusion with a C-terminal purification tag and crystallized at 297 K using a reservoir solution consisting of 0.1 M sodium HEPES pH 7.5, 0.8 M sodium dihydrogen phosphate and 0.8 M potassium dihydrogen phosphate. X-ray diffraction data were collected to 2.70 Å at 100 K.more » The crystals belong to the primitive tetragonal space group P4{sub 1} (or P4{sub 3}), with unit-cell parameters a = b = 160.81, c = 225.68 Å. Four copies of the hexameric molecule are likely to be present in the asymmetric unit, giving a crystal volume per protein weight (V{sub M}) of 3.08 Å{sup 3} Da{sup −1} and a solvent content of 60.1%.« less

Crystallization and preliminary crystallographic analysis of a flavoprotein NADH oxidase from Lactobacillus brevis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuzu, Mutlu; Niefind, Karsten; Hummel, Werner

2005-05-01

The water-forming flavoenzyme NADH oxidase was crystallized successfully for the first time. The crystals diffract X-rays to at least 4.0 Å resolution. NADH oxidase (NOX) from Lactobacillus brevis is a homotetrameric flavoenzyme composed of 450 amino acids per subunit. The molecular weight of each monomer is 48.8 kDa. The enzyme catalyzes the oxidation of two equivalents of NADH and reduces one equivalent of oxygen to yield two equivalents of water, without releasing hydrogen peroxide after the reduction of the first equivalent of NADH. Crystals of this protein were grown in the presence of 34% polyethylene glycol monomethyl ether 2000, 0.1more » M sodium acetate and 0.2 M ammonium sulfate at pH 5.4. They belong to the tetragonal space group P4{sub 3}2{sub 1}2, with unit-cell parameters a = 74.8, b = 95.7, c = 116.9 Å, α = γ = 90, β = 103.8°. The current diffraction limit is 4.0 Å. The self-rotation function of the native data set is consistent with a NOX tetramer in the asymmetric unit.« less

Trypanothione reductase from Leishmania infantum: cloning, expression, purification, crystallization and preliminary X-ray data analysis.

PubMed

Baiocco, Paola; Franceschini, Stefano; Ilari, Andrea; Colotti, Gianni

2009-01-01

The most promising targets for Leishmania-specific drug design are two key enzymes involved in the unique thiol-based metabolism, common to all parasites of the Trypanosomatidae family: trypanothione synthetase (TryS) and trypanothione reductase (TR). Recently, new inhibitors of TR have been identified such as polyamines and tricyclic compounds. The knowledge of the three-dimensional structure of Leishmania TR will shed light on the mechanism of interaction of these inhibitors with TR and will be the starting point to design novel lead candidates to facilitate the development of new effective and affordable drugs. Trypanothione reductase from Leishmania infantum has been cloned, expressed in E. coli and purified. Crystals were obtained at 294 K by the hanging drop vapour diffusion method using ammonium sulfate as precipitant agent and diffract to better than 2.95 A resolution using a synchrotron radiation source. The crystals exhibit an unusually high solvent content of 74 %, belong to the tetragonal space group P41 with units cell parameters a=b=103.45 A, c=192.62 A and two molecules in the asymmetric unit. The protein X-ray structure has been solved by Molecular Replacement and the model is under construction.

Structural stability, electronic structure and mechanical properties of alkali gallium hydrides AGaH{sub 4} (A = Li, Na)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santhosh, M.; Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com; Manikandan, M.

2016-05-06

Ab initio calculations are performed to investigate the structural stability, electronic structure and mechanical properties of alkali gallium hydrides AGaH{sub 4} (A = Li, Na) for three different crystal structures, namely tetragonal (P42{sub 1}c), tetragonal (P4{sub 2}/nmc) and monoclinic (P2{sub 1}/c). Among the considered structures, tetragonal (P42{sub 1}c) phase is found to be the most stable phase for these hydrides at normal pressure. A pressure induced structural phase transition from tetragonal (P42{sub 1}c) to tetragonal (P4{sub 2}/nmc) is observed. The electronic structure reveals that these hydrides are insulators. The calculated elastic constants indicate that these ternary imides are mechanically stablemore » at normal pressure.« less

Metal Insulator transition in Vanadium Dioxide

NASA Astrophysics Data System (ADS)

Jovaini, Azita; Fujita, Shigeji; Suzuki, Akira; Godoy, Salvador

2012-02-01

MAR12-2011-000262 Abstract Submitted for the MAR12 Meeting of The American Physical Society Sorting Category: 03.9 (T) On the metal-insulator-transition in vanadium dioxide AZITA JOVAINI, SHIGEJI FUJITA, University at Buffalo, SALVADOR GODOY, UNAM, AKIRA SUZUKI, Tokyo University of Science --- Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity _/ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop. Prefer Oral Session X Prefer .

Liquid Crystalline Assembly of Coil-Rod-Coil Molecules with Lateral Methyl Groups into 3-D Hexagonal and Tetragonal Assemblies

PubMed Central

Wang, Zhuoshi; Lan, Yu; Zhong, Keli; Liang, Yongri; Chen, Tie; Jin, Long Yi

2014-01-01

In this paper, we report the synthesis and self-assembly behavior of coil-rod-coil molecules, consisting of three biphenyls linked through a vinylene unit as a conjugated rod segment and poly(ethylene oxide) (PEO) with a degree of polymerization (DP) of 7, 12 and 17, incorporating lateral methyl groups between the rod and coil segments as the coil segment. Self-organized investigation of these molecules by means of differential scanning calorimetry (DSC), thermal polarized optical microscopy (POM) and X-ray diffraction (XRD) reveals that the lateral methyl groups attached to the surface of rod and coil segments, dramatically influence the self-assembling behavior in the liquid-crystalline mesophase. Molecule 1 with a relatively short PEO coil length (DP = 7) self-assembles into rectangular and oblique 2-dimensional columnar assemblies, whereas molecules 2 and 3 with DP of 12 and 17 respectively, spontaneously self-organize into unusual 3-dimensional hexagonal close-packed or body-centered tetragonal assemblies. PMID:24699045

Phase field modeling of tetragonal to monoclinic phase transformation in zirconia

NASA Astrophysics Data System (ADS)

Mamivand, Mahmood

Zirconia based ceramics are strong, hard, inert, and smooth, with low thermal conductivity and good biocompatibility. Such properties made zirconia ceramics an ideal material for different applications form thermal barrier coatings (TBCs) to biomedicine applications like femoral implants and dental bridges. However, this unusual versatility of excellent properties would be mediated by the metastable tetragonal (or cubic) transformation to the stable monoclinic phase after a certain exposure at service temperatures. This transformation from tetragonal to monoclinic, known as LTD (low temperature degradation) in biomedical application, proceeds by propagation of martensite, which corresponds to transformation twinning. As such, tetragonal to monoclinic transformation is highly sensitive to mechanical and chemomechanical stresses. It is known in fact that this transformation is the source of the fracture toughening in stabilized zirconia as it occurs at the stress concentration regions ahead of the crack tip. This dissertation is an attempt to provide a kinetic-based model for tetragonal to monoclinic transformation in zirconia. We used the phase field technique to capture the temporal and spatial evolution of monoclinic phase. In addition to morphological patterns, we were able to calculate the developed internal stresses during tetragonal to monoclinic transformation. The model was started form the two dimensional single crystal then was expanded to the two dimensional polycrystalline and finally to the three dimensional single crystal. The model is able to predict the most physical properties associated with tetragonal to monoclinic transformation in zirconia including: morphological patterns, transformation toughening, shape memory effect, pseudoelasticity, surface uplift, and variants impingement. The model was benched marked with several experimental works. The good agreements between simulation results and experimental data, make the model a reliable tool for predicting tetragonal to monoclinic transformation in the cases we lack experimental observations.

Modeling the Growth Rates of Tetragonal Lysozyme Crystal Faces

NASA Technical Reports Server (NTRS)

Li, Meirong; Nadarajah, Arunan; Pusey, Marc L.

1998-01-01

The measured macroscopic growth rates of the (110) and (101) faces of tetragonal lysozyme show an unexpectedly complex dependence on the supersaturation. The growth rates decay asymptotically to zero when the supersaturation is lowered to zero and increase rapidly when the supersaturation is increased. When supersaturations are increased still further the growth rates attain a maximum before starting to decrease. However, growth of these crystals is known to proceed by the classical dislocation and 2D nucleation growth mechanisms. This anomaly can be explained if growth is assumed to occur not by monomer units but by lysozyme aggregates. Analysis of the molecular packing of these crystals revealed that they were constructed of strongly bonded 4(sub 3) helices, while weaker bonds were responsible for binding the helices to each other. It follows that during crystal growth the stronger bonds are formed before the weaker ones. Thus, the growth of these crystals could be viewed as a two step process: aggregate growth units corresponding to the 4(sub 3) helix are first formed in the bulk solution by stronger intermolecular bonds and then attached to the crystal face by weaker bonds on dislocation hillocks or 2D islands. This will lead to a distribution of aggregates in the solution with monomers and lower order aggregates being predominant at low supersaturations and higher order aggregates being predominant at high supersaturations. If the crystal grows mostly by higher order aggregates, such as tetramers and octamers, it would explain the anomalous dependence of the growth rates on the supersaturation. Besides the analysis of molecular packing, a comprehensive analysis of the measured (110) and (101) growth rates was also undertaken in this study. The distribution of aggregates in lysozyme nutrient solutions at various solution conditions were determined from reversible aggregation reactions at equilibrium. The supersaturation was defined for each aggregate species with respect to its concentration at saturation in order to apply growth rate models to this process. The measured growth rates were then compared with the predicted ones from several dislocation and 2D nucleation growth models, employing tetramer and octamer growth units in polydisperse solutions and monomer units in monodisperse solutions. For the (110) face, the calculations consistently showed that the measured growth rates followed the expected model relations with octamer growth units. For the (101) face, it is not possible to obtain a clear agreement between the predicted and measured growth rates for a single growth unit as done for the (110) face. However, the calculations do indicate that the average size of the growth unit is between a tetramer and an octamer. This suggests that tetramers, octamers and other intermediate size growth units all participate in the growth process for this face. These calculations show that it is possible to model the macroscopic protein crystal growth rates if the molecular level processes can be account for, particularly protein aggregation processes in the bulk solution. Our recent investigations of tetragonal lysozyme crystals employing high resolution atomic force microscopy scans have further confirmed the growth of these crystals by aggregate growth units corresponding to 4(sub 3) helices.

Spectroscopic investigation of the electronic structure of yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Götsch, Thomas; Bertel, Erminald; Menzel, Alexander; Stöger-Pollach, Michael; Penner, Simon

2018-03-01

The electronic structure and optical properties of yttria-stabilized zirconia are investigated as a function of the yttria content using multiple experimental and theoretical methods, including electron energy-loss spectroscopy, Kramers-Kronig analysis to obtain the optical parameters, photoelectron spectroscopy, and density functional theory. It is shown that many properties, including the band gaps, the crystal field splitting, the so-called defect gap between acceptor (YZr') and donor (VO••) states, as well as the index of refraction in the visible range exhibit the same "zig-zag-like" trend as the unit cell height does, showing the influence of an increased yttria content as well as of the tetragonal-cubic phase transition between 8 mol % and 20 mol %Y2O3 . Also, with Čerenkov spectroscopy (CS), a new technique is presented, providing information complementary to electron energy-loss spectroscopy. In CS, the Čerenkov radiation emitted inside the TEM is used to measure the onset of optical absorption. The apparent absorption edges in the Čerenkov spectra correspond to the energetic difference between the disorder states close to the valence band and the oxygen-vacancy-related electronic states within the band gap. Theoretical computations corroborate this assignment: they find both, the acceptor states and the donor states, at the expected energies in the band structures for diverse yttria concentrations. In the end, a schematic electronic structure diagram of the area around the band gap is constructed, including the chemical potential of the electrons obtained from photoelectron spectroscopy. The latter reveal that tetragonal YSZ corresponds to a p -type semiconductor, whereas the cubic samples exhibit n -type semiconductor properties.

Manipulation of polar order in the “empty” tetragonal tungsten bronzes: Ba{sub 4-x}Sr{sub x}Dy{sub 0.67}□{sub 1.33}Nb{sub 10}O{sub 30}, x = 0, 0.25, 0.5, 1, 2, 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gardner, Jonathan; Morrison, Finlay D., E-mail: finlay.morrison@st-andrews.ac.uk

2016-08-15

A series of “empty” tetragonal tungsten bronze (TTB) ferroelectrics, Ba{sub 4-x}Sr{sub x}Dy{sub 0.67}□{sub 1.33}Nb{sub 10}O{sub 30} (x = 0, 0.25, 0.5, 1, 2, 3; □ = vacancy), is reported. With increasing x the unit cell contracts in both the ab plane and c-axis; x ≤ 1 compounds are normal ferroelectrics (FE) with decreasing T{sub C} as x increases, while x ≥ 2 are relaxor ferroelectrics (RFE) with associated frequency dependent permittivity peaks and with similar T{sub m} and T{sub f} (Vogel-Fulcher freezing temperatures) values. This observation is rationalised by differing cation occupancies: for x ≤ 1, Sr{sup 2+} principally occupies the A2-site (co-occupied by Ba{sup 2+} with the A1-site occupiedmore » by Dy{sup 3+} and vacancies); for x ≥ 2 significant Sr A1-site occupation leads to the observed RFE characteristics. This FE to RFE crossover is consistent with a previously proposed TTB crystal chemical framework where both a decrease in average A-site size and concurrent increase in A1-site tolerance factor (t{sub A1}) favour destabilization of long range polar order and relaxor behaviour. The effect of increasing t{sub A1} as a result of Sr occupancy at the A1 site is dominant in the compounds reported here.« less

Stable Ferroelectric Behavior of Nb-Modified Bi0.5K0.5TiO3-Bi(Mg0.5Ti0.5)O3 Lead-Free Relaxor Ferroelectric Ceramics

NASA Astrophysics Data System (ADS)

Zaman, Arif; Malik, Rizwan Ahmed; Maqbool, Adnan; Hussain, Ali; Ahmed, Tanveer; Song, Tae Kwon; Kim, Won-Jeong; Kim, Myong-Ho

2018-03-01

Crystal structure, dielectric, ferroelectric, piezoelectric, and electric field-induced strain properties of lead-free Nb-modified 0.96Bi0.5K0.5TiO3-0.04Bi(Mg0.5Ti0.5)O3 (BKT-BMT) piezoelectric ceramics were investigated. Crystal structure analysis showed a gradual phase transition from tetragonal to pseudocubic phase with increasing Nb content. The optimal piezoelectric property of small-signal d 33 was enhanced up to ˜ 68 pC/N with a lower coercive field ( E c) of ˜ 22 kV/cm and an improved remnant polarization ( P r) of ˜ 13 μC/cm2 for x = 0.020. A relaxor-like behavior with a frequency-dependent Curie temperature T m was observed, and a high T m around 320°C was obtained in the investigated system. This study suggests that the ferroelectric properties of BKT-BMT was significantly improved by means of Nb substitution. The possible shift of depolarization temperature T d toward high temperature T m may have triggered the spontaneous relaxor to ferroelectric phase transition with long-range ferroelectric order without any traces of a nonergodic relaxor state in contradiction with Bi0.5Na0.5TiO3-based systems. The possible enhancement in ferroelectric and piezoelectric properties near the critical composition x = 0.020 may be attributed to the increased anharmonicity of lattice vibrations which may facilitate the observed phase transition from a low-symmetry tetragonal to a high-symmetry cubic phase with a decrease in the lattice anisotropy of an undoped sample. This highly flexible (at a unit cell level) narrow compositional range triggers the enhancement of d 33 and P r values.

Pressure-induced half-collapsed-tetragonal phase in CaKFe 4 As 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaluarachchi, Udhara S.; Taufour, Valentin; Sapkota, Aashish

Here, we report the temperature-pressure phase diagram of CaKFe 4As 4 established using high-pressure electrical resistivity, magnetization, and high-energy x-ray diffraction measurements up to 6 GPa. With increasing pressure, both resistivity and magnetization data show that the bulk superconducting transition of CaKFe 4As 4 is suppressed and then disappears at p ≳ 4 GPa. High-pressure x-ray data clearly indicate a phase transition to a collapsed tetragonal phase in CaKFe 4As 4 under pressure that coincides with the abrupt loss of bulk superconductivity near 4 GPa. The x-ray data, combined with resistivity data, indicate that the collapsed tetragonal transition line ismore » essentially independent of pressure, occurring at 4.0(5) GPa for temperatures below 150 K. Density functional theory calculations also find a sudden transition to a collapsed tetragonal state near 4 GPa, as As-As bonding develops across the Ca layer. Bonding across the K layer only occurs for p ≥ 12 GPa. These findings demonstrate a different type of collapsed tetragonal phase in CaKFe 4As 4 as compared to CaFe 2As 2: a half-collapsed tetragonal phase.« less

Pressure-induced half-collapsed-tetragonal phase in CaKFe 4 As 4

DOE PAGES

Kaluarachchi, Udhara S.; Taufour, Valentin; Sapkota, Aashish; ...

2017-10-02

Here, we report the temperature-pressure phase diagram of CaKFe 4As 4 established using high-pressure electrical resistivity, magnetization, and high-energy x-ray diffraction measurements up to 6 GPa. With increasing pressure, both resistivity and magnetization data show that the bulk superconducting transition of CaKFe 4As 4 is suppressed and then disappears at p ≳ 4 GPa. High-pressure x-ray data clearly indicate a phase transition to a collapsed tetragonal phase in CaKFe 4As 4 under pressure that coincides with the abrupt loss of bulk superconductivity near 4 GPa. The x-ray data, combined with resistivity data, indicate that the collapsed tetragonal transition line ismore » essentially independent of pressure, occurring at 4.0(5) GPa for temperatures below 150 K. Density functional theory calculations also find a sudden transition to a collapsed tetragonal state near 4 GPa, as As-As bonding develops across the Ca layer. Bonding across the K layer only occurs for p ≥ 12 GPa. These findings demonstrate a different type of collapsed tetragonal phase in CaKFe 4As 4 as compared to CaFe 2As 2: a half-collapsed tetragonal phase.« less

Pressure-induced half-collapsed-tetragonal phase in CaKFe4As4

NASA Astrophysics Data System (ADS)

Kaluarachchi, Udhara S.; Taufour, Valentin; Sapkota, Aashish; Borisov, Vladislav; Kong, Tai; Meier, William R.; Kothapalli, Karunakar; Ueland, Benjamin G.; Kreyssig, Andreas; Valentí, Roser; McQueeney, Robert J.; Goldman, Alan I.; Bud'ko, Sergey L.; Canfield, Paul C.

2017-10-01

We report the temperature-pressure phase diagram of CaKFe4As4 established using high-pressure electrical resistivity, magnetization, and high-energy x-ray diffraction measurements up to 6 GPa. With increasing pressure, both resistivity and magnetization data show that the bulk superconducting transition of CaKFe4As4 is suppressed and then disappears at p ≳4 GPa. High-pressure x-ray data clearly indicate a phase transition to a collapsed tetragonal phase in CaKFe4As4 under pressure that coincides with the abrupt loss of bulk superconductivity near 4 GPa. The x-ray data, combined with resistivity data, indicate that the collapsed tetragonal transition line is essentially independent of pressure, occurring at 4.0(5) GPa for temperatures below 150 K. Density functional theory calculations also find a sudden transition to a collapsed tetragonal state near 4 GPa, as As-As bonding develops across the Ca layer. Bonding across the K layer only occurs for p ≥12 GPa. These findings demonstrate a different type of collapsed tetragonal phase in CaKFe4As4 as compared to CaFe2As2 : a half-collapsed tetragonal phase.

High-pressure synthesis and characterization of incompressible titanium pernitride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhadram, Venkata S.; Kim, Duck Young; Strobel, Timothy A.

A new transition-metal pernitride, TiN 2, was uncovered from the chemical reaction of TiN with N 2 at 73GPa in a laser-heated diamond anvil cell (DAC). The crystal structure of this compound exhibits tetragonal I 4/ mcm symmetry and consists of single-bonded nitrogen dimers (N–N dumbbells) embedded in the metal lattice as shown by our ab initio calculations and verified by in situ synchrotron x-ray diffraction measurements. The pressure-volume equation of state determined from the experimental data reveals that TiN 2 is incompressible with bulk modulus in the range of 360-385 GPa which is close to that of cubic boronmore » nitride (382 GPa). Here, the origin of high bulk modulus of TiN 2 (which is metallic) is rooted in the nearly filled anti-bonding states of the pernitride units. TiN 2 is fully recoverable to ambient conditions and represents the lowest-density transition metal pernitride synthesized to date.« less

Local atomic and magnetic structure of dilute magnetic semiconductor ( Ba , K ) ( Zn , Mn ) 2 As 2

DOE PAGES

Frandsen, Benjamin A.; Gong, Zizhou; Terban, Maxwell W.; ...

2016-09-06

We studied the atomic and magnetic structure of the dilute ferromagnetic semiconductor system (Ba,K)(Zn,Mn) 2As 2 through atomic and magnetic pair distribution function analysis of temperature-dependent x-ray and neutron total scattering data. Furthermore, we detected a change in curvature of the temperature-dependent unit cell volume of the average tetragonal crystallographic structure at a temperature coinciding with the onset of ferromagnetic order. We also observed the existence of a well-defined local orthorhombic structure on a short length scale of ≲5Å, resulting in a rather asymmetrical local environment of the Mn and As ions. Finally, the magnetic PDF revealed ferromagnetic alignment ofmore » Mn spins along the crystallographic c axis, with robust nearest-neighbor ferromagnetic correlations that exist even above the ferromagnetic ordering temperature. Finally, we discuss these results in the context of other experiments and theoretical studies on this system.« less

Debye temperatures and magnetic structures of UFe xAl 12- x (3.6⩽ x⩽5) intermetallic alloys

NASA Astrophysics Data System (ADS)

Rećko, K.; Dobrzyński, L.; Szymański, K.; Hoser, A.

2000-03-01

Uranium ternary compounds UFe xAl 12- x crystallize in a body-centred tetragonal structure ThMn 12 (I 4/mmm No.139). The neutron powder diffraction, magnetization measurements as well as Mössbauer investigations clearly indicate the magnetic ordering within the iron sites. The rearrangement of iron magnetic moments from uncompensated antiferromagnetic system in UFe xAl 12- x with x<4, through coexistence of antiferro- and ferromagnetic iron components (4⩽ x<5) to pure ferromagnetic ordering for alloy with x=5 is observed. The neutron diffraction studies of magnetic structures of the aforementioned powder samples show a very rich world of possible uranium-iron magnetic interactions. For all these alloys the magnetic neutron scattering is generally weak in comparison to the nuclear one. Because of identical chemical and magnetic unit cells there are no pure magnetic reflections. Therefore, in order to extract magnetic part of the scattering one should be particularly careful in taking proper account of the thermal vibration effects.

Magnetic anisotropy of Fe{sub 1−y}X{sub y}Pt-L1{sub 0} [X = Cr, Mn, Co, Ni, Cu] bulk alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cuadrado, R.; Chantrell, R. W.; Klemmer, Timothy J.

2014-10-13

We demonstrate by means of fully relativistic first principles calculations that, by substitution of Fe by Cr, Mn, Co, Ni, or Cu in FePt-L1{sub 0} bulk alloys, with fixed Pt content, it is possible to tune the magnetocrystalline anisotropy energy by adjusting the content of the non-magnetic species in the material. The changes in the geometry due to the inclusion of each element induces different values of the tetragonality and hence changes in the magnetic anisotropy and in the net magnetic moment. The site resolved magnetic moments of Fe increase with the X content while those of Pt and Xmore » are simultaneously reduced. The calculations are in good quantitative agreement with experimental data and demonstrate that models with fixed band structure but varying numbers of electrons per unit cell are insufficient to describe the experimental data for doped FePt-L1{sub 0} alloys.« less

High-pressure synthesis and characterization of incompressible titanium pernitride

DOE PAGES

Bhadram, Venkata S.; Kim, Duck Young; Strobel, Timothy A.

2016-03-07

A new transition-metal pernitride, TiN 2, was uncovered from the chemical reaction of TiN with N 2 at 73GPa in a laser-heated diamond anvil cell (DAC). The crystal structure of this compound exhibits tetragonal I 4/ mcm symmetry and consists of single-bonded nitrogen dimers (N–N dumbbells) embedded in the metal lattice as shown by our ab initio calculations and verified by in situ synchrotron x-ray diffraction measurements. The pressure-volume equation of state determined from the experimental data reveals that TiN 2 is incompressible with bulk modulus in the range of 360-385 GPa which is close to that of cubic boronmore » nitride (382 GPa). Here, the origin of high bulk modulus of TiN 2 (which is metallic) is rooted in the nearly filled anti-bonding states of the pernitride units. TiN 2 is fully recoverable to ambient conditions and represents the lowest-density transition metal pernitride synthesized to date.« less

Electronic structure of ruthenium-doped iron chalcogenides

NASA Astrophysics Data System (ADS)

Winiarski, M. J.; Samsel-Czekała, M.; Ciechan, A.

2014-12-01

The structural and electronic properties of hypothetical RuxFe1-xSe and RuxFe1-xTe systems have been investigated from first principles within the density functional theory (DFT). Reasonable values of lattice parameters and chalcogen atomic positions in the tetragonal unit cell of iron chalcogenides have been obtained with the use of norm-conserving pseudopotentials. The well known discrepancies between experimental data and DFT-calculated results for structural parameters of iron chalcogenides are related to the semicore atomic states which were frozen in the used here approach. Such an approach yields valid results of the electronic structures of the investigated compounds. The Ru-based chalcogenides exhibit the same topology of the Fermi surface (FS) as that of FeSe, differing only in subtle FS nesting features. Our calculations predict that the ground states of RuSe and RuTe are nonmagnetic, whereas those of the solid solutions RuxFe1-xSe and RuxFe1-xTe become the single- and double-stripe antiferromagnetic, respectively. However, the calculated stabilization energy values are comparable for each system. The phase transitions between these magnetic arrangements may be induced by slight changes of the chalcogen atom positions and the lattice parameters a in the unit cell of iron selenides and tellurides. Since the superconductivity in iron chalcogenides is believed to be mediated by the spin fluctuations in single-stripe magnetic phase, the RuxFe1-xSe and RuxFe1-xTe systems are good candidates for new superconducting iron-based materials.

Evidence of tetragonal distortion as the origin of the ferromagnetic ground state in γ -Fe nanoparticles

NASA Astrophysics Data System (ADS)

Augustyns, V.; van Stiphout, K.; Joly, V.; Lima, T. A. L.; Lippertz, G.; Trekels, M.; Menéndez, E.; Kremer, F.; Wahl, U.; Costa, A. R. G.; Correia, J. G.; Banerjee, D.; Gunnlaugsson, H. P.; von Bardeleben, J.; Vickridge, I.; Van Bael, M. J.; Hadermann, J.; Araújo, J. P.; Temst, K.; Vantomme, A.; Pereira, L. M. C.

2017-11-01

γ -Fe and related alloys are model systems of the coupling between structure and magnetism in solids. Since different electronic states (with different volumes and magnetic ordering states) are closely spaced in energy, small perturbations can alter which one is the actual ground state. Here, we demonstrate that the ferromagnetic state of γ -Fe nanoparticles is associated with a tetragonal distortion of the fcc structure. Combining a wide range of complementary experimental techniques, including low-temperature Mössbauer spectroscopy, advanced transmission electron microscopy, and synchrotron radiation techniques, we unambiguously identify the tetragonally distorted ferromagnetic ground state, with lattice parameters a =3.76 (2 )Å and c =3.50 (2 )Å , and a magnetic moment of 2.45(5) μB per Fe atom. Our findings indicate that the ferromagnetic order in nanostructured γ -Fe is generally associated with a tetragonal distortion. This observation motivates a theoretical reassessment of the electronic structure of γ -Fe taking tetragonal distortion into account.

Suppression of electron correlations in the collapsed tetragonal phase of CaFe2As2 under ambient pressure demonstrated by As75 NMR/NQR measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furukawa, Yuji; Roy, Beas; Ran, Sheng

2014-03-20

The static and the dynamic spin correlations in the low-temperature collapsed tetragonal and the high-temperature tetragonal phase in CaFe2As2 have been investigated by As75 nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements. Through the temperature (T) dependence of the nuclear spin lattice relaxation rates (1/T1) and the Knight shifts, although stripe-type antiferromagnetic (AFM) spin correlations are realized in the high-temperature tetragonal phase, no trace of the AFM spin correlations can be found in the nonsuperconducting, low-temperature, collapsed tetragonal (cT) phase. Given that there is no magnetic broadening in As75 NMR spectra, together with the T-independent behavior of magneticmore » susceptibility χ and the T dependence of 1/T1Tχ, we conclude that Fe spin correlations are completely quenched statically and dynamically in the nonsuperconducting cT phase in CaFe2As2.« less

Crystal structure refinements of tetragonal (OH,F)-rich spessartine and henritermierite garnets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antao, Sytle M.; Cruickshank, Laura A.

Cubic garnet (space group Ia\\overline 3 d) has the general formulaX 3Y 2Z 3O 12, whereX,YandZare cation sites. In the tetragonal garnet (space groupI4 1/acd), the corresponding cation sites areX1 andX2,Y, andZ1 andZ2. In both space groups only theYsite is the same. The crystal chemistry of a tetragonal (OH,F)-rich spessartine sample from Tongbei, near Yunxiao, Fujian Province, China, with composition X(Mn 2.82Fe^{2+}_{0.14}Ca 0.04) Σ3 Y{Al 1.95Fe^{3+}_{0.05}} Σ2 Z[(SiO 4) 2.61(O 4H 4) 0.28(F 4) 0.11] Σ3(Sps 94Alm 5Grs 1) was studied with single-crystal X-ray diffraction and space groupI4 1/acd. The deviation of the unit-cell parameters from cubic symmetry is smallmore » [a= 11.64463(1),c= 11.65481 (2) Å,c/a= 1.0009]. Point analyses and back-scattered electron images, obtained by electron-probe microanalysis, indicate a homogeneous composition. TheZ2 site is fully occupied, but theZ1 site contains vacancies. The occupiedZ1 andZ2 sites with Si atoms are surrounded by four O atoms, as in anhydrous cubic garnets. Pairs of split sites are O1 with F11 and O2 with O22. When theZ1 site is vacant, a larger [(O 2H 2)F 2] tetrahedron is formed by two OH and two F anions in the O22 and F11 sites, respectively. This [(O 2H 2)F 2] tetrahedron is similar to the O 4H 4tetrahedron in hydrogarnets. These results indicate ^{X}{{\\rm Mn}^ {2+}_{3}}\\,^{Y}{\\rm Al}_{2}^{Z}[({\\rm SiO}_{4})_{2}({\\rm O}_{2}{\\rm H}_{2})_{0.5}({\\rm F}_{2})_{0.5}]_{\\Sigma3} as a possible end member, which is yet unknown. The H atom that is bonded to the O22 site is not located because of the small number of OH groups. In contrast, tetragonal henritermierite, ideally ^{X}{\\rm Ca}_{3}\\,^{Y}{\\rm Mn}^{3+}_{2}\\,^{Z}[({\\rm SiO}_{4})_{2}({\\rm O}_{4}{\\rm H}_{4})_1]_{\\Sigma3}, has a vacantZ2 site that contains the O 4H 4tetrahedron. The H atom is bonded to an O3 atom [O3—H3 = 0.73 (2) Å]. Because of O2—Mn 3+—O2 Jahn–Teller elongation of the Mn 3+O 6octahedron, a weak hydrogen bond is formed to the under-bonded O2 atom. This causes a large deviation from cubic symmetry (c/a= 0.9534).« less

High temperature mechanical properties of zirconia tapes used for electrolyte supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Fleischhauer, Felix; Bermejo, Raul; Danzer, Robert; Mai, Andreas; Graule, Thomas; Kuebler, Jakob

2015-01-01

Solid-Oxide-Fuel-Cell systems are efficient devices to convert the chemical energy stored in fuels into electricity. The functionality of the cell is related to the structural integrity of the ceramic electrolyte, since its failure can lead to drastic performance losses. The mechanical property which is of most interest is the strength distribution at all relevant temperatures and how it is affected with time due to the environment. This study investigates the impact of the temperature on the strength and the fracture toughness of different zirconia electrolytes as well as the change of the elastic constants. 3YSZ and 6ScSZ materials are characterised regarding the influence of sub critical crack growth (SCCG) as one of the main lifetime limiting effects for ceramics at elevated temperatures. In addition, the reliability of different zirconia tapes is assessed with respect to temperature and SCCG. It was found that the strength is only influenced by temperature through the change in fracture toughness. SCCG has a large influence on the strength and the lifetime for intermediate temperature, while its impact becomes limited at temperatures higher than 650 °C. In this context the tetragonal 3YSZ and 6ScSZ behave quite different than the cubic 10Sc1CeSZ, so that at 850 °C it can be regarded as competitive compared to the tetragonal compounds.

First-principles calculation of the effects of tetragonal distortions on the Gilbert damping parameter of Co2MnSi

NASA Astrophysics Data System (ADS)

Pradines, B.; Arras, R.; Calmels, L.

2017-05-01

We present an ab initio study of the influence of the tetragonal distortion, on the static and dynamic (Gilbert damping parameter) magnetic properties of a Co2MnSi crystal. This tetragonal distortion can for instance be due to strain, when Co2MnSi is grown on a substrate with a small lattice mismatch. Using fully relativistic Korringa-Kohn-Rostoker (KKR) calculations, in conjunction with the coherent potential approximation (CPA) to describe atomic disorder and the linear response formalism to compute the Gilbert damping parameter, we show that a tetragonal distortion can substantially change the properties of Co2MnSi, in a way which depends on the kind of atomic disorder.

Growth and dissolution kinetics of tetragonal lysozyme

NASA Technical Reports Server (NTRS)

Monaco, L. A.; Rosenberger, F.

1993-01-01

The growth and dissolution kinetics of lysozyme in a 25 ml solution bridge inside a closed growth cell was investigated. It was found that, under all growth conditions, the growth habit forming (110) and (101) faces grew through layer spreading with different growth rate dependence on supersaturation/temperature. On the other hand, (100) faces which formed only at low temperatures underwent a thermal roughening transition around 12 C.

Purification, crystallization and preliminary X-ray characterization of prunin-1, a major component of the almond (Prunus dulcis) allergen amandin.

PubMed

Albillos, Silvia M; Jin, Tengchuan; Howard, Andrew; Zhang, Yuzhu; Kothary, Mahendra H; Fu, Tong-Jen

2008-07-09

The 11S globulins from plant seeds account for a number of major food allergens. Because of the interest in the structural basis underlying the allergenicity of food allergens, we sought to crystallize the main 11S seed storage protein from almond ( Prunus dulcis). Prunin-1 (Pru1) was purified from defatted almond flour by water extraction, cryoprecipitation, followed by sequential anion exchange, hydrophobic interaction, and size exclusion chromatography. Single crystals of Pru1 were obtained in a screening with a crystal screen kit, using the hanging-drop vapor diffusion method. Diffraction quality crystals were grown after optimization. The Pru1 crystals diffracted to at least 3.0 A and belong to the tetragonal space group P4(1)22, with unit cell parameters of a = b = 150.912 A, c = 165.248 A. Self-rotation functions and molecular replacement calculations showed that there are three molecules in the asymmetry unit with water content of 51.41%. The three Pru1 protomers are related by a noncrystallographic 3-fold axis and they form a doughnut-shaped trimer. Two prunin trimers form a homohexamer. Elucidation of prunin structure will allow further characterization of the allergenic features of the 11S protein allergens at the molecular level.

Structure of water clusters on graphene: A classical molecular dynamics approach

NASA Astrophysics Data System (ADS)

Maekawa, Yuki; Sasaoka, Kenji; Yamamoto, Takahiro

2018-03-01

The microscopic structure of surface water adsorbed on graphene is elucidated theoretically by classical molecular dynamics simulation. At a low temperature (100 K), the main polygon consisting of hydrogen bonds in single-layered water on graphene is tetragonal, whereas the dominant polygons in double-layered water are tetragonal, pentagonal, and hexagonal. On the other hand, at room temperature, the tetragonal, pentagonal, and hexagonal water clusters are the main structures in both single- and double-layered water.

Suppression of superconductivity and structural phase transitions under pressure in tetragonal FeS

DOE PAGES

Lai, Xiaofang; Liu, Ying; Lu, Xujie; ...

2016-08-08

Pressure is a powerful tool to study iron-based superconductors. Here, we report systematic high-pressure transport and structural characterizations of the newly discovered superconductor FeS. It is found that superconductor FeS (tetragonal) partly transforms to a hexagonal structure at 0.4 GPa, and then completely transforms to an orthorhombic phase at 7.4 GPa and finally to a monoclinic phase above 9.0 GPa. The superconducting transition temperature of tetragonal FeS was gradually depressed by pressure, different from the case in tetragonal FeSe. With pressure increasing, the S-Fe-S angles only slightly change but the anion height deviates farther from 1.38 Å. This change ofmore » anion height, together with the structural instability under pressure, should be closely related to the suppression of superconductivity. We also observed an anomalous metal-semiconductor transition at 6.0 GPa and an unusual increased resistance with further compression above 9.6 GPa. The former can be ascribed to the tetragonal-orthorhombic structural phase transition, and the latter to the electronic structure changes of the high-pressure monoclinic phase. Lastly, a phase diagram of tetragonal FeS as functions of pressure and temperature was mapped out for the first time, which will shed new light on understanding of the structure and physics of the superconducting FeS.« less

Research on the optical spectra, g factors and defect structures for two tetragonal Y²+ centers in the irradiated CaF₂: Y crystal.

PubMed

Zheng, Wen-Chen; Mei, Yang; Yang, Yu-Guang; Liu, Hong-Gang

2012-11-01

Based on the defect models that the tetragonal Y(2+) (1) center in the irradiated CaF(2): Y crystal is due to Y(2+) at Ca(2+) site associated with a nearest interstitial F(-) ion along C(4) axis and the tetragonal Y(2+) (2) center is Y(2+) at Ca(2+) site where the tetragonal distortion is caused by the static Jahn-Teller effect, the two optical spectral bands and anisotropic g factors for both tetragonal Y(2+) centers are calculated. The calculations are made by using two methods based on the cluster approach, one is the complete diagonalization (of energy matrix) method (CDM) and another is the perturbation theory method (PTM). The calculated results for each Y(2+) center from CDM and PTM coincide and show reasonable agreement with the experimental values. The calculated isotropic g factor for Y(2+) (2) center at higher temperature owing to the dynamical Jahn-Teller effect is also consistent with the observed value. The defect structures (i.e., tetragonal distortion) of the two Y(2+) centers are obtained from the calculation. It appears that both theoretical methods can be applied to explain the optical and EPR data, to study the defect model and to determine the defect structures for d(1) ions in crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

Raman scattering in HfxZr1-xO2 nanoparticles

NASA Astrophysics Data System (ADS)

Robinson, Richard D.; Tang, Jing; Steigerwald, Michael L.; Brus, Louis E.; Herman, Irving P.

2005-03-01

Raman spectroscopy demonstrates that ˜5nm dimension HfxZr1-xO2 nanocrystals prepared by a nonhydrolytic sol-gel synthesis method are solid solutions of hafnia and zirconia, with no discernable segregation within the individual nanoparticles. Zirconia-rich particles are tetragonal and ensembles of hafnia-rich particles show mixed tetragonal/monoclinic phases. Sintering at 1200 °C produces larger particles (20-30 nm) that are monoclinic. A simple lattice dynamics model with composition-averaged cation mass and scaled force constants is used to understand how the Raman mode frequencies vary with composition in the tetragonal HfxZr1-xO2 nanoparticles. Background luminescence from these particles is minimized after oxygen treatment, suggesting possible oxygen defects in the as-prepared particles. Raman scattering is also used to estimate composition and the relative fractions of tetragonal and monoclinic phases. In some regimes there are mixed phases, and Raman analysis suggests that in these regimes the tetragonal phase particles are relatively rich in zirconium and the monoclinic phase particles are relatively rich in hafnium.

From Zirconium Nanograins to Zirconia Nanoneedles

PubMed Central

Zalnezhad, E.; Hamouda, A. M. S.; Jaworski, J.; Do Kim, Young

2016-01-01

Combinations of three simple techniques were utilized to gradually form zirconia nanoneedles from zirconium nanograins. First, a physical vapor deposition magnetron sputtering technique was used to deposit pure zirconium nanograins on top of a substrate. Second, an anodic oxidation was applied to fabricate zirconia nanotubular arrays. Finally, heat treatment was used at different annealing temperatures in order to change the structure and morphology from nanotubes to nanowires and subsequently to nanoneedles in the presence of argon gas. The size of the pure zirconium nanograins was estimated to be approximately 200–300 nm. ZrO2 nanotubular arrays with diameters of 70–120 nm were obtained. Both tetragonal and monoclinic ZrO2 were observed after annealing at 450 °C and 650 °C. Only a few tetragonal peaks appeared at 850 °C, while monoclinic ZrO2 was obtained at 900 °C and 950 °C. In assessing the biocompatibility of the ZrO2 surface, the human cell line MDA-MB-231 was found to attach and proliferate well on surfaces annealed at 850 °C and 450 °C; however, the amorphous ZrO2 surface, which was not heat treated, did not permit extensive cell growth, presumably due to remaining fluoride. PMID:27623486

Thickness-dependent electrocaloric effect in mixed-phase Pb0.87Ba0.1 La0.02(Zr0.6Sn0.33Ti0.07)O3 thin films

PubMed Central

Correia, T. M.

2016-01-01

Full-perovskite Pb0.87Ba0.1La0.02(Zr0.6Sn0.33Ti0.07)O3 (PBLZST) thin films were fabricated by a sol–gel method. These revealed both rhombohedral and tetragonal phases, as opposed to the full-tetragonal phase previously reported in ceramics. The fractions of tetragonal and rhombohedral phases are found to be strongly dependent on film thickness. The fraction of tetragonal grains increases with increasing film thickness, as the substrate constraint throughout the film decreases with film thickness. The maximum of the dielectric constant (εm) and the corresponding temperature (Tm) are thickness-dependent and dictated by the fraction of rhombohedral and tetragonal phase, with εm reaching a minimum at 400 nm and Tm shifting to higher temperature with increasing thickness. With the thickness increase, the breakdown field decreases, but field-induced antiferroelectric–ferroelectric (EAFE−FE) and ferroelectric–antiferroelectric (EFE−AFE) switch fields increase. The electrocaloric effect increases with increasing film thickness. This article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’. PMID:27402937

The p- T phase diagram of KNbO 3 by a dielectric constant measurement

NASA Astrophysics Data System (ADS)

Kobayashi, Y.; Endo, S.; Deguchi, K.; Ming, L. C.; Zou, G.

2001-11-01

A dielectric constant measurement was carried out on perovskite-type ferroelectrics KNbO 3 over a wide range of temperature under high pressure. The temperature- and pressure-dependence of the dielectric constant clarified that all temperatures of the transitions from the ferroelectric rhombohedral to orthorhombic, to tetragonal and then to the paraelectric cubic phase, decrease with increasing pressure. These results indicate that the orthorhombic-tetragonal transition takes place at 8.5 GPa and the tetragonal-cubic transition at 11 GPa, at room temperature.

Effects of Zr/Ce molar ratio and water content on thermal stability and structure of ZrO{sub 2}–CeO{sub 2} mixed oxides prepared via sol–gel process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Wenzhi; Yang, Jili; Wang, Chunjie

2012-09-15

Highlights: ► Tetragonal t″ phase was stabilized in Zr{sub 0.5}Ce{sub 0.5}O{sub 2} solid solution at temperature as high as 1000 °C. ► Specific surface area of powders decreased with the increase of water addition and the Ce content. ► The single stable phase was controlled by adjusting the volume ratio of water and ethanol. ► Tetragonal (t″) phase dissociated into cubic and tetragonal (t′) phases at 1200 °C. -- Abstract: ZrO{sub 2}–CeO{sub 2} mixed oxides were synthesized via sol–gel process. Thermal stability, structure and morphology of samples were investigated by powder X-ray diffraction, FT-Raman spectroscopy, X-ray photoelectron spectroscopy and scanningmore » electron microscopy. In this approach, the solvent composition and Zr/Ce molar ratio have great influences on the structure and morphology of final products. With decreasing water content in the mixed solvent, specific surface area of powders increased and the single tetragonal phase was obtained. Only when the volume ratio of water and ethanol and the Zr/Ce molar ratio were 1:1, tetragonal t″-Zr{sub 0.5}Ce{sub 0.5}O{sub 2} could be stabilized in powders at temperature as high as 1000 °C. Meanwhile, tetragonal (t′) and (t″) phases coexisted in Zr{sub 0.5}Ce{sub 0.5}O{sub 2} solid solution without peak splitting after calcination at 1100 °C, further transforming into cubic and tetragonal (t′) phases at 1200 °C. The effective activation energy for Zr{sub 0.5}Ce{sub 0.5}O{sub 2} nanocrystallite growth during annealing is about 5.24 ± 0.15 kJ/mol.« less

The exchange interactions and the state of manganese atoms in the solid solutions in Bi{sub 3}NbO{sub 7} of cubic and tetragonal modifications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Zhuk, N.A.; Korolev, D.A.

2016-01-15

The comparative analysis of magnetic behavior of manganese-containing solid solutions Bi{sub 3}Nb{sub 1−x}Mn{sub x}O{sub 7−δ} (x=0.01−0.10) of cubic and tetragonal modifications was performed. Based on the results of magnetic susceptibility studies paramagnetic manganese atoms in solid solutions of cubic and tetragonal modifications were found to be in the form of Mn(III), Mn(IV) monomers and exchange-coupled dimers of Mn(III)–O–Mn(III), Mn(IV)–O–Mn(IV), Mn(III)–O–Mn(IV). The exchange parameters and the distribution of monomers and dimers in solid solutions as a function of the content of paramagnetic atoms were calculated. - Graphical abstract: Structural transition of cubic to tetragonal Bi{sub 3}NbO{sub 7−δ}.

Demonstration of Ru as the 4th ferromagnetic element at room temperature.

PubMed

Quarterman, P; Sun, Congli; Garcia-Barriocanal, Javier; Dc, Mahendra; Lv, Yang; Manipatruni, Sasikanth; Nikonov, Dmitri E; Young, Ian A; Voyles, Paul M; Wang, Jian-Ping

2018-05-25

Development of novel magnetic materials is of interest for fundamental studies and applications such as spintronics, permanent magnetics, and sensors. We report on the first experimental realization of single element ferromagnetism, since Fe, Co, and Ni, in metastable tetragonal Ru, which has been predicted. Body-centered tetragonal Ru phase is realized by use of strain via seed layer engineering. X-ray diffraction and electron microscopy confirm the epitaxial mechanism to obtain tetragonal phase Ru. We observed a saturation magnetization of 148 and 160 emu cm -3 at room temperature and 10 K, respectively. Control samples ensure the ferromagnetism we report on is from tetragonal Ru and not from magnetic contamination. The effect of thickness on the magnetic properties is also studied, and it is observed that increasing thickness results in strain relaxation, and thus diluting the magnetization. Anomalous Hall measurements are used to confirm its ferromagnetic behavior.

Glass ceramic toughened with tetragonal zirconia

DOEpatents

Keefer, K.D.

1984-02-10

A phase transformation-toughened glass ceramic and a process for making it are disclosed. A mixture of particulate network-forming oxide, network-modifying oxide, and zirconium oxide is heated to yield a homogeneous melt, and this melt is then heat treated to precipitate an appreciable quantity of tetragonal zirconia, which is retained at ambient temperature to form a phase transformation-toughened glass ceramic. Nuclearing agents and stabilizing agents may be added to the mixture to facilitate processing and improve the ceramic's properties. Preferably, the mixture is first melted at a temperature from 1200 to 1700/sup 0/C and is then heat-treated at a temperature within the range of 800 to 1200/sup 0/C in order to precipitate tetragonal ZrO/sub 2/. The composition, as well as the length and temperature of the heat treatment, must be carefully controlled to prevent solution of the precipitated tetragonal zirconia and subsequent conversion to the monoclinic phase.

Glass ceramic toughened with tetragonal zirconia

DOEpatents

Keefer, Keith D.; Michalske, Terry A.

1986-01-01

A phase transformation-toughened glass ceramic and a process for making it are disclosed. A mixture of particulate network-forming oxide, network-modifying oxide, and zirconium oxide is heated to yield a homogeneous melt, and this melt is then heat-treated to precipitate an appreciable quantity of tetragonal zirconia, which is retained at ambient temperature to form a phase transformation-toughened glass ceramic. Nucleating agents and stabilizing agents may be added to the mixture to facilitate processing and improve the ceramic's properties. Preferably, the mixture is first melted at a temperature from 1200.degree. to 1700.degree. C. and is then heat-treated at a temperature within the range of 800.degree. to 1200.degree. C. in order to precipitate tetragonal ZrO.sub.2. The composition, as well as the length and temperature of the heat-treatment, must be carefully controlled to prevent solution of the precipitated tetragonal zirconia and subsequent conversion to the monoclinic phase.

Crystallization and preliminary X-ray analysis of Der f 2, a potent allergen derived from the house dust mite (Dermatophagoides farinae)

NASA Technical Reports Server (NTRS)

Roeber, Dana; Achari, Aniruddha; Takai, Toshiro; Okumura, Yasushi; Scott, David L.

2003-01-01

Although a number of allergens have been identified and isolated, the underlying molecular basis for the potent immune response is poorly understood. House dust mites (Dermatophagoides sp.) are ubiquitous contributors to atopy in developed countries. The rhinitis, dermatitis and asthma associated with allergic reactions to these arthropods are frequently caused by relatively small (125-129 amino acids) mite proteins of unknown biological function. Der f 2, a major allergen from the mite D. farinae, has been recombinantly expressed, characterized and crystallized. The crystals belong to the tetragonal space group I4(1)22, with unit-cell parameters a = b = 95.2, c = 103.3 A. An essentially complete (97.2%) data set has been collected to 2.4 A at a synchrotron source. Attempts to solve the crystal structure of Der f 2 by molecular replacement using the NMR coordinates for either Der f 2 or Der p 2 (the homologous protein from D. pteronyssinus) failed, but preliminary searches using the crystalline Der p 2 atomic coordinates appear to be promising.

Magneto-transport and magneto-optical studies on SnO2 transparent semiconducting thin films alloyed with Mn over a wide range of concentration

NASA Astrophysics Data System (ADS)

Bagheri Mohagheghi, M. M.; Tabatabai Yazdi, Sh.; Mousavi, M.

2018-03-01

In this work, Mn-alloyed tin oxide transparent thin films with different Mn concentrations up to 60 at% were prepared via the spray pyrolysis method, and their structural, magneto-optical, and magneto-transport properties were studied. The results show that all the deposited films are polycrystalline with the tetragonal rutile structure. The unit cell volume of Sn1- x Mn x O2 films was found to be minimum at the Mn concentration of x = 0.15 indicating to two different mechanisms for Mn addition in the crystal lattice of tin oxide. For the films with Mn concentrations less than 15%, substitutional doping is the working mechanism, while for more Mn concentrations, interstitial one is predominant. A critical Mn concentration about that observed for the structural properties of the films (i.e., x = 0.15) was revealed for their magnetoresistance and magneto-optical properties, as well. This suggests a correlation between the structural and magnetic behaviors of the deposited SnO2:Mn films.

Crystallization and preliminary X-ray characterization of arylamine N-acetyltransferase C (BanatC) from Bacillus anthracis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pluvinage, Benjamin; Li de la Sierra-Gallay, Inés; Martins, Marta

2007-10-01

Bacillus anthracis arylamine N-acetyltransferase C (BanatC) is an enzyme that metabolizes the drug sulfamethoxazole. Crystals of the purified enzyme that diffract at 1.95 Å are reported. The arylamine N-acetyltransferase (NAT) enzymes are xenobiotic metabolizing enzymes that have been found in a large range of eukaryotes and prokaryotes. These enzymes catalyse the acetylation of arylamine drugs and/or pollutants. Recently, a Bacillus anthracis NAT isoform (BanatC) has been cloned and shown to acetylate the sulfonamide antimicrobial sulfamethoxazole (SMX). Subsequently, it was shown that BanatC contributes to the resistance of this bacterium to SMX. Here, the crystallization and the X-ray characterization of BanatCmore » (Y38F mutant) are reported. The crystals belong to the tetragonal space group P4{sub 1}2{sub 1}2 or P4{sub 3}2{sub 1}2, with unit-cell parameters a = b = 53.70, c = 172.40 Å, and diffract to 1.95 Å resolution on a synchrotron source.« less

Increased magnetic moment induced by lattice expansion from α-Fe to α′-Fe{sub 8}N

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dirba, Imants, E-mail: dirba@fm.tu-darmstadt.de; Komissinskiy, Philipp; Alff, Lambert, E-mail: alff@oxide.tu-darmstadt.de

2015-05-07

Buffer-free and epitaxial α-Fe and α′-Fe{sub 8}N{sub x} thin films have been grown by RF magnetron sputtering onto MgO (100) substrates. The film thicknesses were determined with high accuracy by evaluating the Kiessig fringes of X-ray reflectometry measurements allowing a precise volume estimation. A gradual increase of the nitrogen content in the plasma led to an expansion of the iron bcc unit cell along the [001] direction resulting finally in a tetragonal distortion of about 10% corresponding to the formation of α′-Fe{sub 8}N. The α-Fe lattice expansion was accompanied by an increase in magnetic moment to 2.61 ± 0.06μ{sub B} per Femore » atom and a considerable increase in anisotropy. These experiments show that—without requiring any additional ordering of the nitrogen atoms—the lattice expansion of α-Fe itself is the origin of the increased magnetic moment in α′-Fe{sub 8}N.« less

Raman spectra and anomalies of dielectric properties and thermal expansion of lead-free (1-x)Na0.5Bi0.5TiO3-xSrTiO3 (x = 0, 0.08 and 0.1) ceramics

NASA Astrophysics Data System (ADS)

Dutkiewicz, E. M.; Suchanicz, J.; Bovtun, V.; Konieczny, K.; Czaja, P.; Kluczewska, K.; Handke, B.; Antonova, M.; Sternberg, A.

2016-08-01

Thermal expansion, Raman and dielectric properties of the lead-free (1-x)Na0.5Bi0.5TiO3-xSrTiO3 (x = 0, 0.08 and 0.1) ceramic solid solutions, fabricated by the conventional solid-state reaction method, were investigated. The Sr-doping results in an increase of the dielectric permittivity, broadening of the permittivity maximum, enhancement of the relaxation near depolarization temperature, broadening of the Raman bands and shift of all anomalies toward lower temperatures. The observed effects are attributed to an increase of the degree of cationic disorder and enhancement of the relaxor-like features. Anomalies in the thermal expansion strain were observed at the temperatures corresponding to the dielectric anomalies but not related to any phase transitions. These anomalies are supposed to follow changes of the averaged unit cell volume in the temperature interval of tetragonal and rhombohedral phase coexistence.

Structure, microstructure and infrared studies of Ba{sub 0.06}(Na{sub 1/2}Bi{sub 1/2}){sub 0.94}TiO{sub 3}-NaNbO{sub 3} ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roy, Sumit K., E-mail: sumit.sxc13@gmail.com; Singh, S. N., E-mail: snsphyru@gmail.com; Prasad, K., E-mail: k.prasad65@gmail.com

2016-05-06

Lead-free solid solutions (1-x)Ba{sub 0.06}(Na{sub 1/2}Bi{sub 1/2}){sub 0.94}TiO{sub 3}-xNaNbO{sub 3} (0 ≤ x ≤ 1.0) were prepared by conventional ceramic fabrication technique. X-ray diffraction and Rietveld refinement analyses of these ceramics were carried out using X’Pert HighScore Plus software to determine the crystal symmetry, space group and unit cell dimensions. Rietveld refinement revealed that NaNbO{sub 3} with orthorhombic structure was completely diffused into Ba{sub 0.06}(Na{sub 1/2}Bi{sub 1/2}){sub 0.94}TiO{sub 3} lattice having the rhombohedral-tetragonal symmetry. EDS and SEM studies were carried out in order to evaluate the quality and purity of the compounds. SEM images showed a change in grain shapemore » with the increase of NaNbO{sub 3} content. FTIR spectra confirmed the formation of solid solution.« less

Unusual transformation from strong negative to positive thermal expansion in PbTiO3-BiFeO3 perovskite.

PubMed

Chen, Jun; Fan, Longlong; Ren, Yang; Pan, Zhao; Deng, Jinxia; Yu, Ranbo; Xing, Xianran

2013-03-15

Tetragonal PbTiO(3)-BiFeO(3) exhibits a strong negative thermal expansion in the PbTiO(3)-based ferroelectrics that consist of one branch in the family of negative thermal expansion materials. Its strong negative thermal expansion is much weakened, and then unusually transforms into positive thermal expansion as the particle size is slightly reduced. This transformation is a new phenomenon in the negative termal expansion materials. The detailed structure, temperature dependence of unit cell volume, and lattice dynamics of PbTiO(3)-BiFeO(3) samples were studied by means of high-energy synchrotron powder diffraction and Raman spectroscopy. Such unusual transformation from strong negative to positive thermal expansion is highly associated with ferroelectricity weakening. An interesting zero thermal expansion is achieved in a wide temperature range (30-500 °C) by adjusting particle size due to the negative-to-positive transformation character. The present study provides a useful method to control the negative thermal expansion not only for ferroelectrics but also for those functional materials such as magnetics and superconductors.

Structural and electronic properties of ultrathin FeSe films grown on Bi2Se3(0 0 0 1) studied by STM/STS

NASA Astrophysics Data System (ADS)

Singh, Udai Raj; Warmuth, Jonas; Markmann, Verena; Wiebe, Jens; Wiesendanger, Roland

2017-01-01

We report scanning tunnelling microscopy and spectroscopy (STM/STS) studies on one and two unit cell (UC) high FeSe thin films grown on Bi2Se3(0 0 0 1). In our thin films, we find the tetragonal phase of FeSe and dumb-bell shaped defects oriented along Se-Se bond directions. In addition, we observe striped moiré patterns with a periodicity of (7.3  ±  0.1) nm generated by the mismatch between the FeSe lattice and the Bi2Se3 lattice. We could not find any signature of a superconducting gap in the tunneling spectra measured on the surface of one and two UC thick islands of FeSe down to 6.5 K. The spectra rather show an asymmetric behavior across and a finite density of states at the Fermi level (E F) resembling those taken in the normal state of bulk FeSe.

Ultrafast terahertz-field-driven ionic response in ferroelectric BaTiO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, F.; Zhu, Y.; Liu, S.

The dynamical processes associated with electric field manipulation of the polarization in a ferroelectric remain largely unknown but fundamentally determine the speed and functionality of ferroelectric materials and devices. Here we apply subpicosecond duration, single-cycle terahertz pulses as an ultrafast electric field bias to prototypical BaTiO 3 ferroelectric thin films with the atomic-scale response probed by femtosecond x-ray-scattering techniques. We show that electric fields applied perpendicular to the ferroelectric polarization drive large-amplitude displacements of the titanium atoms along the ferroelectric polarization axis, comparable to that of the built-in displacements associated with the intrinsic polarization and incoherent across unit cells. Thismore » effect is associated with a dynamic rotation of the ferroelectric polarization switching on and then off on picosecond time scales. These transient polarization modulations are followed by long-lived vibrational heating effects driven by resonant excitation of the ferroelectric soft mode, as reflected in changes in the c-axis tetragonality. The ultrafast structural characterization described here enables a direct comparison with first-principles-based molecular-dynamics simulations, with good agreement obtained.« less

Ultrafast terahertz-field-driven ionic response in ferroelectric BaTiO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, F.; Zhu, Y.; Liu, S.

The dynamical processes associated with electric field manipulation of the polarization in a ferroelectric remain largely unknown but fundamentally determine the speed and functionality of ferroelectric materials and devices. Here in this paper we apply subpicosecond duration, single-cycle terahertz pulses as an ultrafast electric field bias to prototypical BaTiO 3 ferroelectric thin films with the atomic-scale response probed by femtosecond x-ray-scattering techniques. We show that electric fields applied perpendicular to the ferroelectric polarization drive large-amplitude displacements of the titanium atoms along the ferroelectric polarization axis, comparable to that of the built-in displacements associated with the intrinsic polarization and incoherent acrossmore » unit cells. This effect is associated with a dynamic rotation of the ferroelectric polarization switching on and then off on picosecond time scales. These transient polarization modulations are followed by long-lived vibrational heating effects driven by resonant excitation of the ferroelectric soft mode, as reflected in changes in the c-axis tetragonality. The ultrafast structural characterization described here enables a direct comparison with first-principles-based molecular-dynamics simulations, with good agreement obtained.« less

Ferroelectric and multiferroic domain imaging by Laser-induced photoemission microscopy

NASA Astrophysics Data System (ADS)

Hoefer, Anke; Fechner, Michael; Duncker, Klaus; Mertig, Ingrid; Widdra, Wolf

2013-03-01

The ferroelectric as well as multiferroic surface domain structures of BaTiO3(001) and BiFeO3(001) are imaged based on photoemission electron microscopy (PEEM) by femtosecond laser threshold excitation under UHV conditions. For well-prepared BaTiO3(001), three ferroelectric domain types are clearly discriminable due to work function differences. At room temperature, the surface domains resemble the known ferroelectric domain structure of the bulk. Upon heating above the Curie point of 400 K, the specific surface domain pattern remains up to 500 K. Ab-initio calculations explain this observation by a remaining tetragonal distortion of the topmost unit cells stabilized by a surface relaxation. The (001) surface of the single-phase multiferroic BiFeO3 which is ferroelectric and antiferromagnetic, shows clear ferroelectric work function contrast in PEEM. Additionally, the multiferroic domains show significant linear dichroism. The observation of a varying dichroism for different ferroelectric domains can be explained based on the coupled ferroelectric-antiferromagnetic order in BiFeO3. It demonstrates multiferroic imaging of different domain types within a single, lab-based experiment.

Ultrafast terahertz-field-driven ionic response in ferroelectric BaTiO 3

DOE PAGES

Chen, F.; Zhu, Y.; Liu, S.; ...

2016-11-22

The dynamical processes associated with electric field manipulation of the polarization in a ferroelectric remain largely unknown but fundamentally determine the speed and functionality of ferroelectric materials and devices. Here in this paper we apply subpicosecond duration, single-cycle terahertz pulses as an ultrafast electric field bias to prototypical BaTiO 3 ferroelectric thin films with the atomic-scale response probed by femtosecond x-ray-scattering techniques. We show that electric fields applied perpendicular to the ferroelectric polarization drive large-amplitude displacements of the titanium atoms along the ferroelectric polarization axis, comparable to that of the built-in displacements associated with the intrinsic polarization and incoherent acrossmore » unit cells. This effect is associated with a dynamic rotation of the ferroelectric polarization switching on and then off on picosecond time scales. These transient polarization modulations are followed by long-lived vibrational heating effects driven by resonant excitation of the ferroelectric soft mode, as reflected in changes in the c-axis tetragonality. The ultrafast structural characterization described here enables a direct comparison with first-principles-based molecular-dynamics simulations, with good agreement obtained.« less

Electron doping effect on structural and magnetic phase transitions in Sr{sub 2-x}Nd{sub x}FeMoO{sub 6} double perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Azad, A.K.; Eriksson, S.-G.; Khan, Abdullah

2006-05-15

Polycrystalline Sr{sub 2-x}Nd{sub x}FeMoO{sub 6} (x=0.0, 0.1, 0.2, 0.4) materials have been synthesized by a citrate co-precipitation method and studied by neutron powder diffraction (NPD) and magnetization measurements. Rietveld analysis of the temperature-dependent NPD data shows that the compounds (x=0.0, 0.1, 0.2) crystallize in the tetragonal symmetry in the range 10-400K and converts to cubic symmetry above 450K. The unit cell volume increases with increasing Nd{sup 3+} concentration, which is an electronic effect in order to change the valence state of the B-site cations. Antisite defects at the Fe-Mo sublattice increases with the Nd{sup 3+} doping. The Curie temperature wasmore » increased from 430K for x=0 to 443K for x=0.4. The magnetic moment of the Fe-site decreases while the Mo-site moment increases with electron doping. The antiferromagnetic arrangement causes the system to show a net ferrimagnetic moment.« less

New Rhenium-Doped SrCo1−xRexO3−δ Perovskites Performing as Cathodes in Solid Oxide Fuel Cells

PubMed Central

Troncoso, Loreto; Gardey, María Celeste; Fernández-Díaz, María Teresa; Alonso, José Antonio

2016-01-01

In the aim to stabilize novel three-dimensional perovskite oxides based upon SrCoO3−δ, we have designed and prepared SrCo1−xRexO3−δ phases (x = 0.05 and 0.10), successfully avoiding the competitive hexagonal 2H polytypes. Their performance as cathode materials in intermediate-temperature solid oxide fuel cells (IT-SOFC) has been investigated. The characterization of these oxides included X-ray (XRD) and in situ temperature-dependent neutron powder diffraction (NPD) experiments for x = 0.10. At room temperature, SrCo1−xRexO3−δ perovskites are defined in the P4/mmm space group, which corresponds to a subtle tetragonal perovskite superstructure with unit-cell parameters a = b ≈ ao, c = 2ao (ao = 3.861 and 3.868 Å, for x = 0.05 and 0.10, respectively). The crystal structure evolves above 380 °C to a simple cubic perovskite unit cell, as observed from in-situ NPD data. The electrical conductivity gave maximum values of 43.5 S·cm−1 and 51.6 S·cm−1 for x = 0.05 and x = 0.10, respectively, at 850 °C. The area specific resistance (ASR) polarization resistance determined in symmetrical cells is as low as 0.087 Ω·cm2 and 0.065 Ω·cm2 for x = 0.05 and x = 0.10, respectively, at 850 °C. In single test cells these materials generated a maximum power of around 0.6 W/cm2 at 850 °C with pure H2 as a fuel, in an electrolyte-supported configuration with La0.8Sr0.2Ga0.83Mg0.17O3−δ (LSGM) as the electrolyte. Therefore, we propose the SrCo1−xRexO3−δ (x = 0.10 and 0.05) perovskite oxides as promising candidates for cathodes in IT-SOFC. PMID:28773844

First principles study of the electronic and magnetic structures and bonding properties of UCoC2 ternary, characteristic of C-C units

NASA Astrophysics Data System (ADS)

Matar, Samir F.

2013-03-01

The electronic structure of UCoC2, a di-carbide with the C-C units is examined from ab initio with an assessment of the properties of chemical bonding. The energy-volume equation of state shows large anisotropy effects due to C-C alignment along tetragonal c-axis leading to high linear incompressibility. Relevant features of selective bonding of uranium and cobalt with carbon at two different Wyckoff sites and strong C-C interactions are remarkable. The vibrational frequencies for C⋯C stretching modes indicate closer behavior to aliphatic C-C rather than Cdbnd C double bond. A ferromagnetic ground state is proposed from the calculations.

β -B i2O3 under compression: Optical and elastic properties and electron density topology analysis

NASA Astrophysics Data System (ADS)

Pereira, A. L. J.; Gomis, O.; Sans, J. A.; Contreras-García, J.; Manjón, F. J.; Rodríguez-Hernández, P.; Muñoz, A.; Beltrán, A.

2016-06-01

We report a joint experimental and theoretical study of the optical properties of tetragonal bismuth oxide (β -B i2O3 ) at high pressure by means of optical absorption measurements combined with ab initio electronic band structure calculations. Our results are consistent with previous results that show the presence of a second-order isostructural phase transition in B i2O3 (from β to β') around 2 GPa and a phase transition above 15 GPa combined with a pressure-induced amorphization above 17-20 GPa. In order to further understand the pressure-induced phase transitions and amorphization occurring in β -B i2O3 , we theoretically studied the mechanical and dynamical stability of the tetragonal structures of β - and β'-B i2O3 at high pressure through calculations of their elastic constants, elastic stiffness coefficients, and phonon dispersion curves. The pressure dependence of the elastic stiffness coefficients and phonon dispersion curves confirms that the isostructural phase transition near 2 GPa is of ferroelastic nature. Furthermore, a topological study of the electron density shows that the ferroelastic transition is not caused by a change in number of critical points (cusp catastrophe), but by the equalization of the electron densities of both independent O atoms in the unit cell due to a local rise in symmetry. Finally, from theoretical simulations, β'-B i2O3 is found to be mechanically and dynamically stable at least up to 26.7 GPa under hydrostatic conditions; thus, the pressure-induced amorphization reported above 17-20 GPa in powder β'-B i2O3 using methanol-ethanol-water as pressure-transmitting medium could be related to the frustration of a reconstructive phase transition at room temperature and the presence of mechanical or dynamical instabilities under nonhydrostatic conditions.

Magnetostructural coupling behavior at the ferromagnetic transition in double-perovskite S r2FeMo O6

NASA Astrophysics Data System (ADS)

Yang, Dexin; Harrison, Richard J.; Schiemer, Jason A.; Lampronti, Giulio I.; Liu, Xueyin; Zhang, Fenghua; Ding, Hao; Liu, Yan'gai; Carpenter, Michael A.

2016-01-01

The ordered double-perovskite S r2FeMo O6 (SFMO) possesses remarkable room-temperature low-field colossal magnetoresistivity and transport properties which are related, at least in part, to combined structural and magnetic instabilities that are responsible for a cubic-tetragonal phase transition near 420 K. A formal strain analysis combined with measurements of elastic properties from resonant ultrasound spectroscopy reveal a system with weak biquadratic coupling between two order parameters belonging to Γ4+ and m Γ4+ of parent space group F m 3 ¯m . The observed softening of the shear modulus by ˜50% is due to the classical effects of strain/order parameter coupling at an improper ferroelastic (Γ4+) transition which is second order in character, while the ferromagnetic order parameter (m Γ4+ ) couples only with volume strain. The influence of a third order parameter, for ordering of Fe and Mo on crystallographic B sites, is to change the strength of coupling between the Γ4+ order parameter and the tetragonal shear strain due to the influence of changes in local strain heterogeneity at a unit cell scale. High anelastic loss below the transition point reveals the presence of mobile ferroelastic twin walls which become pinned by oxygen vacancies in a temperature interval near 340 K. The twin walls must be both ferroelastic and ferromagnetic, but due to the weak coupling between the magnetic and structural order parameters it should be possible to pull them apart with a weak magnetic field. These insights into the role of strain coupling and relaxational effects in a system with only weak coupling between three order parameters allow rationalization and prediction of how static and dynamic properties of the material might be tuned in thin film form by choice of strain contrast with a substrate.

Structural investigations of vanadyl doped Nb2O5·K2O·B2O3 glasses

NASA Astrophysics Data System (ADS)

Anshu; Sanghi, S.; Agarwal, A.; Lather, M.; Bhatnagar, V.; Khasa, S.

2009-07-01

Pottasium nioborate glasses of composition xNb2O5·(30-x)K2O·69B2O3 containing 1 mol % of V2O5 were prepared by melt quench technique (1473K, 1h). The electron paramagnetic resonance spectra of VO2+ in these glasses have been recorded in X- band (v approx 9.14 GHz) at room temperature (RT). The spin Hamiltonian parameters, dipolar hyperfine coupling parameters, P and Fermi contact interaction parameter, K have been calculated. It is found that V4+ ions in these glasses exist as VO2+ in octahedral coordination with a tetragonal distortion. The tetragonality of V4+O6 complex decreases with increasing Nb2O5: K2O ratio and also there is an expansion of 3dXY orbit of unpaired electron in the vanadium ion. The study of IR transmission spectra over a range 400- 4000 cm-1 depicts the presence of both BO3 and BO4 structural units and Nb5+ ions are incorporated into the glass network as NbO6 octahedra, substituting BO4 groups.

Effects of poling over the orthorhombic-tetragonal phase transition temperature in compositionally homogeneous (K,Na)NbO3-based ceramics

NASA Astrophysics Data System (ADS)

Morozov, M. I.; Kungl, H.; Hoffmann, M. J.

2011-03-01

Li-, Ta-, and Mn-modified (K,Na)NbO3 ceramics with various compositional homogeneity have been prepared by conventional and precursor methods. The homogeneous ceramic has demonstrated a sharper peak in temperature dependent piezoelectric response. The dielectric and piezoelectric properties of the homogeneous ceramics have been characterized at the experimental subcoercive electric fields near the temperature of the orthorhombic-tetragonal phase transition with respect to poling in both phases. Poling in the tetragonal phase is shown to enhance the low-signal dielectric and piezoelectric properties in the orthorhombic phase.

Direct synthesis of ultrafine tetragonal BaTiO3 nanoparticles at room temperature

PubMed Central

2011-01-01

A large quantity of ultrafine tetragonal barium titanate (BaTiO3) nanoparticles is directly synthesized at room temperature. The crystalline form and grain size are checked by both X-ray diffraction and transmission electron microscopy. The results revealed that the perovskite nanoparticles as fine as 7 nm have been synthesized. The phase transition of the as-prepared nanoparticles is investigated by the temperature-dependent Raman spectrum and shows the similar tendency to that of bulk BaTiO3 materials. It is confirmed that the nanoparticles have tetragonal phase at room temperature. PMID:21781339

Evolution of structure and superconductivity in Ba(Ni 1 -xCox)2As2

NASA Astrophysics Data System (ADS)

Eckberg, Chris; Wang, Limin; Hodovanets, Halyna; Kim, Hyunsoo; Campbell, Daniel J.; Zavalij, Peter; Piccoli, Philip; Paglione, Johnpierre

2018-06-01

The effects of Co substitution on Ba (Ni1-xCox) 2As2 (0 ≤x ≤0.251 ) single crystals grown out of Pb flux are investigated via transport, magnetic, and thermodynamic measurements. BaNi2As2 exhibits a first-order tetragonal to triclinic structural phase transition at Ts=137 K upon cooling, and enters a superconducting phase below Tc=0.7 K. The structural phase transition is sensitive to cobalt content and is suppressed completely by x ≥0.133 . The superconducting critical temperature, Tc, increases continuously with x , reaching a maximum of Tc=2.3 K at x =0.083 and then decreases monotonically until superconductivity is no longer observable well into the tetragonal phase. In contrast to similar BaNi2As2 substitutional studies, which show an abrupt change in Tc at the triclinic-tetragonal boundary that extends far into the tetragonal phase, Ba (Ni1-xCox) 2As2 exhibits a domelike phase diagram centered around the zero-temperature tetragonal-triclinic boundary. Together with an anomalously large heat capacity jump Δ Ce/γ T ˜2.2 near optimal doping, the smooth evolution of Tc in the Ba (Ni1-xCox) 2As2 system suggests a mechanism for pairing enhancement other than phonon softening.

Tetragonal zirconia quantum dots in silica matrix prepared by a modified sol-gel protocol

NASA Astrophysics Data System (ADS)

Verma, Surbhi; Rani, Saruchi; Kumar, Sushil

2018-05-01

Tetragonal zirconia quantum dots (t-ZrO2 QDs) in silica matrix with different compositions ( x)ZrO2-(100 - x)SiO2 were fabricated by a modified sol-gel protocol. Acetylacetone was added as a chelating agent to zirconium propoxide to avoid precipitation. The powders as well as thin films were given thermal treatment at 650, 875 and 1100 °C for 4 h. The silica matrix remained amorphous after thermal treatment and acted as an inert support for zirconia quantum dots. The tetragonal zirconia embedded in silica matrix transformed into monoclinic form due to thermal treatment ≥ 1100 °C. The stability of tetragonal phase of zirconia is found to enhance with increase in silica content. A homogenous dispersion of t-ZrO2 QDs in silica matrix was indicated by the mapping of Zr, Si and O elements obtained from scanning electron microscope with energy dispersive X-ray analyser. The transmission electron images confirmed the formation of tetragonal zirconia quantum dots embedded in silica. The optical band gap of zirconia QDs (3.65-5.58 eV) was found to increase with increase in zirconia content in silica. The red shift of PL emission has been exhibited with increase in zirconia content in silica.

Raman spectroscopy analysis of air grown oxide scale developed on pure zirconium substrate

NASA Astrophysics Data System (ADS)

Kurpaska, L.; Favergeon, J.; Lahoche, L.; El-Marssi, M.; Grosseau Poussard, J.-L.; Moulin, G.; Roelandt, J.-M.

2015-11-01

Using Raman spectroscopy technique, external and internal parts of zirconia oxide films developed at 500 °C and 600 °C on pure zirconium substrate under air at normal atmospheric pressure have been examined. Comparison of Raman peak positions of tetragonal and monoclinic zirconia phases, recorded during the oxide growth at elevated temperature, and after cooling at room temperature have been presented. Subsequently, Raman peak positions (or shifts) were interpreted in relation with the stress evolution in the growing zirconia scale, especially closed to the metal/oxide interface, where the influence of compressive stress in the oxide is the biggest. Reported results, for the first time show the presence of a continuous layer of tetragonal zirconia phase developed in the proximity of pure zirconium substrate. Based on the Raman peak positions we prove that this tetragonal layer is stabilized by the high compressive stress and sub-stoichiometry level. Presence of the tetragonal phase located in the outer part of the scale have been confirmed, yet its Raman characteristics suggest a stress-free tetragonal phase, therefore different type of stabilization mechanism. Presented study suggest that its stabilization could be related to the lattice defects introduced by highstoichiometry of zirconia or presence of heterovalent cations.

Fe moments in the pressure-induced collapsed tetragonal phase of (Ca0.67Sr0.33) Fe2As2

NASA Astrophysics Data System (ADS)

Jeffries, Jason; Butch, Nicha; Bradley, Joseph; Xiao, Yuming; Chow, Paul; Saha, Shanta; Kirshenbaum, Kevin; Paglione, Johnpierre

2013-06-01

The tetragonal AEFe2As2 (AE =alkaline earth element) family of iron-based superconductors exhibits magnetic order at ambient pressure and low temperature. Under pressure, the magnetic order is suppressed, and an isostructural volume collapse is induced due to increased As-As bonding across the mirror plane of the structure. This collapsed tetragonal phase has been shown to support superconductivity under some conditions, and theoretical calculations suggest an unconventional origin. Theoretical calculations also reveal that enhanced As-As bonding and the magnitude of the Fe moments are correlated, suggesting that the Fe moments can be quenched in the collapsed tetragonal phase. Whether the Fe moments persist in the collapsed tetragonal phase has implications for the pairing mechanism of the observed, pressure-induced superconductivity in these compounds. We will present pressure- dependent x-ray emission spectroscopy (XES) measurements that probe the Fe moments through the volume collapse transition of (Ca0.67Sr0.33) Fe2As2. These measurements will be compared with previously reported phase diagrams that include superconductivity. Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the US Department of Energy (DOE), National Nuclear Security Administration under Contract No. DE-AC52-07NA27344.

Fabrication of CuInS2-sensitized solar cells via an improved SILAR process and its interface electron recombination.

PubMed

Xu, Xueqing; Wan, Qingcui; Luan, Chunyan; Mei, Fengjiao; Zhao, Qian; An, Ping; Liang, Zhurong; Xu, Gang; Zapien, Juan Antonio

2013-11-13

Tetragonal CuInS2 (CIS) has been successfully deposited onto mesoporous TiO2 films by in-sequence growth of InxS and CuyS via a successive ionic layer absorption and reaction (SILAR) process and postdeposition annealing in sulfur ambiance. X-ray diffraction and Raman measurements showed that the obtained tetragonal CIS consisted of a chalcopyrite phase and Cu-Au ordering, which related with the antisite defect states. For a fixed Cu-S deposition cycle, an interface layer of β-In2S3 formed at the TiO2/CIS interface with suitable excess deposition of In-S. In the meantime, the content of the Cu-Au ordering phase decreased to a reasonable level. These facts resulted in the retardance of electron recombination in the cells, which is proposed to be dominated by electron transfer from the conduction band of TiO2 to the unoccupied defect states in CIS via exponentially distributed surface states. As a result, a relatively high efficiency of ~0.92% (V(oc) = 0.35 V, J(sc) = 8.49 mA cm(-2), and FF = 0.31) has been obtained. Last, but not least, with an overloading of the sensitizers, a decrease in the interface area between the sensitized TiO2 and electrolytes resulted in deceleration of hole extraction from CIS to the electrolytes, leading to a decrease in the fill factor of the solar cells. It is indicated that the unoccupied states in CIS with energy levels below EF0 of the TiO2 films play an important role in the interface electron recombination at low potentials and has a great influence on the fill factor of the solar cells.

Purification, Crystallization and Preliminary X-ray Characterization of Prunin-1, a Major Component of the Almond (Prunus dulcis) Allergen Amandin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Albillos, Silvia M.; Jin, Tengchuan; Howard, Andrew

2008-08-04

The 11S globulins from plant seeds account for a number of major food allergens. Because of the interest in the structural basis underlying the allergenicity of food allergens, we sought to crystallize the main 11S seed storage protein from almond (Prunus dulcis). Prunin-1 (Pru1) was purified from defatted almond flour by water extraction, cryoprecipitation, followed by sequential anion exchange, hydrophobic interaction, and size exclusion chromatography. Single crystals of Pru1 were obtained in a screening with a crystal screen kit, using the hanging-drop vapor diffusion method. Diffraction quality crystals were grown after optimization. The Pru1 crystals diffracted to at least 3.0more » {angstrom} and belong to the tetragonal space group P4{sub 1}22, with unit cell parameters of a = b = 150.912 {angstrom}, c = 165.248 {angstrom}. Self-rotation functions and molecular replacement calculations showed that there are three molecules in the asymmetry unit with water content of 51.41%. The three Pru1 protomers are related by a noncrystallographic 3-fold axis and they form a doughnut-shaped trimer. Two prunin trimers form a homohexamer. Elucidation of prunin structure will allow further characterization of the allergenic features of the 11S protein allergens at the molecular level.« less

Crystallization and preliminary X-ray crystallographic analysis of the small subunit of the heterodimeric laccase POXA3b from Pleurotus ostreatus

PubMed Central

Ferraroni, Marta; Scozzafava, Andrea; Ullah, Sana; Tron, Thierry; Piscitelli, Alessandra; Sannia, Giovanni

2014-01-01

Laccases are multicopper oxidases of great biotechnological potential. While laccases are generally monomeric glycoproteins, the white-rot fungus Pleurotus ostreatus produces two closely related heterodimeric isoenzymes composed of a large subunit, homologous to the other fungal laccases, and a small subunit. The sequence of the small subunit does not show significant homology to any other protein or domain of known function and consequently its function is unknown. The highest similarity to proteins of known structure is to a putative enoyl-CoA hydratase/isomerase from Acinetobacter baumannii, which shows an identity of 27.8%. Diffraction-quality crystals of the small subunit of the heterodimeric laccase POXA3b (sPOXA3b) from P. ostreatus were obtained using the sitting-drop vapour-diffusion method at 294 K from a solution consisting of 1.8 M sodium formate, 0.1 M Tris–HCl pH 8.5. The crystals belonged to the tetragonal space group P41212 or P43212, with unit-cell parameters a = 126.6, c = 53.9 Å. The asymmetric unit contains two molecules related by a noncrystallographic twofold axis. A complete data set extending to a maximum resolution of 2.5 Å was collected at 100 K using a wavelength of 1.140 Å. PMID:24419623

Overexpression, purification, crystallization and preliminary structural studies of p-coumaric acid decarboxylase from Lactobacillus plantarum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodríguez, Héctor; Rivas, Blanca de las; Muñoz, Rosario

2007-04-01

The enzyme p-coumaric acid decarboxylase (PDC) from L. plantarum has been recombinantly expressed, purified and crystallized. The structure has been solved at 2.04 Å resolution by the molecular-replacement method. The substrate-inducible p-coumaric acid decarboxylase (PDC) from Lactobacillus plantarum has been overexpressed in Escherichia coli, purified and confirmed to possess decarboxylase activity. The recombinant His{sub 6}-tagged enzyme was crystallized using the hanging-drop vapour-diffusion method from a solution containing 20%(w/v) PEG 4000, 12%(w/v) 2-propanol, 0.2 M sodium acetate, 0.1 M Tris–HCl pH 8.0 with 0.1 M barium chloride as an additive. Diffraction data were collected in-house to 2.04 Å resolution. Crystals belongedmore » to the tetragonal space group P4{sub 3}, with unit-cell parameters a = b = 43.15, c = 231.86 Å. The estimated Matthews coefficient was 2.36 Å{sup 3} Da{sup −1}, corresponding to 48% solvent content, which is consistent with the presence of two protein molecules in the asymmetric unit. The structure of PDC has been determined by the molecular-replacement method. Currently, the structure of PDC complexed with substrate analogues is in progress, with the aim of elucidating the structural basis of the catalytic mechanism.« less

Influences of PZT addition on phase formation and magnetic properties of perovskite Pb(Fe0.5Nb0.5)O3-based ceramics

NASA Astrophysics Data System (ADS)

Amonpattaratkit, P.; Jantaratana, P.; Ananta, S.

2015-09-01

In this work, the investigation of phase formation, crystal structure, microstructure, microchemical composition and magnetic properties of perovskite (1-x)PFN-xPZT (x=0.1-0.5) multiferroic ceramics derived from a combination of perovskite stabilizer PZT and a wolframite-type FeNbO4 B-site precursor was carried out by using a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) analyzer and vibrating sample magnetometer (VSM) techniques. The addition of PZT phase and its concentration have been found to have pronounced effects on the perovskite phase formation, densification, grain growth and magnetic properties of the sintered ceramics. XRD spectra from these ceramics reveal transformation of the (pseudo) cubic into the tetragonal perovskite structure. When increasing PZT content, the degree of perovskite phase formation and the tetragonality value of the ceramics increase gradually accompanied with the variation of cell volume, the M-H hysteresis loops, however, become narrower accompanied by the decrease of maximum magnetization (Mmax), remanent polarization (Mr), and coercive field (HC).

Phonon Mode Transformation Across the Orthohombic–Tetragonal Phase Transition in a Lead Iodide Perovskite CH 3 NH 3 PbI 3 : A Terahertz Time-Domain Spectroscopy Approach

DOE PAGES

La-o-vorakiat, Chan; Xia, Huanxin; Kadro, Jeannette; ...

2015-12-03

Here, we study the temperature-dependent phonon modes of the organometallic lead iodide perovskite CH 3NH 3PbI 3 thin film across the terahertz (0.5–3 THz) and temperature (20–300 K) ranges. These modes are related to the vibration of the Pb–I bonds. We found that two phonon modes in the tetragonal phase at room temperature split into four modes in the low-temperature orthorhombic phase. By use of the Lorentz model fitting, we also analyze the critical behavior of this phase transition. The carrier mobility values calculated from the low-temperature phonon mode frequencies, via two theoretical approaches, are found to agree reasonably withmore » the experimental value (~2000 cm 2 V –1 s –1) from a previous time-resolved THz spectroscopy work. Thus, we have established a possible link between terahertz phonon modes and the transport properties of perovskite-based solar cells.« less

Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

NASA Astrophysics Data System (ADS)

Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

2008-09-01

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate ( I), bromo-(2-formylpyridinethiosemicarbazono)copper ( II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate ( III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I III at a concentration of 10-5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

Variation of oxygen content in selected potassium fluorido-oxido-tantalate phases

NASA Astrophysics Data System (ADS)

Boča, Miroslav; Moncoĺ, Ján; Netriová, Zuzana; Velič, Dušan; Jerigová, Monika; Nunney, Tim S.; Baily, Christopher J.; Kubíková, Blanka; Šimko, František; Janderka, Pavel

2011-12-01

The compound K 3[TaO 4]•K 3[TaF 4O 2] crystallises in a tetragonal system (space group I-4) with cell parameters a = 6.2220(3) Å and c = 8.7625(34) Å, respectively. The crystal structure consists of two anions, [TaO 4] 3- and [TaF 4O 2] 3- and cations K +. The tantalum atoms lie in special positions and serve as centres of both anions, which are substitution disorders. XPS measurements confirmed the existence of different binding energies corresponding to the different bonds of Ta sbnd O and Ta sbnd F. Oxygen is bound more strongly in [TaF 4O 2] 3-. By combination of single crystal analysis, XRD, SIMS and XPS it was suggested that previously reported cubic phase K 3TaOF 6 is in fact K 3TaO 2F 4 and previously reported tetragonal phase K 3TaO 2F 4 is in fact K 3[TaO 4]•K 3[TaF 4O 2].

Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells.

PubMed

Hattori, Shigeki; Wada, Yuji; Yanagida, Shozo; Fukuzumi, Shunichi

2005-07-06

The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N'](maleonitriledithiolato-S,S')copper ([Cu(SP)(mmt)])(0/)(-), bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)(2)](2+/+)), and bis(1,10-phenanthroline)copper ([Cu(phen)(2)](2+/+)) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)(2)](2+/+) < [Cu(SP)(mmt)](0/)(-) < [Cu(dmp)(2)](2+/+), in agreement with the order of the smaller structural change between the copper(II) and copper(I) complexes due to the distorted tetragonal geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I(3)(-)/I(-) couple. The light energy conversion efficiency (eta) values under illumination of simulated solar light irradiation (100 mW/cm(2)) of DSSCs using [Cu(phen)(2)](2+/+), [Cu(dmp)(2)](2+/+), and [Cu(SP)(mmt)](0/)(-) were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum eta value (2.2%) was obtained for a DSSC using the [Cu(dmp)(2)](2+/+) redox couple under the light irradiation of 20 mW/cm(2) intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I(3)(-)/I(-) couple.

Effect of Rubidium Incorporation on the Structural, Electrical, and Photovoltaic Properties of Methylammonium Lead Iodide-Based Perovskite Solar Cells.

PubMed

Park, Ik Jae; Seo, Seongrok; Park, Min Ah; Lee, Sangwook; Kim, Dong Hoe; Zhu, Kai; Shin, Hyunjung; Kim, Jin Young

2017-12-06

We report the electrical properties of rubidium-incorporated methylammonium lead iodide ((Rb x MA 1-x )PbI 3 ) films and the photovoltaic performance of (Rb x MA 1-x )PbI 3 film-based p-i-n-type perovskite solar cells (PSCs). The incorporation of a small amount of Rb + (x = 0.05) increases both the open circuit voltage (V oc ) and the short circuit photocurrent density (J sc ) of the PSCs, leading to an improved power conversion efficiency (PCE). However, a high fraction of Rb + incorporation (x = 0.1 and 0.2) decreases the J sc and thus the PCE, which is attributed to the phase segregation of the single tetragonal perovskite phase to a MA-rich tetragonal perovskite phase and a RbPbI 3 orthorhombic phase at high Rb fractions. Conductive atomic force microscopic and admittance spectroscopic analyses reveal that the single-phase (Rb 0.05 MA 0.95 )PbI 3 film has a high electrical conductivity because of a reduced deep-level trap density. We also found that Rb substitution enhances the diode characteristics of the PSC, as evidenced by the reduced reverse saturation current (J 0 ). The optimized (Rb x MA 1-x )PbI 3 PSCs exhibited a PCE of 18.8% with negligible hysteresis in the photocurrent-voltage curve. The results from this work enhance the understanding of the effect of Rb incorporation into organic-inorganic hybrid halide perovskites and enable the exploration of Rb-incorporated mixed perovskites for various applications, such as solar cells, photodetectors, and light-emitting diodes.

Nb5+-Doped SrCoO3-δ Perovskites as Potential Cathodes for Solid-Oxide Fuel Cells.

PubMed

Cascos, Vanessa; Alonso, José Antonio; Fernández-Díaz, María Teresa

2016-07-15

SrCoO 3- δ outperforms as cathode material in solid-oxide fuel cells (SOFC) when the three-dimensional (3C-type) perovskite structure is stabilized by the inclusion of highly-charged transition-metal ions at the octahedral positions. In a previous work we studied the Nb incorporation at the Co positions in the SrCo 1- x Nb x O 3- δ system, in which the stabilization of a tetragonal P4 / mmm perovskite superstructure was described for the x = 0.05 composition. In the present study we extend this investigation to the x = 0.10-0.15 range, also observing the formation of the tetragonal P4 / mmm structure instead of the unwanted hexagonal phase corresponding to the 2H polytype. We also investigated the effect of Nb 5+ doping on the thermal, electrical, and electrochemical properties of SrCo 1- x Nb x O 3- δ ( x = 0.1 and 0.15) perovskite oxides performing as cathodes in SOFC. In comparison with the undoped hexagonal SrCoO 3- δ phase, the resulting compounds present high thermal stability and an increase of the electrical conductivity. The single-cell tests for these compositions ( x = 0.10 and 0.15) with La 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3- δ (LSGM) as electrolyte and SrMo 0.8 Fe 0.2 CoO 3- δ as anode gave maximum power densities of 693 and 550 mW∙cm -2 at 850 °C respectively, using pure H₂ as fuel and air as oxidant.

Room Temperature Monoclinic Phase in BaTiO3 Single Crystals

NASA Astrophysics Data System (ADS)

Denev, Sava; Kumar, Amit; Barnes, Andrew; Vlahos, Eftihia; Shepard, Gabriella; Gopalan, Venkatraman

2010-03-01

BaTiO3 is a well studied ferroelectric material for the last half century. It is well known to show phase transitions to tetragonal, orthorhombic and rhombohedral phases upon cooling. Yet, some old and some recent studies have argued that all these phases co-exist with a second phase with monoclinic distortion. Using optical second harmonic generation (SHG) at room temperature we directly present evidence for such monoclininc phase co-existing with tetragonal phase at room temperature. We observe domains with the expected tetragonal symmetry exhibiting 90^o and 180^o domain walls. However, at points of higher stress at the tips of the interpenetrating tetragonal domains we observe a well pronounced metastable ``staircase pattern'' with a micron-scale fine structure. Polarization studies show that this phase can be explained only by monoclinic symmetry. This phase is very sensitive to external perturbations such as temperature and fields, hence stabilizing this phase at room temperature could lead to large properties' tunability.

Temperature-dependent electron paramagnetic resonance detect oxygen vacancy defects and Cr valence of tetragonal Ba(Ti1-xCrx)O3 ceramics

NASA Astrophysics Data System (ADS)

Han, Dan-Dan; Lu, Da-Yong; Meng, Fan-Ling; Yu, Xin-Yu

2018-03-01

Temperature-dependent electron paramagnetic resonance (EPR) study was employed to detect oxygen vacancy defects in the tetragonal Ba(Ti1-xCrx)O3 (x = 5%) ceramic for the first time. In the rhombohedral phase below -150 °C, an EPR signal at g = 1.955 appeared in the insulating Ba(Ti1-xCrx)O3 (x = 5%) ceramic with an electrical resistivity of 108 Ω cm and was assigned to ionized oxygen vacancy defects. Ba(Ti1-xCrx)O3 ceramics exhibited a tetragonal structure except Ba(Ti1-xCrx)O3 (x = 10%) with a tetragonal-hexagonal mixed phase and a first-order phase transition dielectric behavior (ε‧m > 11,000). Mixed valence Cr ions could coexist in ceramics, form CrTi‧-VOrad rad or CrTirad-TiTi‧ defect complexes and make no contribution to a dielectric peak shift towards low temperature.

[Interface compatibility between tooth-like yttria-stabilized tetragonal zirconia polycrystal by adding rare-earth oxide and Vita VM9 veneering porcelain].

PubMed

Gao, Yan; Zhang, Fu-qiang; He, Fan

2011-10-01

To evaluate the interface compatibility between tooth-like yttria-stabilized tetragonal zirconia polycrystal(Y-TZP) by adding rare-earth oxide and Vita VM9 veneering porcelain. Six kinds(S1,S2,S3,S4,S5,S6) of tooth-like yttria stabilized tetragonal zirconia polycrystal were made by introducing internal colorating technology to detect the thermal shock resistance and interface bonding strength with Vita VM9 Bsaedentin. Statistical analysis was performed using SAS6.12 software package. There was no gap between the layers via hot shocking test.The shear bonding strength between Y-TZP and VitaVM9 was higher and the value was (36.03±3.82) to (37.98±4.89) MPa. By adding rare-earth oxide to yttria-stabilized tetragonal zirconia polycrystal ,better compatibility between the layer (TZP and Vita VM9) can be formed which is of better interface integrate and available for clinical applications.

Thermodynamic analysis of the formation of tetragonal bainite in steels

NASA Astrophysics Data System (ADS)

Mirzayev, D. A.; Mirzoev, A. A.; Buldashev, I. V.; Okishev, K. Yu.

2017-06-01

In the articles of Bkhadeshia, a new class of high-strength steels based on the structure of carbidefree bainite with an enhanced carbon content has been developed. According to Bkhadeshia, the main factor responsible for the high solubility of carbon is the occurrence of a tetragonality of the bainite lattice. To check this effect, in this article, the theory of tetragonality of martensite of iron alloys developed by Zener and Khachaturyan was applied to bainite under the assumption that the precipitation of carbides is prohibited. Equations for the chemical potentials of carbon and iron in austenite and in tetragonal ferrite have been derived. The equilibrium of these phases has been considered, and the calculations of the boundary concentrations of carbon and iron at different temperatures (300-1000 K) and at different parameters of the deformation interaction λ0 have been performed. The rigorous calculations confirmed Bkhadeshia's hypothesis that the suppression of the carbide formation during the formation of bainite leads to an increase in the carbon solubility in the bcc phase.

Y-TZP zirconia regeneration firing: Microstructural and crystallographic changes after grinding.

PubMed

Ryan, Daniel Patrick Obelenis; Fais, Laiza Maria Grassi; Antonio, Selma Gutierrez; Hatanaka, Gabriel Rodrigues; Candido, Lucas Miguel; Pinelli, Ligia Antunes Pereira

2017-07-26

This study evaluated microstructural and crystallographic phase changes after grinding (G) and regeneration firing/anneling (R) of Y-TZP ceramics. Thirty five bars (Lava TM and Ice Zirkon) were divided: Y-TZP pre-sintered, control (C), regeneration firing (R), dry grinding (DG), dry grinding+regeneration firing (DGR), wet grinding (WG) and wet grinding+regeneration firing (WGR). Grinding was conducted using a diamond bur and annealing at 1,000°C. The microstructure was analyzed by SEM and the crystalline phases by X-ray diffraction (XRD). XRD showed that pre-sintered specimens contained tetragonal and monoclinic phases, while groups C and R showed tetragonal, cubic and monoclinic phases. After grinding, the cubic phase was eliminated in all groups. Annealing (DGR and WGR) resulted in only tetragonal phase. SEM showed semi-circular cracks after grinding and homogenization of particles after annealing. After grinding, surfaces show tetragonal and monoclinic phases and R can be assumed to be necessary prior to porcelain layering when grinding is performed.

Pressure induced phase transitions in ceramic compounds containing tetragonal zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sparks, R.G.; Pfeiffer, G.; Paesler, M.A.

Stabilized tetragonal zirconia compounds exhibit a transformation toughening process in which stress applied to the material induces a crystallographic phase transition. The phase transition is accompanied by a volume expansion in the stressed region thereby dissipating stress and increasing the fracture strength of the material. The hydrostatic component of the stress required to induce the phase transition can be investigated by the use of a high pressure technique in combination with Micro-Raman spectroscopy. The intensity of Raman lines characteristic for the crystallographic phases can be used to calculate the amount of material that has undergone the transition as a functionmore » of pressure. It was found that pressures on the order of 2-5 kBar were sufficient to produce an almost complete transition from the original tetragonal to the less dense monoclinic phase; while a further increase in pressure caused a gradual reversal of the transition back to the original tetragonal structure.« less

Crystallization and identification of the glycosylated moieties of two isoforms of the main allergen Hev b 2 and preliminary X-ray analysis of two polymorphs of isoform II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fuentes-Silva, D.; Mendoza-Hernández, G.; Stojanoff, V.

2007-09-01

Crystallization of important glycoenzymes involved in IgE-mediated latex allergy. Latex from Hevea brasiliensis contains several allergenic proteins that are involved in type I allergy. One of them is Hev b 2, which is a β-1,3-glucanase enzyme that exists in different isoforms with variable glycosylation content. Two glucanase isoforms were isolated from trees of the GV-42 clone by gel filtration, affinity and ion-exchange chromatography. Isoform I had a carbohydrate content of about 20%, with N-linked N-acetyl-glucosamine, N-acetyl-galactosamine, fucose and galactose residues as the main sugars, while isoform II showed 6% carbohydrate content constisting of N-acetyl-glucosamine, fucose, mannose and xylose. Both isoformsmore » were crystallized by the hanging-drop vapour-diffusion method. Isoform I crystals were grown using 0.2 M trisodium citrate dihydrate, 0.1 M Na HEPES pH 7.5 and 20%(v/v) 2-propanol, but these crystals were not appropriate for data collection. Isoform II crystals were obtained under two conditions and X-ray diffraction data were collected from both. In the first condition (0.2 M trisodium citrate, 0.1 M sodium cacodylate pH 6.5, 30% 2-propanol), crystals belonging to the tetragonal space group P4{sub 1} with unit-cell parameters a = b = 150.17, c = 77.41 Å were obtained. In the second condition [0.2 M ammonium acetate, 0.1 M trisodium citrate dihydrate pH 5.6, 30%(w/v) polyethylene glycol 4000] the isoform II crystals belonged to the monoclinic space group P2{sub 1}, with unit-cell parameters a = 85.08, b = 89.67, c = 101.80 Å, β = 113.6°. Preliminary analysis suggests that there are four molecules of isoform II in both asymmetric units.« less

M{sub 2}X intermetallics: Nonmetal insertion in a h.c.-like metallic distribution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pivan, J.Y.; Guerin, R.

A simple structural model is proposed on the basis of an ideal hexagonal close-packing (AB){sup {infinity}} of the metal atoms M. The metalloid atoms X, located in an ordered manner in the metallic planes with the stacking sequence ..(A){sup {infinity}}.. or ..(B){sup {infinity}}.., generate two types of elementary units called units U{sub I} and U{sub II}. These units are hexagonal prisms with the fundamental vectors a{sub 0}, b{sub 0}, c{sub 0} and the elementary volume V{sub 0}. When the exclusive occurrence of U{sub I} (or U{sub II}) only yields 6-prismatic and triangular sites of metalloid atoms X, additional tetrahedral andmore » pyramidal sites of X atoms are present when units U{sub I} and U{sub II} exist simultaneously. The structures of compounds with the general formula M{sub 2}X (M = 3d, 4d, 5d and (or) 4f, 5f elements, X = B, P, As, Sb, Si, Ge, {hor_ellipsis}) are described in terms of intergrowth mechanisms. Binary, ternary, or even quaternary structures of compounds, with M/X ratios equal or close to two, appear as superstructures of the elementary units. Insofar as no ordering is considered along the stacking direction, the vectorial combinations of the fundamental vectors in the form A = h.a{sub 0}+s.b{sub 0}, B = k.a{sub 0}+t.b{sub 0}, C = c{sub 0} result in supercells with the volume V = (h.t {minus} k.s).V{sub 0}. The attainable symmetry (hexagonal, tetragonal, orthorhombic, monoclinic, {hor_ellipsis}) strongly depends on the particular values of the integers h, s, k, t. The criteria of occurrence of various series of compounds are presented together with their crystallographic features and structural relationships are emphasized. Moreover, the model demonstrates that numerous compounds with the predicted unit cell parameters should be obtained in each crystal system.« less

Pressure-induced phase transitions and correlation between structure and superconductivity in iron-based superconductor Ce(O(0.84)F(0.16))FeAs.

PubMed

Zhao, Jinggeng; Liu, Haozhe; Ehm, Lars; Dong, Dawei; Chen, Zhiqiang; Liu, Qingqing; Hu, Wanzheng; Wang, Nanlin; Jin, Changqing

2013-07-15

High-pressure angle-dispersive X-ray diffraction experiments on iron-based superconductor Ce(O(0.84)F(0.16))FeAs were performed up to 54.9 GPa at room temperature. A tetragonal to tetragonal isostructural phase transition starts at about 13.9 GPa, and a new high-pressure phase has been found above 33.8 GPa. At pressures above 19.9 GPa, Ce(O(0.84)F(0.16))FeAs completely transforms to a high-pressure tetragonal phase, which remains in the same tetragonal structure with a larger a-axis and smaller c-axis than those of the low-pressure tetragonal phase. The structure analysis shows a discontinuity in the pressure dependences of the Fe-As and Ce-(O, F) bond distances, as well as the As-Fe-As and Ce-(O, F)-Ce bond angles in the transition region, which correlates with the change in T(c) of this compound upon compression. The isostructural phase transition in Ce(O(0.84)F(0.16))FeAs leads to a drastic drop in the superconducting transition temperature T(c) and restricts the superconductivity at low temperature. For the 1111-type iron-based superconductors, the structure evolution and following superconductivity changes under compression are related to the radius of lanthanide cations in the charge reservoir layer.

Enhanced piezoelectricity in A B O3 ferroelectrics via intrinsic stress-driven flattening of the free-energy profile

NASA Astrophysics Data System (ADS)

Feng, Yu; Li, Wei-Li; Yu, Yang; Jia, He-Nan; Qiao, Yu-Long; Fei, Wei-Dong

2017-11-01

An approach to greatly enhance the piezoelectric properties (˜4 00 pC/N) of the tetragonal BaTi O3 polycrystal using a small number of A -site acceptor-donor substitutions [D. Xu et al., Acta Mater. 79, 84 (2014), 10.1016/j.actamat.2014.07.023] has been proposed. In this study, Pb (ZrTi ) O3 (PZT) based polycrystals with various crystal symmetries (tetragonal, rhombohedral, and so on) were chosen to investigate the piezoelectricity enhancement mechanism. X-ray diffraction results show that doping generates an intrinsic uniaxial compressive stress along the [001] pc direction in the A B O3 lattices. Piezoelectric maps in the parameter space of temperature and Ti concentration in the PZT and doped system show a more significant enhancement effect of L i+-A l3 + codoping in tetragonal PZT than in the rhombohedral phase. Phenomenological thermodynamic analysis indicates that the compressive stress results in more serious flattening of the free-energy profile in tetragonal PZT, compared with that in the rhombohedral phase. The chemical stress obtained by this acceptor-donor codoping can be utilized to optimize the piezoelectric performance on the tetragonal-phase site of the morphotropic phase boundary in the PZT system. The present study provides a promising route to the large piezoelectric effect induced by chemical-stress-driven flattening of the free-energy profile.

Structural crossover from nonmodulated to long-period modulated tetragonal phase and anomalous change in ferroelectric properties in the lead-free piezoelectric N a1 /2B i1 /2Ti O3-BaTi O3

NASA Astrophysics Data System (ADS)

Rao, Badari Narayana; Khatua, Dipak Kumar; Garg, Rohini; Senyshyn, Anatoliy; Ranjan, Rajeev

2015-06-01

The highly complex structure-property interrelationship in the lead-free piezoelectric (x )N a1 /2B i1 /2Ti O3- (1 -x ) BaTi O3 is a subject of considerable contemporary debate. Using comprehensive x-ray, neutron diffraction, dielectric, and ferroelectric studies, we have shown the existence of a new criticality in this system at x =0.80 , i.e., well within the conventional tetragonal phase field. This criticality manifests as a nonmonotonic variation of the tetragonality and coercivity and is shown to be associated with a crossover from a nonmodulated tetragonal phase (for x <0.8 ) to a long-period modulated tetragonal phase (for x >0.80 ). It is shown that the stabilization of long-period modulation introduces a characteristic depolarization temperature in the system. While differing qualitatively from the two-phase model often suggested for the critical compositions of this system, our results support the view with regard to the tendency in perovskites to stabilize long-period modulated structures as a result of complex interplay of antiferrodistortive modes [Bellaiche and Iniguez, Phys. Rev. B 88, 014104 (2013), 10.1103/PhysRevB.88.014104; Prosandeev, Wang, Ren, Iniguez, ands Bellaiche, Adv. Funct. Mater. 23, 234 (2013), 10.1002/adfm.201201467].

Microstructure and mechanical properties of bulk and plasma-sprayed y2O3-partially stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.

1980-01-01

Bulk 8.0 weight percent yttria partially stabilied zirconia (PSZ) was studied by light microscopy, transmission electron microscopy, X-ray analysis, microhardness testing, and fracture toughness testing. The as received PSZ contained spheroidal and grain boundary precipitates up to 4 micrometers in size. Spheroids up to 1.26 micrometers were metastable tetragonal; large spheroids were monoclinic. Grinding the PSZ into powder did not cause a significant amount of tetragonal to transform to monoclinic. This indicates that transformation toughness is not a significant mechanism in PSZ. Aging the PSZ at 1500 C caused the fine tetragonal precipitates to grow from 0.06 to 0.12 micrometers, in 250 minutes. A peak hardness of 1400 kg/sq mm was attained after 50 minutes. Solution annealing and quenching the as received PSZ eliminated the large precipitates, but fine tetragonal precipitates reformed on quenching. Aging at 1500 C caused the fine 0.02 micrometers tetragonal precipitates to grow into plates about 0.10 by 0.50 micrometers. A peak hardness of 1517 kg/sq mm was obtained after 250 minutes. On further aging, monoclinic percipitates formed along grain boundaries. The fracture toughness of the aged and unaged solution annealed and quenched PSZ was found to be between 2 and 3 MN /square root of m cubed. This range of fracture toughness is consistent with PSZ's that do not undergo transformation toughening.

Local structures of the tetragonal Gd3 -VM and Gd3 -Li centers in perovskite fluorides

NASA Astrophysics Data System (ADS)

Zheng, W. C.

The zero-field splittings b20 of the tetragonal Gd3+-VM and Gd3+-Li+ centers for Gd3+ ions in fluoroperovskite crystals have been studied on the basis of the superposition model in which the value of t2

Thermodynamic theory of intrinsic finite-size effects in PbTiO3 nanocrystals. I. Nanoparticle size-dependent tetragonal phase stability

NASA Astrophysics Data System (ADS)

Akdogan, E. K.; Safari, A.

2007-03-01

We propose a phenomenological intrinsic finite-size effect model for single domain, mechanically free, and surface charge compensated ΔG-P ⃗s-ξ space, which describes the decrease in tetragonal phase stability with decreasing ξ rigorously.

Crystallization and diffraction analysis of [beta]-N-acetylhexosaminidase from Aspergillus oryzae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vanek, Ondrej; Brynd, Jirí; Hofbauerová, Katerina

2012-05-08

Fungal {beta}-N-acetylhexosaminidases are enzymes that are used in the chemoenzymatic synthesis of biologically interesting oligosaccharides. The enzyme from Aspergillus oryzae was produced and purified from its natural source and crystallized using the hanging-drop vapor-diffusion method. Diffraction data from two crystal forms (primitive monoclinic and primitive tetragonal) were collected to resolutions of 3.2 and 2.4 {angstrom}, respectively. Electrophoretic and quantitative N-terminal protein-sequencing analyses confirmed that the crystals are formed by a complete biologically active enzyme consisting of a glycosylated catalytic unit and a noncovalently attached propeptide.

Effect of intracrystalline water on longitudinal sound velocity in tetragonal hen-egg-white lysozyme crystals.

PubMed

Tachibana, M; Koizumi, H; Kojima, K

2004-05-01

Longitudinal sound velocity of tetragonal hen-egg-white (HEW) lysozyme crystals was measured during air drying by ultrasonic pulseecho method. The sound velocity increases with exposure to open air and approaches a constant value. The maximum value is approximately 2900 m/s that is about 1.6 times as much as that of original one before drying. In addition, the sound velocity clearly recovers to original one after immersing the dried crystal in solution. Therefore, the sound velocity in tetragonal HEW lysozyme crystals can be reversibly changed due to dehydration and rehydration. These changes in sound velocity are discussed in the light of water-mediated intramolecular and intermolecular interactions in the crystals.

Effect of intracrystalline water on longitudinal sound velocity in tetragonal hen-egg-white lysozyme crystals

NASA Astrophysics Data System (ADS)

Tachibana, M.; Koizumi, H.; Kojima, K.

2004-05-01

Longitudinal sound velocity of tetragonal hen-egg-white (HEW) lysozyme crystals was measured during air drying by ultrasonic pulseecho method. The sound velocity increases with exposure to open air and approaches a constant value. The maximum value is ˜2900 m/s that is about 1.6 times as much as that of original one before drying. In addition, the sound velocity clearly recovers to original one after immersing the dried crystal in solution. Therefore, the sound velocity in tetragonal HEW lysozyme crystals can be reversibly changed due to dehydration and rehydration. These changes in sound velocity are discussed in the light of water-mediated intramolecular and intermolecular interactions in the crystals.

Tuning the Curie temperature of FeCo compounds by tetragonal distortion

NASA Astrophysics Data System (ADS)

Jakobsson, A.; Şaşıoǧlu, E.; Mavropoulos, Ph.; Ležaić, M.; Sanyal, B.; Bihlmayer, G.; Blügel, S.

2013-09-01

Combining density-functional theory calculations with a classical Monte Carlo method, we show that for B2-type FeCo compounds, tetragonal distortion gives rise to a strong reduction of the Curie temperature TC. The TC monotonically decreases from 1575 K (for c /a=1) to 940 K (for c /a=√2 ). We find that the nearest neighbor Fe-Co exchange interaction is sufficient to explain the c/a behavior of the TC. Combination of high magnetocrystalline anisotropy energy with a moderate TC value suggests tetragonal FeCo grown on the Rh substrate with c /a=1.24 to be a promising material for heat-assisted magnetic recording applications.

Switchable Ni–Mn–Ga Heusler nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zayak, Alexey T.; Beckman, Scott P.; Tiago, Murilo L.

2008-10-02

Here, we examined bulk-like Heusler nanocrystals using real-space pseudopotentials constructed within density functional theory. The nanocrystals were made of various compositions of Ni-Mn-Ga in the size range from 15 up to 169 atoms. Among these compositions, the closest to the stoichiometric Ni 2MnGa were found to be the most stable. The Ni-based nanocrystals retained a tendency for tetragonal distortion, which is inherited from the bulk properties. Surface effects suppress the tetragonal structure in the smaller Ni-based nanocrystals, while bigger nanocrystals develop a bulk-like tetragonal distortion. We suggest the possibility of switchable Ni-Mn-Ga nanocrystals, which could be utilized for magnetic nano-shape-memorymore » applications.« less

Electron Microscopic Study of the Structure of Tetragonal Martensite in In-4.5% Cd Alloy

NASA Astrophysics Data System (ADS)

Khlebnikova, Yu. V.; Egorova, L. Yu.; Rodionov, D. P.

2018-04-01

In this work, the formation of a packet structure composed of colonies of lamellar plates separated by twin boundary {101}fct in In-4.5 wt % Cd alloy upon cooling below the fcc → fct martensitic transition temperature has been shown using the methods of metallography, X-ray diffraction, transmission electron microscopy, and EBSD analysis. Two neighboring lamellae differ from each other by the direction of their tetragonality axes. Using EBSD analysis, it has been established that neighboring packets always contain three types of tetragonal martensite lamellae, which are in twin positions and differ from each other by the direction of their tetragonality axes. In turn, each martensite lamella consists of a set of smaller lamellae, which are in twin positions. After the cycle of fct → fcc → fct transitions, the alloy recrystallizes with a decrease in the grain size by several times compared with the initial structure such that the size of packets and the length and width of martensitic lamellae in a packet correlate with a change in the size of an alloy grain.

Continuous-wave lasing in an organic-inorganic lead halide perovskite semiconductor

NASA Astrophysics Data System (ADS)

Jia, Yufei; Kerner, Ross A.; Grede, Alex J.; Rand, Barry P.; Giebink, Noel C.

2017-12-01

Hybrid organic-inorganic perovskites have emerged as promising gain media for tunable, solution-processed semiconductor lasers. However, continuous-wave operation has not been achieved so far1-3. Here, we demonstrate that optically pumped continuous-wave lasing can be sustained above threshold excitation intensities of 17 kW cm-2 for over an hour in methylammonium lead iodide (MAPbI3) distributed feedback lasers that are maintained below the MAPbI3 tetragonal-to-orthorhombic phase transition temperature of T ≈ 160 K. In contrast with the lasing death phenomenon that occurs for pure tetragonal-phase MAPbI3 at T > 160 K (ref. 4), we find that continuous-wave gain becomes possible at T ≈ 100 K from tetragonal-phase inclusions that are photogenerated by the pump within the normally existing, larger-bandgap orthorhombic host matrix. In this mixed-phase system, the tetragonal inclusions function as carrier recombination sinks that reduce the transparency threshold, in loose analogy to inorganic semiconductor quantum wells, and may serve as a model for engineering improved perovskite gain media.

Spatially modulated magnetic structure of EuS due to the tetragonal domain structure of SrTiO3

NASA Astrophysics Data System (ADS)

Rosenberg, Aaron J.; Katmis, Ferhat; Kirtley, John R.; Gedik, Nuh; Moodera, Jagadeesh S.; Moler, Kathryn A.

2017-12-01

The combination of ferromagnets with topological superconductors or insulators allows for new phases of matter that support excitations such as chiral edge modes and Majorana fermions. EuS, a wide-bandgap ferromagnetic insulator with a Curie temperature around 16 K, and SrTiO3 (STO), an important substrate for engineering heterostructures, may support these phases. We present scanning superconducting quantum interference device measurements of EuS grown epitaxially on STO that reveal micron-scale variations in ferromagnetism and paramagnetism. These variations are oriented along the STO crystal axes and only change their configuration upon thermal cycling above the STO cubic-to-tetragonal structural transition temperature at 105 K, indicating that the observed magnetic features are due to coupling between EuS and the STO tetragonal structure. We speculate that the STO tetragonal distortions may strain the EuS, altering the magnetic anisotropy on a micron scale. This result demonstrates that local variation in the induced magnetic order from EuS grown on STO needs to be considered when engineering new phases of matter that require spatially homogeneous exchange.

Atomistic study on the site preference and lattice vibration of Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} (T=Al and Ge)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Hai-Xia; Wang, Xiao-Xu; Department of Materials Engineering, National Ping Tung University of Technology and Science, Ping-Tung 91201, Taiwan

The effects of the Y substitution for Gd on the structural stability and the site preference of intermetallics Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} (T=Al and Ge) are studied by using a series of interatomic pair potentials. The calculated results show Y can stabilize Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} with the tetragonal structure, and Y substitute for Gd with a strong preference for the 2b sites. The calculated lattice parameters are in good agreement with the experimental data. Furthermore, the total and partial phonon densities of states are evaluated for the Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} compounds withmore » the tetragonal structure. A qualitative analysis is carried out with the relevant potentials for the vibrational modes, which makes it possible to predict some properties related to lattice vibration. - Graphical abstract: The lattice cell of Gd{sub 3}Co{sub 29}T{sub 4}B{sub 10} consists of 92 atoms, or two Gd{sub 3}Co{sub 29}T{sub 4}B{sub 10} formula units, with fourteen distinct kinds of site. Rare-earth atoms occupy 2b and 4d sites, Co atoms occupy the Co1(2c), Co2(8i1), Co3(8i2), Co4(8i3), Co5(8j1), Co6(8j2) and Co7(16k), T atoms occupy the T(8i) sites, and B atoms occupy the B1(2c1), B2(2c2), B3(8i) and B4(8j) sites. - Highlights: • The application of the pair potentials obtained from lattice-inversion method. • The lattice vibrations for Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} (T=Ge and Al) are first evaluated. • The Y atoms should prefer the 2b site of Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} compounds. • The total and partial phonon densities of states are evaluated for the Gd{sub 3−x}Y{sub x}Co{sub 29}T{sub 4}B{sub 10} compounds with the tetragonal structure. • A qualitative analysis is carried out with the relevant potentials for the vibrational modes.« less

A comparison study of the Born effective charges and dielectric properties of the cubic, tetragonal, monoclinic, ortho-I, ortho-II and ortho-III phases of zirconia

NASA Astrophysics Data System (ADS)

Zhang, Yan; Chen, Hua-Xin; Duan, Li; Fan, Ji-Bin; Ni, Lei; Ji, Vincent

2018-07-01

Using density-functional perturbation theory, we systematically investigate the Born effective charges and dielectric properties of cubic, tetragonal, monoclinic, ortho-I (Pbca), ortho-II (Pnma) and ortho-III (Pca21) phases of ZrO2. The magnitudes of the Born effective charges of the Zr and oxygen atoms are greater than their nominal ionic valences (+4 for Zr and -2 for oxygen), indicating a strong dynamic charge transfer from Zr atoms to O atoms and a mixed covalent-ionic bonding in six phases of ZrO2. For all six phases of ZrO2, the electronic contributions εij∞ to the static dielectric constant are rather small (range from 5 to 6.5) and neither strongly anisotropic nor strongly dependent on the structural phase, while the ionic contributions εijion to the static dielectric constant are large and not only anisotropic but also dependent on the structural phase. The average dielectric constant εbar0 of the six ZrO2 phases decreases in the sequence of tetragonal, cubic, ortho-II (Pnma), ortho-I (Pbca), ortho-III (Pca21) and monoclinic. So among six phases of ZrO2, the tetragonal and cubic phases are two suitable phases to replace SiO2 as the gate dielectric material in modern integrated-circuit technology. Furthermore, for the tetragonal ZrO2 the best orientation is [100].

Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions

DOE PAGES

Appavoo, Kannatassen; Nie, Wanyi; Blancon, Jean -Christophe; ...

2017-11-15

In this paper, connecting the complex electronic excitations of hybrid perovskites to their intricate organic-inorganic lattice structure has critical implications for energy conversion and optoelectronic technologies. Here we detail the multiband, multivalley electronic structure of a halide hybrid perovskite by measuring the absorption transients of a millimeter-scale-grain thin film as it undergoes a thermally controlled reversible tetragonal-to-orthogonal phase transition. Probing nearly single grains of this hybrid perovskite, we observe an unreported energy splitting (degeneracy lifting) of the high-energy 2.6 eV band in the tetragonal phase that further splits as the rotational degrees of freedom of the disordered CH 3NH 3more » + molecules are reduced when the sample is cooled. This energy splitting drastically increases during an extended phase-transition coexistence region that persists from 160 to 120 K, becoming more pronounced in the orthorhombic phase. By tracking the temperature-dependent optical transition energies and using symmetry analysis that describes the evolution of electronic states from the tetragonal phase to the orthorhombic phase, we assign this energy splitting to the nearly degenerate transitions in the tetragonal phase from both the R- and M-point-derived states. Importantly, these assignments explain how momentum conservation effects lead to long hot-carrier lifetimes in the room-temperature tetragonal phase, with faster hot-carrier relaxation when the hybrid perovskite structurally transitions to the orthorhombic phase due to enhanced scattering at the Γ point.« less

Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Appavoo, Kannatassen; Nie, Wanyi; Blancon, Jean -Christophe

In this paper, connecting the complex electronic excitations of hybrid perovskites to their intricate organic-inorganic lattice structure has critical implications for energy conversion and optoelectronic technologies. Here we detail the multiband, multivalley electronic structure of a halide hybrid perovskite by measuring the absorption transients of a millimeter-scale-grain thin film as it undergoes a thermally controlled reversible tetragonal-to-orthogonal phase transition. Probing nearly single grains of this hybrid perovskite, we observe an unreported energy splitting (degeneracy lifting) of the high-energy 2.6 eV band in the tetragonal phase that further splits as the rotational degrees of freedom of the disordered CH 3NH 3more » + molecules are reduced when the sample is cooled. This energy splitting drastically increases during an extended phase-transition coexistence region that persists from 160 to 120 K, becoming more pronounced in the orthorhombic phase. By tracking the temperature-dependent optical transition energies and using symmetry analysis that describes the evolution of electronic states from the tetragonal phase to the orthorhombic phase, we assign this energy splitting to the nearly degenerate transitions in the tetragonal phase from both the R- and M-point-derived states. Importantly, these assignments explain how momentum conservation effects lead to long hot-carrier lifetimes in the room-temperature tetragonal phase, with faster hot-carrier relaxation when the hybrid perovskite structurally transitions to the orthorhombic phase due to enhanced scattering at the Γ point.« less

Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions

NASA Astrophysics Data System (ADS)

Appavoo, Kannatassen; Nie, Wanyi; Blancon, Jean-Christophe; Even, Jacky; Mohite, Aditya D.; Sfeir, Matthew Y.

2017-11-01

Connecting the complex electronic excitations of hybrid perovskites to their intricate organic-inorganic lattice structure has critical implications for energy conversion and optoelectronic technologies. Here we detail the multiband, multivalley electronic structure of a halide hybrid perovskite by measuring the absorption transients of a millimeter-scale-grain thin film as it undergoes a thermally controlled reversible tetragonal-to-orthogonal phase transition. Probing nearly single grains of this hybrid perovskite, we observe an unreported energy splitting (degeneracy lifting) of the high-energy 2.6 eV band in the tetragonal phase that further splits as the rotational degrees of freedom of the disordered C H3N H3 + molecules are reduced when the sample is cooled. This energy splitting drastically increases during an extended phase-transition coexistence region that persists from 160 to 120 K, becoming more pronounced in the orthorhombic phase. By tracking the temperature-dependent optical transition energies and using symmetry analysis that describes the evolution of electronic states from the tetragonal phase to the orthorhombic phase, we assign this energy splitting to the nearly degenerate transitions in the tetragonal phase from both the R - and M -point-derived states. Importantly, these assignments explain how momentum conservation effects lead to long hot-carrier lifetimes in the room-temperature tetragonal phase, with faster hot-carrier relaxation when the hybrid perovskite structurally transitions to the orthorhombic phase due to enhanced scattering at the Γ point.

Ideal strength of bcc molybdenum and niobium

NASA Astrophysics Data System (ADS)

Luo, Weidong; Roundy, D.; Cohen, Marvin L.; Morris, J. W.

2002-09-01

The behavior of bcc Mo and Nb under large strain was investigated using the ab initio pseudopotential density-functional method. We calculated the ideal shear strength for the {211}<111> and {011}<111> slip systems and the ideal tensile strength in the <100> direction, which are believed to provide the minimum shear and tensile strengths. As either material is sheared in either of the two systems, it evolves toward a stress-free tetragonal structure that defines a saddle point in the strain-energy surface. The inflection point on the path to this tetragonal ``saddle-point'' structure sets the ideal shear strength. When either material is strained in tension along <100>, it initially follows the tetragonal, ``Bain,'' path toward a stress-free fcc structure. However, before the strained crystal reaches fcc, its symmetry changes from tetragonal to orthorhombic; on continued strain it evolves toward the same tetragonal saddle point that is reached in shear. In Mo, the symmetry break occurs after the point of maximum tensile stress has been passed, so the ideal strength is associated with the fcc extremum as in W. However, a Nb crystal strained in <100> becomes orthorhombic at tensile stress below the ideal strength. The ideal tensile strength of Nb is associated with the tetragonal saddle point and is caused by failure in shear rather than tension. In dimensionless form, the ideal shear and tensile strengths of Mo (τ*=τm/G111=0.12, σ*=σm/E100=0.078) are essentially identical to those previously calculated for W. Nb is anomalous. Its dimensionless shear strength is unusually high, τ*=0.15, even though the saddle-point structure that causes it is similar to that in Mo and W, while its dimensionless tensile strength, σ*=0.079, is almost the same as that of Mo and W, even though the saddle-point structure is quite different.

Local and average structures of BaTiO 3-Bi(Zn 1/2Ti 1/2)O 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Usher, Tedi-Marie; Iamsasri, Thanakorn; Forrester, Jennifer S.

The complex crystallographic structures of (1-x)BaTiO 3-xBi(Zn 1/2Ti 1/2)O 3 (BT-xBZT) are examined using high resolution synchrotron X-ray diffraction, neutron diffraction, and neutron pair distribution function (PDF) analyses. The short-range structures are characterized from the PDFs, and a combined analysis of the X-ray and neutron diffraction patterns is used to determine the long-range structures. Our results demonstrate that the structure appears different when averaged over different length scales. In all compositions, the local structures determined from the PDFs show local tetragonal distortions (i.e., c/a > 1). But, a box-car fitting analysis of the PDFs reveals variations at different length scales.more » For 0.80BT-0.20BZT and 0.90BT-0.10BZT, the tetragonal distortions decrease at longer atom-atom distances (e.g., 30 vs. 5 ). When the longest distances are evaluated (r > 40 ), the lattice parameters approach cubic. Neutron and X-ray diffraction yield further information about the long-range structure. Compositions 0.80BT-0.20BZT and 0.90BT-0.10BZT appear cubic by Bragg diffraction (no peak splitting), consistent with the PDFs at long distances. However, these patterns cannot be adequately fit using a cubic lattice model; modeling their structures with the P4mm space group allows for a better fit to the patterns because the space group allows for c-axis atomic displacements that occur at the local scale. Furthermore, for the compositions 0.92BT-0.08BZT and 0.94BT-0.06BZT, strong tetragonal distortions are observed at the local scale and a less-distorted tetragonal structure is observed at longer length scales. In Rietveld refinements, the latter is modeled using a tetragonal phase. Since the peak overlap in these two-phase compositions limits the ability to model the local-scale structures as tetragonal, it is approximated in the refinements as a cubic phase. These results demonstrate that alloying BT with BZT results in increased disorder and disrupts the long-range ferroelectric symmetry present in BT, while the large tetragonal distortion present in BZT persists at the local scale.« less

Local and average structures of BaTiO 3-Bi(Zn 1/2Ti 1/2)O 3

DOE PAGES

Usher, Tedi-Marie; Iamsasri, Thanakorn; Forrester, Jennifer S.; ...

2016-11-11

The complex crystallographic structures of (1-x)BaTiO 3-xBi(Zn 1/2Ti 1/2)O 3 (BT-xBZT) are examined using high resolution synchrotron X-ray diffraction, neutron diffraction, and neutron pair distribution function (PDF) analyses. The short-range structures are characterized from the PDFs, and a combined analysis of the X-ray and neutron diffraction patterns is used to determine the long-range structures. Our results demonstrate that the structure appears different when averaged over different length scales. In all compositions, the local structures determined from the PDFs show local tetragonal distortions (i.e., c/a > 1). But, a box-car fitting analysis of the PDFs reveals variations at different length scales.more » For 0.80BT-0.20BZT and 0.90BT-0.10BZT, the tetragonal distortions decrease at longer atom-atom distances (e.g., 30 vs. 5 ). When the longest distances are evaluated (r > 40 ), the lattice parameters approach cubic. Neutron and X-ray diffraction yield further information about the long-range structure. Compositions 0.80BT-0.20BZT and 0.90BT-0.10BZT appear cubic by Bragg diffraction (no peak splitting), consistent with the PDFs at long distances. However, these patterns cannot be adequately fit using a cubic lattice model; modeling their structures with the P4mm space group allows for a better fit to the patterns because the space group allows for c-axis atomic displacements that occur at the local scale. Furthermore, for the compositions 0.92BT-0.08BZT and 0.94BT-0.06BZT, strong tetragonal distortions are observed at the local scale and a less-distorted tetragonal structure is observed at longer length scales. In Rietveld refinements, the latter is modeled using a tetragonal phase. Since the peak overlap in these two-phase compositions limits the ability to model the local-scale structures as tetragonal, it is approximated in the refinements as a cubic phase. These results demonstrate that alloying BT with BZT results in increased disorder and disrupts the long-range ferroelectric symmetry present in BT, while the large tetragonal distortion present in BZT persists at the local scale.« less

Effect of Rubidium Incorporation on the Structural, Electrical, and Photovoltaic Properties of Methylammonium Lead Iodide-Based Perovskite Solar Cells

DOE PAGES

Park, Ik Jae; Seo, Seongrok; Park, Min Ah; ...

2017-11-10

We report the electrical properties of rubidium-incorporated methylammonium lead iodide ((Rb xMA 1-x)PbI 3) films and the photovoltaic performance of (Rb xMA 1-x)PbI 3 film-based p-i-n-type perovskite solar cells (PSCs). The incorporation of a small amount of Rb + (x = 0.05) increases both the open circuit voltage (V oc) and the short circuit photocurrent density (J sc) of the PSCs, leading to an improved power conversion efficiency (PCE). However, a high fraction of Rb + incorporation (x = 0.1 and 0.2) decreases the J sc and thus the PCE, which is attributed to the phase segregation of the singlemore » tetragonal perovskite phase to a MA-rich tetragonal perovskite phase and a RbPbI 3 orthorhombic phase at high Rb fractions. Conductive atomic force microscopic and admittance spectroscopic analyses reveal that the single-phase (Rb 0.05MA 0.95)PbI 3 film has a high electrical conductivity because of a reduced deep-level trap density. We also found that Rb substitution enhances the diode characteristics of the PSC, as evidenced by the reduced reverse saturation current (J 0). The optimized (Rb xMA 1-x)PbI 3 PSCs exhibited a PCE of 18.8% with negligible hysteresis in the photocurrent-voltage curve. The results from this work enhance the understanding of the effect of Rb incorporation into organic-inorganic hybrid halide perovskites and enable the exploration of Rb-incorporated mixed perovskites for various applications, such as solar cells, photodetectors, and light-emitting diodes.« less

Effect of Rubidium Incorporation on the Structural, Electrical, and Photovoltaic Properties of Methylammonium Lead Iodide-Based Perovskite Solar Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Ik Jae; Seo, Seongrok; Park, Min Ah

We report the electrical properties of rubidium-incorporated methylammonium lead iodide ((Rb xMA 1-x)PbI 3) films and the photovoltaic performance of (Rb xMA 1-x)PbI 3 film-based p-i-n-type perovskite solar cells (PSCs). The incorporation of a small amount of Rb + (x = 0.05) increases both the open circuit voltage (V oc) and the short circuit photocurrent density (J sc) of the PSCs, leading to an improved power conversion efficiency (PCE). However, a high fraction of Rb + incorporation (x = 0.1 and 0.2) decreases the J sc and thus the PCE, which is attributed to the phase segregation of the singlemore » tetragonal perovskite phase to a MA-rich tetragonal perovskite phase and a RbPbI 3 orthorhombic phase at high Rb fractions. Conductive atomic force microscopic and admittance spectroscopic analyses reveal that the single-phase (Rb 0.05MA 0.95)PbI 3 film has a high electrical conductivity because of a reduced deep-level trap density. We also found that Rb substitution enhances the diode characteristics of the PSC, as evidenced by the reduced reverse saturation current (J 0). The optimized (Rb xMA 1-x)PbI 3 PSCs exhibited a PCE of 18.8% with negligible hysteresis in the photocurrent-voltage curve. The results from this work enhance the understanding of the effect of Rb incorporation into organic-inorganic hybrid halide perovskites and enable the exploration of Rb-incorporated mixed perovskites for various applications, such as solar cells, photodetectors, and light-emitting diodes.« less

Enhancing the Bioactivity of Yttria-Stabilized Tetragonal Zirconia Ceramics via Grain-Boundary Activation.

PubMed

Ke, Jinhuan; He, Fupo; Ye, Jiandong

2017-05-17

Yttria-stabilized tetragonal zirconia (Y-TZP) has been proposed as a potential dental implant because of its good biocompatibility, excellent mechanical properties, and distinctive aesthetic effect. However, Y-TZP cannot form chemical bonds with bone tissue because of its biological inertness, which affects the reliability and long-term efficacy of Y-TZP implants. In this study, to improve the bioactivity of Y-TZP ceramics while maintaining their good mechanical performance, Y-TZP was modified by grain-boundary activation via the infiltration of a bioactive glass (BG) sol into the surface layers of Y-TZP ceramics under different negative pressures (atmospheric pressure, -0.05 kPa, and -0.1 kPa), followed by gelling and sintering. The in vitro bioactivity, mechanical properties, and cell behavior of the Y-TZP with improved bioactivity were systematically investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), electron probe microanalysis (EPMA), and Raman spectroscopy. The results of the bioactivity test conducted by immersing Y-TZP in simulated body fluid (SBF) showed that a bonelike apatite layer was produced on the entire surface. The mechanical properties of the modified Y-TZP decreased as the negative pressure in the BG-infiltration process increased relative to those of the Y-TZP blank group. However, the samples infiltrated with the BG sol under -0.05 kPa and atmospheric pressure still retained good mechanical performance. The cell-culture results revealed that the bioactive surface modification of Y-TZP could promote cell adhesion and differentiation. The present work demonstrates that the bioactivity of Y-TZP can be enhanced by grain-boundary activation, and the bioactive Y-TZP is expected to be a potential candidate for use as a dental implant material.

Electrical switching of an antiferromagnet

NASA Astrophysics Data System (ADS)

Jungwirth, Tomas

Louis Néel pointed out in his Nobel lecture that while abundant and interesting from theoretical viewpoint, antiferromagnets did not seem to have any applications. Indeed, the alternating directions of magnetic moments on individual atoms and the resulting zero net magnetization make antiferromagnets hard to control by tools common in ferromagnets. Strong coupling would be achieved if the externally generated field had a sign alternating on the scale of a lattice constant at which moments alternate in AFMs. However, generating such a field has been regarded unfeasible, hindering the research and applications of these abundant magnetic materials. We have recently predicted that relativistic quantum mechanics may offer staggered current induced fields with the sign alternating within the magnetic unit cell which can facilitate a reversible switching of an antiferromagnet by applying electrical currents with comparable efficiency to ferromagnets. Among suitable materials is a high Néel temperature antiferromagnet, tetragonal-phase CuMnAs, which we have recently synthesized in the form of single-crystal epilayers structurally compatible with common semiconductors. We demonstrate electrical writing and read-out, combined with the insensitivity to magnetic field perturbations, in a proof-of-concept antiferromagnetic memory device. We acknowledge support from European Research Council Advanced Grant No. 268066.

Observation of multiple dielectric relaxations in BaTiO3-Bi(Li1/3Ti2/3)O3 ceramics

NASA Astrophysics Data System (ADS)

Zhou, Changrong; Feteira, Antonio

2017-11-01

Dense (1 - x)BaTiO3- xBi(Li1/3Ti2/3)O3 ceramics were fabricated by the solid state reaction route. Powder X-ray diffraction analyses revealed an increase in the unit cell volume with increasing x and a change on the average crystal structure from tetragonal (space group P4mm) to cubic ( Pm\\bar{3}m ) at x > 0.10. Raman spectroscopy analyses corroborated a change of symmetry, but also showed the local structure for x > 0.10 to be inconsistent with the centrosymmetric ( Pm\\bar{3}m ) space group. The dielectric measurements revealed for the first time, to our knowledge, a double relaxor behaviour in a BaTiO3-based solid solution. Basically, with increasing x, the sharp ferroelectric anomaly at the Curie temperature ( T c) shifts towards lower temperatures until a relaxor-type response is observed, but simultaneously, another relaxation emerges above T c. The first arises from poor coupling between polar nanoregions, whereas the later obeys the Arrhenius Law and may be associated either with a defect-dipole reorientation or a Skanavi-type mechanism.

Chemical Trend of Superconducting Critical Temperatures in Hole-Doped CuBO2, CuAlO2, CuGaO2, and CuInO2

NASA Astrophysics Data System (ADS)

Nakanishi, Akitaka; Katayama-Yoshida, Hiroshi; Ishikawa, Takahiro; Shimizu, Katsuya

2016-09-01

We calculated the superconducting critical temperature (Tc) for hole-doped CuXO2 (X = B, Al, Ga, and In) compounds using first-principles calculations based on rigid band model. The compounds with X = Al, Ga, and In have delafosite-type structures and take maximum Tc values at 0.2-0.3 with respect to the number of holes (Nh) in the unit-cell: 50 K for CuAlO2, 10 K for CuGaO2, and 1 K for CuInO2. The decrease of Tc for this change in X is involved by covalency reduction and lattice softening associated with the increase of ionic mass and radius. For CuBO2 which is a lighter compound than CuAlO2, the delafosite structure is unstable and a body-centered tetragonal structure emerges as the most stable structure. As the results, the electron-phonon interaction is decreased and Tc is lower by approximately 43 K than that of CuAlO2 at the hole-doping conditions of Nh = 0.2-0.3.

Copper doped TiO2 nanoparticles characterized by X-ray absorption spectroscopy, total scattering, and powder diffraction--a benchmark structure-property study.

PubMed

Lock, Nina; Jensen, Ellen M L; Mi, Jianli; Mamakhel, Aref; Norén, Katarina; Qingbo, Meng; Iversen, Bo B

2013-07-14

Metal functionalized nanoparticles potentially have improved properties e.g. in catalytic applications, but their precise structures are often very challenging to determine. Here we report a structural benchmark study based on tetragonal anatase TiO2 nanoparticles containing 0-2 wt% copper. The particles were synthesized by continuous flow synthesis under supercritical water-isopropanol conditions. Size determination using synchrotron PXRD, TEM, and X-ray total scattering reveals 5-7 nm monodisperse particles. The precise dopant structure and thermal stability of the highly crystalline powders were characterized by X-ray absorption spectroscopy and multi-temperature synchrotron PXRD (300-1000 K). The combined evidence reveals that copper is present as a dopant on the particle surfaces, most likely in an amorphous oxide or hydroxide shell. UV-VIS spectroscopy shows that copper presence at concentrations higher than 0.3 wt% lowers the band gap energy. The particles are unaffected by heating to 600 K, while growth and partial transformation to rutile TiO2 occur at higher temperatures. Anisotropic unit cell behavior of anatase is observed as a consequence of the particle growth (a decreases and c increases).

Post-deposition control of ferroelastic stripe domains and internal electric field by thermal treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feigl, L.; Iwanowska, M.; Sandu, C. S.

The dependence of the formation of ferroelastic stripe domain patterns on the thermal history is investigated by detailed piezoresponse force microscopy and X-ray diffraction experiments after and during annealing of tensile strained tetragonal Pb(Ti,Zr)O{sub 3} epitaxial thin films on DyScO{sub 3} substrates. In particular, the ferroelastic pattern is reversibly interchanged between a cross-hatched and a stripe domain pattern if the films are cooled at different rates after annealing above the formation temperature of a-domains. Different types of 180° and non-180° patterns can be created, depending on the thermal treatment. The changes in the 180° domain structure and lattice parameters aremore » attributed to a change of oxygen vacancy concentration, which results in a modification of the internal electric field and unit cell size, causing also a shift of T{sub C}. Thermal treatment is done on rhombohedral La:BiFeO{sub 3} thin films as well. It is observed that also in these films, appropriate heat treatment modifies the domain pattern and films with a stripe domain pattern can be created, confirming the general validity of the developed model.« less

Post-deposition control of ferroelastic stripe domains and internal electric field by thermal treatment

NASA Astrophysics Data System (ADS)

Feigl, L.; Janolin, P.-E.; Yamada, T.; Iwanowska, M.; Sandu, C. S.; Setter, N.

2015-01-01

The dependence of the formation of ferroelastic stripe domain patterns on the thermal history is investigated by detailed piezoresponse force microscopy and X-ray diffraction experiments after and during annealing of tensile strained tetragonal Pb(Ti,Zr)O3 epitaxial thin films on DyScO3 substrates. In particular, the ferroelastic pattern is reversibly interchanged between a cross-hatched and a stripe domain pattern if the films are cooled at different rates after annealing above the formation temperature of a-domains. Different types of 180° and non-180° patterns can be created, depending on the thermal treatment. The changes in the 180° domain structure and lattice parameters are attributed to a change of oxygen vacancy concentration, which results in a modification of the internal electric field and unit cell size, causing also a shift of TC. Thermal treatment is done on rhombohedral La:BiFeO3 thin films as well. It is observed that also in these films, appropriate heat treatment modifies the domain pattern and films with a stripe domain pattern can be created, confirming the general validity of the developed model.

Au3+ ion implantation on FTO coated glasses: Effect on structural, electrical, optical and phonon properties

NASA Astrophysics Data System (ADS)

Sahu, Bindu; Dey, Ranajit; Bajpai, P. K.

2017-06-01

Effects of 11.00 MeV Au3+ ions implanted in FTO coated (thickness ≈300 nm) silicate glasses on structural, electrical optical and phonon behavior have been explored. It has been observed that metal clustering near the surface and sub-surface region below glass-FTO interface changes electrical and optical properties significantly. Ion implantation does not affect the crystalline structure of the coated films; however, the unit cell volume decreases with increase in fluence and the tetragonal distortion (c/a ratio) also decreases systematically in the implanted samples. The sheet resistivity of the films increases from 11 × 10-5 ohm-cm (in pristine) to 7.5 × 10-4 ohm-cm for highest ion beam fluence ≈1015 ions/cm2. The optical absorption decreases with increasing fluence whereas, the optical transmittance as well as reflectance increases with increasing fluence. The Raman spectra are observed at ∼530 cm-1 and ∼1103 cm-1 in pristine sample. The broad band at 530 cm-1 shifts towards higher wave number in the irradiated samples. This may be correlated with increased disorder and strain relaxation in the samples as a result of ion beam irradiation.

Tetragonal Lysozyme Interactions Studied by Site Directed Mutagenesis

NASA Technical Reports Server (NTRS)

Crawford, Lisa; Karr, Laurel J.; Nadarajah, Arunan; Pusey, Marc

1999-01-01

A number of recent experimental and theoretical studies have indicated that tetragonal lysozyme crystal growth proceeds by the addition of aggregates, formed by reversible self association of the solute molecules in the bulk solution. Periodic bond chain and atomic force microscopy studies have indicated that the probable growth unit is at minimum a 43 tetramer, and most likely an octamer composed of two complete turns about the 43 axis. If these results are correct, then there are intermolecular interactions which are only formed in the solution and others only formed at the joining of the growth unit to the crystal surface. We have set out to study these interactions, and the correctness of this hypothesis, using site directed mutagenesis of specific amino acid residues involved in the different bonds. We had initially expressed wild type lysozyme in S. cervasiae with yields of approximately 5 mg/L, which were eventually raised to approximately 40 mg/L. We are now moving the expression to the Pichia system, with anticipated yields of 300 to (3)500 mg/L, comparable to what can be obtained from egg whites. An additional advantage of using recombinant protein is the greater genetic homogeneity of the material obtained and the absence of any other contaminating egg proteins. The first mutation experiments are TYR 23 (Registered) PHE or ALA and ASN 113 (Registered) ALA or ASP. Both TYR 23 and ASN 113 form part of the postulated dimerization intermolecular binding site which lead to the formation of the 43 helix. Tyrosine also participates in an intermolecular hydrogen bond with ARG 114. The results of these and subsequent experiments will be discussed.

Tetragonal Lysozyme Interactions Studied by Site Directed Mutagenesis

NASA Technical Reports Server (NTRS)

Crawford, Lisa; Karr, Laurel; Pusey, Marc

1998-01-01

A number of recent experimental and theoretical studies have indicated that tetragonal lysozyme crystal growth proceeds by the addition of aggregates, formed by reversible self association of the solute molecules in the bulk'solution. Periodic bond chain and atomic force microscopy studies have indicated that the probable growth unit is at minimum a 43 tetramer, and most likely an octamer composed of two complete turns about the 4(sub 3) axis. If these results are correct, then there are intermolecular interactions which are only formed in the solution and others only formed at the joining of the growth unit to the crystal surface. We have set out to study these interactions, and the correctness of this hypothesis, using site directed mutagenesis of specific amino acid residues involved in the different bonds. We had initially expressed wild type lysozyme in S. cervasiae with yields of approximately 5 mg/L, which were eventually raised to approximately 40 mg/L. We are now moving the expression to the Pichia system, with anticipated yields of 300 to greater than 500 mg/L, comparable to what can be obtained from egg whites. An additional advantage of using recombinant protein is the greater genetic homogeneity of the material obtained and the absence of any other contaminating egg proteins. The first mutation experiments are TYR 23 yields PHE or ALA and ASN 113 yields ALA or ASP. Both TYR 23 and ASN 113 form part of the postulated dimerization intermolecular binding site which lead to the formation of the 4(sub 3) helix. Tyrosine also participates in an intermolecular hydrogen bond with ARG 114. The results of these and subsequent experiments will be discussed.

Structural, thermal and optical properties of TeO2-ZnO-CdO-BaO glasses doped with VO(2+).

PubMed

Sreenivasulu, V; Upender, G; Chandra Mouli, V; Prasad, M

2015-09-05

The glasses with composition 64TeO2-15ZnO-(20-x)CdO-xBaO-1V2O5 (0⩽x⩽20 mol%) were prepared by conventional melt quenching technique. X-ray diffraction analysis was used to confirm the amorphous nature of the glasses. The optical absorption studies revealed that the cut-off wavelength (λα) decreases while optical band gap energy (Eopt) and Urbach energy (ΔE) values increase with an increase of BaO content. Refractive index (n) evaluated from Eopt was found to decrease with an increase of BaO content. The physical parameters such as density (ρ), molar volume (Vm), oxygen packing density (OPD), optical basicity (Λ), molar refraction (Rm), and metallization criterion (M) evaluated and discussed. FTIR and Raman spectroscopic studies showed that the glass network consists of TeO4, TeO3+1/TeO3 and ZnO4 units as basic structural units. The glass transition temperature (Tg) of glass sample, onset crystallization temperature (To) and thermal stability ΔT were determined from Differential Scanning Calorimetry (DSC). Using electron paramagnetic resonance (EPR) spectra of vanadium glasses the spin Hamiltonian parameters and dipolar hyperfine coupling parameters of VO(2+) ions were calculated. It was found that V(4+) ions in these glasses exist as VO(2+) in octahedral coordination with a tetragonal distortion and have C4V symmetry with ground state dxy. Tetragonality (Δg∥/Δg⊥) of vanadium ion sites exhibited non-linear variation with BaO content. Copyright © 2015 Elsevier B.V. All rights reserved.

Orientation-resolved domain mapping in tetragonal SrTiO 3 using polarized Raman spectroscopy

DOE PAGES

Gray, Jr., Dodd J.; Merz, Tyler A.; Hikita, Yasuyuki; ...

2016-12-16

Here, we present microscopically resolved, polarized spectroscopy of Raman scattering collected from tetragonal SrTiO 3. The anisotropic response of first-order Raman peaks within a single tetragonal domain has been measured. From these data, we assign symmetries to the phonons seen in the first-order Raman spectrum which is normally complicated by uncontrolled domain structure. Using a translation stage, we map the local domain orientation of a 3–μm 3 crystal volume near the laser focus and compare it to wide-field polarized images. This technique can be performed with readily available instruments and is relevant to the study of a wide range ofmore » related materials, interfaces, and devices.« less

Electronic Degeneracy and Intrinsic Magnetic Properties of EpitaxialNb : SrTiO3 Thin Films Controlled by Defects

NASA Astrophysics Data System (ADS)

Sarantopoulos, A.; Ferreiro-Vila, E.; Pardo, V.; Magén, C.; Aguirre, M. H.; Rivadulla, F.

2015-10-01

We report thermoelectric power experiments in e -doped thin films of SrTiO3 (STO) which demonstrate that the electronic band degeneracy can be lifted through defect management during growth. We show that even small amounts of cationic vacancies, combined with epitaxial stress, produce a homogeneous tetragonal distortion of the films, resulting in a Kondo-like resistance upturn at low temperature, large anisotropic magnetoresistance, and nonlinear Hall effect. Ab initio calculations confirm a different occupation of each band depending on the degree of tetragonal distortion. The phenomenology reported in this Letter for tetragonally distorted e -doped STO thin films, is similar to that observed in LaAlO3 /STO interfaces and magnetic STO quantum wells.

The crystal structure and morphology of NiO-YSZ composite that prepared from local zircon concentrate of Bangka Island

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rahmawati, F., E-mail: fitria@mipa.uns.ac.id; Apriyani, K.; Heraldy, E.

2016-03-29

In order to increase the economic value of local zircon concentrate from Bangka Island, NiO-YSZ was synthesized from Zirconia, ZrO{sub 2} that was prepared from local zircon concentrate. The NiO-YSZ composite was synthesized by solid state reaction method. XRD analysis equipped with Le Bail refinement was carried out to analyze the crystal structure and cell parameters of the prepared materials. The result showed that zirconia was crystallized in tetragonal structure with a space group of P42/NMC. Yttria-Stabilized-Zirconia (YSZ) was prepared by doping 8% mol yttrium oxide into zirconia and then sintered at 1250°C for 3 hours. Doping of 8% molmore » Yttria allowed phase transformation of zirconia from tetragonal into the cubic structure. Meanwhile, the composite of NiO-YSZ consists of two crystalline phases, i.e. the NiO with cubic structure and the YSZ with cubic structure. SEM analysis of the prepared materials shows that the addition of NiO into YSZ allows the morphology to become more roughness with larger grain size.« less

Temperature controlled evolution of monoclinic to super-tetragonal phase of epitaxial BiFeO3 thin films on La0.67Sr0.33MnO3 buffered SrTiO3 substrate

NASA Astrophysics Data System (ADS)

Singh, Anar; Kaifeng, Dong; Chen, Jing-Sheng

2018-03-01

Epitaxial BiFeO3 thin films of 130nm were deposited by pulsed laser deposition (PLD) technique on La0.67Sr0.33MnO3 buffered SrTiO3 (001) substrate at various temperatures under different ambient oxygen pressures. Reciprocal space mapping reveals that, with decreasing temperature and oxygen pressure, the broadly reported monoclinic phase (MA) of BiFeO3 thin film initially transforms to a tetragonal phase (T1) with c/a =1.05 (1) in a narrow girth of deposition condition and then to a super-tetragonal phase (T2) with giant c/a = 1.24 (1), as confirmed by reciprocal space mapping using high resolution x-ray diffraction. The surface morphology of the films reveals the island growth of the BiFeO3 films deposited at low temperatures. We propose that the transformation from monoclinic to the super-tetragonal phase is essentially due to the manifestation of excess local strain as a result of the island growth. This study offers a recipe to grow the super-tetragonal phase of BiFeO3, with giant c/a =1.24 (1) which exhibits exceptionally large ferroelectric polarization, on ferromagnetic layer La0.67Sr0.33MnO3. This phase of BiFeO3 can be utilized for the ferroelectric control of magnetism at the interface of BiFeO3 and La0.67Sr0.33MnO3.

Pressure-induced phase transitions in the CdC r2S e4 spinel

NASA Astrophysics Data System (ADS)

Efthimiopoulos, I.; Liu, Z. T. Y.; Kucway, M.; Khare, S. V.; Sarin, P.; Tsurkan, V.; Loidl, A.; Wang, Y.

2016-11-01

We have conducted high-pressure x-ray diffraction and Raman spectroscopic studies on the CdC r2S e4 spinel at room temperature up to 42 GPa. We have resolved three structural transitions up to 42 GPa, i.e., the starting F d 3 ¯m phase transforms at ˜11 GPa into a tetragonal I 41/a m d structure, an orthorhombic distortion was observed at ˜15 GPa , whereas structural disorder initiates beyond 25 GPa. Our ab initio density functional theory studies successfully reproduced the observed crystalline-to-crystalline structural transitions. In addition, our calculations propose an antiferromagnetic ordering as a potential magnetic ground state for the high-pressure tetragonal and orthorhombic modifications, compared with the starting ferromagnetic phase. Furthermore, the computational results indicate that all phases remain insulating in their stability pressure range, with a direct-to-indirect band gap transition for the F d 3 ¯m phase taking place at 5 GPa. We attempted also to offer an explanation behind the peculiar first-order character of the F d 3 ¯m (cubic ) →I 41/a m d (tetragonal) transition observed for several relevant Cr spinels, i.e., the sizeable volume change at the transition point, which is not expected from space group symmetry considerations. We detected a clear correlation between the cubic-tetragonal transition pressures and the next-nearest-neighbor magnetic exchange interactions for the Cr-bearing sulfide and selenide members, a strong indication that the cubic-tetragonal transitions in these systems are principally governed by magnetic effects.

The Effects of Thermal History on Nucleation of Tetragonal Lysozyme Crystals, or Hot Protein and Cold Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael; Judge, Russell; Pusey, Marc

2000-01-01

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.2 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubilities are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to addition of precipitant solution. Warming a lysozyme solution above the phase transition point, then cooling it back below this point, has been shown to affect the subsequent nucleation rate, as determined by the numbers and size of crystals formed, but not the growth rate for the tetragonal crystal form . We have now measured the kinetics of this process and investigated its reversibility. The transition effects are progressive with temperature, having a half time of about 1 hour at 37C at pH 4.8. After holding a lysozyme solution at 37C (prior to addition of precipitant) for 16 hours, then cooling it back to 4C no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. Putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. This differential behaviour may be exploited to elucidate how and where flow affects the lysozyme crystal growth process. The presentation will focus on the results of these and ongoing studies in this area.

Spatially modulated magnetic structure of EuS due to the tetragonal domain structure of SrTiO 3

DOE PAGES

Rosenberg, Aaron J.; Katmis, Ferhat; Kirtley, John R.; ...

2017-12-15

The combination of ferromagnets with topological superconductors or insulators allows for new phases of matter that support excitations such as chiral edge modes and Majorana fermions. EuS, a wide-bandgap ferromagnetic insulator with a Curie temperature around 16K, and SrTiO 3 (STO), an important substrate for engineering heterostructures, may support these phases. We present scanning superconducting quantum interference device measurements of EuS grown epitaxially on STO that reveal micron-scale variations in ferromagnetism and paramagnetism. These variations are oriented along the STO crystal axes and only change their configuration upon thermal cycling above the STO cubic-to-tetragonal structural transition temperature at 105 K,more » indicating that the observed magnetic features are due to coupling between EuS and the STO tetragonal structure. Here, we speculate that the STO tetragonal distortions may strain the EuS, altering the magnetic anisotropy on a micron scale. This result demonstrates that local variation in the induced magnetic order from EuS grown on STO needs to be considered when engineering new phases of matter that require spatially homogeneous exchange.« less

Ferroelectricity of strained SrTiO3 in lithium tetraborate glass-nanocomposite and glass-ceramic

NASA Astrophysics Data System (ADS)

Abdel-Khalek, E. K.; Mohamed, E. A.; Kashif, I.

2018-02-01

Glass-nanocomposite (GNCs) sample of the composition [90Li2B4O7-10SrTiO3] (mol %) was prepared by conventional melt quenching technique. The glassy phase and the amorphous nature of the GNCs sample were identified by Differential thermal analysis (DTA) and X-ray diffraction (XRD) studies, respectively. DTA of the GNCs exhibits sharp and broad exothermic peaks which represent the crystallization of Li2B4O7 and SrTiO3, respectively. The tetragonal Li2B4O7 and tetragonal SrTiO3 crystalline phases in glass-ceramic (GC) were identified by XRD and scanning electron microscopic (SEM). The strain tetragonal SrTiO3 phase in GNCs and GC has been confirmed by SEM. The values of crystallization activation energies (Ec1 and Ec2) for the first and second exothermic peaks are equal to 174 and 1452 kJ/mol, respectively. The Ti3+ ions in tetragonal distorted octahedral sites in GNCs were identified by optical transmission spectrum. GNCs and GC samples exhibit broad dielectric anomalies at 303 and 319 K because of strained SrTiO3 ferroelectric, respectively.

Controlled synthesis, characterization and photoluminescence property of olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Youjin, E-mail: zyj@ustc.edu.cn; Zheng, Ao; Yang, Xiaozhi

2012-09-15

Highlights: ► The olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3} was gained with EDTA assisted hydrothermal method. ► The product was characterized by XRD, XPS, FTIR, FESEM, and PL. ► The possible formation mechanism for olive-like α-Nd{sub 2}(MoO{sub 4}){sub 3} was proposed. ► The PL in visible region of the olive-like α-Nd{sub 2}(MoO{sub 4}){sub 3} was studied. -- Abstract: The olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3} was obtained by a convenient and facile complex agent assisted hydrothermal method. The product was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, field-emission scanning electron microscopy (FESEM) andmore » photoluminescence (PL). The possible formation mechanism of the olive-like α-Nd{sub 2}(MoO{sub 4}){sub 3} was proposed. The photoluminescence property in visible region of the olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3} was studied.« less

Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites.

PubMed

Dobrovolsky, Alexander; Merdasa, Aboma; Unger, Eva L; Yartsev, Arkady; Scheblykin, Ivan G

2017-06-26

Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

Spatially modulated magnetic structure of EuS due to the tetragonal domain structure of SrTiO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosenberg, Aaron J.; Katmis, Ferhat; Kirtley, John R.

The combination of ferromagnets with topological superconductors or insulators allows for new phases of matter that support excitations such as chiral edge modes and Majorana fermions. EuS, a wide-bandgap ferromagnetic insulator with a Curie temperature around 16K, and SrTiO 3 (STO), an important substrate for engineering heterostructures, may support these phases. We present scanning superconducting quantum interference device measurements of EuS grown epitaxially on STO that reveal micron-scale variations in ferromagnetism and paramagnetism. These variations are oriented along the STO crystal axes and only change their configuration upon thermal cycling above the STO cubic-to-tetragonal structural transition temperature at 105 K,more » indicating that the observed magnetic features are due to coupling between EuS and the STO tetragonal structure. Here, we speculate that the STO tetragonal distortions may strain the EuS, altering the magnetic anisotropy on a micron scale. This result demonstrates that local variation in the induced magnetic order from EuS grown on STO needs to be considered when engineering new phases of matter that require spatially homogeneous exchange.« less

Collapsed tetragonal phase as a strongly covalent and fully nonmagnetic state: Persistent magnetism with interlayer As-As bond formation in Rh-doped Ca0 .8Sr0 .2Fe2As2

NASA Astrophysics Data System (ADS)

Zhao, K.; Glasbrenner, J. K.; Gretarsson, H.; Schmitz, D.; Bednarcik, J.; Etter, M.; Sun, J. P.; Manna, R. S.; Al-Zein, A.; Lafuerza, S.; Scherer, W.; Cheng, J. G.; Gegenwart, P.

2018-02-01

A well-known feature of the CaFe2As2 -based superconductors is the pressure-induced collapsed tetragonal phase that is commonly ascribed to the formation of an interlayer As-As bond. Using detailed x-ray scattering and spectroscopy, we find that Rh-doped Ca0.8Sr0.2Fe2As2 does not undergo a first-order phase transition and that local Fe moments persist despite the formation of interlayer As-As bonds. Our density functional theory calculations reveal that the Fe-As bond geometry is critical for stabilizing magnetism and the pressure-induced drop in the c lattice parameter observed in pure CaFe2As2 is mostly due to a constriction within the FeAs planes. The collapsed tetragonal phase emerges when covalent bonding of strongly hybridized Fe 3 d and As 4 p states completely wins out over their exchange splitting. Thus the collapsed tetragonal phase is properly understood as a strong covalent phase that is fully nonmagnetic with the As-As bond forming as a by-product.

Marigold-like nanocrystals: controllable synthesis, field emission, and photocatalytic properties

NASA Astrophysics Data System (ADS)

Song, Changqing; Yu, Ke; Yin, Haihong; Zhang, Yuanyuan; Li, Shouchuan; Wang, Yang; Zhu, Ziqiang

2014-06-01

Cubic marigold-like Cu2S nanostructures were synthesized from a facile hydrothermal process without using any additives or surfactants. After thermal annealed at different condition, monoclinic Cu2S and tetragonal Cu1.81S nanostructures were obtained for the first time, maintaining the marigold-like morphology undestroyed. Field emission (FE) properties of these three types of nanostructures were investigated for the first time. The results indicated that the tetragonal Cu1.81S nanostructures had excellent field emission performance with turn-on field of and threshold field of . Moreover, their photocatalytic properties of the three nanostructures were also investigated by photodegradating methylene blue (MB). The results showed that the tetragonal Cu1.81S nanostructures may be a competitive material in both field emission and photocatalytic applications.

Ferromagnetism in tetragonally distorted LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Mehta, Virat Vasav; Liberati, Marco; Wong, Franklin J.; Chopdekar, Rajesh Vilas; Arenholz, Elke; Suzuki, Yuri

2009-04-01

Thin films of epitaxial LaCoO3 were synthesized on SrTiO3 and (La ,Sr)(Al,Ta)O3 substrates, varying the oxygen background pressure in order to evaluate the impact of epitaxial growth as well as oxygen vacancies on the long range magnetic order. The epitaxial constraints from the substrate impose a tetragonal distortion compared to the bulk form. X-ray absorption and x-ray magnetic circular dichroism measurements confirmed that the ferromagnetism arises from the Co ions and persists through the entire thickness of the film. It was found that for the thin films to show ferromagnetic order they have to be grown under the higher oxygen pressures. A correlation of the structure and magnetism suggests that the tetragonal distortions induce the ferromagnetism.

Thermoelectric properties of n and p-type cubic and tetragonal XTiO3 (X = Ba,Pb): A density functional theory study

NASA Astrophysics Data System (ADS)

Rahman, Gul; Rahman, Altaf Ur

2017-12-01

Thermoelectric properties of cubic (C) and tetragonal (T) BaTiO3 (BTO) and PbTiO3 (PTO) are investigated using density functional theory together with semiclassical Boltzmann's transport theory. Both electron and hole doped BTO and PTO are considered in 300-500 K temperature range. We observed that C-BTO has larger power factor(PF) when doped with holes, whereas n-type carrier concentration in C-PTO has larger PF. Comparing both BTO and PTO, C-PTO has larger figure of merit ZT. Tetragonal distortion reduces the Seebeck coefficient S in n-doped PTO, and the electronic structures revealed that such reduction in S is mainly caused by the increase in the optical band gaps (Γ - Γ and Γ-X).

Electronic Degeneracy and Intrinsic Magnetic Properties of EpitaxialNb: SrTiO3 Thin Films Controlled by Defects.

PubMed

Sarantopoulos, A; Ferreiro-Vila, E; Pardo, V; Magén, C; Aguirre, M H; Rivadulla, F

2015-10-16

We report thermoelectric power experiments in e-doped thin films of SrTiO3 (STO) which demonstrate that the electronic band degeneracy can be lifted through defect management during growth. We show that even small amounts of cationic vacancies, combined with epitaxial stress, produce a homogeneous tetragonal distortion of the films, resulting in a Kondo-like resistance upturn at low temperature, large anisotropic magnetoresistance, and nonlinear Hall effect. Ab initio calculations confirm a different occupation of each band depending on the degree of tetragonal distortion. The phenomenology reported in this Letter for tetragonally distorted e-doped STO thin films, is similar to that observed in LaAlO3/STO interfaces and magnetic STO quantum wells.

Note on the Occurrence of Thorite at Alter Pedroso (Portugal). Report No. 29; NOTA SOBRE UMA OCORRENCIA DE TORITE EM ALTER PEDROSO. Memoria No. 29

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pacheco, J.T.; Gomes, R.A.D.

1960-01-01

The first known occurrence of thorite in Portugal is reported. The mineral was found as small dark reddishbrown euhedral grains scattered in a soil sample from the hyper-alkaline syerdte region of Alter Pedroso, in prospecting for radioactive materials. Zircon, riebeckite, aegirine, feldspar, biotite, magnetite (all of these common minerals of the hyper-alkaline syenite), and a few other urddentified minerals were found in the soil associated with thorite. This suggests the weathering of a local pegmatitic differentiation of the syenite as the origin of the thorite. Microscopic examination shows the mineral to be only partially metumict, and it is probably alteredmore » to a variable degree. Euhedral grains are constituted by several nearly colorless anisotropic nuclei (n/sub p/ near 1.69, n/sub g/ near 1.71, and sometimes anomalous B+ with variable 2V averaging 10/sup 0/) surrounded by a golden-brown isotropic material (n about 1.67). Specific gravity determinations were somewhat impaired by zircon inclusions and led to a value of 4.79. The chemical composition was determined by emission and x-ray fluorescence spectrography and shows a high yttrium content. A partial semiquantitative analysis gave the following results: ThO/sub 2/ (58.0%), SiO/sub 2/ (14.5%), Fe/sub 2/O/sub 3/ (2.5%), Y/sub 2/O/sub / 3>i (2.5%), CaO (l.1%), U/sub 3/O/sub 8/ (0.5%), and PbO (0.2%). The elements Be, Mg, Al, Mn, and P were also detected. X-raypowder patterns obtained before and after heating the sample to 1000 ts C for 1 hr in air confirmed the mineral to be only slightly metamict and showed that the tetragonal phase still prevails above 950 ts C. Calculations based on these patterns led to a tetragonal unit cell with a/sub 0/ = 7.05 0.01 A, c/sub 0/ = 6.27 0.01 A, and c/sub 0//a/sub 0/ = 0.889. (auth).« less

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Forsythe, Elizabeth; Sumida, John; Maxwell, Daniel; Gorti, Sridhar; Curreri, Peter A. (Technical Monitor)

2002-01-01

Experimental evidence indicates a dominant role of solution phase interactions in nucleating and growing tetragonal lysozyme crystals. These interactions are extensive, even at saturation, and may be a primary cause of misoriented regions in crystals grown on Earth. Microgravity, by limiting interfacial concentrations to diffusion-controlled levels, may benefit crystal quality by also reducing the extent of associated species present at the interface.

Large structural modulations in the relaxor ferroelectric and intermediate state of strontium rich members (x>0.6) of the Sr{sub x}Ba{sub 1−x}Nb{sub 2}O{sub 6} (sbn) solid solution series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graetsch, H.A., E-mail: heribert.graetsch@rub.de

The amplitudes of the positional, occupational and adp modulations of sbn mixed crystals are strongly enhanced for high strontium contents. The increase of structural modulations is accompanied by reduced spontaneous electric polarization largely due to smaller off-center shifts of the niobium atoms. Beyond the room temperature ferroelectric – intermediate transition near x=0.77, anomal large U{sub 33} atomic displacement parameters of the niobium atoms indicate static disorder caused by loss of orientational coupling between residual shifts of Nb atoms in neighboring NbO{sub 6} octahedra. Change of satellite intensities show a reduction from two-dimensional to one-dimensional modulation which is not consistent withmore » tetragonal symmetry. The pseudo-tetragonally twinned crystal structure of sbn82 was refined in the orthorhombic super-space group A2mm(½0γ)000. The apparent tetragonal symmetry of the other investigated sbn samples also seems to be due to pseudo tetragonal twinning with equal twin volumes. The modulations mainly consist of cooperatively tilted NbO{sub 6} octahedra and wave-like ordered incomplete occupation of the largest cation sites (Me2a and b) by Ba{sup 2+} and Sr{sup 2+}. Furthermore, the atomic displacement parameters of the Me2 sites are strongly modulated. - Graphical abstract: Satellite reflections and modulation coefficients in the solid solution series Sr{sub x}Ba{sub 1−x}Nb{sub 2}O{sub 6}. - Highlights: • The modulationed structures are refined for the whole composition range of sbn32–sbn82 in tetragonal and orthorhombic setting. • The amplitudes of positional, occupational and adp modulations increase strongly with the strontium content. • Evidence is presented that the sbn crystals are pseudo tetragonally twinned. • The ferroelectric–intermediate paraelectric transition is not accompanied by a change of symmetry. • Anomal adp of intermediate (non-ferroelectric) sbn82 indicate loss of coupling between off-center shifts of neighboring niobium.« less

Pseudo-merohedral twinning and noncrystallographic symmetry in orthorhombic crystals of SIVmac239 Nef core domain bound to different-length TCRζ fragments

PubMed Central

Kim, Walter M.; Sigalov, Alexander B.; Stern, Lawrence J.

2010-01-01

HIV/SIV Nef mediates many cellular processes through interactions with various cytoplasmic and membrane-associated host proteins, including the signalling ζ subunit of the T-­cell receptor (TCRζ). Here, the crystallization strategy, methods and refinement procedures used to solve the structures of the core domain of the SIVmac239 isolate of Nef (Nefcore) in complex with two different TCRζ fragments are described. The structure of SIVmac239 Nefcore bound to the longer TCRζ polypeptide (Leu51–Asp93) was determined to 3.7 Å resolution (R work = 28.7%) in the tetragonal space group P43212. The structure of SIVmac239 Nefcore in complex with the shorter TCRζ polypeptide (Ala63–Arg80) was determined to 2.05 Å resolution (R work = 17.0%), but only after the detection of nearly perfect pseudo-merohedral crystal twinning and proper assignment of the orthorhombic space group P212121. The reduction in crystal space-group symmetry induced by the truncated TCRζ polypeptide appears to be caused by the rearrangement of crystal-contact hydrogen-bonding networks and the substitution of crystallographic symmetry operations by similar noncrystallographic symmetry (NCS) operations. The combination of NCS rotations that were nearly parallel to the twin operation (k, h, −l) and a and b unit-cell parameters that were nearly identical predisposed the P212121 crystal form to pseudo-merohedral twinning. PMID:20124696

Multiple-component covalent organic frameworks

PubMed Central

Huang, Ning; Zhai, Lipeng; Coupry, Damien E.; Addicoat, Matthew A.; Okushita, Keiko; Nishimura, Katsuyuki; Heine, Thomas; Jiang, Donglin

2016-01-01

Covalent organic frameworks are a class of crystalline porous polymers that integrate molecular building blocks into periodic structures and are usually synthesized using two-component [1+1] condensation systems comprised of one knot and one linker. Here we report a general strategy based on multiple-component [1+2] and [1+3] condensation systems that enable the use of one knot and two or three linker units for the synthesis of hexagonal and tetragonal multiple-component covalent organic frameworks. Unlike two-component systems, multiple-component covalent organic frameworks feature asymmetric tiling of organic units into anisotropic skeletons and unusually shaped pores. This strategy not only expands the structural complexity of skeletons and pores but also greatly enhances their structural diversity. This synthetic platform is also widely applicable to multiple-component electron donor–acceptor systems, which lead to electronic properties that are not simply linear summations of those of the conventional [1+1] counterparts. PMID:27460607

Multiple-component covalent organic frameworks

NASA Astrophysics Data System (ADS)

Huang, Ning; Zhai, Lipeng; Coupry, Damien E.; Addicoat, Matthew A.; Okushita, Keiko; Nishimura, Katsuyuki; Heine, Thomas; Jiang, Donglin

2016-07-01

Covalent organic frameworks are a class of crystalline porous polymers that integrate molecular building blocks into periodic structures and are usually synthesized using two-component [1+1] condensation systems comprised of one knot and one linker. Here we report a general strategy based on multiple-component [1+2] and [1+3] condensation systems that enable the use of one knot and two or three linker units for the synthesis of hexagonal and tetragonal multiple-component covalent organic frameworks. Unlike two-component systems, multiple-component covalent organic frameworks feature asymmetric tiling of organic units into anisotropic skeletons and unusually shaped pores. This strategy not only expands the structural complexity of skeletons and pores but also greatly enhances their structural diversity. This synthetic platform is also widely applicable to multiple-component electron donor-acceptor systems, which lead to electronic properties that are not simply linear summations of those of the conventional [1+1] counterparts.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Peigong; Fan, Caimei, E-mail: fancm@163.com; Wang, Yawen

Graphical abstract: The cubic phase BaTiO{sub 3} nanoparticles can be obtained at 600 °C and changed into tetragonal phase at 900 °C by a dual chelating sol–gel method, and the photocatalytic activities of the photocatalysts calcined at different temperatures were investigated by the removal of humic acid (HA) from water under UV light irradiation. Highlights: ► The humic acid in water was firstly degradated by BaTiO{sub 3} photocatalyst. ► The cubic BaTiO{sub 3} was obtained and changed into tetragonal phase at lower temperature. ► The chelating agents had an important influence on the phase formation of BaTiO{sub 3}. ► Themore » tetragonal phase BaTiO{sub 3} calcined at 900 °C exhibited higher photocatalytic activity under UV irradiation. -- Abstract: In this paper, a dual chelating sol–gel method was used to synthesize BaTiO{sub 3} nanoparticles by using acetylacetone and citric acid as chelating agents. The samples calcined at different temperatures were analyzed by thermogravimetric and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), scanning electron microscope (SEM) and UV–vis diffuse reflectance spectra (UV–vis). The results indicated that cubic phase BaTiO{sub 3} nanoparticles about 19.6 nm can be obtained at 600 °C and changed into tetragonal phase at 900 °C about 97.1 nm. All the BaTiO{sub 3} nanoparticles showed effective photocatalytic activities on the removal of humic acid (HA) under UV light irradiation. A comparison of single (acetylacetone or citric acid) and dual chelating (acetylacetone and citric acid) synthetic processes was also studied and the results demonstrated that the dual chelating agents indeed reduced phase transformation temperature from cubic to tetragonal BaTiO{sub 3}.« less

A comprehensive study on the structural evolution of HfO 2 thin films doped with various dopants

DOE PAGES

Park, Min Hyuk; Schenk, Tony; Fancher, Christopher M.; ...

2017-04-19

The origin of the unexpected ferroelectricity in doped HfO 2 thin films is now considered to be the formation of a non-centrosymmetric Pca2 1 orthorhombic phase. Due to the polycrystalline nature of the films as well as their extremely small thickness (~10 nm) and mixed orientation and phase composition, structural analysis of doped HfO 2 thin films remains a challenging task. As a further complication, the structural similarities of the orthorhombic and tetragonal phase are difficult to distinguish by typical structural analysis techniques such as X-ray diffraction. To resolve this issue, the changes in the grazing incidence X-ray diffraction (GIXRD)more » patterns of HfO 2 films doped with Si, Al, and Gd are systematically examined. For all dopants, the shift of o111/ t101 diffraction peak is observed with increasing atomic layer deposition (ALD) cycle ratio, and this shift is thought to originate from the orthorhombic to P4 2/ nmc tetragonal phase transition with decreasing aspect ratio (2 a/(b + c) for orthorhombic and c/a for the tetragonal phase). For quantitative phase analysis, Rietveld refinement is applied to the GIXRD patterns. A progressive phase transition from P2 1/c monoclinic to orthorhombic to tetragonal is confirmed for all dopants, and a strong relationship between orthorhombic phase fraction and remanent polarization value is uniquely demonstrated. The concentration range for the ferroelectric properties was the narrowest for the Si-doped HfO 2 films. As a result, the dopant size is believed to strongly affect the concentration range for the ferroelectric phase stabilization, since small dopants can strongly decrease the free energy of the tetragonal phase due to their shorter metal–oxygen bonds.« less

Synthesis and thermal stability of zirconia and yttria-stabilized zirconia microspheres.

PubMed

Leib, Elisabeth W; Vainio, Ulla; Pasquarelli, Robert M; Kus, Jonas; Czaschke, Christian; Walter, Nils; Janssen, Rolf; Müller, Martin; Schreyer, Andreas; Weller, Horst; Vossmeyer, Tobias

2015-06-15

Zirconia microparticles produced by sol-gel synthesis have great potential for photonic applications. To this end, identifying synthetic methods that yield reproducible control over size uniformity is important. Phase transformations during thermal cycling can disintegrate the particles. Therefore, understanding the parameters driving these transformations is essential for enabling high-temperature applications. Particle morphology is expected to influence particle processability and stability. Yttria-doping should improve the thermal stability of the particles, as it does in bulk zirconia. Zirconia and YSZ particles were synthesized by improved sol-gel approaches using fatty acid stabilizers. The particles were heated to 1500 °C, and structural and morphological changes were monitored by SEM, ex situ XRD and high-energy in situ XRD. Zirconia particles (0.4-4.3 μm in diameter, 5-10% standard deviation) synthesized according to the modified sol-gel approaches yielded significantly improved monodispersities. As-synthesized amorphous particles transformed to the tetragonal phase at ∼450 °C with a volume decrease of up to ∼75% and then to monoclinic after heating from ∼650 to 850 °C. Submicron particles disintegrated at ∼850 °C and microparticles at ∼1200 °C due to grain growth. In situ XRD revealed that the transition from the amorphous to tetragonal phase was accompanied by relief in microstrain and the transition from tetragonal to monoclinic was correlated with the tetragonal grain size. Early crystallization and smaller initial grain sizes, which depend on the precursors used for particle synthesis, coincided with higher stability. Yttria-doping reduced grain growth, stabilized the tetragonal phase, and significantly improved the thermal stability of the particles. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

A comprehensive study on the structural evolution of HfO 2 thin films doped with various dopants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Min Hyuk; Schenk, Tony; Fancher, Christopher M.

The origin of the unexpected ferroelectricity in doped HfO 2 thin films is now considered to be the formation of a non-centrosymmetric Pca2 1 orthorhombic phase. Due to the polycrystalline nature of the films as well as their extremely small thickness (~10 nm) and mixed orientation and phase composition, structural analysis of doped HfO 2 thin films remains a challenging task. As a further complication, the structural similarities of the orthorhombic and tetragonal phase are difficult to distinguish by typical structural analysis techniques such as X-ray diffraction. To resolve this issue, the changes in the grazing incidence X-ray diffraction (GIXRD)more » patterns of HfO 2 films doped with Si, Al, and Gd are systematically examined. For all dopants, the shift of o111/ t101 diffraction peak is observed with increasing atomic layer deposition (ALD) cycle ratio, and this shift is thought to originate from the orthorhombic to P4 2/ nmc tetragonal phase transition with decreasing aspect ratio (2 a/(b + c) for orthorhombic and c/a for the tetragonal phase). For quantitative phase analysis, Rietveld refinement is applied to the GIXRD patterns. A progressive phase transition from P2 1/c monoclinic to orthorhombic to tetragonal is confirmed for all dopants, and a strong relationship between orthorhombic phase fraction and remanent polarization value is uniquely demonstrated. The concentration range for the ferroelectric properties was the narrowest for the Si-doped HfO 2 films. As a result, the dopant size is believed to strongly affect the concentration range for the ferroelectric phase stabilization, since small dopants can strongly decrease the free energy of the tetragonal phase due to their shorter metal–oxygen bonds.« less

Decagonal quasicrystal and related crystalline phases in Mn-Ga alloys with 52 to 63 a/o Ga

NASA Astrophysics Data System (ADS)

Wu, J. S.; Kuo, K. H.

1997-03-01

A decagonal quasicrystal (DQC) and six related intermetallic phases with large unit cells have been found in binary Mn-Ga alloys with 52 to 63 at. pct Ga by means of transmission electron microscopy (TEM). As does the Al-Mn DQC, the Ga-Mn DQC also has a periodicity of 1.25 nm along its tenfold axis. However, its Mn content, determined by electron microprobe X-ray analysis (about 45 to 50 at. pct Mn), is much higher than that of the Al-Mn DQC (about 20 to 30 at. pct Mn). The compositions of the intermetallic phases are about 53, 56, 58, and 62 at. pct Ga, corresponding respectively to the unknown structures of MnGa (50.7 to 53.4 at. pct Ga), Mn5Ga6 (55 at pct Ga), Mn5Ga7 (57.9 at. pct Ga), and Mn3Ga5 (62.9 at. pct Ga) given in the binary Mn-Ga phase diagram ( Metals Hand-book, T.B. Massalski, J.L. Murray, L.H. Benneft, and H. Baker, eds., ASM, Metals Park, OH, 1986, vol. 2, p. 1144). Their lattice types have been determined by selected area electron diffraction. The ferromagnetic Mn3Ga5 is tetragonal, a=1.25 nm and c=2.50 nm; Mn5Ga7 is orthorhombic, a=4.57 nm, b=1.25 nm, and c=1.44 nm; Mn5Ga6 has two different but closely related orthorhombic unit cells, a=1.26 nm, b=1.25 nm, and c=1.48 nm as well as a=0.77 nm, b=1.25 nm, and c=2.36 nm; MnGa also has two different and related unit cells, one orthorhombic with a=2.04 nm, b=1.25 nm, and c=1.48 nm and the other monoclinic with a=2.59 nm, b=1.25 nm, c=1.15 nm, and β≈=110 deg. All these orthorhombic phases have b=1.25 nm, being the same as the periodicity along the tenfold axis of the Ga-Mn and Al-Mn DQCs. Moreover, all these six intermetallic phases give electron diffraction patterns displaying a pseudo-tenfold distribution of strong diffraction spots and are considered to be crystalline approximants of the Ga-Mn DQC.

Optical properties of tetragonal and nanoscale BiFeO3

NASA Astrophysics Data System (ADS)

Chen, P.; Xu, X. S.; Musfeldt, J. L.; Santulli, A. C.; Koenigsmann, C.; Wong, S. S.; Podraza, N. J.; Melville, A.; Vlahos, E.; Gopalan, V.; Schlom, D. G.; Ramesh, R.

2010-03-01

We measured the optical properties of tetragonal thin film and nanoscale rhombohedral BiFeO3 in the range from near infrared to the near ultraviolet. The absorption spectrum in the tetragonal film is overall blue-shifted compared with that of the rhombohedral BiFeO3 film. It shows an absorption onset near 2.25 eV, a direct 3.1 eV band gap, and charge transfer excitations that are ˜0.4 eV higher than those of the rhombohedral counterpart. In the nanoparticles, the band gap decreases from 2.7 eV to ˜2.3 eV, and the well-known 3.2 and 4.5 eV charge transfer excitations split into multiplets. We discuss these results in terms of structural strain, surface strain, and local symmetry breaking.

Towards novel multiferroic and magnetoelectric materials: dipole stability in tetragonal tungsten bronzes

PubMed Central

Rotaru, Andrei; Miller, Andrew J.; Arnold, Donna C.; Morrison, Finlay D.

2014-01-01

We discuss the strategy for development of novel functional materials with the tetragonal tungsten bronze structure. From the starting composition Ba6GaNb9O30, the effect of A- and B-site substitutions on the dielectric properties is used to develop an understanding of the origin and stability of the dipolar response in these compounds. Both tetragonal strain induced by large B-site cations and local strain variations created by isovalent A-site substitutions enhance dipole stability but result in a dilute, weakly correlated dipolar response and canonical relaxor behaviour. Decreasing cation size at the perovskite A2-site increases the dipolar displacements in the surrounding octahedra, but insufficiently to result in dipole ordering. Mechanisms introducing small A-site lanthanide cations and incorporation of A-site vacancies to induce ferroelectricity and magnetism are presented. PMID:24421377

Change in surface properties of zirconia and initial attachment of osteoblastlike cells with hydrophilic treatment.

PubMed

Watanabe, Hiroaki; Saito, Kensuke; Kokubun, Katsutoshi; Sasaki, Hodaka; Yoshinari, Masao

2012-01-01

The objectives of this study were to characterize change in surface properties of tetragonal zirconia polycrystals (TZP) after hydrophilic treatment, and to determine the effect of such changes on initial attachment of osteoblast-like cells. Roughened surfaces were produced by alumina-blasting and acid-etching. Hydrophilic treatment comprised application of immediately after blasting and acid-etching (Blast/Etch), oxygen plasma (O2-Plasma), ultraviolet light (UV). Specimens stored in air were used as a control. The water contact angle was determined and surface analysis was performed using an X-ray photoelectron spectroscopy. Blast/Etch, O2-Plasma and UV specimens showed superhydrophilicity, and these hydrophilic treatments to TZP elicited a marked decrease in carbon content and an increase in hydroxyl groups. Hydrophilic treatments enhanced initial attachment of osteoblast-like cells and a change in cell morphologies. These results indicate that Blast/Etch, O2-Plasma, or UV treatment has potential in the creation and maintenance of superhydrophilic surfaces and enhancing initial attachment of osteoblast-like cells.

Temperature dependence of field-responsive mechanisms in lead zirconate titanate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, Ching-Chang; Fancher, Chris M.; Isaac, Catherine

2017-05-17

An electric field loading stage was designed for use in a laboratory diffractometer that enables in situ investigations of the temperature dependence in the field response mechanisms of ferroelectric materials. The stage was demonstrated in this paper by measuring PbZr 1-xTi xO 3 (PZT) based materials—a commercially available PZT and a 1% Nb-doped PbZr 0.56Ti 0.44O 3 (PZT 56/44)—over a temperature range of 25°C to 250°C. The degree of non-180° domain alignment (η 002) of the PZT as a function of temperature was quantified. η 002 of the commercially available PZT increases exponentially with temperature, and was analyzed as amore » thermally activated process as described by the Arrhenius law. The activation energy for thermally activated domain wall depinning process in PZT was found to be 0.47 eV. Additionally, a field-induced rhombohedral to tetragonal phase transition was observed 5°C below the rhombohedral-tetragonal transition in PZT 56/44 ceramic. The field-induced tetragonal phase fraction was increased 41.8% after electrical cycling. Finally, a large amount of domain switching (η 002=0.45 at 1.75 kV/mm) was observed in the induced tetragonal phase.« less

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

Domain wall and interphase boundary motion in (1-x)Bi(Mg 0.5 Ti 0.5 )O 3 –xPbTiO 3 near the morphotropic phase boundary

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tutuncu, Goknur; Chen, Jun; Fan, Longlong

Electric field-induced changes in the domain wall motion of (1-x)Bi(Mg 0.5Ti 0.5)O 3–xPbTiO 3 (BMT-xPT) near the morphotropic phase boundary (MPB) where x = 0.37 (BMT-37PT) and x =0.38 (BMT-38PT), are studied by means of synchrotron x-ray diffraction. Through Rietveld analysis and profile fitting, a mixture of coexisting monoclinic (Cm) and tetragonal (P4mm) phases is identified at room temperature. Extrinsic contributions to the property coefficients are evident from electric-field-induced domain wall motion in both the tetragonal and monoclinic phases, as well as through the interphase boundary motion between the two phases. Domain wall motion in the tetragonal and monoclinic phasesmore » for BMT-37PT is larger than that of BMT-38PT, possibly due to this composition's closer proximity to the MPB. Increased interphase boundary motion was also observed in BMT-37PT. Lattice strain, which is a function of both intrinsic piezoelectric strain and elastic interactions of the grains (the latter originating from domain wall and interphase boundary motion), is similar for the respective tetragonal and monoclinic phases.« less

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

DOE PAGES

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.; ...

2017-08-28

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

Crystal growth and physical properties of SrCu2As2, SrCu2Sb2, and BaCu2Sb2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anand, V.K.; Perera, P. Kanchana; Pandey, Abhishek

2012-06-25

We report the growth of single crystals of SrCu2As2, SrCu2Sb2, SrCu2(As0.84Sb0.16)2, and BaCu2Sb2 using the self-flux technique and their structural, magnetic, thermal, and transport properties that were investigated by powder x-ray diffraction (XRD), magnetic susceptibility χ, specific heat Cp, and electrical resistivity ρ measurements versus temperature T from 1.8 to 350 K. Rietveld refinements of XRD patterns for crushed crystals confirm that SrCu2As2 crystallizes in the ThCr2Si2-type body-centered tetragonal structure (space group I4/mmm) and SrCu2Sb2 crystallizes in the CaBe2Ge2-type primitive tetragonal structure (space group P4/nmm). However, as reported previously, BaCu2Sb2 is found to have a large unit cell consisting ofmore » three blocks. Here a ThCr2Si2-type block is sandwiched between two CaBe2Ge2-type blocks along the c axis with an overall symmetry of I4/mmm, as reported, but likely with a monoclinic distortion. The χ data of all these compounds are diamagnetic and reveal nearly T-independent anisotropic behavior. The χ of SrCu2As2 is found to be larger in the ab plane than along the c axis, as also previously reported for pure and doped BaFe2As2, whereas the χ values of SrCu2Sb2 and BaCu2Sb2 are larger along the c axis. This difference in anisotropy appears to arise from the differences between the crystal structures. The finite values of the Sommerfeld linear specific heat coefficients γ and the T dependences of ρ reveal metallic character of all four compounds. The electronic and magnetic properties indicate that these compounds are sp metals with Cu in the nonmagnetic 3d10 electronic configuration corresponding to the oxidation state Cu+1, as previously predicted theoretically for SrCu2As2 by Singh [ Phys. Rev. B 79 153102 (2009)]. We present a brief review of theoretical and experimental work on the doping character of transition metals for Fe in BaFe2As2. The As–As covalent interlayer bond distances in the collapsed-tetragonal (Ca,Sr,Ba)Cu2As2 compounds are much shorter than the nonbonding As–As distances in BaFe2As2. Thus, the electronic character of the Cu and the strength of the As–As interlayer bonding are both expected to drastically change between weakly Cu-substituted BaFe2As2 and pure BaCu2As2, perhaps via a first-order lattice instability such as a miscibility gap in the Ba(Fe1−xCux)2As2 system.« less

Thermal stability of simple tetragonal and hexagonal diamond germanium

DOE PAGES

Huston, Larissa Q.; Johnson, Brett C.; Haberl, Bianca; ...

2017-11-07

Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursormore » materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.« less

Controllable Photovoltaic Effect of Microarray Derived from Epitaxial Tetragonal BiFeO3 Films.

PubMed

Lu, Zengxing; Li, Peilian; Wan, Jian-Guo; Huang, Zhifeng; Tian, Guo; Pan, Danfeng; Fan, Zhen; Gao, Xingsen; Liu, Jun-Ming

2017-08-16

Recently, the ferroelectric photovoltaic (FePV) effect has attracted great interest due to its potential in developing optoelectronic devices such as solar cell and electric-optical sensors. It is important for actual applications to realize a controllable photovoltaic process in ferroelectric-based materials. In this work, we prepared well-ordered microarrays based on epitaxially tetragonal BiFeO 3 (T-BFO) films by the pulsed laser deposition technique. The polarization-dependent photocurrent image was directly observed by a conductive atomic force microscope under ultraviolet illumination. By choosing a suitable buffer electrode layer and controlling the ferroelectric polarization in the T-BFO layer, we realized the manipulation of the photovoltaic process. Moreover, based on the analysis of the band structure, we revealed the mechanism of manipulating the photovoltaic process and attributed it to the competition between two key factors, i.e., the internal electric field caused by energy band alignments at interfaces and the depolarization field induced by the ferroelectric polarization in T-BFO. This work is very meaningful for deeply understanding the photovoltaic process of BiFeO 3 -based devices at the microscale and provides us a feasible avenue for developing data storage or logic switching microdevices based on the FePV effect.

Thermal stability of simple tetragonal and hexagonal diamond germanium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huston, Larissa Q.; Johnson, Brett C.; Haberl, Bianca

Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursormore » materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.« less

Template assisted strain tuning and phase stabilization in epitaxial BiFeO3 thin films

NASA Astrophysics Data System (ADS)

Saj Mohan M., M.; Ramadurai, Ranjith

2018-04-01

Strain engineering is a key to develop novel properties in functional materials. We report a strain mediated phase stabilization and epitaxial growth of bismuth ferrite(BiFeO3) thin films on LaAlO3 (LAO) substrates. The strain in the epitaxial layer is controlled by controlling the thickness of bottom electrode where the thickness of the BFO is kept constant. The thickness of La0.7Sr0.3MnO3(LSMO) template layer was optimized to grow completely strained tetragonal, tetragonal/rhombohedral mixed phase and fully relaxed rhombohedral phase of BFO layers. The results were confirmed with coupled-θ-2θ scan, and small area reciprocal space mapping. The piezoelectric d33 (˜ 45-48 pm/V) coefficient of the mixed phase was relatively larger than the strained tetragonal and relaxed rhombohedral phase for a given thickness.

Protein solubilities determined by a rapid technique and modification of that technique to a micro-method

NASA Technical Reports Server (NTRS)

Cacioppo, Elizabeth; Pusey, Marc Lee; Munson, Sibyl

1989-01-01

A simple, rapid method for determination of protein solubilities has been developed which is based upon maximization of the free solution volume to be brought into equilibrium. The tetragonal lysozome solubility diagram has been determined from pH 4.0 to 5.2 (0.1 M sodium acetate), 2-7 percent NaCl, 3-25 C, and portions of the orthorhombic solubility diagram using this technique. Both tetragonal and orthorhombic solubilities were found to increase smoothly with decreasing salt concentration and increasing temperature; no retrograde solubilities were observed. Using column volumes of 75, 300, and 900 microliters, identical tetragonal lysozyme solubility diagrams were obtained. Chymotrypsinogen solubilities have also been determined using this apparatus, being retrograde over the temperature range tested. It is noted that the primary limiting factor in reducing the crystalline volume is the minimum solution sample size needed to accurately quantitate the protein.

Giant magnetostriction in nanoheterogeneous Fe-Al alloys

NASA Astrophysics Data System (ADS)

Han, Yongjun; Wang, Hui; Zhang, Tianli; He, Yangkun; Jiang, Chengbao

2018-02-01

As a potential magnetostrictive material, Fe-Al alloys exhibit excellent mechanical properties, low cost, and moderate magnetostriction, but the magnetostriction mechanism is still a mystery. Here, we elucidate the structural origin of magnetostriction in Fe-Al alloys and further improve the magnetostriction five-fold via Tb doping. Nanoinclusions with a size of 3-5 nm were found dispersed in the A2 matrix in Fe82Al18 ribbons. The structure of the nanoinclusions is identified to be tetragonally modified-D03 (L60), which are considered to create the tetragonal distortion of the matrix, leading to the enhanced magnetostriction. Furthermore, a drastic enhancement of the magnetostriction up to 5 times was achieved by trace Tb doping (0.2 at. %). Synchrotron X-ray diffraction directly revealed the increased tetragonal distortion of the matrix caused by these Tb dopants. The results further enrich the heterogeneous magnetostriction and guide the development of magnetostrictive materials.

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.; Mitchell, T. E.

1981-01-01

A commercially available bulk 4.5 mole percent yttria-(Y2O3) partially stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging curves were constructed for both the as received and the solution annealed and quenched materials; the curves showed hardness peaks at 1397 and 1517 Kg/sq mm respectively. The rectangular plate shaped tetragonal precipitates were found to have a 110 habit plane. A total of twelve different types of tetragonal precipitates were found. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinc phase, thus indicating that transformation toughening is not a significant mechanism for the material.

Aqueous Combustion Synthesis and Characterization of Nanosized Tetragonal Zirconia Single Crystals

NASA Astrophysics Data System (ADS)

Reddy, B. S. B.; Mal, Indrajit; Tewari, Shanideep; Das, Karabi; Das, Siddhartha

2007-08-01

Nanocrystalline zirconia powder has been synthesized by an aqueous combustion synthesis route using glycine as fuel and nitrate as oxidizer. The powders have been prepared by using different glycine to zirconyl nitrate molar ratios (G/N). The powders produced with different G/N ratios have been characterized by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) to determine the parameters resulting from powder with attractive properties. The theoretical combustion temperature (T ad ) has been calculated for different G/N ratios, and it is correlated with powder characteristics. An attempt is also made to explain the stability of tetragonal zirconia on the basis of extrinsic factors such as the morphology of nanocrystallites. Nanocrystalline metastable tetragonal zirconia (˜25 nm) powder (TZ) with disc-shaped morphology has been produced with a weak agglomeration in fuel deficient mixtures.

Local Orthorhombicity in the Magnetic C 4 Phase of the Hole-Doped Iron-Arsenide Superconductor Sr 1 - x Na x Fe 2 As 2

DOE PAGES

Frandsen, Benjamin A.; Taddei, Keith M.; Yi, Ming; ...

2017-10-30

We report on temperature-dependent pair distribution function measurements of Sr 1-xNa xFe 2As 2, an iron-based superconductor system that contains a magnetic phase with reentrant tetragonal symmetry, known as the magnetic C 4 phase. Quantitative refinements indicate that the instantaneous local structure in the C 4 phase comprises fluctuating orthorhombic regions with a length scale of similar to 2 nm, despite the tetragonal symmetry of the average static structure. Additionally, local orthorhombic fluctuations exist on a similar length scale at temperatures well into the paramagnetic tetragonal phase. Furthermore, these results highlight the exceptionally large nematic susceptibility of iron-based superconductors andmore » have significant implications for the magnetic C 4 phase and the neighboring C 2 and superconducting phases.« less

Local Orthorhombicity in the Magnetic C 4 Phase of the Hole-Doped Iron-Arsenide Superconductor Sr 1 - x Na x Fe 2 As 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frandsen, Benjamin A.; Taddei, Keith M.; Yi, Ming

We report on temperature-dependent pair distribution function measurements of Sr 1-xNa xFe 2As 2, an iron-based superconductor system that contains a magnetic phase with reentrant tetragonal symmetry, known as the magnetic C 4 phase. Quantitative refinements indicate that the instantaneous local structure in the C 4 phase comprises fluctuating orthorhombic regions with a length scale of similar to 2 nm, despite the tetragonal symmetry of the average static structure. Additionally, local orthorhombic fluctuations exist on a similar length scale at temperatures well into the paramagnetic tetragonal phase. Furthermore, these results highlight the exceptionally large nematic susceptibility of iron-based superconductors andmore » have significant implications for the magnetic C 4 phase and the neighboring C 2 and superconducting phases.« less

Strain-induced nanostructure of Pb(Mg1/3Nb2/3)O3-PbTiO3 on SrTiO3 epitaxial thin films with low PbTiO3 concentration

NASA Astrophysics Data System (ADS)

Kiguchi, Takanori; Fan, Cangyu; Shiraishi, Takahisa; Konno, Toyohiko J.

2017-10-01

The singularity of the structure in (1 - x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-xPT) (x = 0-50 mol %) epitaxial thin films of 100 nm thickness was investigated from the viewpoint of the localized residual strain in the nanoscale. The films were deposited on SrTiO3 (STO) (001) single-crystal substrates by chemical solution deposition (CSD) using metallo-organic decomposition (MOD) solutions. X-ray and electron diffraction patterns revealed that PMN-xPT thin films included a single phase of the perovskite-type structure with the cube-on-cube orientation relationship between PMN-xPT and STO: (001)Film ∥ (001)Sub, [100]Film ∥ [100]Sub. X-ray reciprocal space maps showed an in-plane tensile strain in all the compositional ranges considered. Unit cells in the films were strained from the rhombohedral (pseudocubic) (R) phase to a lower symmetry crystal system, the monoclinic (MB) phase. The morphotropic phase boundary (MPB) that split the R and tetragonal (T) phases was observed at x = 30-35 for bulk crystals of PMN-xPT, whereas the strain suppressed the transformation from the R phase to the T phase in the films up to x = 50. High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) analysis and its related local strain analysis revealed that all of the films have a bilayer morphology. The nanoscale strained layer formed only above the film/substrate semi-coherent interface. The misfit dislocations generated the localized and periodic strain fields deformed the unit cells between the dislocation cores from the R to an another type of the monoclinic (MA) phase. Thus, the singular and localized residual strains in the PMN-xPT/STO (001) epitaxial thin films affect the phase stability around the MPB composition and result in the MPB shift phenomena.

Crystallization and X-ray diffraction analysis of the HMG domain of the chondrogenesis master regulator Sox9 in complex with a ChIP-Seq-identified DNA element

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vivekanandan, Saravanan; Moovarkumudalvan, Balasubramanian; Lescar, Julien

Sox9 is a fundamental sex-determining gene and the master regulator of chondrogenesis, and is involved in the development of various vital organs such as testes, kidney, heart and brain, and in skeletal development. Similar to other known Sox transcription factors, Sox9 recognizes and binds DNA with the consensus sequence C(T/A)TTG(T/A)(T/A) through the highly conserved HMG domain. Nonetheless, the molecular basis of the functional specificity of Sox9 in key developmental processes is still unclear. As an initial step towards a mechanistic understanding of Sox9 transcriptional regulation, the current work describes the details of the purification of the mouse Sox9 HMG domainmore » (mSox9HMG), its crystallization in complex with a ChIP-Seq-identified FOXP2 promoter DNA element and the X-ray diffraction data analysis of this complex. The mSox9HMG–FOXP2 promoter DNA complex was crystallized by the hanging-drop vapour-diffusion method using 20% PEG 3350 in 200 mMsodium/potassium phosphate with 100 mMbis-tris propane at pH 8.5. The crystals diffracted to 2.7 Å resolution and the complex crystallized in the tetragonal space groupP4 12 12, with unit-cell parametersa=b= 99.49,c= 45.89 Å. Crystal-packing parameters revealed that asymmetric unit contained one mSox9HMG–FOXP2 promoter DNA complex with an estimated solvent content of 64%.« less

Structural properties of zirconia - in-situ high temperature XRD characterization

NASA Astrophysics Data System (ADS)

Kurpaska, Lukasz

2018-07-01

In this work, the effect of high temperature on structural properties of pure zirconium have been investigated. In-situ X-ray diffraction analysis of the oxide layer formed at temperature window 25-600 °C on pure zirconium were performed. Conducted experiment aimed at investigation of the zirconia phases developed on surface of the metallic substrate. Based on the conducted studies, possible stress state (during heating, continuous oxidation and cooling), cell parameters and HWHM factor were analyzed. A tetragonal and monoclinic phases peak shifts and intensities change were observed, suggesting that different phases react in different way upon temperature effect.

Study of iridium silicide monolayers using density functional theory

NASA Astrophysics Data System (ADS)

Popis, Minh D.; Popis, Sylvester V.; Oncel, Nuri; Hoffmann, Mark R.; ćakır, Deniz

2018-02-01

In this study, we investigated physical and electronic properties of possible two-dimensional structures formed by Si (silicon) and Ir (iridium). To this end, different plausible structures were modeled by using density functional theory and the cohesive energies calculated for the geometry of optimized structures, with the lowest equilibrium lattice constants. Among several candidate structures, we identified three mechanically (via elastic constants and Young's modulus), dynamically (via phonon calculations), and thermodynamically stable iridium silicide monolayer structures. The lowest energy structure has a chemical formula of Ir2Si4 (called r-IrSi2), with a rectangular lattice (Pmmn space group). Its cohesive energy was calculated to be -0.248 eV (per IrSi2 unit) with respect to bulk Ir and bulk Si. The band structure indicates that the Ir2Si4 monolayer exhibits metallic properties. Other stable structures have hexagonal (P-3m1) and tetragonal (P4/nmm) cell structures with 0.12 and 0.20 eV/f.u. higher cohesive energies, respectively. Our calculations showed that Ir-Si monolayers are reactive. Although O2 molecules exothermically dissociate on the surface of the free-standing iridium silicide monolayers with large binding energies, H2O molecules bind to the monolayers with a rather weak interaction.

The Effect of Eu Doping on Microstructure, Morphology and Methanal-Sensing Performance of Highly Ordered SnO2 Nanorods Array

PubMed Central

Zhao, Yanping; Li, Yuehua; Ren, Xingping; Gao, Fan; Zhao, Heyun

2017-01-01

Layered Eu-doped SnO2 ordered nanoarrays constructed by nanorods with 10 nm diameters and several hundred nanometers length were synthesized by a substrate-free hydrothermal route using alcohol and water mixed solvent of sodium stannate and sodium hydroxide at 200 °C. The Eu dopant acted as a crystal growth inhibitor to prevent the SnO2 nanorods growth up, resulting in tenuous SnO2 nanorods ordered arrays. The X-ray diffraction (XRD) revealed the tetragonal rutile-type structure with a systematic average size reduction and unit cell volume tumescence, while enhancing the residual strain as the Eu-doped content increases. The surface defects that were caused by the incorporation of Eu ions within the surface oxide matrix were observed by high-resolution transmission electron microscope (HRTEM). The results of the response properties of sensors based on the different levels of Eu-doped SnO2 layered nanoarrays demonstrated that the 0.5 at % Eu-doped SnO2 layered nanorods arrays exhibited an excellent sensing response to methanal at 278 °C. The reasons of the enhanced sensing performance were discussed from the complicated defect surface structure, the large specific surface area, and the excellent catalytic properties of Eu dopant. PMID:29168796

Interfacial coupling and polarization of perovskite ABO3 heterostructures

NASA Astrophysics Data System (ADS)

Wu, Lijun; Wang, Zhen; Zhang, Bangmin; Yu, Liping; Chow, G. M.; Tao, Jing; Han, Myung-Geun; Guo, Hangwen; Chen, Lina; Plummer, E. W.; Zhang, Jiandi; Zhu, Yimei

2017-02-01

Interfaces with subtle difference in atomic and electronic structures in perovskite ABO3 heterostructures often yield intriguingly different properties, yet their exact roles remain elusive. In this article, we report an integrated study of unusual transport, magnetic, and structural properties of Pr0.67Sr0.33MnO3 (PSMO) films and La0.67Sr0.33MnO3 (LSMO) films of various thicknesses on SrTiO3 (STO) substrate. In particular, using atomically resolved imaging and electron energy-loss spectroscopy (EELS), we measured interface related local lattice distortion, BO6 octahedral rotation and cation-anion displacement induced polarization. In the very thin PSMO film, an unexpected interface-induced ferromagnetic polaronic insulator phase was observed during the cubic-to-tetragonal phase transition of the substrate STO, due to the enhanced electron-phonon interaction and atomic disorder in the film. On the other hand, for the very thin LSMO films we observed a remarkably deep polarization in non-ferroelectric STO substrate near the interface. Combining the experimental results with first principles calculations, we propose that the observed deep polarization is induced by an electric field originating from oxygen vacancies that extend beyond a dozen unit-cells from the interface, thus providing important evidence of the role of defects in the emergent interface properties of transition metal oxides.

Controlling octahedral rotations in a perovskite via strain doping

DOE PAGES

Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; ...

2016-05-24

The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film canmore » be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO 3 films coherently grown on SrTiO 3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.« less

Photocatalytic CO2 reduction by Cr-substituted Ba2(In2-xCrx)O5·(H2O)δ (0.04 ≤ x ≤ 0.60)

NASA Astrophysics Data System (ADS)

Yoon, Songhak; Gaul, Michael; Sharma, Sitansh; Son, Kwanghyo; Hagemann, Hans; Ziegenbalg, Dirk; Schwingenschlogl, Udo; Widenmeyer, Marc; Weidenkaff, Anke

2018-04-01

Cr-substituted polycrystalline Ba2(In2-xCrx)O5·(H2O)δ powders (0.04 ≤ x ≤ 0.60) were synthesized by solid state reaction to investigate the relation of crystal structure, thermochemical, magnetic, and optical properties. The Cr-substitution results in an unit cell expansion and formation of the higher-symmetric tetragonal phase together with increased oxygen and hydrogen contents. Magnetic property measurements reveal that the diamagnetic pristine Ba2In2O5·(H2O)δ becomes magnetically ordered upon Cr-substitution. By UV-vis spectroscopy a gradual shift of the absorption-edge energy to lower values was observed. Numerical calculations showed that the observed bandgap narrowing was ascribed to the Cr induced states near the Fermi level. The correlation between the changes of crystal chemistry, magnetic, and optical properties of Cr-substituted Ba2(In2-xCrx)O5·(H2O)δ can be explained by the replacement of In by Cr. Consequently, an enhanced photocatalytic CO2 reduction activity was observed with increasing Cr substitution, compatible with the state-of-the-art high surface area TiO2 photocatalyst (P-25).

Neutron Powder Diffraction Study on the Magnetic Structure of NdPd 5 Al 2

DOE PAGES

Metoki, Naoto; Yamauchi, Hiroki; Kitazawa, Hideaki; ...

2017-02-24

The magnetic structure of NdPd 5Al 2 has been studied by neutron powder diffraction. Here, we observed the magnetic reflections with the modulation vector q=(1/2,0,0)q=(1/2,0,0) below the ordering temperature T N. We also found a collinear magnetic structure with a Nd moment of 2.7(3) μB at 0.5 K parallel to the c-axis, where the ferromagnetically ordered a-planes stack with a four-Nd-layer period having a ++-- sequence along the a-direction with the distance between adjacent Nd layers equal to a/2 (magnetic space group P anma). This “stripe”-like modulation is very similar to that in CePd 5Al 2 with q=(0.235,0.235,0)q=(0.235,0.235,0) with themore » Ce moment parallel to the c-axis. These structures with in-plane modulation are a consequence of the two-dimensional nature of the Fermi surface topology in this family, originating from the unique crystal structure with a very long tetragonal unit cell and a large distance of >7 Å between the rare-earth layers separated by two Pd and one Al layers.« less

Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA) 2MCl 6 (M = U, Np, Pt, Sn, Hf, Zr)

DOE PAGES

Autillo, Matthieu; Wilson, Richard E.

2017-09-22

A study of the phase transitions occurring in tetramethylammonium hexachlorometalate compounds with M = U IV, Np IV, Zr IV, Sn IV, Hf IV and Pt IV were performed using single-crystal X-ray diffraction across the temperature range 120 - 400K. When the crystals were cooled, movement of the octahedral [MCl 6] 2- anions induces a phase transition from Fm3m to Fd3c with a doubling of the unit cell. For the actinide compounds, no correlation between the f-electron configuration and the transition temperature was observed, instead, a correlation between the transition temperatures and both the [MCl 6] 2- anion and themore » TMA cation size is highlighted. Two phase transitions were observed and characterized. The first phase transition occurs with the ordering of the TMA cation and the second from a rotation of the [MCl 6] 2- octahedra. A third phase transition was observed at lower temperatures and was ascribed to a tetragonal distortion of the [MCl 6] 2- anions. Synthesis and study of their deuterated compounds did not show a significant isotope effect. As a result, Raman spectra performed on the protonated and deuterated compounds indicate only weak hydrogen bonding interactions between the TMA cations and the [MCl 6] 2- octahedra.« less

Neutron Powder Diffraction Study on the Magnetic Structure of NdPd 5 Al 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Metoki, Naoto; Yamauchi, Hiroki; Kitazawa, Hideaki

The magnetic structure of NdPd 5Al 2 has been studied by neutron powder diffraction. Here, we observed the magnetic reflections with the modulation vector q=(1/2,0,0)q=(1/2,0,0) below the ordering temperature T N. We also found a collinear magnetic structure with a Nd moment of 2.7(3) μB at 0.5 K parallel to the c-axis, where the ferromagnetically ordered a-planes stack with a four-Nd-layer period having a ++-- sequence along the a-direction with the distance between adjacent Nd layers equal to a/2 (magnetic space group P anma). This “stripe”-like modulation is very similar to that in CePd 5Al 2 with q=(0.235,0.235,0)q=(0.235,0.235,0) with themore » Ce moment parallel to the c-axis. These structures with in-plane modulation are a consequence of the two-dimensional nature of the Fermi surface topology in this family, originating from the unique crystal structure with a very long tetragonal unit cell and a large distance of >7 Å between the rare-earth layers separated by two Pd and one Al layers.« less

Modeling of Materials for Energy Storage: A Challenge for Density Functional Theory

NASA Astrophysics Data System (ADS)

Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

Hollandite α-MnO2 is a promising material for rechargeable batteries and is studied extensively in the community because of its interesting tunnel structure and the corresponding large capacity for lithium as well as sodium ions. However, the presence of partially reduced Mn ions due to doping with Ag or during lithiation makes hollandite a challenging system for density functional theory and the conventionally employed PBE+U method. A naive attempt to model the ternary system LixAgyMnO2 with density functionals, similar to those employed for the case y = 0 , fails and predicts a strong monoclinic distortion of the experimentally observed tetragonal unit cell for Ag2Mn8O16. Structure and binding energies are compared with experimental data and show the importance of van der Waals interactions as well as the necessity for an accurate description of the cooperative Jan-Teller effects for silver hollandite AgyMnO2. Based on these observations a ternary phase diagram is calculated allowing to predict the physical and chemical properties of LixAgyMnO2, such as stable stoichiometries, open circuit voltages, the formation of Ag metal and the structural change during lithiation. Department of Energy (DOE) under award #DE-SC0012673.

Electronic transport properties of MFe2As2 (M = Ca, Eu, Sr) at ambient and high pressures up to 20 GPa

NASA Astrophysics Data System (ADS)

Morozova, Natalia V.; Karkin, Alexander E.; Ovsyannikov, Sergey V.; Umerova, Yuliya A.; Shchennikov, Vladimir V.; Mittal, R.; Thamizhavel, A.

2015-12-01

We experimentally investigated the electronic transport properties of four iron pnictide crystals, namely, EuFe2As2, SrFe2As2, and CaFe2As2 parent compounds, and superconducting CaFe1.94Co0.06As2 at ambient and high pressures up to 20 GPa. At ambient pressure we examined the electrical resistivity, Hall and magnetoresistance effects of the samples in a temperature range from 1.5 to 380 K in high magnetic fields up to 13.6 T. In this work we carried out the first simultaneous investigations of the in-plane and out-of-plane Hall coefficients, and found new peculiarities of the low-temperature magnetic and structural transitions that occur in these materials. In addition, the Hall coefficient data suggested that the parent compounds are semimetals with a multi-band conductivity that includes hole-type and electron-type bands. We measured the pressure dependence of the thermoelectric power (the Seebeck effect) of these samples up to 20 GPa, i.e. across the known phase transition from the tetragonal to the collapsed tetragonal lattice. The high-pressure behavior of the thermopower of EuFe2As2 and CaFe2As2 showing the p-n sign inversions was consistent with the semimetal model described above. By means of thermopower, we found in single-crystalline CaFe2As2 direct evidence of the band structure crossover related to the formation of As-As bonds along the c-axis on the tetragonal → collapsed tetragonal phase transition near 2 GPa. We showed that this feature is distinctly observable only in high-quality samples, and already for re-pressurization cycles this crossover was strongly smeared because of the moderate deterioration of the sample. We also demonstrated by means of thermopower that the band structure crossover that should accompany the tetragonal → collapsed tetragonal phase transition in EuFe2As2 near 8 GPa is hardly visible even in high-quality single crystals. This behavior may be related to a gradual valence change of the Eu ions under pressure that leads to an injection of free electrons and the steady shift of the conduction to n-type.

Thermal Aging Behavior of Axial Suspension Plasma-Sprayed Yttria-Stabilized Zirconia (YSZ) Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Zhao, Yuexing; Wang, Liang; Yang, Jiasheng; Li, Dachuan; Zhong, Xinghua; Zhao, Huayu; Shao, Fang; Tao, Shunyan

2015-02-01

7.5YSZ thermal barrier coatings (TBCs) were deposited onto the stainless steel substrates using axial suspension plasma spraying (ASPS). Free-standing coatings were isothermally aged in air from 1200 to 1600 °C for 24 h and at 1550 °C for 20 to 100 h, respectively. Thermal aging behavior such as phase composition, microstructure evolutions, grain growth, and mechanical properties for thermal-aged coatings were investigated. Results show that the as-sprayed metastable tetragonal (t'-ZrO2) phase decomposes into equilibrium tetragonal (t-ZrO2) and cubic (c-ZrO2) phases during high-temperature exposures. Upon further cooling, the c-ZrO2 may be retained or transform into another metastable tetragonal (t″-ZrO2) phase, and tetragonal → monoclinic phase transformation occurred after 1550 °C/40 h aging treatment. The coating exhibits a unique structure with segmentation cracks and micro/nano-size grains, and the grains grow gradually with increasing aging temperature and time. In addition, the hardness ( H) and Young's modulus ( E) significantly increased as a function of temperature due to healing of pores or cracks and grain growth of the coating. And a nonmonotonic variation is found in the coatings thermal aged at a constant temperature (1550 °C) with prolonged time, this is a synergetic effect of coating sintering and m-ZrO2 phase formation.

S = 1 on a Diamond Lattice in NiRh2O4

NASA Astrophysics Data System (ADS)

Chamorro, Juan; McQueen, Tyrel

An S = 1 system has the potential of rich physics, and has been the subject of intense theoretical work. Extensive work has been done on one-dimensional and two-dimensional S = 1 systems, yet three dimensional systems remain elusive. Experimental realizations of three-dimensional S = 1, however, are limited, and no system to date has been found to genuinely harbor this. Recent theoretical work suggests that S = 1 on a diamond lattice would enable a novel topological paramagnet state, generated by fluctuating Haldane chains within the structure, with topologically protected end states. Here we present data on NiRh2O4, a tetragonal spinel that has a structural phase transition from cubic to tetragonal at T = 380 K. High resolution XRD shows it to have a tetragonally distorted spinel structure, with Ni2+ (d8, S = 1) on the tetrahedral, diamond sublattice site. Magnetic susceptibility and specific heat measurements show that it does not order magnetically down to T = 0.1 K. Nearest neighbor interactions remain the same despite the cubic to tetragonal phase transition. Comparison to theoretical models indicate that this system might fulfill the requirements necessary to have both highly entangled and topological behaviors. IQM Is Funded by US Department of Energy, Office of Basic Energy Sciences, Division of Material Sciences and Engineering, under Grant No. DE-FG02-08ER46544.

Composition-dependent properties and phase stability of Fe-Pd ferromagnetic shape memory alloys: A first-principles study

NASA Astrophysics Data System (ADS)

Li, Chun-Mei; Hu, Yan-Fei

2017-12-01

The composition-dependent properties and their correlation with the phase stability of Fe75+xPd25-x (- 10.0 ≤x ≤10.0 ) alloys are systematically investigated by using first-principles exact muffin-tin orbitals (EMTO)-coherent potential approximation (CPA) calculations. It is shown that the martensitic transformation (MT) from L 12 to body-centered-tetragonal (bct) occurs in the ordered alloys with about -5.0 ≤x ≤10.0 . In both the L 12 and bct phases, the evaluated a and c/a agree well with the available experimental data; the average magnetic moment per atom increases whereas the local magnetic moments of Fe atoms, dependent on both their positions and the structure of the alloy, decrease with increasing x. The tetragonal shear elastic constant of the L 12 phase ( C ' ) decreases whereas that of the bct phase (Cs) increases with x. The tetragonality of the martensite ( |1 -c /a | ) increases whereas its energy relative to the austenite with a negative value decreases with Fe addition. All these effects account for the increase of MT temperature (TM) with x. The MT from L 12 to bct is finally confirmed originating from the splitting of Fe 3d Eg and T2 g bands upon tetragonal distortion due to the Jahn-Teller effect.

Electrocaloric effect in BaTiO3 at all three ferroelectric transitions: Anisotropy and inverse caloric effects

NASA Astrophysics Data System (ADS)

Marathe, Madhura; Renggli, Damian; Sanlialp, Mehmet; Karabasov, Maksim O.; Shvartsman, Vladimir V.; Lupascu, Doru C.; Grünebohm, Anna; Ederer, Claude

2017-07-01

We study the electrocaloric (EC) effect in bulk BaTiO3 (BTO) using molecular dynamics simulations of a first principles-based effective Hamiltonian, combined with direct measurements of the adiabatic EC temperature change in BTO single crystals. We examine in particular the dependence of the EC effect on the direction of the applied electric field at all three ferroelectric transitions, and we show that the EC response is strongly anisotropic. Most strikingly, an inverse caloric effect, i.e., a temperature increase under field removal, can be observed at both ferroelectric-ferroelectric transitions for certain orientations of the applied field. Using the generalized Clausius-Clapeyron equation, we show that the inverse effect occurs exactly for those cases where the field orientation favors the higher temperature/higher entropy phase. Our simulations show that temperature changes of around 1 K can, in principle, be obtained at the tetragonal-orthorhombic transition close to room temperature, even for small applied fields, provided that the applied field is strong enough to drive the system across the first-order transition line. Our direct EC measurements for BTO single crystals at the cubic-tetragonal and at the tetragonal-orthorhombic transitions are in good qualitative agreement with our theoretical predictions, and in particular confirm the occurrence of an inverse EC effect at the tetragonal-orthorhombic transition for electric fields applied along the [001] pseudocubic direction.

Origin of superconductivity in KFe2As2 under positive and negative pressures and relation to other Fe-based families

NASA Astrophysics Data System (ADS)

Valenti, Roser

KFe2As2 shows an intricate behavior as a function of pressure. At ambient pressure the system is superconductor with a low critical temperature Tc=3.4 K and follows a V-shaped pressure dependence of Tc for moderate pressures with a local minimum at a pressure of 1.5 GPa. Under high pressures Pc=15 GPa, KFe2As2 exhibits a structural phase transition from a tetragonal to a collapsed tetragonal phase accompanied by a boost of the superconducting critical temperature up to 12 K. On the other hand, negative pressures realized through substitution of K by Cs or Rb decrease Tc down to 2.25K. In this talk we will discuss recent progress on the understanding of the microscopic origin of this pressure-dependent behavior by considering a combination of ab initio density functional theory with dynamical mean field theory and spin fluctuation theory calculations. We will argue that a Lifshitz transition associated with the structural collapse changes the pairing symmetry from d-wave (tetragonal) to s+/- (collapsed tetragonal) at high pressures while at ambient and negative pressures correlation effects appear to be detrimental for superconductivity. Further, we shall establish cross-links to the chalcogenide family, in particular FeSe under pressure. The Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged for financial support.

The effects of temperature and NaCl concentration on tetragonal lysozyme face growth rates

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth; Pusey, Marc Lee

1994-01-01

Measurements were made of the (110) and (101) face growth rates of the tetragonal form of hen egg white lysozyme at 0.1M sodium acetate buffer, pH 4.0, from 4 to 22 C and with 3.0%, 5.0%, and 7.0% NaCl used as the precipitating salt. The data were collected at supersaturation ratios ranging from approximately 4 to approximately 63. Both decreasing temperature and increasing salt concentrations shifted plots of the growth rate versus C/C(sat) to the right, i.e. higher supersaturations were required for comparable growth rates. The observed trends in the growth data are counter to those expected from the solubility data. If tetragonal lysozyme crystal growth is by addition of ordered aggregates from the solution, then the observed growth data could be explained as a result of the effects of lowered temperature and increased salt concentration on the kinetics and equilibrium processes governing protein-protein interactions in solution. The data indicate that temperature would be a more tractable means of controlling the growth rate for tetragonal lysozyme crystals contrary to the usual practice in, e.g., vapor diffusion protein crystal growth, where both the precipitant and protein concentrations are simultaneously increased. However, the available range for control is dependent upon the protein concentration, with the greatest growth rate control being at the lower concentration.

Domain wall and interphase boundary motion in (1−x)Bi(Mg{sub 0.5}Ti{sub 0.5})O{sub 3}–xPbTiO{sub 3} near the morphotropic phase boundary

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tutuncu, Goknur; Chen, Jun; Fan, Longlong

Electric field-induced changes in the domain wall motion of (1−x)Bi(Mg{sub 0.5}Ti{sub 0.5})O{sub 3}–xPbTiO{sub 3} (BMT-xPT) near the morphotropic phase boundary (MPB) where x = 0.37 (BMT-37PT) and x = 0.38 (BMT-38PT), are studied by means of synchrotron x-ray diffraction. Through Rietveld analysis and profile fitting, a mixture of coexisting monoclinic (Cm) and tetragonal (P4mm) phases is identified at room temperature. Extrinsic contributions to the property coefficients are evident from electric-field-induced domain wall motion in both the tetragonal and monoclinic phases, as well as through the interphase boundary motion between the two phases. Domain wall motion in the tetragonal and monoclinic phases for BMT-37PT ismore » larger than that of BMT-38PT, possibly due to this composition's closer proximity to the MPB. Increased interphase boundary motion was also observed in BMT-37PT. Lattice strain, which is a function of both intrinsic piezoelectric strain and elastic interactions of the grains (the latter originating from domain wall and interphase boundary motion), is similar for the respective tetragonal and monoclinic phases.« less

Anisotropic physical properties of single-crystal U2Rh2Sn in high magnetic fields

NASA Astrophysics Data System (ADS)

Prokeš, K.; Gorbunov, D. I.; Reehuis, M.; Klemke, B.; Gukasov, A.; Uhlířová, K.; Fabrèges, X.; Skourski, Y.; Yokaichiya, F.; Hartwig, S.; Andreev, A. V.

2017-05-01

We report on the crystal and magnetic structures, magnetic, transport, and thermal properties of U2Rh2Sn single crystals studied in part in high magnetic fields up to 58 T. The material adopts a U3Si2 -related tetragonal crystal structure and orders antiferromagnetically below TN=25 K. The antiferromagnetic structure is characterized by a propagation vector k =(00 1/2 ) . The magnetism in U2Rh2Sn is found to be associated mainly with 5 f states. However, both unpolarized and polarized neutron experiments reveal at low temperatures in zero field non-negligible magnetic moments also on Rh sites. U moments of 0.50(2) μB are directed along the tetragonal axis while Rh moments of 0.06(4) μB form a noncollinear arrangement confined to the basal plane. The response to applied magnetic field is highly anisotropic. Above ˜15 K the easy magnetization direction is along the tetragonal axis. At lower temperatures, however, a stronger response is found perpendicular to the c axis. While for the a axis no magnetic phase transition is observed up to 58 T, for the field applied at 1.8 K along the tetragonal axis we observe above 22.5 T a field-polarized state. A magnetic phase diagram for the field applied along the c axis is presented.

[Structure and properties of colored dental tetragonal zirconia stabilized by yttrium ceramics].

PubMed

Yi, Yuan-fu; Wang, Chen; Wen, Ning; Lin, Yong-zhao; Tian, Jie-mo

2009-10-01

To investigate the structure, mechanical and low temperature aging properties of colored dental zirconia ceramics. 5 graded colored dental zirconia ceramics were made by adding colorants and their combinations into a 3Y-TZP (tetragonal zirconia stabilized by 3mol% yttrium) powder, the green body were compacted at 200 MPa, pre-sinter at 1,050 degrees C and maintained for 2 h, then densely sintered at 1,500 degrees C for 2 h. Specimens were cut from each of the 5 graded colored blocks. Physical, mechanical properties as well as chemical stability were tested, microstructure were observed, crystalline phase were identified by X-ray diffraction (XRD), aging properties were assessed by measurement of the relative content of monoclinic phase and bending strength testing. The overall density of colored zirconia ceramics was over 99.7%, linear shrinkage was about 20%, while thermal expansion coefficient was about 11 x 10(-6) x degrees C(-1), the crystalline phase was tetragonal, bending strength was over 900 MPa which was slightly lowered than that of the uncolored zirconia, fracture toughness was slightly higher. Good chemical stability in acetic acid was observed. After aging treatment, tetragonal-to-monoclinic phase transformation was detected up to 40%, while bending strength was not significantly degraded. The results showed that colored 3Y-TZP ceramics presented good mechanical properties even after aging treatments, and was suitable for dental clinical use.

Finite element analysis of the tetragonal to monoclinic phase transformation during oxidation of zirconium alloys

NASA Astrophysics Data System (ADS)

Platt, P.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

2014-11-01

Corrosion is a key limiting factor in the degradation of zirconium alloys in light water reactors. Developing a mechanistic understanding of the corrosion process offers a route towards improving safety and efficiency as demand increases for higher burn-up of fuel. Oxides formed on zirconium alloys are composed of both monoclinic and meta-stable tetragonal phases, and are subject to a number of potential mechanical degradation mechanisms. The work presented investigates the link between the tetragonal to monoclinic oxide phase transformation and degradation of the protective character of the oxide layer. To achieve this, Abaqus finite element analysis of the oxide phase transformation has been carried out. Study of the change in transformation strain energy shows how relaxation of oxidation induced stress and fast fracture at the metal-oxide interface could destabilise the tetragonal phase. Central to this is the identification of the transformation variant most likely to form, and understanding why twinning of the transformed grain is likely to occur. Development of transformation strain tensors and analysis of the strain components allows some separation of dilatation and shear effects. Maximum principal stress is used as an indication of fracture in the surrounding oxide layer. Study of the stress distributions shows the way oxide fracture is likely to occur and the differing effects of dilatation and shape change. Comparison with literature provides qualitative validation of the finite element simulations.

Fabrication of dense and porous Li2ZrO3 nanofibers with electrospinning method

NASA Astrophysics Data System (ADS)

Yuan, Kangkang; Jin, Xiaotong; Xu, Chonghe; Wang, Xinqiang; Zhang, Guanghui; Zhu, Luyi; Xu, Dong

2018-06-01

Lithium zirconate (Li2ZrO3) has been extensively studied as CO2 capture material, electrolyte material and coating material. Most of the previous studies were focused on the powder structure, while seldom taking a consideration of fiber structure. In the present work, dense and porous Li2ZrO3 nanofibers with surface area of 16 m2 g-1 were prepared by electrospinning method. IR spectral results showed that lithium carbonate was the intermediate for the formation of Li2ZrO3. The phase transformation of Li2ZrO3 underwent the pathway of amorphous precursor fibers, tetragonal zirconia and Li2CO3, tetragonal Li2ZrO3, and monoclinic Li2ZrO3. XRD and XPS results further suggested that Li2O diffusion from the fiber body to surface occurred for Li2ZrO3 nanofibers when heat-treated above 900 °C, and the tetragonal Li2ZrO3 with high surface area could be obtained at 800 °C. Bamboo structure appeared both for the dense and porous nanofibers heat-treated at 1000 °C. The high surface area and high thermal stability of tetragonal phase of Li2ZrO3 make it a promising candidate in CO2 absorption, electrolyte and coating material.

First-Principles Study of the Jahn-Teller Distortion in the Ti1-XVXH2 and Zr1-XNbxH2 Alloys

NASA Astrophysics Data System (ADS)

Quijano, Ramiro; de Coss, Romeo; Singh, David

2008-03-01

The transition metal dihydrides TiH2 and ZrH2 present the fluorite structure (CaF2) at high temperature but undergoes a tetragonal distortion with c/a<1 at low temperature. Electronic band structure calculations have shown that TiH2 and ZrH2 in the cubic phase display a very flat band at the Fermi level. Thus the low temperature tetragonal distortion has been associated to a Jahn-Teller effect. In order to understand the role of band filling in controlling the structural instability of the transition metal dihydrides, we have performed a first-principles total energy study of the Ti1-XVxH2 and Zr1-xNbxH2 alloys. The calculations were performed using FP-LAPW method within the (DFT) and we use the GGA for exchange correlation functional energy. The critical concentration for which the Jahn-Teller effect is suppressed, was determined from the evolution of the tetragonal-cubic energy barrier. We discuss the electronic mechanism of the structural-instability, in terms of the band filling. From the obtained results we conclude that the tetragonal distortion in TiH2 and ZrH2 is not produced only by a Jahn-Teller Effect. This research was supported by Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grant No. 43830-F.

Chemical vapor deposition of yttria-stabilized zirconia as a thermal barrier coating for gas turbine engines

NASA Astrophysics Data System (ADS)

Varanasi, Venu Gopal

The gas turbine engine uses an yttria-stabilized zirconia (YSZ) coating to provide thermal insulation for its turbine blades. This YSZ coating must be tetragonal in crystal structure, columnar in microstructure, and be 100--250 mum thick to provide for adequate protection for the turbine blades in the severe engine environment. Currently, YSZ coatings are fabricated by electron-beam physical vapor deposition (EB-PVD), but this fabrication method is cost intensive. Chemical vapor deposition (CVD) is a more commercially viable processing method and a possible alternative to EB-PVD. The deposition of tetragonal YSZ from gaseous metal and oxidation sources were studied. A chemical equilibrium analysis modeled the feasibility of depositing tetragonal YSZ for both chloride CVD (Zr-Y-C-O-Cl-H-Inert system) and metal-organic CVD (MOCVD) (Zr-Y-C-O-H system). Pure thermochemical properties and the assessed YSZ phase diagram were used in this analysis. Using the molar input of metals ((nY + nZr) and ( nY/(nY + nZr ) = 0.08)) as bases, equilibrium calculations showed that tetragonal YSZ formation was feasible. Tetragonal YSZ formation was feasible with high oxygen content (nO/(nY + nZr) > 8) and high temperature (T > 100°C) in the case of chloride CVD (Zr-Y-C-O-Cl-H-Inert). Tetragonal YSZ formation was feasible with high oxygen content (nO/( nY + nZr) > 5) and high temperature (T > 950°C) in the case of MOCVD (Zr-Y-C-O-H). Although solid carbon formation did not appear in chloride CVD, additional oxygen (nO/( nY + nZr) > 32) and low hydrogen content relative to carbon (nH/nC < 2) were required to avoid solid carbon formation in MOCVD. Coatings were deposited using a set of base conditions derived from the chemical equilibrium analysis. In chloride CVD, YCl3 was not included because of its low vapor pressure, thus, ZrCl4 was oxidized with the H2-CO2 gas mixture. Monoclinic ZrO2 coatings were deposited at the thermochemically optimized conditions (n O/(nY + nZr) > 8, T > 1004°C) with approximately 5.5 mum h-1 growth rate. In metal-organic CVD (MOCVD), liquid precursor solutions of Y- and Zr-beta-diketonate and Y- and Zr-n-butoxide precursors were used as the metal sources and O2 gas was used as the oxidation source. Using the Y- and Zr-beta-diketonate liquid precursor solution, tetragonal YSZ was deposited with a layered microstructure apparent and a maximum growth rate of approximately 14 mum h-1 (activation energy (E a) of 50.9 +/- 4.3 kJ mol-1). The growth rate (approximately 43 mum h-1 with Ea = 53.8 +/- 7.9 kJ mol-1) was improved using Y- and Zr- n-butoxide liquid precursor solutions, and the microstructure was columnar. Yet, two-phase deposition of monoclinic ZrO2 and tetragonal YSZ occurred. Results of electron-probe micro-analysis showed that the nY/(nY + nZr ) ratio was less than 45% of the nY/( nY + nZr) ratio in the liquid precursor solution.

Electronic structure and energetics of the tetragonal distortion for TiH2, ZrH2 and HfH2: a first principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Quijano, Ramiro; DeCoss, Romeo; Singh, David J

2009-01-01

The electronic structure and energetics of the tetragonal distortion for the fluorite-type dihydrides TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} are studied by means of highly accurate first-principles total-energy calculations. For HfH{sub 2}, in addition to the calculations using the scalar relativistic (SR) approximation, calculations including the spin-orbit coupling have also been performed. The results show that TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} in the cubic phase are unstable against tetragonal strain. For the three systems, the total energy shows two minima as a function of the c/a ratio with the lowest-energy minimum at c/a < 1 in agreementmore » with the experimental observations. The band structure of TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} (SR) around the Fermi level shows two common features along the two major symmetry directions of the Brillouin zone, {Lambda}?L and {Lambda}?K, a nearly flat doubly degenerate band, and a van Hove singularity, respectively. In cubic HfH{sub 2} the spin-orbit coupling lifts the degeneracy of the partially filled bands in the {Lambda}?L path, while the van Hove singularity in the {Lambda}?K path remains unchanged. The density of states of the three systems in the cubic phase shows a sharp peak at the Fermi level. We found that the tetragonal distortion produces a strong reduction in the density of states at the Fermi level resulting mainly from the splitting of the doubly-degenerate bands in the {Lambda}?L direction and the shift of the van Hove singularity to above the Fermi level. The validity of the Jahn-Teller model in explaining the tetragonal distortion in this group of dihydrides is discussed.« less

Anharmonicity and Disorder in the Black Phases of Cesium Lead Iodide Used for Stable Inorganic Perovskite Solar Cells.

PubMed

Marronnier, Arthur; Roma, Guido; Boyer-Richard, Soline; Pedesseau, Laurent; Jancu, Jean-Marc; Bonnassieux, Yvan; Katan, Claudine; Stoumpos, Constantinos C; Kanatzidis, Mercouri G; Even, Jacky

2018-04-24

Hybrid organic-inorganic perovskites emerged as a new generation of absorber materials for high-efficiency low-cost solar cells in 2009. Very recently, fully inorganic perovskite quantum dots also led to promising efficiencies, making them a potentially stable and efficient alternative to their hybrid cousins. Currently, the record efficiency is obtained with CsPbI 3 , whose crystallographical characterization is still limited. Here, we show through high-resolution in situ synchrotron XRD measurements that CsPbI 3 can be undercooled below its transition temperature and temporarily maintained in its perovskite structure down to room temperature, stabilizing a metastable perovskite polytype (black γ-phase) crucial for photovoltaic applications. Our analysis of the structural phase transitions reveals a highly anisotropic evolution of the individual lattice parameters versus temperature. Structural, vibrational, and electronic properties of all the experimentally observed black phases are further inspected based on several theoretical approaches. Whereas the black γ-phase is shown to behave harmonically around equilibrium, for the tetragonal phase, density functional theory reveals the same anharmonic behavior, with a Brillouin zone-centered double-well instability, as for the cubic phase. Using total energy and vibrational entropy calculations, we highlight the competition between all the low-temperature phases of CsPbI 3 (γ, δ, β) and show that avoiding the order-disorder entropy term arising from double-well instabilities is key to preventing the formation of the yellow perovskitoid phase. A symmetry-based tight-binding model, validated by self-consistent GW calculations including spin-orbit coupling, affords further insight into their electronic properties, with evidence of Rashba effect for both cubic and tetragonal phases when using the symmetry-breaking structures obtained through frozen phonon calculations.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

DOEpatents

Sachtler, W.M.H.; Huang, Y.Y.

1998-07-28

Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

DOEpatents

Sachtler, Wolfgang M. H.; Huang, Yin-Yan

1998-01-01

Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

Structural investigation of the C-O complex in GaAs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alt, H. Ch.; Kersch, A.; Wagner, H. E.

A carbon-oxygen complex occurring in gallium arsenide crystals after annealing at around 700 °C is studied. Fourier transform infrared absorption measurements on the associated vibrational band at 2060 cm-1 under uniaxial stress reveal that the center has tetragonal symmetry. From the intensity of the {sup 18}O-related satellite band it is concluded that four oxygen atoms are involved. Ab initio local density calculations show that a tetragonal CO{sub 4} molecule forms a stable entity in the gallium arsenide lattice.

Metal-organic chemical vapour deposition of polycrystalline tetragonal indium sulphide (InS) thin films

NASA Technical Reports Server (NTRS)

Macinnes, Andrew N.; Cleaver, William M.; Barron, Andrew R.; Power, Michael B.; Hepp, Aloysius F.

1992-01-01

The dimeric indium thiolate /(t Bu)2In(mu-S sup t Bu)/2 has been used as a single-source precursor for the MOCVD of InS thin films. The dimeric In2S2 core is proposed to account for the formation of the nonequilibrium high-pressure tetragonal phase in the deposited films. Analysis of the deposited films has been obtained by TEM, with associated energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy.

Structure of junctions of multiwalled carbon nanotubes with tetragonal cross section and flattened nanotubes revealed by electron-beam tomography

NASA Astrophysics Data System (ADS)

Nagano, Yuta; Kohno, Hideo

2017-11-01

Multiwalled carbon nanotubes with tetragonal cross section frequently form junctions with flattened multi-walled carbon nanotubes, a kind of carbon nanoribbon. The three-dimensional structure of the junctions is revealed by transmission-electron-microscopy-based tomography. Two types of junction, parallel and diagonal, are found. The formation mechanism of these two types of junction is discussed in terms of the origami mechanism that was previously proposed to explain the formation of carbon nanoribbons and nanotetrahedra.

Clarification of the Hashin-Shtrikman bounds on the effective elastic moduli of polycrystals with hexagonal, trigonal, and tetragonal symmetries

USGS Publications Warehouse

Watt, J.P.; Peselnick, L.

1980-01-01

Bounds on the effective elastic moduli of randomly oriented aggregates of hexagonal, trigonal, and tetragonal crystals are derived using the variational principles of Hashin and Shtrikman. The bounds are considerably narrower than the widely used Voigt and Reuss bounds. The Voigt-Reuss-Hill average lies within the Hashin-Shtrikman bounds in nearly all cases. Previous bounds of Peselnick and Meister are shown to be special cases of the present results.

Reflection of thermoelastic wave on the interface of isotropic half-space and tetragonal syngony anisotropic medium of classes 4, 4/m with thermomechanical effect

NASA Astrophysics Data System (ADS)

Nurlybek, A. Ispulov; Abdul, Qadir; M, A. Shah; Ainur, K. Seythanova; Tanat, G. Kissikov; Erkin, Arinov

2016-03-01

The thermoelastic wave propagation in a tetragonal syngony anisotropic medium of classes 4, 4/m having heterogeneity along z axis has been investigated by employing matrizant method. This medium has an axis of second-order symmetry parallel to z axis. In the case of the fourth-order matrix coefficients, the problems of wave refraction and reflection on the interface of homogeneous anisotropic thermoelastic mediums are solved analytically.

Synthesis, Characterization, and Self-Controlled Orthorhombic to Tetragonal Polymorphic Transformation in BaTiO3 Nanoparticles

NASA Astrophysics Data System (ADS)

Ram, S.; Jana, A.; Kundu, T. K.

The phase formation and thermal-induced phase transformation are studied in BaTiO3 nanoparticles. 2 h of heating a polymer precursor at 550°C in air formed a single phase BaTiO3 of 15 nm average crystallite size D. The X-ray diffraction peaks are analyzed assuming a Pnma orthorhombic (o) crystal structure of lattice parameters a = 0.6435 nm, b = 0.5306 nm, and c = 0.8854 nm. The lattice volume V = 0.3023 nm3, with z = 4 formula units, yields a density ρ = 5.124 g/cm3. This is a new polymorph in comparison to well-known Pm3m tetragonal (t) structure, V = 0.0644 nm3 or ρ = 6.016 g/cm3 (z = 1). An o ↦ t transformation appears on heating at temperature as high as 650°C in air. A proposed model explains the transformation above a certain D value in terms of the Gibbs free energy. Unless heating above 750°C, the two phases coexist in a composite structure (D≤27 nm), with as much residual o-phase trace as ~28 vol%. As a function of temperature both the phases decrease in the V values up to 0.2975 and 0.0643 nm3 at 750°C respectively (0.0650 nm3 at 650°C). This is an important parameter for designing useful ferroelectric and other properties in a hybrid composite structure.

Modeling Tetragonal Lysozyme Crystal Growth Rates

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2003-01-01

Tetragonal lysozyme 110 face crystal growth rates, measured over 5 orders of magnitude in range, can be described using a model where growth occurs by 2D nucleation on the crystal surface for solution supersaturations of c/c(sub eq) less than or equal to 7 +/- 2. Based upon the model, the step energy per unit length, beta was estimated to be approx. 5.3 +/- 0.4 x 10(exp -7) erg/mol-cm, which for a step height of 56 A corresponds to barrier of approx. 7 +/- 1 k(sub B)T at 300 K. For supersaturations of c/c(sub eq) > 8, the model emphasizing crystal growth by 2D nucleation not only could not predict, but also consistently overestimated, the highest observable crystal growth rates. Kinetic roughening is hypothesized to occur at a cross-over supersaturation of c/c(sub eq) > 8, where crystal growth is postulated to occur by a different process such as adsorption. Under this assumption, all growth rate data indicated that a kinetic roughening transition and subsequent crystal growth by adsorption for all solution conditions, varying in buffer pH, temperature and precipitant concentration, occurs for c/c(sub eq)(T, pH, NaCl) in the range between 5 and 10, with an energy barrier for adsorption estimated to be approx. 20 k(sub B)T at 300 K. Based upon these and other estimates, we determined the size of the critical surface nucleate, at the crossover supersaturation and higher concentrations, to range from 4 to 10 molecules.

Influences of annealing temperature on structural characterization and magnetic properties of Mn-doped BaTiO3 ceramics

NASA Astrophysics Data System (ADS)

Phan, The-Long; Zhang, P.; Grinting, D.; Yu, S. C.; Nghia, N. X.; Dang, N. V.; Lam, V. D.

2012-07-01

Polycrystalline samples of BaTiO3 doped with 2.0 at. % Mn were prepared by solid-state reaction at various temperatures (Tan) ranging from 500 to 1350 °C, used high-pure powders of BaCO3, TiO2, and MnCO3 as precursors. Experimental results obtained from x-ray diffraction patterns and Raman scattering spectra reveal that tetragonal Mn-doped BaTiO3 starts constituting as Tan ≈ 500 °C. The Tan increase leads to the development of this phase. Interestingly, there is the tetragonal-hexagonal transformation in the crystal structure of BaTiO3 as Tan ≈ 1100 °C. Such the variations influence directly magnetic properties of the samples. Besides paramagnetic contributions of Mn2+ centers traced to electron spin resonance, the room-temperature ferromagnetism found in the samples is assigned to exchange interactions taking place between Mn3+ and Mn4+ ions located in tetragonal BaTiO3 crystals.

Dramatic changes in the electronic structure upon transition to the collapsed tetragonal phase in CaFe 2As 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhaka, R. S.; Jiang, Rui; Ran, S.

2014-01-31

We use angle-resolved photoemission spectroscopy and density functional theory calculations to study the electronic structure of CaFe 2As 2 in the collapsed tetragonal (CT) phase. This unusual phase of iron arsenic high-temperature superconductors was hard to measure as it exists only under pressure. By inducing internal strain, via the postgrowth thermal treatment of single crystals, we were able to stabilize the CT phase at ambient pressure. We find significant differences in the Fermi surface topology and band dispersion data from the more common orthorhombic-antiferromagnetic or tetragonal-paramagnetic phases, consistent with electronic structure calculations. The top of the hole bands sinks belowmore » the Fermi level, which destroys the nesting present in parent phases. The absence of nesting in this phase, along with an apparent loss of Fe magnetic moment, are now clearly experimentally correlated with the lack of superconductivity in this phase.« less

Substitutional Cd and Cd-Oxygen Vacancy Complexes in ZrO2 and Ce-doped ZrO_2

NASA Astrophysics Data System (ADS)

Zacate, Matthew O.; Karapetrova, E.; Platzer, R.; Gardner, J. A.; Evenson, W. E.; Sommers, J. A.

1996-03-01

We are using Perturbed Angular Correlation Spectroscopy (PAC) to study oxygen vacancy (V_O) dynamics in tetragonal ZrO2 and Ce-doped ZrO_2. PAC requires a radioactive probe atom, Cd in this study, which sits substitutionally for a Zr ion. Cd is doubly-negatively charged relative to the lattice and attracts doubly-positively charged V_Os. Pure tetragonal zirconia exists only above 950 ^circC and in this temperature range, the V_Os are very mobile. Above 950 ^circC we observe V_Os rapidly hopping about the Cd allowing us to determine the VO concentration and the trapping energy. We have been Ce-doping to stabilize the tetragonal phase to lower temperature to determine the electric field gradient the Cd experiences due to a stationary V_O. As a consequence of the Ce-doping, we observe a local lattice distortion about the Cd which increases with Ce-doping.

Nanotwin and phase transformation in tetragonal Pb(Fe1/2Nb1/2)1-xTixO3 single crystal

NASA Astrophysics Data System (ADS)

Tu, C.-S.; Tseng, C.-T.; Chien, R. R.; Schmidt, V. Hugo; Hsieh, C.-M.

2008-09-01

This work is a study of phase transformation in (001)-cut Pb(Fe1/2Nb1/2)1-xTixO3 (x =48%) single crystals by means of dielectric permittivity, domain structure, and in situ x-ray diffraction. A first-order T(TNT)-C(TNT) phase transition was observed at the Curie temperature TC≅518 K upon zero-field heating. T, TNT, and C are tetragonal, tetragonal nanotwin, and cubic phases, respectively. T(TNT) and C(TNT) indicate that minor TNT domains reside in the T and C matrices. Nanotwins, which can cause broad diffraction peak, remain above TC≅518 K and give an average microscopic cubic symmetry in the polarizing microscopy. Colossal dielectric permittivity (>104) was observed above room temperature with strong frequency dispersion. This study suggests that nanotwins can play an important role in relaxor ferroelectric crystals while phase transition takes place. The Fe ion is a potential candidate as a B-site dopant for enhancing dielectric permittivity.

Effect of starting powders on the sintering of nanostructured ZrO2 ceramics by colloidal processing

NASA Astrophysics Data System (ADS)

Suárez, Gustavo; Sakka, Yoshio; Suzuki, Tohru S.; Uchikoshi, Tetsuo; Zhu, Xinwen; Aglietti, Esteban F.

2009-04-01

The effect of starting powders on the sintering of nanostructured tetragonal zirconia was evaluated. Suspensions were prepared with a concentration of 10 vol.% by mixing a bicomponent mixture of commercial powders (97 mol.% monoclinic zirconia with 3 mol.% yttria) and by dispersing commercially available tetragonal zirconia (3YTZ, Tosoh). The preparation of the slurry by bead-milling was optimized. Colloidal processing using 50 μm zirconia beads at 4000 rpm generated a fully deagglomerated suspension leading to the formation of high-density consolidated compacts (62% of the theoretical density (TD) for the bicomponent suspension). Optimum colloidal processing of the bicomponent suspension followed by the sintering of yttria and zirconia allowed us to obtain nanostructured tetragonal zirconia. Three different sintering techniques were investigated: normal sintering, two-step sintering and spark plasma sintering. The inhibition of grain growth in the bicomponent mixed powders in comparison with 3YTZ was demonstrated. The inhibition of the grain growth may have been caused by inter-diffusion of cations during the sintering.

Cubic-to-tetragonal structural phase transition in Rb1-xCsxCaF3 solid solutions: Thermal expansion and EPR studies

NASA Astrophysics Data System (ADS)

Lahoz, F.; Villacampa, B.; Alcalá, R.; Marquina, C.; Ibarra, M. R.

1997-04-01

The influence of crystal mixing on the structural phase transitions in Rb1-xCsxCaF3 (0=0.44. This transition shows a weak first-order component in the x=0 and 0.1 samples, which is progressively smeared out for x>0.1, indicating a spatial distribution of the critical temperature in those crystals with high ionic substitution rate. In RbCaF3 , another structural phase transition was observed at 20 K with a thermal hysteresis between 20 and 40 K. This transition has not been found in any of the mixed crystals.

Lead-free Bi(Mg0.5Ti0.5)O3-modified 0.875Bi0.5Na0.5TiO3-0.125BaTiO3 ferroelectric ceramics with tetragonal structure and large field-induced strains

NASA Astrophysics Data System (ADS)

Li, Ling; Zhu, Mankang; Ren, Xiaowei; Wei, Qiumei; Zheng, Mupeng; Hou, Yudong

2017-12-01

A electrostrictive ceramics were designed by introducing Bi(Mg0.5Ti0.5)O3 into 0.875Bi0.5Na0.5TiO3-0.125BaTiO3 with tetragonal structure. All the specimens prepared by a conventional solid sintering technique exhibit the excellent sintering ability with a high relative density over 97%. It is found that, as BMT added, the specimens undergo a structure crossover from ferroelectric P4mm to ergodic P4bm, and the coexistence of both tetragonal structures takes bridge between them. A large field-induced strain of 0.30% and field-independent strain coefficient of 0.0254 m4/C2 occur at 4 mol.% BMT added. This material with excellent sinterability is suitable for the application in actuators and microposition controllers.

Barium Titanate Nanoparticles for Biomarker Applications

NASA Astrophysics Data System (ADS)

Matar, O.; Posada, O. M.; Hondow, N. S.; Wälti, C.; Saunders, M.; Murray, C. A.; Brydson, R. M. D.; Milne, S. J.; Brown, A. P.

2015-10-01

A tetragonal crystal structure is required for barium titanate nanoparticles to exhibit the nonlinear optical effect of second harmonic light generation (SHG) for use as a biomarker when illuminated by a near-infrared source. Here we use synchrotron XRD to elucidate the tetragonal phase of commercially purchased tetragonal, cubic and hydrothermally prepared barium titanate (BaTiO3) nanoparticles by peak fitting with reference patterns. The local phase of individual nanoparticles is determined by STEM electron energy loss spectroscopy (EELS), measuring the core-loss O K-edge and the Ti L3-edge energy separation of the t2g, eg peaks. The results show a change in energy separation between the t2g and eg peak from the surface and core of the particles, suggesting an intraparticle phase mixture of the barium titanate nanoparticles. HAADF-STEM and bright field TEM-EDX show cellular uptake of the hydrothermally prepared BaTiO3 nanoparticles, highlighting the potential for application as biomarkers.

Real-time atomistic observation of structural phase transformations in individual hafnia nanorods

DOE PAGES

Hudak, Bethany M.; Depner, Sean W.; Waetzig, Gregory R.; ...

2017-05-12

High-temperature phases of hafnium dioxide have exceptionally high dielectric constants and large bandgaps, but quenching them to room temperature remains a challenge. Scaling the bulk form to nanocrystals, while successful in stabilizing the tetragonal phase of isomorphous ZrO 2, has produced nanorods with a twinned version of the room temperature monoclinic phase in HfO 2. Here we use in situ heating in a scanning transmission electron microscope to observe the transformation of an HfO 2 nanorod from monoclinic to tetragonal, with a transformation temperature suppressed by over 1000°C from bulk. When the nanorod is annealed, we observe with atomic-scale resolutionmore » the transformation from twinned-monoclinic to tetragonal, starting at a twin boundary and propagating via coherent transformation dislocation; the nanorod is reduced to hafnium on cooling. Unlike the bulk displacive transition, nanoscale size-confinement enables us to manipulate the transformation mechanism, and we observe discrete nucleation events and sigmoidal nucleation and growth kinetics.« less

Location of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg white lysozyme from salt solutions. Previous studies employing X-ray crystallography had found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystal grown in bromide and chloride solutions. Five possible anion binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four of these sites corresponded to four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion binding sites in lysozyme remain unchanged, even when different anions and different crystal forms of lysozyme are employed.

Locations of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg-white lysozyme from salt solutions. Previous studies employing X-ray crystallography have found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystals grown in bromide and chloride solutions. Five possible anion-binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four further sites were found which corresponded to the four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion-binding sites in lysozyme remain unchanged even when different anions and different crystal forms of lysozyme are employed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe 2As 2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, nding in particular that tetragonal superconducting domains are very elongated, more than several tens of μm long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic eld. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the rstmore » order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.« less

Theoretical Studies of the Electron Paramagnetic Resonance Parameters and Local Structure for VO2+ in Oxyfluoroborate Glasses

NASA Astrophysics Data System (ADS)

Zhang, Huaming; Yu, Xiaopeng; Xiao, Wenbo

2017-12-01

The electron paramagnetic resonance parameters (g factors g ‖, g ⊥ and hyperfine structure constants A ‖, A ⊥) of a tetragonal V4+ center in oxyfluoroborate glasses (20Li2O-10Li2F2-70B2O3) are theoretically investigated by using the perturbation formulas for a 3d1 ion in tetragonally compressed octahedra. The calculated results are in good agreement with the experimental data. Local structure parameters of [VO6]8- clusters are obtained from the calculation (i.e., R‖ ≈ 1.74 Å and R⊥ ≈ 1.985 Å for the metal-ligand distances parallel and perpendicular to the C4 axis, respectively). It is shown that the local structure around the V4+ ion possesses a compressed tetragonal distortion along C 4 axis. The signs of the hyperfine structure constants A‖ and A ⊥ for V4+ centers in oxyfluoroborate glasses were also suggested in the discussion.

A sol-powder coating technique for fabrication of yttria stabilised zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wattanasiriwech, Darunee; Wattanasiriwech, Suthee; Stevens, Ron

Yttria stabilised zirconia has been prepared using a simple sol-powder coating technique. The polymeric yttria sol, which was prepared using 1,3 propanediol as a network modifier, was homogeneously mixed with nanocrystalline zirconia powder and it showed a dual function: as a binder which promoted densification and a phase modifier which stabilised zirconia in the tetragonal and cubic phases. Thermal analysis and X-ray diffraction revealed that the polymeric yttria sol which decomposed at low temperature into yttrium oxide could change the m {sup {yields}} t phase transformation behaviour of the zirconia, possibly due to the small particle size and very highmore » surface area of both yttria and zirconia particles allowing rapid alloying. The sintered samples exhibited three crystalline phases: monoclinic, tetragonal and cubic, in which cubic and tetragonal are the major phases. The weight fractions of the individual phases present in the selected specimens were determined using quantitative Rietveld analysis.« less

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.; Mitchell, T. E.

1981-01-01

A commercially available bulk 4.5 mole percent yttria-Y2O3)-partially-stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging cuves were constructed for both the as-received and the solution-annealed-and-quenched materials; the curves showed hardness peaks at 1397 and 1517 kg/sq mm, respectively. A total of twelve different types of tetragonal precipitates were found. The rectangular plate-shaped tetragonal precipitates were found to have a (110) habit plane. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinic phase, thus indicating that transformation toughening is not a significant mechanism for the material. The fracture toughness of the aged and of the unaged solution-annealed-and-quenched PSZ was found to be between 2 and 3 MN/cu m/2.

Revealing the hidden structural phases of FeRh

NASA Astrophysics Data System (ADS)

Kim, Jinwoong; Ramesh, R.; Kioussis, Nicholas

2016-11-01

Ab initio electronic structure calculations reveal that tetragonal distortion has a dramatic effect on the relative stability of the various magnetic structures (C-, A-, G-, A'-AFM, and FM) of FeRh giving rise to a wide range of novel stable/metastable structures and magnetic phase transitions between these states. We predict that the cubic G-AFM structure, which was believed thus far to be the ground state, is metastable and that the tetragonally expanded G-AFM is the stable structure. The low energy barrier separating these states suggests phase coexistence at room temperature. We propose an A'-AFM phase to be the global ground state among all magnetic phases which arises from the strain-induced tuning of the exchange interactions. The results elucidate the underlying mechanism for the recent experimental findings of electric-field control of magnetic phase transition driven via tetragonal strain. The magnetic phase transitions open interesting prospects for exploiting strain engineering for the next-generation memory devices.

Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

NASA Astrophysics Data System (ADS)

Francillon, Wesley

This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is a single tetragonal phase. Thus, compositions are of single phase tetragonal phase, theoretically, should not undergo high temperature partitioning. Single Tetragonal phase oxides of Ti-YSZ also offer the possibility of enhanced toughness and higher temperature stability akin to those observed in yttria partially stabilized zirconia. Many pyrochlore oxides are under review because they have shown to have lower thermal conductivity than YSZ oxides. This study focused on chemically synthesizing homogeneous starting material compositions in a metastable state (preferably amorphous), following its evolution according to the phase hierarchy under conditions of kinetic constraints. The current equilibrium diagram of YO1.5-TiO2-ZrO 2 is based on theoretical calculations. One of the contributions of this work is the redefined phase fields in YO1.5-TiO2-ZrO 2 based on our experimental results. Investigated compositions were based on tie lines of Y2-xTi2ZrxO7+x/2 and Y2Ti2-yZryO7 representing substitution of Zr4+ for Y3+ and Zr4+ for Ti4+ respectively. More notably, we observed extended metastable phases in pyrochlore and fluorite oxides at low temperature. The significance of this result is that it offers a larger compositional range for investing pyrochlore oxides with associated high temperature phase stability for TBC applications. In tetragonal oxides, our results showed that Ti-YSZ results have slower partitioning kinetics in comparison to YSZ at high temperature. This study also emphasized the deposition of advanced ceramic coatings by plasma spray for tetragonal and pyrochlore systems, compositionally complex functional oxides that may potentially have lower thermal conductivity values compared to current YSZ oxides. Next generation thermal barrier coatings require powders with high chemical purity, chemical homogeneity, controlled particle size/shape and pertinent phase state. Thermal spray offers an avenue to create novel materials and deposits directly from the precursor and compositionally controlled powder feedstock. This study contributed to investigating an unexplored field that offers a variety of opportunities in materials synthesis that would not be possible by conventional methods. Understanding processing-microstructure-property correlations is of considerable importance in thermal spray of functional oxide materials. This thesis demonstrated by radio-frequency thermal spray that the complex pyrochlore oxide Y 2Ti2O7 could be deposited by directly injecting molecularly mixed precursors to form oxide coatings. Structural analysis revealed the metastable fluorite phase; however, with thermal treatments at relatively low temperature of 700°C the pyrochlore phase was obtained. For Ti-YSZ coatings, the tetragonal phase oxides were obtained with unique microstructures, however, the tetragonal prime destabilized at 1200°C. This dissertation explored novel oxide compositions through detailed structural analysis. The approach presented a comprehensive and integrated investigation as it pertains to phase evolution of oxides in powder feedstock to coating characteristics (phase/properties).

Investigation of La and Al substitution on the spontaneous polarization and lattice dynamics of the Pb(1-x)LaxTi(1-x)AlxO3 ceramics

NASA Astrophysics Data System (ADS)

Yadav, Arun Kumar; Verma, Anita; Kumar, Sunil; Srihari, Velaga; Sinha, A. K.; Reddy, V. Raghavendra; Liu, Shun Wei; Biring, Sajal; Sen, Somaditya

2018-03-01

The phase purity and crystal structure of Pb(1-x)LaxTi(1-x)AlxO3 (0 ≤ x ≤ 0.25) samples (synthesized via the sol-gel process) were confirmed using synchrotron x-ray powder diffraction (XRD) (wavelength, λ = 0.44573 Å). Rietveld analyses of powder x-ray diffraction data confirmed the tetragonal structure for compositions with x ≤ 0.18 and cubic structure for the sample with x = 0.25. Temperature-dependent XRD was performed to investigate the structural change from tetragonal to cubic structure phase transition. Raman spectroscopy at room temperature also confirmed this phase transition with compositions. Field emission scanning electron microscopy (FESEM) provided information about the surface morphology while an energy dispersive x-ray spectrometer attached with FESEM confirmed the chemical compositions of samples. Temperature and frequency dependent dielectric studies showed that the tetragonal to cubic phase transition decreased from 680 K to 175 K with an increase in the x from 0.03 to 0.25, respectively. This is correlated with the structural studies. Electric field dependent spontaneous polarization showed a proper ferroelectric loop for 0.06 ≤ x ≤ 0.18 belonging to a tetragonal phase, while for x ≥ 0.25, the spontaneous polarization vanishes. Bipolar strain versus electric field revealed a butterfly loop for 0.06 ≤ x ≤ 0.18 compositions. Energy storage efficiency initially increases nominally with substitution but beyond x = 0.18 enhances considerably.

Effect of texture dispersion on the effective biaxial modulus of fiber-textured hexagonal, tetragonal, and orthorhombic films

NASA Astrophysics Data System (ADS)

Wu, Huaping; Wu, Linzhi; Du, Shanyi

2008-04-01

The effective biaxial modulus (Meff) of fiber-textured hexagonal, tetragonal, and orthorhombic films is estimated by using the Voigt-Reuss-Hill and Vook-Witt grain-interaction models. The orientation distribution function with Gaussian distributions of the two Euler angles θ and ϕ is adopted to analyze the effect of texture dispersion degree on Meff. Numerical results that are based on ZnO, BaTiO3, and yttrium barium copper oxide (YBCO) materials show that the Vook-Witt average of Meff is identical to the Voigt-Reuss-Hill average of Meff for the (001) plane of ideally fiber-textured hexagonal and tetragonal films. The ϕ distribution has no influence on Meff of the (hkl)-fiber-textured hexagonal film at any θ distribution in terms of the isotropy in the plane perpendicular to the [001] direction. Comparably, tetragonal and orthorhombic films represent considerable actions of ϕ dispersion on Meff, and the effect of ϕ dispersion on Meff of a (001)-fiber-textured YBCO film is smaller than that for a (001)-fiber-textured BaTiO3 film since the shear anisotropic factor in the (001) shear plane of a YBCO film more closely approaches 1. Enhanced θ and ϕ distributions destroy the perfect fiber textures, and as a result, the films exhibit an evolution from ideal (hkl) fiber textures to random textures with varying full widths at half maximums of θ and ϕ.

Instability of the layered orthorhombic post-perovskite phase of SrTiO3 and other candidate orthorhombic phases under pressure

NASA Astrophysics Data System (ADS)

Bhandari, Churna; Lambrecht, Walter R. L.

2018-06-01

While the tetragonal antiferro-electrically distorted (AFD) phase with space group I 4 / mcm is well known for SrTiO3 to occur below 105 K, there are also some hints in the literature of an orthorhombic phase, either at the lower temperature or at high pressure. A previously proposed orthorhombic layered structure of SrTiO3, known as the post-perovskite or CaIrO3 structure with space group Cmcm is shown to have significantly higher energy than the cubic or tetragonal phase and to have its minimum volume at larger volume than cubic perovskite. The Cmcm structure is thus ruled out. We also study an alternative Pnma phase obtained by two octahedral rotations about different axes. This phase is found to have slightly lower energy than the I 4 / mcm phase in spite of the fact that its parent, in-phase tilted P 4 / mbm phase is not found to occur. Our calculated enthalpies of formation show that the I 4 / mcm phase occurs at slightly higher volume than the cubic phase and has a negative transition pressure relative to the cubic phase, which suggests that it does not correspond to the high-pressure tetragonal phase. The enthalpy of the Pnma phase is almost indistinguishable from the I 4 / mcm phase. Alternative ferro-electric tetragonal and orthorhombic structures previously suggested in literature are discussed.

Preisach modeling of temperature-dependent ferroelectric response of piezoceramics at sub-switching regime

NASA Astrophysics Data System (ADS)

Ochoa, Diego Alejandro; García, Jose Eduardo

2016-04-01

The Preisach model is a classical method for describing nonlinear behavior in hysteretic systems. According to this model, a hysteretic system contains a collection of simple bistable units which are characterized by an internal field and a coercive field. This set of bistable units exhibits a statistical distribution that depends on these fields as parameters. Thus, nonlinear response depends on the specific distribution function associated with the material. This model is satisfactorily used in this work to describe the temperature-dependent ferroelectric response in PZT- and KNN-based piezoceramics. A distribution function expanded in Maclaurin series considering only the first terms in the internal field and the coercive field is proposed. Changes in coefficient relations of a single distribution function allow us to explain the complex temperature dependence of hard piezoceramic behavior. A similar analysis based on the same form of the distribution function shows that the KNL-NTS properties soften around its orthorhombic to tetragonal phase transition.

Liebermannite, KAlSi3O8, a new shock-metamorphic, high-pressure mineral from the Zagami Martian meteorite

NASA Astrophysics Data System (ADS)

Ma, Chi; Tschauner, Oliver; Beckett, John R.; Rossman, George R.; Prescher, Clemens; Prakapenka, Vitali B.; Bechtel, Hans A.; MacDowell, Alastair

2018-01-01

In this paper, we discuss the occurrence of liebermannite (IMA 2013-128), KAlSi3O8, a new, shock-generated, high-pressure tetragonal hollandite-type structure silicate mineral, in the Zagami basaltic shergottite meteorite. Liebermannite crystallizes in space group I4/m with Z = 2, cell dimensions of a = 9.15 ± 0.14 (1σ) Å, c = 2.74 ± 0.13 Å, and a cell volume of 229 ± 19 Å3 (for the type material), as revealed by synchrotron diffraction. In Zagami, liebermannite likely formed via solid-state transformation of primary igneous K-feldspar during an impact event that achieved pressures of 20 GPa or more. The mineral name is in honor of Robert C. Liebermann, a high-pressure mineral physicist at Stony Brook University, New York, USA.

Publisher's Note: High-temperature superconductivity stabilized by electron-hole interband coupling in collapsed tetragonal phase of KFe 2 As 2 under high pressure [Phys. Rev. B 91 , 060508(R) (2015)

DOE PAGES

Nakajima, Yasuyuki; Wang, Renxiong; Metz, Tristin; ...

2015-03-09

Here, we report a high-pressure study of simultaneous low-temperature electrical resistivity and Hall effect measurements on high quality single-crystalline KFe 2As 2 using designer diamond anvil cell techniques with applied pressures up to 33 GPa. In the low pressure regime, we show that the superconducting transition temperature T c finds a maximum onset value of 7 K near 2 GPa, in contrast to previous reports that find a minimum T c and reversal of pressure dependence at this pressure. Upon applying higher pressures, this T c is diminished until a sudden drastic enhancement occurs coincident with a first-order structural phasemore » transition into a collapsed tetragonal phase. The appearance of a distinct superconducting phase above 13 GPa is also accompanied by a sudden reversal of dominant charge carrier sign, from hole- to electron-like, which agrees with our band calculations predicting the emergence of an electron pocket and diminishment of hole pockets upon Fermi surface reconstruction. Our results suggest the high-temperature superconducting phase in KFe 2As 2 is substantially enhanced by the presence of nested electron and hole pockets, providing the key ingredient of high-T c superconductivity in iron pnictide superconductors.« less

Temperature Dependent Surface Structures and Electronic Properties of Organic-Inorganic Hybrid Perovskite Single Crystals

NASA Astrophysics Data System (ADS)

Jao, M.-H.; Teague, M. L.; Huang, J.-S.; Tseng, W.-S.; Yeh, N.-C.

Organic-inorganic hybrid perovskites, arising from research of low-cost high performance photovoltaics, have become promising materials not only for solar cells but also for various optoelectronic and spintronic applications. An interesting aspect of the hybrid perovskites is that their material properties, such as the band gap, can be easily tuned by varying the composition, temperature, and the crystalline phases. Additionally, the surface structure is critically important for their optoelectronic applications. It is speculated that different crystalline facets could show different trap densities, thus resulting in microscopically inhomogeneous performance. Here we report direct studies of the surface structures and electronic properties of hybrid perovskite CH3NH3PbI3 single crystals by scanning tunneling microscopy and spectroscopy (STM/STS). We found long-range spatially homogeneous tunneling conductance spectra with a well-defined energy gap of (1.55 +/- 0.1) eV at 300 K in the tetragonal phase, suggesting high quality of the single crystals. The energy gap increased to (1.81 +/- 0.1) eV in the orthorhombic phase, below the tetragonal-to-orthorhombic phase transition temperature at 150 K. Detailed studies of the temperature evolution in the spatially resolved surface structures and local density of states will be discussed to elucidate how these properties may influence the optoelectronic performance of the hybrid perovskites. We thank the support from NTU in Taiwan and from NSF in the US.

Fracture Toughness Evaluation of a Ni2MnGa Alloy Through Micro Indentation Under Magneto-Mechanical Loading

NASA Astrophysics Data System (ADS)

Goanţă, Viorel; Ciocanel, Constantin

2017-12-01

Ni2MnGa is a ferromagnetic alloy that exhibits the shape memory effect either induced by an externally applied magnetic field or mechanical stress. Due to the former, the alloy is commonly called magnetic shape memory alloy or MSMA. The microstructure of the MSMA consists of tetragonal martensite variants (three in the most general case) that are characterized by a magnetization vector which is aligned with the short side of the tetragonal unit cell. Exposing the MSMA to a magnetic field causes the magnetization vector to rotate and align with the external field, eventually leading to variant reorientation. The variant reorientation is observed macroscopically in the form of recoverable strain of up to 6% [1, 2]. As the magnetic field induced reorientation happens instantaneously [1, 3], MSMAs are suitable for fast actuation, sensing, or power harvesting applications. However, actuation applications are limited by the maximum actuation stress of the material that is about 3.5MPa at approximately 2 to 3% reorientation strain. During MSMA fatigue magneto-mechanical characterization studies [4, 5] it was observed that cracks nucleate and grow on the surface of material samples, after a relatively small number of cycles, leading to loss in material performance. This triggered the need for understanding the mechanisms that govern crack nucleation and growth in MSMAs, as well as the nature of the material, i.e. ductile or brittle. The experimental study reported in this paper was carried out to determine material's fracture toughness, the predominant crack growth directions, and the orientation of the cracks relative to the mechanical loading direction and to the material's microstructure. A fixture has been developed to allow Vickers micro indentation of 3mm by 3mm by 20mm Ni2MnGa samples exposed to different levels of magnetic field and/or mechanical stress. Using the measured characteristics of the impression generated during micro indentation, the lengths of propagated cracks, and appropriate equations (introduced in the paper), and the fracture toughness was evaluated as a function of the magneto-mechanical loading experienced by the material. The influence of the magneto-mechanical loading on the growth of already nucleated cracks has also been evaluated.

On the Tetragonal Forms of KMo 4O 6

NASA Astrophysics Data System (ADS)

McCarroll, W. H.; Ramanujachary, K. V.; Greenblatt, M.; Marsh, Richard E.

1995-06-01

A reexamination of the X-ray diffraction data for the tetragonal form of KMo4O6 prepared by fused salt electrolysis leads to the conclusion that the crystal structure is better described by using space group P 4/mbm and not P4¯ as previously reported. However, refinement in the new space group does not result in any significant changes in the atomic arrangement. Possible reasons for the significant difference between the c lattice parameter of this form of KMo4O6 and that prepared at high pressures are also discussed.

Ultrasound-assisted sol-gel synthesis of ZrO2.

PubMed

Guel, Marlene Lariza Andrade; Jiménez, Lourdes Díaz; Hernández, Dora Alicia Cortés

2017-03-01

Synthesis of tetragonal ZrO 2 by both conventional sol-gel and ultrasound-assisted sol-gel methods and using a non-ionic surfactant Tween-20, was performed. A porous microstructure composed of nanometric particles was observed. Tetragonal ZrO 2 was obtained using a low heat treatment temperature of powders, 500°C by both methods. A higher crystallinity and a shorter reaction time were observed when ultrasound was used in the sol-gel method due to the cavitation phenomenon. Copyright © 2016 Elsevier B.V. All rights reserved.

Formation of nanocrystalline tetragonal oxide tungsten bronzes on platinum

NASA Astrophysics Data System (ADS)

Kosov, A. V.; Semerikova, O. L.; Vakarin, S. V.; Pankratov, A. A.; Plaksin, S. V.; Zaykov, Yu. P.

2017-02-01

Cyclic voltammetry is used to study the formation of tetragonal oxide tungsten bronze of the composition K x Na y WO3 on a Pt(110) substrate during electrodeposition from a K2WO4-Na2WO4-WO3 melt. The potential ranges in which cathode products of various compositions and morphologies form are found. K x Na(0.66- x)WO3 crystals are shown to form according to the nucleation/growth mechanism. A general scheme is proposed and used to write equations for cathode reactions.

Variational method of determining effective moduli of polycrystals with tetragonal symmetry

USGS Publications Warehouse

Meister, R.; Peselnick, L.

1966-01-01

Variational principles have been applied to aggregates of randomly oriented pure-phase polycrystals having tetragonal symmetry. The bounds of the effective elastic moduli obtained in this way show a substantial improvement over the bounds obtained by means of the Voigt and Reuss assumptions. The Hill average is found to be a good approximation in most cases when compared to the bounds found from the variational method. The new bounds reduce in their limits to the Voigt and Reuss values. ?? 1966 The American Institute of Physics.

Multifunctional luminescent nanomaterials from NaLa(MoO4)2:Eu3+/Tb3+ with tunable decay lifetimes, emission colors, and enhanced cell viability

PubMed Central

Yang, Mei; Liang, Youlong; Gui, Qingyuan; Zhao, Bingxin; Jin, Dayong; Lin, Mimi; Yan, Lu; You, Hongpeng; Dai, Liming; Liu, Yong

2015-01-01

A facile, but effective, method has been developed for large-scale preparation of NaLa(MoO4)2 nanorods and microflowers co-doped with Eu3+ and Tb3+ ions (abbreviated as: NLM:Ln3+). The as-synthesized nanomaterials possess a pure tetragonal phase with variable morphologies from shuttle-like nanorods to microflowers by controlling the reaction temperature and the amount of ethylene glycol used. Consequently, the resulting nanomaterials exhibit superb luminescent emissions over the visible region from red through yellow to green by simply changing the relative doping ratios of Eu3+ to Tb3+ ions. Biocompatibility study indicates that the addition of NLM:Ln3+ nanomaterials can stimulate the growth of normal human retinal pigment epithelium (ARPE-19) cells. Therefore, the newly-developed NaLa(MoO4)2 nanomaterials hold potentials for a wide range of multifunctional applications, including bioimaging, security protection, optical display, optoelectronics for information storage, and cell stimulation. PMID:26259515

Synthesis and morphology of Ba1-xRE2x/3Nb2O6 nanocrystals with tungsten bronze structure in RE2O3-BaO-Nb2O5-B2O3 glasses (RE: Sm, Eu, Gd, Dy, Er)

NASA Astrophysics Data System (ADS)

Ida, H.; Shinozaki, K.; Honma, T.; Oh-ishi, K.; Komatsu, T.

2012-12-01

Ba1-xRE2x/3Nb2O6 nanocrystals with a tetragonal tungsten bronze (TTB) structure are synthesized using a conventional glass crystallization technique in 2.3RE2O3-27.4BaO-34.3Nb2O5-36B2O3 (mol%) (RE=Sm, Eu, Gd, Dy, and Er) glasses. One sharp crystallization peak is observed at ∼670 °C in both powdered and bulk glasses, and the formation of Ba1-xRE2x/3Nb2O6 nanocrystals with unit cell parameters of a∼1.24 nm and c∼0.39 nm was confirmed. It is found from high resolution transmission electron microscope observations that the morphology of Ba1-xRE2x/3Nb2O6 nanocrystals is ellipsoidal. Their average particle size is in the range of 15-60 nm and decreases with decreasing ionic radius of RE3+ being present in the precursor glasses. The optical transparent crystallized glass (bulk) shows the total photoluminescence (PL) quantum yield of 53% in the visible region of Eu3+ ions, suggesting a high potential of Ba1-xRE2x/3Nb2O6 nanocrystals as PL materials.

Structure and physical properties of EuTa{sub 2}O{sub 6} tungsten bronze polymorph

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kolodiazhnyi, T., E-mail: kolodiazhnyi.taras@nims.go.jp; Sakurai, H.; Vasylkiv, O.

A tetragonal tungsten bronze (TTB) polymorph of EuTa{sub 2}O{sub 6} was prepared and analyzed. EuTa{sub 2}O{sub 6} crystallizes in the centrosymmetric Pnam space group (with unit cell: a = 12.3693, b = 12.4254, and c = 7.7228 Å) isomorphous with orthorhombic β-SrTa{sub 2}O{sub 6}. In contrast to early reports, we see no evidence of deviation from paramagnetic Curie-Weiss behavior among the Eu{sup 2+} 4f{sup 7}spins in EuTa{sub 2}O{sub 6} down to 2 K. Dielectric constant shows a broad peak at ca. 50 K with dielectric dispersion resembling diffuse phase transition. The relaxation time, however, follows a simple (non-freezing) thermally activated process with an activation energy of 92 meV and anmore » attempt frequency of f{sub 0} = 5.79 × 10{sup 12 }Hz. A thermal conductivity of EuTa{sub 2}O{sub 6} shows a low-temperature (T ≈ 30 K) “plateau” region reminiscent of a glass-like behaviour in Nb-based TTB compounds. This behaviour can be attributed to the loosely bound Eu{sup 2+} ions occupying large tricapped trigonal prismatic sites in the EuTa{sub 2}O{sub 6} structure.« less

Modifying Thermal Switchability of Liquid Crystalline Nanoparticles by Alkyl Ligands Variation

PubMed Central

Żuk, Maciej; Tupikowska, Martyna

2018-01-01

By coating plasmonic nanoparticles (NPs) with thermally responsive liquid crystals (LCs) it is possible to prepare reversibly reconfigurable plasmonic nanomaterials with prospective applications in optoelectronic devices. However, simple and versatile methods to precisely tailor properties of liquid-crystalline nanoparticles (LC NPs) are still required. Here, we report a new method for tuning structural properties of assemblies of nanoparticles grafted with a mixture of promesogenic and alkyl thiols, by varying design of the latter. As a model system, we used Ag and Au nanoparticles that were coated with three-ring promesogenic molecules and dodecanethiol ligand. These LC NPs self-assemble into switchable lamellar (Ag NPs) or tetragonal (Au NPs) aggregates, as determined with small angle X-ray diffraction and transmission electron microscopy. Reconfigurable assemblies of Au NPs with different unit cell symmetry (orthorombic) are formed if hexadecanethiol and 1H,1H,2H,2H-perfluorodecanethiol were used in the place of dodecanethiol; in the case of Ag NPs the use of 11-hydroxyundecanethiol promotes formation of a lamellar structure as in the reference system, although with substantially broader range of thermal stability (140 vs. 90 °C). Our results underline the importance of alkyl ligand functionalities in determining structural properties of liquid-crystalline nanoparticles, and, more generally, broaden the scope of synthetic tools available for tailoring properties of reversibly reconfigurable plasmonic nanomaterials. PMID:29518916

Preparation, electronic structure, and chemical bonding of lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3 solid solution

NASA Astrophysics Data System (ADS)

Sasikumar, S.; Saravanan, R.; Saravanakumar, S.; Robert, M. Charles

2018-01-01

Polycrystalline lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3, ((1 - x)KBT- xBT) ( x = 0.00, 0.08, 0.12) ceramics were synthesized via solid-state reaction method. The powder X-ray diffraction (PXRD) and structural refinement results confirm that a single-phase tetragonal structure with space group P4mm. Charge density distribution inside the unit cell of (1 - x)KBT- xBT was investigated by the maximum entropy method. Charge density analysis reveals the reduction in ionic nature along K/Bi-O bond and enhancement of covalent nature along Ti-O bond with the addition of BaTiO3. The charge density distribution studies done using maximum entropy method for (1 - x)KBT- xBT have not been done so far. The surface morphology study was done using scanning electron microscopy (SEM). Energy dispersive X-rays spectra (EDS) were used to investigate the elemental compositions present in the system. The dielectric constant and loss tangent were studied as a function of frequency. The dielectric constant and loss were decreased with increase of frequency. Room temperature dielectric constant ( ɛ) and loss (tan δ) were measured for x = 0.00 about 511 and 0.51, respectively, at a frequency of 10 kHz.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowley, S.; Okumura, N; Lord, S

'A:a' knob-hole interactions and D:D interfacial interactions are important for fibrin polymerization. Previous studies with recombinant ?N308K fibrinogen, a substitution at the D:D interface, showed impaired polymerization. We examined the molecular basis for this loss of function by solving the crystal structure of ?N308K fragment D. In contrast to previous fragment D crystals, the ?N308K crystals belonged to a tetragonal space group with an unusually long unit cell (a = b = 95 Angstroms, c = 448.3 Angstroms). Alignment of the normal and ?N308K structures showed the global structure of the variant was not changed and the knob 'A' peptidemore » GPRP was bound as usual to hole 'a'. The substitution introduced an elongated positively charged patch in the D:D region. The structure showed novel, symmetric D:D crystal contacts between ?N308K molecules, indicating the normal asymmetric D:D interface in fibrin would be unstable in this variant. We examined GPRP binding to ?N308K in solution by plasmin protection assay. The results showed weaker peptide binding, suggesting that 'A:a' interactions were altered. We examined fibrin network structures by scanning electron microscopy and found the variant fibers were thicker and more heterogeneous than normal fibers. Considered together, our structural and biochemical studies indicate both 'A:a' and D:D interactions are weaker. We conclude that stable protofibrils cannot assemble from ?N308K monomers, leading to impaired polymerization.« less

Magnetic structure of the ferromagnetic new ternary silicide Nd5CoSi2.

PubMed

Mayer, C; Gaudin, E; Gorsse, S; Porcher, F; André, G; Chevalier, B

2012-04-04

Nd(5)CoSi(2) was obtained from the elements by arc-melting followed by annealing at 883 K. Its investigation by single-crystal x-ray and neutron powder diffraction shows that this ternary silicide crystallizes as Nd(5)Si(3) in a tetragonal structure deriving from the Cr(5)B(3)-type (I4/mcm space group; a = 7.7472(2) and c = 13.5981(5) Å as unit cell parameters). The structural refinements confirm the mixed occupancy on the 8h site between Si and Co atoms, as already observed for Gd(5)CoSi(2). Magnetization and specific heat measurements reveal a ferromagnetic behavior below T(C) = 55 K for Nd(5)CoSi(2). This magnetic ordering is further evidenced by neutron powder diffraction investigation revealing between 1.8 K and T(C) a canted ferromagnetic structure in the direction of the c-axis described by a propagation vector k = (0 0 0). At 1.8 K, the two Nd(3+) ions carry ordered magnetic moments equal respectively to 1.67(7) and 2.37(7) μ(B) for Nd1 and Nd2; these two moments exhibit a canting angle of θ = 4.3(6)°. This magnetic structure presents some similarities with that reported for Nd(5)Si(3). © 2012 IOP Publishing Ltd

Electron paramagnetic resonance spectra of CdO-Al2O3-Bi2O3-B2O3 quaternary glasses containing VO2+ ions

NASA Astrophysics Data System (ADS)

Lalithaphani, A. V.; Srinivas, B.; Hameed, Abdul; Chary, M. Narasimha; Shareefuddin, Md.

2018-04-01

Borate glasses containing different concentrations of heavy metal oxide (CdO) with 2mol% of V2O5 as the paramagnetic probe were prepared by the conventional melt quenching technique. The prepared glasses were characterized by XRD to confirm the amorphous nature. EPR and Optical absorption studies were carried out at room temperature. EPR spectra of these glass samples were recorded at X-band frequency with 100 kHz field modulation at room temperature. From the EPR spectra the spin-Hamiltonian parameters were evaluated. The spin-Hamiltonian parameter values indicated that g|| < g┴ < ge [=2.0023] and A∥︀ > A┴. This suggests that VO2+ ions are present in octahedral sites with tetragonal compression and belong to C4v symmetry with dxy being the ground state. The measure of tetragonal distortion (Δg∥︀/Δg┴)varies non-linearly with glass composition indicating change in tetragonal distortion. The covalency rates were estimated. The number of spins participating in the resonance [N] and susceptibility (χ) values were also evaluated.

Abnormal cubic-tetragonal phase transition of barium strontium titanate nanoparticles studied by in situ Raman spectroscopy and transmission electron microscopy heating experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yin; Chen, Chen; Gao, Ran

2015-11-02

Phase stability of the ferroelectric materials at high temperature is extremely important to their device performance. Ba{sub x}Sr{sub 1−x}TiO{sub 3} (BST) nanoparticles with different Sr contents (x = 1, 0.91, 0.65, 0.4, and 0) are prepared by a facile hydrothermal method. Using Raman spectroscopy and transmission electron microscopy (TEM) analyses under in situ heating conditions (up to 300 °C), the phase transitions of BST nanoparticles between 25 °C and 280 °C are comprehensively investigated. The original Curie temperature of BST nanoparticles decreases abruptly with the increase in Sr content, which is more obvious than in the bulk or film material. Besides, an abnormal phase transitionmore » from cubic to tetragonal structure is observed from BST nanoparticles and the transition temperature rises along with the increase in Sr content. Direct TEM evidences including a slight lattice distortion have been provided. Differently, BaTiO{sub 3} nanoparticles remained in the tetragonal phase during the above temperature ranges.« less

Lattice parameters and structural phase transition of lanthanum titanate perovskite, La0.68(Ti0.95,Al0.05)O3.

PubMed

Ali, Roushown; Yashima, Masatomo

2003-05-01

Lattice parameters and the structural phase transition of La(0.68)(Ti(0.95),Al(0.05))O(3) have been investigated in situ in the temperature range 301-689 K by the synchrotron radiation powder diffraction (SR-PD) technique. High-angular-resolution SR-PD is confirmed to be a powerful technique for determining precise lattice parameters around a phase-transition temperature. The title compound exhibits a reversible phase transition between orthorhombic and tetragonal phases at 622.3 +/- 0.6 K. The following results were obtained: (i) the lattice parameters increased continuously with temperature, while the b/a ratio decreased continuously with temperature and became unity at the orthorhombic-tetragonal transition point; (ii) no hysteresis was observed between the lattice-parameter values measured on heating and on cooling. Results (i) and (ii) indicate that the orthorhombic-tetragonal phase transition is continuous and reversible. The b/a ratio is found to exhibit a more continuous temperature evolution than does the order parameter for a typical second-order phase transition based on Landau theory.

Luminescence properties of Eu2+ in M2MgSi2O7 (M=Ca, Sr, and Ba) phosphors

NASA Astrophysics Data System (ADS)

Kim, T.; Kim, Y.; Kang, S.

2012-03-01

The photoluminescence properties of alkali-earth magnesium silicates (M2MgSi2O7, M=Ca, Sr, and Ba) doped with Eu2+ were investigated. Solid solutions of Ba x Sr2- x Si2O7, Ca2MgSi2O7, and Sr2MgSi2O7 were prepared. Ba x Sr2- x Si2O7 retained a tetragonal crystal structure similar to the structure of the other compounds up to a stoichiometry of x=1.6, which enabled a systematic study of the common structure. Monoclinic Ba2MgSi2O7 was prepared, and the luminescence properties were compared with those of other samples. The emission and excitation spectra of tetragonal M2MgSi2O7 (M=Ca, Sr, and Ba) changed as a function of the covalency, site symmetry, and crystal field strength. The luminescence properties showed excellent agreement with theoretical predictions based on these factors. The Stokes shift differentiated the emission behaviors of the tetragonal and monoclinic structures.

One pot synthesis of pure micro/nano photoactive α-PbO crystals

NASA Astrophysics Data System (ADS)

Bhagat, Dharini; Waldiya, Manmohansingh; Vanpariya, Anjali; Mukhopadhyay, Indrajit

2018-05-01

The present study reports a simple, fast and cost effective precipitation technique for synthesis of pure α-PbO powder. Lead monoxide powder with tetragonal structure was synthesized chemically at an elevated temperature using lead acetate and sodium hydroxide solution bath. XRD powder diffraction was used to find the structural properties as well as phase transition from alpha to beta. Study revealed that synthesized PbO powder was crystalline with tetragonal symmetry, having an average crystallite size of 70 nm and lattice constants; a=3.97Å, b=3.97Å, and c=5.02Å. Phase transition from tetragonal to orthorhombic structure was studied by comparing the XRD data of the annealed samples in the temperature range from 200 °C to 600 °C. UV-Visible spectroscopy was used to find out the optical properties of prepared PbO powder. Diffuse reflectance and absorbance spectra confirmed the formation of α-PbO with obtained direct band gap of 1.9 eV. Synthesized lead monoxide (α-PbO) powder has promising application in energy conversion as well as energy storage applications.

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe2As2 close to a first-order phase transition

NASA Astrophysics Data System (ADS)

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; Kreyssig, Andreas; Ran, S.; Bud'ko, Sergey L.; Canfield, Paul C.; Mompean, Federico J.; García-Hernández, Mar; Munuera, Carmen; Guillamón, Isabel; Suderow, Hermann

2018-01-01

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co-substituted CaFe2As2 . We use atomic force, magnetic force, and scanning tunneling microscopy to identify the domains and characterize their properties, finding in particular that tetragonal superconducting domains are very elongated, more than several tens of micrometers long and about 30 nm wide; have the same Tc as unstrained samples; and hold vortices in a magnetic field. Thus, biaxial strain produces a phase-separated state, where each phase is equivalent to what is found on either side of the first-order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of the order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first-order quantum phase transitions lead to nanometric-size phase separation under the influence of strain.

Theoretical and experimental evaluation of piezo-optic parameters and photoelastic constant in tetragonal PWO.

PubMed

Natali, Pier Paolo; Montalto, Luigi; Daví, Fabrizio; Mengucci, Paolo; Ciriaco, Andrea; Paone, Nicola; Rinaldi, Daniele

2018-02-01

The tetragonal PbWO 4 (PWO) is one of the most important scintillating crystals, being used both in the Compact Muon Solenoid (CMS) experiment at the European Organization for Nuclear Research (CERN) and in the PANDA project at the Facility for Antiproton and Ion Research (FAIR). Light yield and other relevant scintillation properties depend, among many factors, also on the crystal mechanical quality. Accordingly, a detailed knowledge of crystal piezo-optic properties is a mandatory step toward understanding elasto-optic behavior and performing crystal quality control. In this paper, we evaluate for the first time, to the best of our knowledge, by means of both photoelastic and x-ray measurements, some components of the piezo-optic tensor; moreover, when the crystal is acted upon by a uniaxial stress, we obtain an evaluation for the rotation angle of the optic plane under stress as well as the photoelastic constant. These parameters are necessary to detect the residual stresses within the crystal, if any, and to give an overall quality measure. Such a methodology is in general suitable for any tetragonal crystals.

Spin-orbital model of stoichiometric LaMnO3 with tetragonal distortions

NASA Astrophysics Data System (ADS)

Snamina, Mateusz; Oleś, Andrzej M.

2018-03-01

The spin-orbital superexchange model is derived for the cubic (perovskite) symmetry of LaMnO3, whereas real crystal structure is strongly deformed. We identify and explain three a priori important physical effects arising from tetragonal deformation: (i) the splitting of eg orbitals ∝Ez , (ii) the directional renormalization of d -p hybridization tp d, and (iii) the directional renormalization of charge excitation energies. Using the example of LaMnO3 crystal we evaluate their magnitude. It is found that the major effects of deformation are an enhanced amplitude of x2-y2 orbitals induced in the orbital order by Ez≃300 meV and anisotropic tp d≃2.0 (2.35) eV along the a b (c ) cubic axis, in very good agreement with Harrison's law. We show that the improved tetragonal model analyzed within mean field approximation provides a surprisingly consistent picture of the ground state. Excellent agreement with the experimental data is obtained simultaneously for: (i) eg orbital mixing angle, (ii) spin exchange constants, and (iii) the temperatures of spin and orbital phase transition.

Tunable magnetic and transport properties of Mn3Ga thin films on Ta/Ru seed layer

NASA Astrophysics Data System (ADS)

Hu, Fang; Xu, Guizhou; You, Yurong; Zhang, Zhi; Xu, Zhan; Gong, Yuanyuan; Liu, Er; Zhang, Hongguo; Liu, Enke; Wang, Wenhong; Xu, Feng

2018-03-01

Hexagonal D019-type Mn3Z alloys that possess large anomalous and topological-like Hall effects have attracted much attention due to their great potential in antiferromagnetic spintronic devices. Herein, we report the preparation of Mn3Ga films in both tetragonal and hexagonal phases with a tuned Ta/Ru seed layer on a thermally oxidized Si substrate. Large coercivity together with large anomalous Hall resistivity is found in the Ta-only sample with a mixed tetragonal phase. By increasing the thickness of the Ru layer, the tetragonal phase gradually disappears and a relatively pure hexagonal phase is obtained in the Ta(5)/Ru(30) buffered sample. Further magnetic and transport measurements revealed that the anomalous Hall conductivity nearly vanishes in the pure hexagonal sample, while an abnormal asymmetric hump structure emerges in the low field region. The extracted additional Hall term is robust in a large temperature range and presents a sign reversal above 200 K. The abnormal Hall properties are proposed to be closely related to the frustrated spin structure of D019 Mn3Ga.

Electronic and Structural Properties of ABO3: Role of the B-O Coulomb Repulsions for Ferroelectricity

PubMed Central

Miura, Kaoru; Azuma, Masaki; Funakubo, Hiroshi

2011-01-01

We have investigated the role of the Ti–O Coulomb repulsions in the appearance of the ferroelectric state in BaTiO3 as well as the role of the Zn–O Coulomb repulsions in BiZn0.5Ti0.5O3, using a first-principles calculation with optimized structures. In tetragonal BaTiO3, it is found that the Coulomb repulsions between Ti 3s and 3p states and O 2s and 2p states have an important role for the appearance of Ti ion displacement. In BiZn0.5Ti0.5O3, on the other hand, the stronger Zn–O Coulomb repulsions, which are due to the 3s, 3p, and 3d (d10) states of the Zn ion, have more important role than the Ti–O Coulomb repulsions for the appearance of the tetragonal structure. Our suggestion is consistent with the other ferroelectric perovskite oxides ABO3 in the appearance of tetragonal structures as well as rhombohedral structures. PMID:28879987

Electronic and Structural Properties of ABO3: Role of the B-O Coulomb Repulsions for Ferroelectricity.

PubMed

Miura, Kaoru; Azuma, Masaki; Funakubo, Hiroshi

2011-01-17

We have investigated the role of the Ti-O Coulomb repulsions in the appearance of the ferroelectric state in BaTiO3 as well as the role of the Zn-O Coulomb repulsions in BiZn0.5Ti0.5O3, using a first-principles calculation with optimized structures. In tetragonal BaTiO3, it is found that the Coulomb repulsions between Ti 3s and 3p states and O 2s and 2p states have an important role for the appearance of Ti ion displacement. In BiZn0.5Ti0.5O3, on the other hand, the stronger Zn-O Coulomb repulsions, which are due to the 3s, 3p, and 3d (d10) states of the Zn ion, have more important role than the Ti-O Coulomb repulsions for the appearance of the tetragonal structure. Our suggestion is consistent with the other ferroelectric perovskite oxides ABO3 in the appearance of tetragonal structures as well as rhombohedral structures.

Tetragonal (K, Na)NbO3 based lead-free single crystal: Growth, full tensor properties, and their orientation dependence

NASA Astrophysics Data System (ADS)

Zheng, Limei; Wang, Junjun; Liu, Xuedong; Yang, Liya; Lu, Xiaoyan; Li, Yanran; Huo, Da; Lü, Weiming; Yang, Bin; Cao, Wenwu

2017-10-01

A Li and Ta modified (K, Na)NbO3 lead-free single crystal with a large size (13 × 10 × 20 mm3) has been grown by using the top-seeded solution growth method. The large size allows us to carry out an extensive study on this tetragonal crystal. We have measured a complete set of elastic, dielectric, and piezoelectric constants for the [001]C poled crystal with the single domain state. The crystal exhibits high shear piezoelectricity with d15 = 518 pC/N and k15 = 0.733, showing excellent potential in shear electro-sonic energy transformation devices. It is found that the high shear piezoelectricity originates from the vicinity of orthorhombic-tetragonal phase transition, which favors polarization rotation greatly. The orientation dependence of longitudinal dielectric, piezoelectric, and elastic constants and electromechanical coupling factor in the 3-dimentional space were calculated based on the single domain dataset. We believe that this work is of great importance for both fundamental studies and device designs for lead-free materials.

Control of magnetic, nonmagnetic, and superconducting states in annealed Ca(Fe 1–xCo x)₂As₂

DOE PAGES

Ran, S.; Bud'ko, S. L.; Straszheim, W. E.; ...

2012-06-22

We have grown single-crystal samples of Co substituted CaFe₂As₂ using an FeAs flux and systematically studied the effects of annealing/quenching temperature on the physical properties of these samples. Whereas the as-grown samples (quenched from 960°C) all enter the collapsed tetragonal phase upon cooling, annealing/quenching temperatures between 350 and 800°C can be used to tune the system to low-temperature antiferromagnetic/orthorhomic or superconducting states as well. The progression of the transition temperature versus annealing/quenching temperature (T-T anneal) phase diagrams with increasing Co concentration shows that, by substituting Co, the antiferromagnetic/orthorhombic and the collapsed tetragonal phase lines are separated and bulk superconductivity ismore » revealed. We established a 3D phase diagram with Co concentration and annealing/quenching temperature as two independent control parameters. At ambient pressure, for modest x and T anneal values, the Ca(Fe₁₋ xCox)₂As₂ system offers ready access to the salient low-temperature states associated with Fe-based superconductors: antiferromagnetic/orthorhombic, superconducting, and nonmagnetic/collapsed tetragonal.« less

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe 2 As 2 close to a first-order phase transition

DOE PAGES

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; ...

2018-01-09

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe 2As 2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, nding in particular that tetragonal superconducting domains are very elongated, more than several tens of μm long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic eld. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the rstmore » order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.« less

Electronic structure and electron-phonon coupling in TiH$$_2$$

DOE PAGES

Shanavas, Kavungal Veedu; Lindsay, Lucas R.; Parker, David S.

2016-06-15

Calculations using first principles methods and strong coupling theory are carried out to understand the electronic structure and superconductivity in cubic and tetragonal TiHmore » $$_2$$. A large electronic density of states at the Fermi level in the cubic phase arises from Ti-$$t_{2g}$$ states and leads to a structural instability against tetragonal distortion at low temperatures. However, constraining the in-plane lattice constants diminishes the energy gain associated with the tetragonal distortion, allowing the cubic phase to be stable at low temperatures. Furthermore, calculated phonon dispersions show decoupled acoustic and optic modes arising from Ti and H vibrations, respectively and frequencies of optic modes to be rather high. The cubic phase has a large electron-phonon coupling parameter $$\\lambda$$ and critical temperature of several K. Contribution of the hydrogen sublattice to $$\\lambda$$ is found to be small in this material, which we understand from strong coupling theory to be due to the small H-$s$ DOS at the Fermi level and high energy of hydrogen modes at the tetrahedral sites.« less

The influence of the concentration of Sr ions on the crystal and magnetic structures of Ba{sub 2} –{sub x}Sr{sub x}FeMoO{sub 6} double perovskites (x = 0–1.6)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turchenko, V. A., E-mail: turchenko@jinr.ru; Kalanda, N. A.; Kovalev, L. V.

2017-01-15

The crystal and magnetic structures of a solid solution of double perovskite Ba{sub 2–} {sub x}Sr{sub x}FeMoO{sub 6} (x = 0–1.6) have been investigated by neutron diffraction. The high-resolution diffraction patterns have provided precise information about the changes in the crystal and magnetic structures with an increase in the strontium content and data on the behavior of the sample microstructure. Replacement of barium with strontium leads to a change in the lattice symmetry from cubic (x = 0, sp. gr. Fm3̄m)) to tetragonal (x = 0.4, sp. gr. I4/m). At x = 1.0, the symmetry is either tetragonal (sp. gr.more » I4/m) or orthorhombic (sp. gr. Fmmm), and at x = 1.6 the symmetry becomes again tetragonal (sp. gr. I4/m). The values of the Curie temperature and microstrain increase with an increase in the strontium content.« less

Paramagnetic-to-nonmagnetic transition in antiperovskite nitride Cr3GeN studied by 14N-NMR and µSR

NASA Astrophysics Data System (ADS)

Takao, K.; Liu, Z.; Uji, K.; Waki, T.; Tabata, Y.; Watanabe, I.; Nakamura, H.

2017-06-01

The antiperovskite-related nitride Cr3GeN forms a tetragonal structure with the space group P\\bar{4}{2}1m at room temperature. It shows a tetragonal (P\\bar{4}{2}1m) to tetragonal (I4/mcm) structural transition with a large hysteresis at 300-400 K. The magnetic susceptibility of Cr3GeN shows Curie-Weiss type temperature dependence at high temperature, but is almost temperature-independent below room temperature. We carried out µSR and 14N-NMR microscopy measurements to reveal the magnetic ground state of Cr3GeN. Gradual muon spin relaxation, which is nearly temperature-independent below room temperature, was observed, indicating that Cr3GeN is magnetically inactive. In the 14N-NMR measurement, a quadrupole-split spectrum was obtained at around 14 K = 0. The temperature dependence of 14(1/T1) satisfies the Korringa relation. These experimental results indicate that the ground state of Cr3GeN is Pauli paramagnetic, without antiferromagnetic long-range order.

Modeling the SHG activities of diverse protein crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haupert, Levi M.; DeWalt, Emma L.; Simpson, Garth J.

2012-10-18

A symmetry-additiveab initiomodel for second-harmonic generation (SHG) activity of protein crystals was applied to assess the likely protein-crystal coverage of SHG microscopy. Calculations were performed for 250 proteins in nine point-group symmetries: a total of 2250 crystals. The model suggests that the crystal symmetry and the limit of detection of the instrument are expected to be the strongest predictors of coverage of the factors considered, which also included secondary-structural content and protein size. Much of the diversity in SHG activity is expected to arise primarily from the variability in the intrinsic protein response as well as the orientation within themore » crystal lattice. Two or more orders-of-magnitude variation in intensity are expected even within protein crystals of the same symmetry. SHG measurements of tetragonal lysozyme crystals confirmed detection, from which a protein coverage of ~84% was estimated based on the proportion of proteins calculated to produce SHG responses greater than that of tetragonal lysozyme. Good agreement was observed between the measured and calculated ratios of the SHG intensity from lysozyme in tetragonal and monoclinic lattices.« less

Raman spectroscopic studies of defect structures and phase transition in hyper-stoichiometric UO(2+x).

PubMed

He, Heming; Shoesmith, David

2010-07-28

A method to determine the defect structures in hyper-stoichiometric UO(2+x) using a combination of XRD and Raman spectroscopy has been developed. A sequence of phase transitions, from cubic to tetragonal symmetry, occurs with increasing degree of non-stoichiometry. This sequence proceeds from a cubic phase through an intermediate t''-type tetragonal (axial ratio c/a = 1) phase to a final t-type tetragonal (c/a not = 1) phase. Four distinct structural defect regions can be identified in the stoichiometry range, UO(2) to U(3)O(7): (i) a random point defect structure (x (in UO(2+x)) < or = 0.05); (ii) a non-stoichiometry region (0.05 < or = x < or = 0.15) over which point defects are gradually eliminated and replaced by the Willis 2:2:2 cluster; (iii) a mixture of Willis and cuboctahedral clusters (0.15 < or = x < or = 0.23); (iv) the cuboctahedral cluster (x > or = 0.23). The geometry and steric arrangement of these defects is primarily determined by the concentration of the excess-oxygen interstitials.

Hybrid-exchange density-functional theory study of the electronic structure of MnV2O4 : Exotic orbital ordering in the cubic structure

NASA Astrophysics Data System (ADS)

Wu, Wei

2015-05-01

The electronic structures of cubic and tetragonal MnV2O4 have been studied using hybrid-exchange density-functional theory. The computed electronic structure of the tetragonal phase shows an antiferro-orbital ordering on V sites and a ferrimagnetic ground state (the spins on V and Mn are antialigned). These results are in good agreement with the previous theoretical result obtained from the local-density approximation + U methods [S. Sarkar et al., Phys. Rev. Lett. 102, 216405 (2009), 10.1103/PhysRevLett.102.216405]. Moreover, the electronic structure, especially the projected density of states of the cubic phase, has been predicted with good agreement with the recent soft x-ray spectroscopy experiment. Similar to the tetragonal phase, the spins on V and Mn in the cubic structure favor a ferrimagnetic configuration. Most interesting is that the computed charge densities of the spin-carrying orbitals on V in the cubic phase show an exotic orbital ordering, i.e., a ferro-orbital ordering along [110] but an antiferro-orbital ordering along [1 ¯10 ] .

Microbial adhesion on novel yttria-stabilized tetragonal zirconia (Y-TZP) implant surfaces with nitrogen-doped hydrogenated amorphous carbon (a-C:H:N) coatings.

PubMed

Schienle, Stefanie; Al-Ahmad, Ali; Kohal, Ralf Joachim; Bernsmann, Falk; Adolfsson, Erik; Montanaro, Laura; Palmero, Paola; Fürderer, Tobias; Chevalier, Jérôme; Hellwig, Elmar; Karygianni, Lamprini

2016-09-01

Biomaterial surfaces are at high risk for initial microbial colonization, persistence, and concomitant infection. The rationale of this study was to assess the initial adhesion on novel implant surfaces of Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans upon incubation. The tested samples were 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) samples with nitrogen-doped hydrogenated amorphous carbon (a-C:H:N) coating (A) and 3Y-TZP samples coated with ceria-stabilized zirconia-based (Ce-TZP) composite and a-C:H:N (B). Uncoated 3Y-TZP samples (C) and bovine enamel slabs (BES) served as controls. Once the surface was characterized, the adherent microorganisms were quantified by estimating the colony-forming units (CFUs). Microbial vitality was assessed by live/dead staining, and microbial-biomaterial surface topography was visualized by scanning electron microscopy (SEM). Overall, A and B presented the lowest CFU values for all microorganisms, while C sheltered significantly less E. faecalis, P. aeruginosa, and C. albicans than BES. Compared to the controls, B demonstrated the lowest vitality values for E. coli (54.12 %) and C. albicans (67.99 %). Interestingly, A (29.24 %) exhibited higher eradication rates for S. aureus than B (13.95 %). Within the limitations of this study, a-C:H:N-coated 3Y-TZP surfaces tended to harbor less initially adherent microorganisms and selectively interfered with their vitality. This could enable further investigation of the new multi-functional zirconia surfaces to confirm their favorable antimicrobial properties in vivo.

Calculations of single crystal elastic constants for yttria partially stabilised zirconia from powder diffraction data

NASA Astrophysics Data System (ADS)

Lunt, A. J. G.; Xie, M. Y.; Baimpas, N.; Zhang, S. Y.; Kabra, S.; Kelleher, J.; Neo, T. K.; Korsunsky, A. M.

2014-08-01

Yttria Stabilised Zirconia (YSZ) is a tough, phase-transforming ceramic that finds use in a wide range of commercial applications from dental prostheses to thermal barrier coatings. Micromechanical modelling of phase transformation can deliver reliable predictions in terms of the influence of temperature and stress. However, models must rely on the accurate knowledge of single crystal elastic stiffness constants. Some techniques for elastic stiffness determination are well-established. The most popular of these involve exploiting frequency shifts and phase velocities of acoustic waves. However, the application of these techniques to YSZ can be problematic due to the micro-twinning observed in larger crystals. Here, we propose an alternative approach based on selective elastic strain sampling (e.g., by diffraction) of grain ensembles sharing certain orientation, and the prediction of the same quantities by polycrystalline modelling, for example, the Reuss or Voigt average. The inverse problem arises consisting of adjusting the single crystal stiffness matrix to match the polycrystal predictions to observations. In the present model-matching study, we sought to determine the single crystal stiffness matrix of tetragonal YSZ using the results of time-of-flight neutron diffraction obtained from an in situ compression experiment and Finite Element modelling of the deformation of polycrystalline tetragonal YSZ. The best match between the model predictions and observations was obtained for the optimized stiffness values of C11 = 451, C33 = 302, C44 = 39, C66 = 82, C12 = 240, and C13 = 50 (units: GPa). Considering the significant amount of scatter in the published literature data, our result appears reasonably consistent.

Low-cost and eco-friendly nebulizer spray coated CuInAlS2 counter electrode for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Dhas, C. Ravi; Christy, A. Jennifer; Venkatesh, R.; Esther Santhoshi Monica, S.; Panda, Subhendu K.; Subramanian, B.; Ravichandran, K.; Sudhagar, P.; Raj, A. Moses Ezhil

2018-05-01

CuInAlS2 thin films for different substrate temperatures were deposited by a novel nebulizer spray technique. The polycrystalline CIAS thin film exhibited tetragonal structure with the preferential orientation of (1 1 2) plane. Nanoflakes were observed from the surface morphology of CIAS film. The peak position of core level spectra confirms the presence of CuInAlS2 from XPS analysis. The absorbance spectra and optical band gap were observed from the optical property. The activation energy, carrier concentration, hole mobility and resistivity were determined by linear four probe and Hall effect measurements. The CIAS film was used as a counter electrode (CE) in dye-sensitized solar cells (DSSCs) and is characterized by cyclic voltammetry, electrochemical impedance spectroscopy and Tafel measurements. DSSC fabricated with the CIAS CE achieved the photo conversion efficiency of about 2.55%.

Optical properties of quasi-tetragonal BiFeO3 thin films

NASA Astrophysics Data System (ADS)

Chen, P.; Podraza, N. J.; Xu, X. S.; Melville, A.; Vlahos, E.; Gopalan, V.; Ramesh, R.; Schlom, D. G.; Musfeldt, J. L.

2010-03-01

Optical transmission spectroscopy and spectroscopic ellipsometry were used to extract the optical properties of an epitaxially grown quasi-tetragonal BiFeO3 thin film in the near infrared to near ultraviolet range. The absorption spectrum is overall blue shifted compared with that of rhombohedral BiFeO3, with an absorption onset near 2.25 eV, a direct 3.1 eV band gap, and charge transfer excitations that are ˜0.4 eV higher than those of the rhombohedral counterpart. We interpret these results in terms of structural strain and local symmetry breaking.

3D Photonic Crystals Build Up By Self-Organization Of Nanospheres

DTIC Science & Technology

2006-05-23

variance for simple tetragonal Vst , of which general form is defined in Equation (5), could be an important parameter affecting band structure, and it is...plotted along with gap size both as a function of lattice parameter ratio c/a in Figure 2. Apparently, the inverse of variance, i.e. 1/ Vst , shows a...possible. 0.8 1.0 1.2 1.4 1.6 1.8 -2 0 2 4 6 8 10 12 14 16 18 20 22 24 26 gap size (%) 1/ Vst c/a of simple tetragonal g ap s iz e (% ) 0.85 0.86

Comment on "An experimental study of symmetry lowering of analcime"

NASA Astrophysics Data System (ADS)

Nespolo, Massimo

2018-04-01

In a recent article (Phys Chem Minerals. https://doi.org/10.1007/s00269-017-0922-1, 2018), analcime hydrothermally synthesized from a gel and then reheated was reported to have undergone a loss of symmetry to Ibca. We show that the reheated samples, reported as different, are identical to each other and actually tetragonal. The fact that the tetragonal axis was oriented along the a or b vector in the two reheated samples instead of the c vector as in the conventional setting seems to have been the cause of the misinterpretation of the diffraction pattern.

High-pressure behaviour of Cs{sub 2}V{sub 3}O{sub 8} fresnoite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grzechnik, Andrzej, E-mail: grzechnik@xtal.rwth-aachen.de; Yeon, Jeongho; Zur Loye, Hans-Conrad

2016-06-15

Crystal structure of Cs{sub 2}V{sub 3}O{sub 8} fresnoite (P4bm, Z=2) has been studied using single-crystal X-ray diffraction in a diamond anvil cell to 8.6 GPa at room temperature. Cs{sub 2}V{sub 3}O{sub 8} undergoes a reversible first-order phase transition at about 4 GPa associated with anomalies in the pressure dependencies of the lattice parameters and unit-cell volume but without any symmetry change. Both structures consist of layers of corner-sharing V{sup 5+}O{sub 4} tetrahedra and V{sup 4+}O{sub 5} tetragonal pyramids separated by the Cs{sup +} cations located between the layers. At low pressures, the compression has little effect on the polarity ofmore » the structure. Above 4 GPa, the pseudosymmetry with respect to the corresponding centrosymmetric space group P4/mbm abruptly increases. The effects of external pressure and of the A{sup +} cation substitution in the vanadate fresnoites A{sub 2}V{sub 3}O{sub 8} (A{sup +}: K{sup +}, Rb{sup +}, NH{sub 4}{sup +}, Cs{sup +}) are discussed. - Graphical abstract: Non-centrosymmetric Cs{sub 2}V{sub 3}O{sub 8} undergoes a reversible first-order phase transition at about 4 GPa associated with an abrupt change of the pseudosymmetry with respect to the centrosymmetric space group P4/mbm. Display Omitted - Highlights: • High-pressure behaviour of vanadate fresnoites depends on alkali metal cations. • The size of the alkali metal cation determines whether the high-pressure phase is centrosymmetric. • No incommensurate structures are observed upon compression.« less

High-pressure x-ray diffraction study on lithium borohydride using a synchrotron radiation

NASA Astrophysics Data System (ADS)

Nakano, S.; Nakayama, A.; Kikegawa, T.

2008-07-01

Lithium borohydride (LiBH4) was compressed up to 10 GPa using a diamond-anvil-cell to investigate its high-pressure structure. In-situ x-ray diffraction profiles indicated a pressure-induced transformation at 1.1 GPa, which was consistent with the previous experimental observation such as Raman scattering spectroscopy. The high-pressure phase was indexed on a tetragonal symmetry of P42/mmc, which was not corresponding some structural models proposed by previous calculation studies. An unknown substance (presumably another Li-B-H compound), which was contained in the starting material, also transformed into its high-pressure phase at 0.6 GPa without any relation to the transformation of LiBH4.

Evidence for negative thermal expansion in the superconducting precursor phase SmFeAsO

NASA Astrophysics Data System (ADS)

Zhou, H. D.; Sarte, P. M.; Conner, B. S.; Balicas, L.; Wiebe, C. R.; Chen, X. H.; Wu, T.; Wu, G.; Liu, R. H.; Chen, H.; Fang, D. F.

2018-03-01

The fluorine-doped rare-earth iron oxypnictide series SmFeAsO1-x F x (0 ≤slant x ≤slant 0.10) was investigated with high resolution powder x-ray scattering. In agreement with previous studies (Margadonna et al 2009 Phys. Rev. B. 79 014503), the parent compound SmFeAsO exhibits a tetragonal-to-orthorhombic structural distortion at T{S}   =  130 K which is rapidly suppressed by x ≃ 0.10 deep within the superconducting dome. The change in unit cell symmetry is followed by a previously unreported magnetoelastic distortion at 120 K. The temperature dependence of the thermal expansion coefficient αV reveals a rich phase diagram for SmFeAsO: (i) a global minimum at 125 K corresponds to the opening of a spin-density wave instability as measured by pump-probe femtosecond spectroscopy (Mertelj et al 2010 Phys. Rev. B 81 224504) whilst (ii) a global maximum at 110 K corresponds to magnetic ordering of the Sm and Fe sublattices as measured by magnetic x-ray scattering (Nandi et al 2011 Phys. Rev. B 84 055419). At much lower temperatures than T{N} , SmFeAsO exhibits a significant negative thermal expansion on the order of  -40 ppm · K-1 in contrast to the behaviour of other rare-earth oxypnictides such as PrFeAsO (Kimber et al 2008 Phys. Rev. B 78 140503) and the actinide oxypnictide NpFeAsO (Klimczuk et al 2012 Phys. Rev. B 85 174506) where the onset of αV < 0 only appears in the vicinity of magnetic ordering. Correlating this feature with the temperature and doping dependence of the resistivity and the unit cell parameters, we interpret the negative thermal expansion as being indicative of the possible condensation of itinerant electrons accompanying the opening of a SDW gap, consistent with transport measurements (Tropeano et al 2009 Supercond. Sci. Technol. 22 034004).

Uranyl peroxide nanoclusters at high-pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turner, Katlyn M.; Szymanowski, Jennifer E. S.; Zhang, Fuxiang

Here, U 60 ([UO 2(O 2)(OH)] 60 60– in water) is a uranyl peroxide nanocluster with a fullerene topology and O h symmetry. U 60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U 60-bearing material: Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 ( Fm3¯; a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), andmore » the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U 60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U 60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U 60 clusters at high pressure may have been enhanced by the interaction between U 60 nanoclusters and the alcohol pressure medium. Once formed, U 60 nanoclusters persist regardless of their associated long-range ordering—in crystals, amorphous solids, or solutions.« less

Uranyl peroxide nanoclusters at high-pressure

DOE PAGES

Turner, Katlyn M.; Szymanowski, Jennifer E. S.; Zhang, Fuxiang; ...

2017-08-14

Here, U 60 ([UO 2(O 2)(OH)] 60 60– in water) is a uranyl peroxide nanocluster with a fullerene topology and O h symmetry. U 60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U 60-bearing material: Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 ( Fm3¯; a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), andmore » the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U 60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U 60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U 60 clusters at high pressure may have been enhanced by the interaction between U 60 nanoclusters and the alcohol pressure medium. Once formed, U 60 nanoclusters persist regardless of their associated long-range ordering—in crystals, amorphous solids, or solutions.« less

Nonstoichiometric control of tunnel-filling order, thermal expansion, and dielectric relaxation in tetragonal tungsten Bronzes Ba0.5-xTaO3-x.

PubMed

Pan, Fengjuan; Li, Xiaohui; Lu, Fengqi; Wang, Xiaoming; Cao, Jiang; Kuang, Xiaojun; Véron, Emmanuel; Porcher, Florence; Suchomel, Matthew R; Wang, Jing; Allix, Mathieu

2015-09-21

Ordering of interpolated Ba(2+) chains and alternate Ta-O rows (TaO)(3+) in the pentagonal tunnels of tetragonal tungsten bronzes (TTB) is controlled by the nonstoichiometry in the highly nonstoichiometric Ba0.5-xTaO3-x system. In Ba0.22TaO2.72, the filling of Ba(2+) and (TaO)(3+) groups is partially ordered along the ab-plane of the simple TTB structure, resulting in a √2-type TTB superstructure (Pbmm), while in Ba0.175TaO2.675, the pentagonal tunnel filling is completely ordered along the b-axis of the simple TTB structure, leading to a triple TTB superstructure (P21212). Both superstructures show completely empty square tunnels favoring Ba(2+) conduction and feature unusual accommodation of Ta(5+) cations in the small triangular tunnels. In contrast with stoichiometric Ba6GaTa9O30, which shows linear thermal expansion of the cell parameters and monotonic decrease of permittivity with temperature within 100-800 K, these TTB superstructures and slightly nonstoichiometric simple TTB Ba0.4TaO2.9 display abnormally broad and frequency-dependent extrinsic dielectric relaxations in 10(3)-10(5) Hz above room temperature, a linear deviation of the c-axis thermal expansion around 600 K, and high dielectric permittivity ∼60-95 at 1 MHz at room temperature.

Effect of Cs content on K1-xCsxAlSi2O6 ceramic solidification forms

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Jianxia; Hou, Li; Lu, Zhongyuan

2018-02-01

K1-xCsx-geopolymers with chemical compositions of about K1-xCsxAlSi2O6·nH2O were used as precursors to prepare K1-xCsxAlSi2O6 ceramic solidification forms through the thermal treatment method. The structures of K1-xCsxAlSi2O6 ceramic solidification forms obtained at different sintering temperatures have been characterized by X-ray diffraction, scanning electron microscopy and fourier transform infrared spectroscopy. It has been observed that the crystallization temperature and phase of K1-xCsxAlSi2O6 ceramic were significantly influenced by the Cs content. An increase in the Cs content resulted in a decrease in the crystallization temperature of the K1-xCsxAlSi2O6 cubic phase. K1-xCsxAlSi2O6 ceramic obtained at 850 °C was lecucite cubic or pollucite cubic phase when x ≥ 0.2, and the lattice parameters of cubic phase increased with increasing of Cs content. However, leucite tetragonal phase formed at elevated heating temperature (1100 °C and 1300 °C) except for the case x = 0.3, 0.4, 0.5 and 1. The c/a ratio of leucite tetragonal phase obtained at 1100 °C and 1300 °C was much more closed to 1 with Cs content increased, which made it hard to be indexed between cubic and tetragonal phase. In this case, leucite tetragonal phase could also be considered as pseudo-cubic phase. Additionally, the product consistency test leaching results showed that K1-xCsxAlSi2O6 ceramics possessed superior chemical durability.

Substrate-dependent structural and CO sensing properties of LaCoO3 epitaxial films

NASA Astrophysics Data System (ADS)

Liu, Haifeng; Sun, Hongjuan; Xie, Ruishi; Zhang, Xingquan; Zheng, Kui; Peng, Tongjiang; Wu, Xiaoyu; Zhang, Yanping

2018-06-01

LaCoO3 thin films were grown on different (0 0 1) oriented LaAlO3, SrTiO3 and (LaAlO3)0.3(Sr2AlTaO6)0.7 by the polymer assisted deposition method, respectively. All the LaCoO3 thin films are in epitaxial growth on these substrates, with tetragonal distortion of CoO6 octahedrons. Due to different in-plane lattice mismatch, the LaCoO3 film on LaAlO3 has the largest tetragonal distortion of CoO6 octahedrons while the film grown on (LaAlO3)0.3(Sr2AlTaO6)0.7 has the smallest tetragonal distortion. The relative contents of the surface absorbed oxygen species are found to increase for the LaCoO3 epitaxial films grown on (0 0 1) oriented (LaAlO3)0.3(Sr2AlTaO6)0.7, SrTiO3 and LaAlO3 substrates, sequentially. The film sensors exhibit good CO sensing properties at 150 °C, and the LaCoO3 film on LaAlO3 shows the highest response but the film on (LaAlO3)0.3(Sr2AlTaO6)0.7 shows the lowest. It reveals that the larger degree of Jahn-Teller-like tetragonal distortion of CoO6 octahedrons may greatly improve the surface absorbing and catalytic abilities, corresponding to more excellent CO sensing performance. The present study suggests that the formation of epitaxial films is an efficient methodology for controlling the octahedral distortion and thereby improving the gas sensing performance of perovskite transition metal oxides.

Local conductivity enhancement due to the tetragonal domain structure in LaAlO3- SrTiO3 heterointerfaces

NASA Astrophysics Data System (ADS)

Moler, Kathryn

2014-03-01

Progress in the difficult task of growing oxide heterostructures has enabled the field of oxide interface engineering. The ability to control materials properties through interface engineering is demonstrated by the appearance of conductivity at the interface of certain insulators, most famously the {001}interface of the band insulators LaAlO3 (LAO) and TiO2-terminated SrTiO3 (STO). The prevailing explanation of conduction at the interface is electronic reconstruction due to a `polar catastrophe' in which charge migrates from the top LAO layer to the interface. Transport and other measurements in this system display a plethora of diverse physical phenomena. To better understand the interface conductivity, we used scanning superconducting quantum interference device (SQUID) microscopy to image the magnetic field locally generated by current in an interface. At low temperature, we found that the current flowed in conductive narrow paths oriented along the crystallographic axes, embedded in a less conductive background. The configuration of these paths changed upon thermal cycling above the STO cubic to tetragonal structural transition temperature, implying that the local conductivity is strongly modified by the STO tetragonal domain structure. In this talk, I will summarize these results and also report on measurements of conductivity and diamagnetism in related materials that firmly establish the influence of the STO tetragonal domains on electronic properties. Coauthors C. Bell, H.K. Sato, M. Hosoda, Y. Xie, Y. Hikita, & H.Y. Hwang (SIMES); R. Jany & C. Richter (Augsburg); C. Woltmann, G. Pfanzelt, & J. Mannhart (MP Stuttgart); B. Kalisky, E.M. Spanton, H. Noad, K.C. Nowack, A. Rosenberg, & J.R. Kirtley.

Expansion of the tetragonal magnetic phase with pressure in the iron arsenide superconductor Ba 1 - x K x Fe 2 As 2

DOE PAGES

Hassinger, Elena; Gredat, G.; Valade, F.; ...

2016-04-01

In the temperature-concentration phase diagram of most iron-based superconductors, antiferromagnetic order is gradually suppressed to zero at a critical point, and a dome of superconductivity forms around that point. The nature of the magnetic phase and its fluctuations is of fundamental importance for elucidating the pairing mechanism. In Ba 1–xK xFe 2As 2 and Ba 1–xNa xFe 2As 2, it has recently become clear that the usual stripelike magnetic phase, of orthorhombic symmetry, gives way to a second magnetic phase, of tetragonal symmetry, near the critical point, in the range from x = 0.24 to x = 0.28 for Bamore » 1–xK xFe 2As 2. In a prior study, an unidentified phase was discovered for x < 0.24 but under applied pressure, whose onset was detected as a sharp anomaly in the resistivity. Here we report measurements of the electrical resistivity of Ba 1–xK xFe 2As 2 under applied hydrostatic pressures up to 2.75 GPa, for x = 0.22, 0.24, and 0.28. The critical pressure above which the unidentified phase appears is seen to decrease with increasing x and vanish at x = 0.24, thereby linking the pressure-induced phase to the tetragonal magnetic phase observed at ambient pressure. In the temperature-concentration phase diagram of Ba 1–xK xFe 2As 2, we find that pressure greatly expands the tetragonal magnetic phase, while the stripelike phase shrinks. As a result, this reveals that pressure may be a powerful tuning parameter with which to explore the interplay between magnetism and superconductivity in this material.« less

Mechanical properties of metal dihydrides

DOE PAGES

Schultz, Peter A.; Snow, Clark S.

2016-02-04

First-principles calculations are used to characterize the bulk elastic properties of cubic and tetragonal phase metal dihydrides,more » $$\\text{M}{{\\text{H}}_{2}}$$ {$$\\text{M}$$ = Sc, Y, Ti, Zr, Hf, lanthanides} to gain insight into the mechanical properties that govern the aging behavior of rare-earth di-tritides as the constituent 3H, tritium, decays into 3He. As tritium decays, helium is inserted in the lattice, the helium migrates and collects into bubbles, that then can ultimately create sufficient internal pressure to rupture the material. The elastic properties of the materials are needed to construct effective mesoscale models of the process of bubble growth and fracture. Dihydrides of the scandium column and most of the rare-earths crystalize into a cubic phase, while dihydrides from the next column, Ti, Zr, and Hf, distort instead into the tetragonal phase, indicating incipient instabilities in the phase and potentially significant changes in elastic properties. We report the computed elastic properties of these dihydrides, and also investigate the off-stoichiometric phases as He or vacancies accumulate. As helium builds up in the cubic phase, the shear moduli greatly soften, converting to the tetragonal phase. Conversely, the tetragonal phases convert very quickly to cubic with the removal of H from the lattice, while the cubic phases show little change with removal of H. Finally, the source and magnitude of the numerical and physical uncertainties in the modeling are analyzed and quantified to establish the level of confidence that can be placed in the computational results, and this quantified confidence is used to justify using the results to augment and even supplant experimental measurements.« less

Crystal structure and properties of tetragonal EuAg{sub 4}In{sub 8} grown by metal flux technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subbarao, Udumula; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

The compound EuAg{sub 4}In{sub 8} has been obtained as single crystals in high yield from reactions run in liquid indium. X-ray diffraction on single crystals suggests that EuAg{sub 4}In{sub 8} crystallizes in the CeMn{sub 4}Al{sub 8} structure type, tetragonal space group I4/mmm with lattice constants a=b=9.7937(2) Å and c=5.7492(2) Å. Crystal structure of EuAg{sub 4}In{sub 8} is composed of pseudo Frank–Kasper cages occupied by one europium atom in each ring, which are shared through the corner along the ab plane resulting in a three dimensional network. The magnetic susceptibility of EuAg{sub 4}In{sub 8} was measured in the temperature range 2–300more » K, which obeyed Curie–Weiss law above 50 K. Magnetic moment value calculated from the fitting indicates the presence of divalent europium, which was confirmed by X-ray absorption near edge spectroscopy. Electrical resistivity measurements suggest that EuAg{sub 4}In{sub 8} is metallic in nature with a probable Fermi liquid behavior at low temperature. - Graphical abstract: The tetragonal EuAg{sub 4}In{sub 8} has been grown as single crystals from reactions run in liquid indium. Magnetic and XANES measurements suggest divalent nature of Eu and resistivity measurements suggest metallic nature. - Highlights: • EuAg{sub 4}In{sub 8} phase having tetragonal phase is grown by metal flux technique. • Magnetic and XANES measurements exhibit divalent nature of Eu in EuAg{sub 4}In{sub 8}. • Resistivity measurement suggests metallic nature and probable Fermi liquid behavior.« less

The solubility of the tetragonal form of hen egg white lysozyme from pH 4.0 to 5.4

NASA Technical Reports Server (NTRS)

Cacioppo, Elizabeth; Pusey, Marc L.

1991-01-01

Hen egg white lysozyme solubilities in the presence of the tetragonal crystal form have been determined. Conditions investigated cover the pH range 4.0 to 5.4, varying from 2.0 to 7.0 percent NaCl concentrations and from 4 to 25 C. In all instances, the solubilities were found to increase with temperature and decrease with increasing salt concentration. The effects of pH were more complex, showing a decreasing solubility with increasing pH at low salt concentration and an increasing solubility with increasing pH at high salt concentration.

Determination of the electric field gradient in RbCaF3 near the phase transition

NASA Astrophysics Data System (ADS)

Hepp, M. A.; Man, P. P.; Trokiner, A.; Zanni, H.; Fraissard, J.

1992-12-01

The fluoroperovskite, RbCaF 3 undergoes a phase transition at 195.5K from a cubic to a tetragonal phase. The order parameter for this transition is directly related to the electric field gradient which arises in the tetragonal phase. In this work, we have used three NMR methods to measure the electric field gradient at the 87Rb site in a single crystal of RbCaF 3, very near this transition. These experiments are based on recent theoretical developments which allow the measurement of quadrupole parameters even for nuclei in a weak electric field gradient.

Electron microscopy of a Gd-Ba-Cu-O superconductor

NASA Technical Reports Server (NTRS)

Ramesh, R.; Thomas, G.; Meng, R. L.; Hor, P. H.; Chu, C. W.

1989-01-01

An electron microscopy study has been carried out to characterize the microstructure of a sintered Gd-Ba-Cu-O superconductor alloy. The GdBa2Cu3O(7-x) phase in the oxygen annealed sample is orthorhombic, while in the vacuum annealed sample it is tetragonal. It is shown that the details of the fine structure in the 001-line zone axis convergent beam patterns can be used to distinguish between the orthorhombic form and the tetragonal form. In addition to this matrix phase, an amorphous phase is frequently observed at the triple grain junctions. Gd-rich inclusions have been observed inside the matrix phase.

Orthorhombic-tetragonal phase coexistence and enhanced piezo-response at room temperature in Zr, Sn, and Hf modified BaTiO{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalyani, Ajay Kumar; Brajesh, Kumar; Ranjan, Rajeev, E-mail: rajeev@materials.iisc.ernet.in

2014-06-23

The effect of Zr, Hf, and Sn in BaTiO{sub 3} has been investigated at close composition intervals in the dilute concentration limit. Detailed structural analysis by x-ray and neutron powder diffraction revealed that merely 2 mol. % of Zr, Sn, and Hf stabilizes a coexistence of orthorhombic (Amm2) and tetragonal (P4mm) phases at room temperature. As a consequence, all the three systems show substantial enhancement in the longitudinal piezoelectric coefficient (d{sub 33}), with Sn modification exhibiting the highest value ∼425 pC/N.

Thermal effects on domain orientation of tetragonal piezoelectrics studied by in situ x-ray diffraction

NASA Astrophysics Data System (ADS)

Chang, Wonyoung; King, Alexander H.; Bowman, Keith J.

2006-06-01

Thermal effects on domain orientation in tetragonal lead zirconate titanate (PZT) and lead titanate (PT) have been investigated by using in situ x-ray diffraction with an area detector. In the case of a soft PZT, it is found that the texture parameter called multiples of a random distribution (MRD) initially increases with temperature up to approximately 100°C and then falls to unity at temperatures approaching the Curie temperature, whereas the MRD of hard PZT and PT initially undergoes a smaller increase or no change. The relationship between the mechanical strain energy and domain wall mobility with temperature is discussed.

Surface crystalline phases and nanoindentation hardness of explanted zirconia femoral heads.

PubMed

Catledge, Shane A; Cook, Monique; Vohra, Yogesh K; Santos, Erick M; McClenny, Michelle D; David Moore, K

2003-10-01

One new and nine explanted zirconia femoral heads were studied using glancing angle X-ray diffraction, scanning electron microscopy, and nanoindentation hardness techniques. All starting zirconia implants consisted only of tetragonal zirconia polycrystals (TZP). For comparison, one explanted alumina femoral head was also studied. Evidence for a surface tetragonal-to-monoclinic zirconia phase transformation was observed in some implants, the extent of which was varied for different in-service conditions. A strong correlation was found between increasing transformation to the monoclinic phase and decreasing surface hardness. Microscopic investigations of some of the explanted femoral heads revealed ultra high molecular weight polyethylene and metallic transfer wear debris.

Phase stability of zirconium oxide films during focused ion beam milling

NASA Astrophysics Data System (ADS)

Baxter, Felicity; Garner, Alistair; Topping, Matthew; Hulme, Helen; Preuss, Michael; Frankel, Philipp

2018-06-01

Focused ion beam (FIB) is a widely used technique for preparation of electron transparent samples and so it is vital to understand the potential for introduction of FIB-induced microstructural artefacts. The bombardment of both Xe+ and Ga+ ions is observed to cause extensive monoclinic to tetragonal phase transformation in ZrO2 corrosion films, however, this effect is diminished with reduced energy and is not observed below 5 KeV. This study emphasises the importance of careful FIB sample preparation with a low energy cleaning step, and also gives insight into the stabilisation mechanism of the tetragonal phase during oxidation.

Domain wall motion and electromechanical strain in lead-free piezoelectrics: Insight from the model system (1 - x)Ba(Zr 0.2Ti 0.8)O 3-x(Ba 0.7Ca 0.3)TiO 3 using in situ high-energy X-ray diffraction during application of electric fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tutuncu, Goknur; Li, Binzhi; Bowman, Keith

The piezoelectric compositions (1 - x)Ba(Zr 0.2Ti 0.8)O 3–x(Ba 0.7Ca 0.3)TiO 3 (BZT-xBCT) span a model lead-free morphotropic phase boundary (MPB) between room temperature rhombohedral and tetragonal phases at approximately x = 0.5. In the present work, in situ X-ray diffraction measurements during electric field application are used to elucidate the origin of electromechanical strain in several compositions spanning the tetragonal compositional range 0.6 ≤ x ≤ 0.9. As BCT concentration decreases towards the MPB, the tetragonal distortion (given by c/a-1) decreases concomitantly with an increase in 90° domain wall motion. The increase in observed macroscopic strain is predominantly attributedmore » to the increased contribution from 90° domain wall motion. The results demonstrate that domain wall motion is a significant factor in achieving high strain and piezoelectric coefficients in lead-free polycrystalline piezoelectrics.« less

Magnetically induced ferroelectricity in Bi2CuO4

NASA Astrophysics Data System (ADS)

Zhao, L.; Guo, H.; Schmidt, W.; Nemkovski, K.; Mostovoy, M.; Komarek, A. C.

2017-08-01

The tetragonal copper oxide Bi2CuO4 has an unusual crystal structure with a three-dimensional network of well separated CuO4 plaquettes. The spin structure of Bi2CuO4 in the magnetically ordered state below TN˜43 K remains controversial. Here we present the results of detailed studies of specific heat, magnetic, and dielectric properties of Bi2CuO4 single crystals grown by the floating zone technique, combined with the polarized neutron scattering and high-resolution x-ray measurements. Down to 3.5 K our polarized neutron scattering measurements reveal ordered magnetic Cu moments which are aligned within the a b plane. Below the onset of the long range antiferromagnetic ordering we observe an electric polarization induced by an applied magnetic field, which indicates inversion symmetry breaking by the ordered state of Cu spins. For the magnetic field applied perpendicular to the tetragonal axis, the spin-induced ferroelectricity is explained in terms of the linear magnetoelectric effect that occurs in a metastable magnetic state. A relatively small electric polarization induced by the field parallel to the tetragonal axis may indicate a more complex magnetic ordering in Bi2CuO4 .

Tetragonal distortions of some tetragonal Cr 3+ centers in fluoroperovskite ABF 3 crystals

NASA Astrophysics Data System (ADS)

Zhou, Qing; Wu, Hong-Ye; Wu, Xiao-Xuan; Zheng, Wen-Chen

2006-07-01

The tetragonal distortions [characterized by the displacement Δ R of the F - ion intervening in Cr 3+ and V B (B 2+ vacancy) or M + ion in B 2+ site] for Cr 3+-V B and Cr 3+-Li + centers in Cr 3+-doped fluoroperovskites KBF 3 (B = Mg, Zn) and ACdF 3 (A = K, Rb, Cs) and also for Cr 3+-Na + center in KZnF 3 have been studied by calculating the EPR parameters D, g|| and g⊥ from the crystal-field theory. From the studies, an interesting trend is suggested, i.e., when the size of the co-doped monovalent impurity M + in the nearest neighbor B 2+ site is comparable to that of the replaced B 2+ ion, the displacement Δ R of the intervening F - ion in Cr 3+-M + center is smaller than that in Cr 3+-V B center and if the M + iron is much smaller or much larger than that of the replaced B 2+ ion, the displacement Δ R in Cr 3+-M + center is greater than that in Cr 3+-V B center. The causes of the trend are discussed.

Cubic-to-tetragonal structural phase transition in Rb{sub 1{minus}x}Cs{sub x}CaF{sub 3} solid solutions: Thermal expansion and EPR studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lahoz, F.; Villacampa, B.; Alcala, R.

1997-04-01

The influence of crystal mixing on the structural phase transitions in Rb{sub 1{minus}x}Cs{sub x}CaF{sub 3} (0{lt}x{lt}1) fluoroperovskite crystals has been studied by thermal expansion and EPR measurements of Ni{sup 2+} and Ni{sup 3+} paramagnetic probes. A cubic-to-tetragonal phase transition has been detected in crystals with x=0, 0.1, 0.21, 0.27, and 0.35. The critical temperature and the tetragonal distortion decrease as x increases. No transition was observed for x{ge}0.44. This transition shows a weak first-order component in the x=0 and 0.1 samples, which is progressively smeared out for x{gt}0.1, indicating a spatial distribution of the critical temperature in those crystals withmore » high ionic substitution rate. In RbCaF{sub 3}, another structural phase transition was observed at 20 K with a thermal hysteresis between 20 and 40 K. This transition has not been found in any of the mixed crystals.« less

Tetragonal distortions of some tetragonal Cr3+ centers in fluoroperovskite ABF3 crystals.

PubMed

Zhou, Qing; Wu, Hong-Ye; Wu, Xiao-Xuan; Zheng, Wen-Chen

2006-07-01

The tetragonal distortions [characterized by the displacement DeltaR of the F(-) ion intervening in Cr(3+) and V(B) (B(2+) vacancy) or M(+) ion in B(2+) site] for Cr(3+)-V(B) and Cr(3+)-Li(+) centers in Cr(3+)-doped fluoroperovskites KBF(3) (B=Mg, Zn) and ACdF(3) (A=K, Rb, Cs) and also for Cr(3+)-Na(+) center in KZnF(3) have been studied by calculating the EPR parameters D, g(parallel) and g(perpendicular) from the crystal-field theory. From the studies, an interesting trend is suggested, i.e., when the size of the co-doped monovalent impurity M(+) in the nearest neighbor B(2+) site is comparable to that of the replaced B(2+) ion, the displacement DeltaR of the intervening F(-) ion in Cr(3+)-M(+) center is smaller than that in Cr(3+)-V(B) center and if the M(+) iron is much smaller or much larger than that of the replaced B(2+) ion, the displacement DeltaR in Cr(3+)-M(+) center is greater than that in Cr(3+)-V(B) center. The causes of the trend are discussed.

Photocatalytic performance of freestanding tetragonal zirconia nanotubes formed in H2O2/NH4F/ethylene glycol electrolyte by anodisation of zirconium

NASA Astrophysics Data System (ADS)

Rozana, Monna; Izza Soaid, Nurul; Kian, Tan Wai; Kawamura, Go; Matsuda, Atsunori; Lockman, Zainovia

2017-04-01

ZrO2 nanotubes (ZrNTs) were produced by anodisation of zirconium foil in H2O2/NH4F/ethylene glycol electrolyte. The as-anodised foils were then soaked in the anodising electrolyte for 12 h. Soaking weakens the adherence of the anodic layer from the substrate resulting in freestanding ZrNTs (FS-ZrNTs). Moreover, the presence of H2O2 in the electrolyte also aids in weakening the adhesion of the film from the foil, as foil anodised in electrolyte without H2O2 has good film adherence. The as-anodised FS-ZrNTs film was amorphous and crystallised to predominantly tetragonal phase upon annealing at >300 °C. Annealing must, however, be done at <500 °C to avoid monoclinic ZrO2 formation and nanotubes disintegration. FS-ZrNTs annealed at 450 °C exhibited the highest photocatalytic ability to degrade methyl orange (MO), whereby 82% MO degradation was observed after 5 h, whereas FS-ZrNTs with a mixture of monoclinic and tetragonal degraded 70% of MO after 5 h.

Pressure-induced collapsed-tetragonal phase in SrCo2As2 at ambient temperature

NASA Astrophysics Data System (ADS)

Jayasekara, W. T.; Kaluarachchi, U. S.; Ueland, B. G.; Pandey, A.; Lee, Y. B.; Taufour, V.; Sapkota, A.; Kothapalli, K.; Sangeetha, N. S.; Bud'Ko, S. L.; Harmon, B. N.; Canfield, P. C.; Johnston, D. C.; Kreyssig, A.; Goldman, A. I.; Fabbris, G.; Feng, Y.; Veiga, L. S. I.; Dos Santos, A. M.

Our recent high-energy (HE) high-pressure (HP) x-ray powder diffraction measurements on tetragonal (T) SrCo2As2 have revealed a first-order pressure-induced structural phase transition to a collapsed tetragonal (cT) phase with a reduction in c by -7.9% and the c / a ratio by -9.9%. The T and cT phases coexist for applied pressures 6 GPa to 18 GPa at 7 K. Resistance measurements up to 5.9 GPa and down to 1.8 K signatures likely associated with the cT phase above 5.5 GPa and found no evidence for superconductivity. Neutron diffraction data show no evidence of magnetic order up to 1.1 GPa. Here, we show that the T to cT transition occurs around 6.8 GPa at ambient temperature, and that the transition is nearly temperature-independent from 300 K down to 7 K, which indicates a steep p - T phase line. Work at Ames Lab. was supported by US DOE, BES, DMSE under DE-AC02-07CH11358. This research used resources at the APS and ORNL, US DOE, SC, User Facilities.

The Effect of Poling on the Properties of 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 Ceramics

NASA Astrophysics Data System (ADS)

Uršič, Hana; Tellier, Jenny; Hrovat, Marko; Holc, Janez; Drnovšek, Silvo; Bobnar, Vid; Alguero, Miguel; Kosec, Marija

2011-03-01

The effects of the poling field on the structural and electrical properties of 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 (0.65PMN-0.35PT) ceramics were investigated. The highest piezoelectric coefficient d33, coupling coefficients kp, kt, and mechanical quality factor Qm were achieved for ceramics poled at electric fields between 2 and 3.5 kV/mm, whereas the d33, kp, kt, and Qm of ceramics poled at higher electric fields, i.e., 4 and 4.5 kV/mm, were lower. The non-poled ceramics contained 86% of the monoclinic phase with the space group Pm and 14% of the tetragonal phase with the space group P4mm. However, the ceramics poled at 2.5 kV/mm contained 99% of the monoclinic phase and the rest is the tetragonal phase. The results show that the ratio of the monoclinic to the tetragonal phases can be changed by the application of a poling electric field and that the extent of this change is dependent on the field strength.

Dependence of e31,f on polar axis texture for tetragonal Pb(Zrx,Ti1-x)O3 thin films

NASA Astrophysics Data System (ADS)

Yeager, Charles B.; Ehara, Yoshitaka; Oshima, Naoya; Funakubo, Hiroshi; Trolier-McKinstry, Susan

2014-09-01

It was shown by Ouyang et al. [Appl. Phys. Lett. 86, 152901 (2005)] that the piezoelectric e31,f coefficient is largest parallel to the spontaneous polarization in tetragonal PbZrxTi1-xO3 (PZT) films. However, the expected piezoelectric data are typically calculated from phenomenological constants derived from data on ceramic PZT. In this work, the dependence of e31,f on c-axis texture fraction, f001, for {001}PZT thin films was measured by growing films with systematically changed f001 using CaF2, MgO, SrTiO3, and Si substrates. An approximately linear increase in e31,f with f001 was observed for compositions up to 43 mol. % Zr, and 100% c-domain properties were extrapolated. It was demonstrated that c-axis PZT films can achieve e31,f exceeding -12 C/m2 for many tetragonal compositions. The energy harvesting figure of merit, e31,f2/ɛr, for c-axis PZT films surpassed 0.8 C2/m4. This is larger than the figure of merit of gradient-free PZT films grown on Si substrates by a factor of four.

Effects of strain on the half-metallicity and spin gapless feature of Ti2YSi (Y = Fe, Co) alloys

NASA Astrophysics Data System (ADS)

Fan, Xiaoguang; Li, Jincheng; Jin, Yingjiu

2018-05-01

Half-metals and spin gapless semiconductors (SGSs), which exhibit 100% spin polarization at the Fermi level, are considered important candidates for spintronics. Using first-principles calculations, we have investigated the effects of uniform strain and tetragonal distortion on the half-metallicity and spin gapless feature of inverse Heusler Ti2YSi (Y = Fe and Co) alloys. Results show that for uniform strains, the half-metallicity occurs in the ranges of lattice parameters from 5.938 Å to 6.535 Å for Ti2FeSi and from 5.924 Å to 6.840 Å for Ti2CoSi. Tetragonal distortions over the ranges of ‑2.0% to +2.5% and ‑2.6% to +4.1% could destroy the half-metallicity for Ti2FeSi and Ti2CoSi, respectively. On the other hand, Ti2CoSi is an SGS at lattice constants of 5.968-6.023 Å. An interesting finding is that Ti2CoSi reproduces the SGS character with increasing the lattice parameters to 6.784-6.840 Å. Small tetragonal distortions with ±0.2% will destroy the SGS character of Ti2CoSi.

Rapid synthesis of barium titanate microcubes using composite-hydroxides-mediated avenue

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Xi; Ouyang, Jing, E-mail: jingouyang@csu.edu.cn; Jin, Jiao

2014-04-01

Highlights: • Barium titanate oxides microcubes can be synthesized within 1 min. • Composite-hydroxides-mediated strategy provided a possible large scale production. • BST obtained in the strategy showed fairly good crystallinity and tetragonality. - Abstract: This paper reports the rapid synthesis of barium titanate (BaTiO{sub 3}, BTO) microcubes via composite-hydroxides-mediated reaction within 1 min. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersion spectrum (EDS) results confirmed both cubic and tetragonal lattices in the sample and the uniform microcubes with an average size of 1 μm. Ultraviolet–visible (UV–vis) spectrum indicated that the band gap of the BTO powder wasmore » 3.05 eV. Ferroelectric polarization vs. electric field (P–E) tests showed that the ferroelectric domains had formed in the as-synthesized BTO microcubes and sintered ceramics. BTO ceramics sintered at 1100 °C for 3 h showed fairly good tetragonality and possessed a maximum polarization of 0.21 μC/cm{sup 2}, indicating that the sintering temperature for the BTO powders prepared via this method was relatively low. The process and equipment reported herein provided a potential method for the rapid synthesis of titanate based perovskites.« less

One- and two-dimensional search of an equation of state using a newly released 2DRoptimize package

NASA Astrophysics Data System (ADS)

Jamal, M.; Reshak, A. H.

2018-05-01

A new package called 2DRoptimize has been released for performing two-dimensional searches of the equation of state (EOS) for rhombohedral, tetragonal, and hexagonal compounds. The package is compatible and available with the WIEN2k package. The 2DRoptimize package performs a convenient volume and c/a structure optimization. First, the package finds the best value for c/a and the associated energy for each volume. In the second step, it calculates the EoS. The package then finds the equation of the c/a ratio vs. volume to calculate the c/a ratio at the optimized volume. In the last stage, by using the optimized volume and c/a ratio, the 2DRoptimize package calculates a and c lattice constants for tetragonal and hexagonal compounds, as well as the a lattice constant with the α angle for rhombohedral compounds. We tested our new package based on several hexagonal, tetragonal, and rhombohedral structures, and the 2D search results for the EOS showed that this method is more accurate than 1D search. Our results agreed very well with the experimental data and they were better than previous theoretical calculations.

Effects of Purification on the Crystallization of Lysozyme

NASA Technical Reports Server (NTRS)

Ewing, Felecia L.; Forsythe, Elizabeth L.; Van Der Woerd, Mark; Pusey, Marc L.

1996-01-01

We have additionally purified a commercial lysozyme preparation by cation exchange chromatography, followed by recrystallization. This material is 99.96% pure with respect to macromolecular impurities. At basic pH, the purified lysozyme gave only tetragonal crystals at 20 C. Protein used directly from the bottle, prepared by dialysis against distilled water, or which did not bind to the cation exchange column had considerably altered crystallization behavior. Lysozyme which did not bind to the cation exchange column was subsequently purified by size exclusion chromatography. This material gave predominately bundles of rod-shaped crystals with some small tetragonal crystals at lower pHs. The origin of the bundled rod habit was postulated to be a thermally dependent tetragonal- orthorhombic change in the protein structure. This was subsequently ruled out on the basis of crystallization behavior and growth rate experiments. This suggests that heterogeneous forms of lysozyme may be responsible. These results demonstrate three classes of impurities: (1) small molecules, which may be removed by dialysis; (2) macromolecules, which are removable by chromatographic techniques; and (3) heterogeneous forms of the protein, which can be removed in this case by cation exchange chromatography. Of these, heterogeneous forms of the lysozyme apparently have the greatest affect on its crystallization behavior.

Accelerated aging characteristics of three yttria-stabilized tetragonal zirconia polycrystalline dental materials.

PubMed

Flinn, Brian D; deGroot, Dirk A; Mancl, Lloyd A; Raigrodski, Ariel J

2012-10-01

Concerns have been expressed about the effect of aging on the mechanical properties of zirconia. The purpose of this study was to assess the accelerated aging characteristics of 3 commercially available yttria-stabilized tetragonal zirconia polycrystalline (Y-TZP) materials by exposing specimens to hydrothermal treatments at 134°C, 0.2 MPa and 180°C, 1.0 MPa in steam. Thin bars of Y-TZP from 3 manufacturers, Lava, Zirkonzahn, and Zirprime, n=30 for each brand (22 × 3 × 0.2 mm), were cut and ground from blocks and sintered according to the manufacturer's specifications. Control specimens (n=10) for each brand were evaluated in the as-received condition. Experimental specimens were artificially aged at standard autoclave sterilization conditions,134°C at 0.2 MPa (n=5 per group at 50, 100, 150, and 200 hours) and standard industrial ceramic aging conditions, 180°C at 1.0 MPa (n=5 per group at 8, 16, 24, 28, and 48 hours). Tetragonal to monoclinic transformation was measured by using X-ray diffraction (XRD) for all groups. Flexural strength was measured in 4-point bending (ASTM1161-B) for all groups. Fracture surfaces were examined by scanning electron microscopy (SEM). Data were analyzed as a function of aging time. The statistical comparisons were based on the log value and 2-way ANOVA with heteroscedasticity-consistent standard errors used to compare mean strength among conditions (α=.05). After 200 hours at 134°C and 0.2 MPa, flexural strength (SD) decreased significantly from 1156 (87.6) MPa to 829.5 (71) MPa for Lava; 1406 (243) MPa to 882.7 (91) MPa for Zirkonzahn; and 1126 (92.4) MPa to 976 (36.4) MPa for Zirprime with P<.001 for all 3 comparisons. After 200 hours at 134°C and 0.2 MPa, some tetragonal crystals transformed to the monoclinic phase. The relative XRD peak intensity of the monoclinic to tetragonal crystal phases increased from 0.07 to 1.82 for Lava, from 0.06 to 2.43 for Zirkonzahn, and from 0.05 to 0.53 for Zirprime. After 28 hours at 180°C and 1.0 MPa, all Lava and Zirkonzahn specimens spontaneously fractured during aging. The Noritake specimens were intact after 48 hours, and the flexural strength showed no significant change, 1156 (87.6) MPa to 1122 (108) MPa. The flexural strength decreased with an increase in the monoclinic phase. SEM micrographs revealed a transformed layer on the fracture surfaces. Hydrothermal aging of Y-TZP can cause significant transformation from tetragonal to monoclinic crystal structure, which results in a statistically significant decrease in the flexural strength of thin bars. Although the strengths of all 3 Y-TZP materials are higher than other materials used for ceramic restorations, there are notable differences among them. Copyright © 2012 The Editorial Council of the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

Disentangling the Mn moments on different sublattices in the half-metallic ferrimagnet Mn3?xCoxGa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klaer, P.; Jenkins, C.A.; Alijani, V.

2011-05-03

Ferrimagnetic Mn{sub 3-x}Co{sub x}Ga compounds have been investigated by magnetic circular dichroism in x-ray absorption (XMCD). Compounds with x > 0.5 crystallize in the CuHg{sub 2}Ti structure. A tetragonal distortion of the cubic structure occurs for x {le} 0.5. For the cubic phase, magnetometry reveals a linearly increasing magnetization of 2x Bohr magnetons per formula unit obeying the generalized Slater-Pauling rule. XMCD confirms the ferrimagnetic character with Mn atoms occupying two different sublattices with antiparallel spin orientation and different degrees of spin localization and identifies the region 0.6 < x {le} 0.8 as most promising for a high spin polarizationmore » at the Fermi level. Individual Mn moments on inequivalent sites are compared to theoretical predictions.« less

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Forsythe, Elizabeth; Sumida, John; Maxwell, Daniel; Gorti, Sridhar

2002-01-01

Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aliev, Ziya S., E-mail: ziyasaliev@gmail.com; Institute of Physics, ANAS, H.Javid ave. 131, AZ1143 Baku; Donostia International Physics Center

Single crystals of the ternary copper compounds CuTlS and CuTlSe have been successfully grown from stoichiometric melt by using vertical Bridgman-Stockbarger method. The crystal structure of the both compounds has been determined by powder and single crystal X-Ray diffraction. They crystallize in the PbFCl structure type with two formula units in the tetragonal system, space group P4/nmm, a=3.922(2); c=8.123(6); Z=2 and a=4.087(6); c=8.195(19) Å; Z=2, respectively. The band structure of the reported compounds has been analyzed by means of full-potential linearized augmented plane-wave (FLAPW) method based on the density functional theory (DFT). Both compounds have similar band structures and aremore » narrow-gap semiconductors with indirect band gap. The resistivity measurements agree with a semiconductor behavior although anomalies are observed at low temperature. - Graphical abstract: The crystal structures of CuTl and CuTlSe are isostructural with the PbFCl-type and the superconductor LiFeAs-type tetragonal structure. The band structure calculations confirmed that they are narrow-gap semiconductors with indirect band gaps of 0.326 and 0.083 eV. The resistivity measurements, although confirming the semiconducting behavior of both compounds exhibit unusual anomalies at low temperatures. - Highlights: • Single crystals of CuTlS and CuTlSe have been successfully grown by Bridgman-Stockbarger method. • The crystal structure of the both compounds has been determined by single crystal XRD. • The band structure of the both compounds has been analyzed based on the density functional theory (DFT). • The resistivity measurements have been carried out from room temperature down to 10 K.« less

Calculations of single crystal elastic constants for yttria partially stabilised zirconia from powder diffraction data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lunt, A. J. G., E-mail: alexander.lunt@eng.ox.ac.uk; Xie, M. Y.; Baimpas, N.

2014-08-07

Yttria Stabilised Zirconia (YSZ) is a tough, phase-transforming ceramic that finds use in a wide range of commercial applications from dental prostheses to thermal barrier coatings. Micromechanical modelling of phase transformation can deliver reliable predictions in terms of the influence of temperature and stress. However, models must rely on the accurate knowledge of single crystal elastic stiffness constants. Some techniques for elastic stiffness determination are well-established. The most popular of these involve exploiting frequency shifts and phase velocities of acoustic waves. However, the application of these techniques to YSZ can be problematic due to the micro-twinning observed in larger crystals.more » Here, we propose an alternative approach based on selective elastic strain sampling (e.g., by diffraction) of grain ensembles sharing certain orientation, and the prediction of the same quantities by polycrystalline modelling, for example, the Reuss or Voigt average. The inverse problem arises consisting of adjusting the single crystal stiffness matrix to match the polycrystal predictions to observations. In the present model-matching study, we sought to determine the single crystal stiffness matrix of tetragonal YSZ using the results of time-of-flight neutron diffraction obtained from an in situ compression experiment and Finite Element modelling of the deformation of polycrystalline tetragonal YSZ. The best match between the model predictions and observations was obtained for the optimized stiffness values of C11 = 451, C33 = 302, C44 = 39, C66 = 82, C12 = 240, and C13 = 50 (units: GPa). Considering the significant amount of scatter in the published literature data, our result appears reasonably consistent.« less

A New Lead Iodide Perovskite based on Large Organic Cation for Solar Cell Application.

PubMed

Ma, Chunqing; Shen, Dong; Lo, Ming Fai; Lee, Chun-Sing

2018-06-06

Methylammonium (CH3NH3+) and formamidinium ((NH2)2CH+) based lead iodide perovskites are currently the two commonly used organic-inorganic lead iodide perovskites for solar cell application. Till now, there is still no alternative organic cations, which can produce perovskites with bandgaps spanning the visible spectrum (i.e. < 1.7 eV) for solar cell application. Here, a new perovskite using large propane-1,3-diammonium cation (n-Pr(NH3)22+) with a chemical structure of (n-Pr(NH3)2)0.5PbI3 is demonstrated. X-ray diffraction (XRD) result shows that the new perovskite exhibits a three-dimensional (3D), tetragonal phase. The bandgap of the new perovskite is ~ 1.6 eV, which is desirable for photovoltaic application. A (n-Pr(NH3)2)0.5PbI3 perovskite solar cell (PSC) yields a power conversion efficiency (PCE) of 5.1%. More importantly, this new perovskite is composed of larger hydrophobic cation that provides a better moisture resistance compared to CH3NH3PbI3 perovskite. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and Stoichiometry of MgxZny in Hot-Dipped Zn-Mg-Al Coating Layer on Interstitial-Free Steel

NASA Astrophysics Data System (ADS)

Kim, Jaenam; Lee, Chongsoo; Jin, Youngsool

2018-03-01

Correlations of stoichiometry and phase structure of MgxZny in hot-dipped Zn-Mg-Al coating layer which were modified by additive element have been established on the bases of diffraction and phase transformation principles. X-ray diffraction (XRD) results showed that MgxZny in the Zn-Mg-Al coating layers consist of Mg2Zn11 and MgZn2. The additive elements had a significant effect on the phase fraction of Mg2Zn11 while the Mg/Al ratio had a negligible effect. Transmission electron microscope (TEM) assisted selected area electron diffraction (SAED) results of small areas MgxZny were indexed dominantly as MgZn2 which have different Mg/Zn stoichiometry between 0.10 and 0.18. It is assumed that the MgxZny have deviated stoichiometry of the phase structure with additive element. The deviated Mg2Zn11 phase structure was interpreted as base-centered orthorhombic by applying two theoretical validity: a structure factor rule explained why the base-centered orthorhombic Mg2Zn11 has less reciprocal lattice reflections in the SAED compared to hexagonal MgZn2, and a phase transformation model elucidated its reasonable lattice point sharing of the corresponding unit cell during hexagonal MgZn2 (a, b = 0.5252 nm, c = 0.8577 nm) transform to intermediate tetragonal and final base-centered orthorhombic Mg2Zn11 (a = 0.8575 nm, b = 0.8874 nm, c = 0.8771 nm) in the equilibrium state.

Search for unconventional superconductors among the YTE 2Si2 compounds (TE  =  Cr, Co, Ni, Rh, Pd, Pt)

NASA Astrophysics Data System (ADS)

Pikul, A. P.; Samsel–Czekała, M.; Chajewski, G.; Romanova, T.; Hackemer, A.; Gorzelniak, R.; Wiśniewski, P.; Kaczorowski, D.

2017-05-01

Motivated by the recent discovery of exotic superconductivity in YFe2Ge2 we undertook reinvestigation of formation and physical properties of yttrium-based 1:2:2 silicides. Here we report on syntheses and crystal structures of the YTE 2Si2 compounds with TE  =  Cr, Co, Ni, Rh, Pd and Pt, and their low-temperature physical properties measurements, supplemented by results of fully relativistic full-potential local-orbital minimum basis band structure calculations. We confirm that most of the members of that family crystallize in a tetragonal ThCr2Si2-type structure (space group I4/mmm) and have three-dimensional Fermi surface, while only one of them (YPt2Si2) forms with a closely-related primitive CaBe2Ge2-type unit cell (space group P4/nmm) and possess quasi-two-dimensional Fermi surface sheets. Physical measurements indicated that BCS-like superconductivity is observed only in YPt2Si2 (T c  =  1.54 K) and YPd2Si2 (T c  =  0.43 K), while no superconducting phase transition was found in other systems at least down to 0.35 K. Thermal analysis showed no polymorphism in both superconducting phases. No clear relation between the superconductivity and the crystal structure (and dimensionality of the Fermi surface) was observed.

Synchrotron x-ray scattering study of charge-density-wave order in HgBa2CuO4 +δ

NASA Astrophysics Data System (ADS)

Tabis, W.; Yu, B.; Bialo, I.; Bluschke, M.; Kolodziej, T.; Kozlowski, A.; Blackburn, E.; Sen, K.; Forgan, E. M.; Zimmermann, M. v.; Tang, Y.; Weschke, E.; Vignolle, B.; Hepting, M.; Gretarsson, H.; Sutarto, R.; He, F.; Le Tacon, M.; Barišić, N.; Yu, G.; Greven, M.

2017-10-01

We present a detailed synchrotron x-ray scattering study of the charge-density-wave (CDW) order in simple tetragonal HgBa2CuO4 +δ (Hg1201). Resonant soft x-ray scattering measurements reveal that short-range order appears at a temperature that is distinctly lower than the pseudogap temperature and in excellent agreement with a prior transient reflectivity result. Despite considerable structural differences between Hg1201 and YBa2Cu3O6 +δ , the CDW correlations exhibit similar doping dependencies, and we demonstrate a universal relationship between the CDW wave vector and the size of the reconstructed Fermi pocket observed in quantum oscillation experiments. The CDW correlations in Hg1201 vanish already below optimal doping, once the correlation length is comparable to the CDW modulation period, and they appear to be limited by the disorder potential from unit cells hosting two interstitial oxygen atoms. A complementary hard x-ray diffraction measurement, performed on an underdoped Hg1201 sample in magnetic fields along the crystallographic c axis of up to 16 T, provides information on the form factor of the CDW order. As expected from the single-CuO2-layer structure of Hg1201, the CDW correlations vanish at half-integer values of L and appear to be peaked at integer L . We conclude that the atomic displacements associated with the short-range CDW order are mainly planar, within the CuO2 layers.

Optimization of a Non-arsenic Iron-based Superconductor for Wire Fabrication

DOE PAGES

Mitchell, Jonathan E; Hillesheim, D A; Bridges, Craig A; ...

2015-03-13

Here we report on the optimization of synthesis of iron selenide-based superconducting powders and the fabrication of selenide-based wire. The powders were synthesized by an ammonothermal method, whereby Ba is intercalated between FeSe layers to produce Ba x(NH 3) yFe 2Se 2, with tetragonal structure similar to AFe 2X 2 (X: As, Se), '122', superconductors. The optimal T c (up to 38 K) and Meissner and shielding superconducting fractions are obtained from the shortest reaction time (t) of reactants in liquid ammonia (30 min). With the increase of t, a second crystalline 122 phase, with a smaller unit cell, emerges.more » A small amount of NH 3 is released from the structure above ~200 °C, which results in loss of superconductivity. However, in the confined space of niobium/Monel tubing, results indicate there is enough pressure for some of NH 3 to remain in the crystal lattice, and thermal annealing can be performed at temperatures of up to 780 °C, increasing wire density and yielded a reasonable T c ≈ 16 K. Here, we report of the first successful wire fabrication of non-arsenic high-T c iron-based superconductor. We find that although bulk materials are estimated to carry critical current densities >100 kA cm ₋2 (4 K, self-field), the current transport within wires need to be optimized (J c ~ 1 kA cm ₋2).« less

Magnetic anisotropy of the antiferromagnetic ring [Cr8F8Piv16].

PubMed

van Slageren, Joris; Sessoli, Roberta; Gatteschi, Dante; Smith, Andrew A; Helliwell, Madeleine; Winpenny, Richard E P; Cornia, Andrea; Barra, Anne-Laure; Jansen, Aloysius G M; Rentschler, Eva; Timco, Grigore A

2002-01-04

A new tetragonal (P42(1)2) crystalline form of [Cr8F8Piv16] (HPiv = pivalic acid, trimethyl acetic acid) is reported. The ring-shaped molecules, which are aligned in a parallel fashion in the unit cell, form almost perfectly planar, regular octagons. The interaction between the CrIII ions is antiferromagnetic (J = 12 cm(-1)) which results in a S = 0 spin ground state. The low-lying spin excited states were investigated by cantilever torque magnetometry (CTM) and high-frequency EPR (HFEPR). The compound shows hard-axis anisotropy. The axial zero-field splitting (ZFS) parameters of the first two spin excited states (S = 1 and S = 2, respectively) are D1 = 1.59(3) cm(-1) or 1.63 cm(-1) (from CTM and HFEPR, respectively) and D2 = 0.37 cm(-1) (from HFEPR). The dipolar contributions to the ZFS of the S = 1 and S = 2 spin states were calculated with the point dipolar approximation. These contributions proved to be less than the combined single-ion contributions. Angular overlap model calculations that used parameters obtained from the electronic absorption spectrum, showed that the unique axis of the single-ion ZFS is at an angle of 19.3(1) degrees with respect to the ring axis. The excellent agreement between the experimental and the theoretical results show the validity of the used methods for the analysis of the magnetic anisotropy in antiferromagnetic CrIII rings.

Strain relaxation in the epitaxy of La2/3Sr1/3MnO3 grown by pulsed-laser deposition on SrTiO3(001)

NASA Astrophysics Data System (ADS)

Maurice, J.-L.; Pailloux, F.; Barthélémy, A.; Durand, O.; Imhoff, D.; Lyonnet, R.; Rocher, A.; Contour, J.-P.

2003-10-01

With a Curie point at 370 K, the half-metal (La0.7Sr0.3)MnO3 (LSMO) is one of the most interesting candidates for electronic devices based on tunnel magnetoresistance. SrTiO3 (STO) is up to now the best substrate for the epitaxy of suitable thin films of LSMO. The pseudocubic unit cell of rhombohedral LSMO has a parameter aLSMO such that (aSTO m aLSMO)/aLSMO = + 0.83% (where aSTO is the parameter of cubic STO) and an angle of 90.26°. As strained growth is tetragonal, relaxation implies recovery of both the pseudocubic parameter and of the original angle. In the LSMO layers that we prepare by pulsed-laser deposition, we show that these two processes are quite independent. The angular distortion is partially recovered by twinning in films 25 nm thick, while recovery of the parameter never occurs in the thickness range that we explored (up to 432 nm). A relaxation, however, takes place above a thickness of 100 nm, associated with a transition from two-dimensional to three-dimensional columnar growth. It is accompanied by chemical fluctuations. Our magnetic measurements exhibit Curie temperatures and magnetic moments very close to the bulk values in those layers where the crystal parameter is strained but the angle partially relaxed.