Streaming simplification of tetrahedral meshes.

Science.gov (United States)

Vo, Huy T; Callahan, Steven P; Lindstrom, Peter; Pascucci, Valerio; Silva, Cláudio T

2007-01-01

Unstructured tetrahedral meshes are commonly used in scientific computing to represent scalar, vector, and tensor fields in three dimensions. Visualization of these meshes can be difficult to perform interactively due to their size and complexity. By reducing the size of the data, we can accomplish real-time visualization necessary for scientific analysis. We propose a two-step approach for streaming simplification of large tetrahedral meshes. Our algorithm arranges the data on disk in a streaming, I/O-efficient format that allows coherent access to the tetrahedral cells. A quadric-based simplification is sequentially performed on small portions of the mesh in-core. Our output is a coherent streaming mesh which facilitates future processing. Our technique is fast, produces high quality approximations, and operates out-of-core to process meshes too large for main memory.

Electron emission induced modifications in amorphous tetrahedral diamondlike carbon

International Nuclear Information System (INIS)

Mercer, T.W.; DiNardo, N.J.; Rothman, J.B.; Siegal, M.P.; Friedmann, T.A.; Martinez-Miranda, L.J.

1998-01-01

The cold-cathode electron emission properties of amorphous tetrahedral diamondlike carbon are promising for flat-panel display and vacuum microelectronics technologies. The onset of electron emission is, typically, preceded by open-quotes conditioningclose quotes where the material is stressed by an applied electric field. To simulate conditioning and assess its effect, we combined the spatially localized field and current of a scanning tunneling microscope tip with high-spatial-resolution characterization. Scanning force microscopy shows that conditioning alters surface morphology and electronic structure. Spatially resolved electron-energy-loss spectroscopy indicates that the predominant bonding configuration changes from predominantly fourfold to threefold coordination. copyright 1998 American Institute of Physics

BeP2: a tetrahedral structure of type order-disorder which obeys a coordination rule for short-range order

International Nuclear Information System (INIS)

L'Haridon, P.; David, J.; Lang, J.; Parthe, E.

1976-01-01

Single-crystal studies on BeP 2 indicate that this compound possesses an OD structure. The substructure has a tetragonal unit cell with: a = 3.546 A, c = 15.01 A, Z = 4, space group: I4 1 /amd. The final R factor has a value of 0.033. The atom sites in this substructure correspond to the sites of diamond if the latter is described with a tetragonal cell, where a = (2/sup 1/2//a/sub diamond/ and c = 3a/sub diamond/. A short-range order governs the occupation of these sites with Be and P atoms. Each Be has four tetrahedral P neighbors and every P has two Be and two P neighbors. Consideration of the maxima on the diffuse streaks between the sharp reflectins of the substructure leads to an intermediate unit cell with a = 7.09 A and c = 30.02 A. Coordination considerations allow a structure proposal to be formulated for this intermediate structure which is triclinic but pseudotetragonal. The true unit cell is also pseudotetragonal with a = 7.09 A and c = N . 15.01 A, where N is a large integer

Vitreous Anorthite (CaAl2Si2O8) at High Pressure: A First-Principles Molecular Dynamics Study

Science.gov (United States)

Ghosh, D. B.; Karki, B. B.

2017-12-01

Due to the high abundance of silicates and aluminosilicates inside the earth, their corresponding melts are likely to be one of the key transport agents in the chemical and thermal evolution of our planet and therefore, have long been the subject of investigations. Experimentally, in-situ melt properties of these materials, particularly at high pressure-temperature conditions are extremely difficult to constrain and the corresponding glass phases are considered as analogs. This, however, prohibits one-to-one comparison between the properties of silicate melt and its corresponding glass. With the aim to enable such comparison, we investigate the equation of state and structural properties of CaAl2Si2O8 glass at 300 K as a function of pressure up to 160 GPa from first principles molecular dynamics simulation results. Our results show that at ambient pressure: (i) Si's remain mostly (> 95%) under tetrahedral oxygen surroundings, (ii) unlike anorthite crystal, presence of high coordination (> 4) Al's with 30% abundance, (iii) and significant presence of both non bridging (8%) and triply (17%) coordinated oxygen. In the 0-10 GPa interval, mainly topological changes occur in the Si-O (also Al-O to some extent) surroundings in the cold compressed case in comparison to smooth increase in the average bond distance and coordination in the hot compressed case. Further compression results in gradual increases in: mean coordination, proportion of O-triclusters and increasing appearance of tetrahedral oxgyens, with Si-O (Al-O) reaching 6 (6.5) and O-T > 3 (T=Si and Al) at the highest compression. Due to the absence of kinetic barrier, the hot compressed glasses consistently produce greater densities and higher coordination numbers than the cold compression cases. Decompressed glasses show irreversible compaction along with retention of high coordination species when decompressed from > 10 GPa and degree of irreversibility depends on the peak pressure of decompression. These

Feature-Sensitive Tetrahedral Mesh Generation with Guaranteed Quality

OpenAIRE

Wang, Jun; Yu, Zeyun

2012-01-01

Tetrahedral meshes are being extensively used in finite element methods (FEM). This paper proposes an algorithm to generate feature-sensitive and high-quality tetrahedral meshes from an arbitrary surface mesh model. A top-down octree subdivision is conducted on the surface mesh and a set of tetrahedra are constructed using adaptive body-centered cubic (BCC) lattices. Special treatments are given to the tetrahedra near the surface such that the quality of the resulting tetrahedral mesh is prov...

Ion-Assisted Pulsed Laser Deposition of amorphous tetrahedral-coordinated carbon films

Science.gov (United States)

Friedmann, T. A.; Tallant, D. R.; Sullivan, J. P.; Siegal, M. P.; Simpson, R. L.

1994-04-01

A parametric study has been performed of amorphous tetrahedral carbon (a-tC) films produced by ion-assisted pulsed laser deposition (IAPLD). The ion voltage, current density, and feed gas composition (nitrogen in argon) have been varied. The resultant films were characterized by thickness, residual stress, Raman spectroscopy, and electrical resistivity. The Raman spectra have been fit to two gaussian peaks, the so called graphitic (G) peak and the disorder (D) peak. It has been found that the magnitude of the D peak and the residual compressive stress are inversely correlated. At low beam voltages and currents, the magnitude of the D peak is low, increasing as the ion beam voltage and current are raised. The ion beam voltage has the most dramatic effect on the magnitude of the D peak. At low voltages (200-500 V) the magnitude of the D peak is greater for ion beams with high percentages of nitrogen possibly indicative of C-N bonding in the films. At higher voltages (500-1500 V) the D peak intensity is less sensitive to the nitrogen content of the beam.

Chemisorption of carbon dioxide and ethene on eta-Al2O3

International Nuclear Information System (INIS)

Schubart, W.; Knoezinger, H.

1985-01-01

The chemisorption of ethene on eta-Al 2 O 3 has been studied by thermal desorption spectroscopy (TDS) as a function of the degree of surface hydroxylation. The effect of CO 2 poisoning and the D 2 exchange with chemisorbed C 2 H 4 was investigated. While CO 2 shows a broad distribution of interaction energies, three (or four) distinct chemisorption states can be detected for C 2 H 4 . It is suggested that C 2 H 4 forms vinyl species via heterolytic cleavage of C-H bonds on acid-base pair sites. These presumably contain strong defects (ensembles of anion vacanies) and OH-groups coordinated to tetrahedral Al 3+ in immediate vicinity. Differences in coordination and local environment are assumed to be responsible for the formation of the three (or four) distinct chemisorption states. (orig.) [de

A suitable low-order, eight-node tetrahedral finite element for solids

International Nuclear Information System (INIS)

Key, S.W.; Heinstein, M.S.; Stone, C.M.; Mello, F.J.; Blanford, M.L.; Budge, K.G.

1998-03-01

To use the all-tetrahedral mesh generation existing today, the authors have explored the creation of a computationally efficient eight-node tetrahedral finite element (a four-node tetrahedral finite element enriched with four mid-face nodal points). The derivation of the element's gradient operator, studies in obtaining a suitable mass lumping, and the element's performance in applications are presented. In particular they examine the eight-node tetrahedral finite element's behavior in longitudinal plane wave propagation, in transverse cylindrical wave propagation, and in simulating Taylor bar impacts. The element samples only constant strain states and, therefore, has 12 hour-glass modes. In this regard it bears similarities to the eight-node, mean-quadrature hexahedral finite element. Comparisons with the results obtained from the mean-quadrature eight-node hexahedral finite element and the four-node tetrahedral finite element are included. Given automatic all-tetrahedral meshing, the eight-node, constant-strain tetrahedral finite element is a suitable replacement for the eight-node hexahedral finite element in those cases where mesh generation requires an inordinate amount of user intervention and direction to obtain acceptable mesh properties

Coordination Environment of Copper Sites in Cu-CHA Zeolite Investigated by Electron Paramagnetic Resonance

DEFF Research Database (Denmark)

Godiksen, Anita; Stappen, Frederick N.; Vennestrøm, Peter N. R.

2014-01-01

Cu-CHA combines high activity for the selective catalytic reduction (SCR) reaction with better hydrothermal stability and selectivity compared to other copper-substituted zeolites. At the same time Cu-CHA offers an opportunity for unraveling the coordination environment of the copper centers since...... the zeolite framework is very simple with only one crystallographically independent tetrahedral site (T-site). In this study the results of an X-band electron paramagnetic resonance (EPR) investigation of ion-exchanged Cu-CHA zeolite with a Si/Al ratio of 14 ± 1 is presented. Different dehydration treatments...... of the EPR silent monomeric Cu2+ in copper-substituted zeolites is suggested to be copper species with an approximate trigonal coordination sphere appearing during the dehydration. After complete dehydration at 250 °C the majority of the EPR silent Cu2+ is suggested to exist as Cu2+–OH– coordinated to two...

Nonlinear relationship between the Product Consistency Test (PCT) response and the Al/B ratio in a soda-lime aluminoborosilicate glass

Energy Technology Data Exchange (ETDEWEB)

Farooqi, Rahmat Ullah, E-mail: rufarooqi@postech.ac.kr [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 77 Cheongam-Ro, Nam-Gu, Pohang, Gyeongbuk 790-784 (Korea, Republic of); Hrma, Pavel [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 77 Cheongam-Ro, Nam-Gu, Pohang, Gyeongbuk 790-784 (Korea, Republic of); Pacific Northwest National Laboratory, Richland, WA (United States)

2016-06-15

We have investigated the effect of Al/B ratio on the Product Consistency Test (PCT) response. In an aluminoborosilicate soda-lime glass based on a modified International Simple Glass, ISG-3, the Al/B ratio varied from 0 to 0.55 (in mole fractions). In agreement with various models of the PCT response as a function of glass composition, we observed a monotonic increase of B and Na releases with decreasing Al/B mole ratio, but only when the ratio was higher than 0.05. Below this value (Al/B < 0.05), we observed a sharp decrease that we attribute to B in tetrahedral coordination.

73Ge, 119Sn and 207Pb: general cooperative effects of single atom ligands on the NMR signals observed in tetrahedral [MXnY4-n] (M = Ge, Sn, Pb; 1 ≤ n ≤ 4; X, Y = Cl, Br, I) coordination compounds of heavier XIV group elements.

Science.gov (United States)

Benedetti, M; De Castro, F; Fanizzi, F P

2017-02-28

An inverse linear relationship between 73 Ge, 119 Sn and 207 Pb NMR chemical shifts and the overall sum of ionic radii of coordinated halido ligands has been discovered in tetrahedral [MX n Y 4-n ] (M = Ge, Sn, Pb; 1 ≤ n ≤ 4; X, Y = Cl, Br, I) coordination compounds. This finding is consistent with a previously reported correlation found in octahedral, pentacoordinate and square planar platinum complexes. The effect of the coordinated halido ligands acting on the metal as shielding conducting rings is therefore confirmed also by 73 Ge, 119 Sn and 207 Pb NMR spectroscopy.

Video Vectorization via Tetrahedral Remeshing.

Science.gov (United States)

Wang, Chuan; Zhu, Jie; Guo, Yanwen; Wang, Wenping

2017-02-09

We present a video vectorization method that generates a video in vector representation from an input video in raster representation. A vector-based video representation offers the benefits of vector graphics, such as compactness and scalability. The vector video we generate is represented by a simplified tetrahedral control mesh over the spatial-temporal video volume, with color attributes defined at the mesh vertices. We present novel techniques for simplification and subdivision of a tetrahedral mesh to achieve high simplification ratio while preserving features and ensuring color fidelity. From an input raster video, our method is capable of generating a compact video in vector representation that allows a faithful reconstruction with low reconstruction errors.

A suitable low-order, eight-node tetrahedral finite element for solids

Energy Technology Data Exchange (ETDEWEB)

Key, S.W.; Heinstein, M.S.; Stone, C.M.; Mello, F.J.; Blanford, M.L.; Budge, K.G.

1998-03-01

To use the all-tetrahedral mesh generation existing today, the authors have explored the creation of a computationally efficient eight-node tetrahedral finite element (a four-node tetrahedral finite element enriched with four mid-face nodal points). The derivation of the element`s gradient operator, studies in obtaining a suitable mass lumping, and the element`s performance in applications are presented. In particular they examine the eight-node tetrahedral finite element`s behavior in longitudinal plane wave propagation, in transverse cylindrical wave propagation, and in simulating Taylor bar impacts. The element samples only constant strain states and, therefore, has 12 hour-glass modes. In this regard it bears similarities to the eight-node, mean-quadrature hexahedral finite element. Comparisons with the results obtained from the mean-quadrature eight-node hexahedral finite element and the four-node tetrahedral finite element are included. Given automatic all-tetrahedral meshing, the eight-node, constant-strain tetrahedral finite element is a suitable replacement for the eight-node hexahedral finite element in those cases where mesh generation requires an inordinate amount of user intervention and direction to obtain acceptable mesh properties.

Vibrational Spectra of Tetrahedral Fullerenes.

Science.gov (United States)

Cheng; Li; Tang

1999-01-01

From the topological structures of the following classes of tetrahedral fullerenes-(1) Cn(h, h; -i, i), Cn(h, 0; -i, 2i), Cn(2h + i, -h + i; i, i), Cn(h - i, h + 2i; -i, 2i), and Cn(h, i; 0, i) for Td symmetry; (2) Cn(h, k; k, h), Cn(h, k; -h - k, k), and Cn(h, k; -h, h + k) for Th symmetry; (3) Cn(h, k; i, j) for T symmetry-we have obtained theoretically the formulas for the numbers of their IR and Raman active modes for all of the tetrahedral fullerenes through the decomposition of their nuclear motions into irreducible representations by means of group theory. Copyright 1999 Academic Press.

Experimental Determination of the Effect of the Ratio of B/Al on Glass Dissolution along the Nepheline (NaAlSiO₄) – Malinkoite (NaBSiO₄) Join

Energy Technology Data Exchange (ETDEWEB)

Pierce, Eric M; Reed, Lunde R; Shaw, Wendy J; McGrail, B Peter; Icenhower, Jonathan P; Windisch, Charles F; Cordova, Elsa A; Broady, Johnathan W

2010-03-27

The dissolution kinetics of five glasses along the NaAlSiO₄-NaBSiO₄ join were used to evaluate how the structural variations associated with boron-aluminum substitution affect the rate of dissolution. The composition of each glass varied inversely in mol% of Al₂O₃ (5 to 25 mol%) and B₂O₃ (20 to 0 mol%) with Na₂O (25 mol%) and SiO₂ (50 mol%) making up the remaining amount, in every case Na/(Al+B) = 1.0. Single-pass flow-through experiments (SPFT) were conducted under dilute conditions as a function of solution pH (from 7.0 to 12.0) and temperature (from 23° to 90°C). Analysis by ²⁷Al and ²⁹Si MAS-NMR suggests Al (~98% ^[4]Al) and Si atoms (~100% ^[4]Si) occupy a tetrahedral coordination whereas, B atoms occupy both tetrahedral ([4]B) and trigonal (^[3]B) coordination. The distribution of [3]B fractionated between ^[3]B(ring) and ^[3]B(non-ring) moieties, with the ^[3]B(ring)/^[3]B(non-ring) ratio increases with the B/Al ratio. The MAS-NMR results also indicated an increase in the fraction of ^[4]B with an increase in the B/Al ratio. But despite the changes in the B/Al ratio and B coordination, the ²⁹Si spectra maintain a chemical shift between -88 to -84 ppm for each glass. Unlike the ²⁹Si spectra, the ²⁷Al resonances shift to more positive values with an increase in the B/Al ratio which suggests mixing between the ^[4]Al and ^[3]B sites, assuming avoidance between tetrahedral trivalent cations (^[4]Al-O-^[4]B avoidance). Raman spectroscopy was use to augment the results collected from MAS-NMR and demonstrated that NeB4 (glass sample with the highest B content) was glass-glass phase separated (e.g., heterogeneous glass). Results from SPFT experiments suggest a forward rate of reaction and pH power law

An X-ray absorption spectroscopic study of the metal site preference in Al1−xGaxFeO3

International Nuclear Information System (INIS)

Walker, James D.S.; Grosvenor, Andrew P.

2013-01-01

Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO 3 (Pna2 1 ; A=Al, Ga) system has received attention to better understand the origins of magnetoelectric coupling. The magnetoelectric properties this system exhibits depend on the amount of anti-site disorder present, which is affected by the composition and the method of synthesis. In this study, Al 1−x Ga x FeO 3 was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L 2,3 -, Ga K-, and Fe K-edge spectra were collected to examine how the average metal coordination number changes with composition. Examination of XANES spectra from Al 1−x Ga x FeO 3 indicate that with increasing Ga content, Al increasingly occupies octahedral sites while Ga displays a preference for occupying the tetrahedral site. The Fe K-edge spectra indicate that more Fe is present in the tetrahedral site in AlFeO 3 than in GaFeO 3 , implying more anti-site disorder is present in AlFeO 3 . - Graphical abstract: Al 1−x Ga x FeO 3 has been investigated by XANES. Through examination of Al L 2,3 -, Ga K-, and Fe K-edge XANES spectra, it was found that more anti-site disorder of the Fe atoms is present in AlFeO 3 compared to in GaFeO 3 . Highlights: ► Al 1−x Ga x FeO 3 was investigated by X-ray absorption spectroscopy. ► Ga prefers to occupy the tetrahedral site in Al 1−x Ga x FeO 3 . ► Fe prefers to occupy the octahedral sites in Al 1−x Ga x FeO 3 as x increases. ► More anti-site disorder is present in AlFeO 3 compared to in GaFeO 3.

Relativistic Jahn-Teller effect in tetrahedral systems

International Nuclear Information System (INIS)

Opalka, Daniel; Domcke, Wolfgang; Segado, Mireia; Poluyanov, Leonid V.

2010-01-01

It is shown that orbitally degenerate states in highly symmetric systems are split by Jahn-Teller forces which are of relativistic origin (that is, they arise from the spin-orbit coupling operator). For the example of tetrahedral systems, the relativistic Jahn-Teller Hamiltonians of orbitally degenerate electronic states with spin 1/2 are derived. While both electrostatic and relativistic forces contribute to the Jahn-Teller activity of vibrational modes of E and T 2 symmetry in 2 T 2 states of tetrahedral systems, the electrostatic and relativistic Jahn-Teller couplings are complementary for 2 E states: The E mode is Jahn-Teller active through electrostatic forces, while the T 2 mode is Jahn-Teller active through the relativistic forces. The relativistic Jahn-Teller parameters have been computed with ab initio relativistic electronic-structure methods. It is shown for the example of the tetrahedral cluster cations of the group V elements that the relativistic Jahn-Teller couplings can be of the same order of magnitude as the familiar electrostatic Jahn-Teller couplings for the heavier elements.

Aluminium hydro(oxide)–based (AO) adsorbent for defluoridation of ...

African Journals Online (AJOL)

High resolution 27Al Magic Angle Spinning Nuclear Magnetic Resonance (27Al MAS NMR) spectra of AO, AA, and PB were recorded, to analyse the coordination geometry of solid Al species and the results showed that aluminium is coordinated octahedrally and tetrahedrally in all cases. Regeneration experiments showed ...

Unlocking the secrets of Al-tobermorite in Roman seawater concrete

KAUST Repository

Jackson, Marie D.; Chae, Sejungrosie; Mulcahy, Sean R.; Meral, Cagla; Taylor, Rae; Li, Penghui; Emwas, Abdul-Hamid M.; Moon, Juhyuk; Yoon, Seyoon; Vola, Gabriele; Wenk, Hans Rudolf; Monteiro, Paulo José Meleragno

2013-01-01

Ancient Roman syntheses of Al-tobermorite in a 2000-year-old concrete block submerged in the Bay of Pozzuoli (Baianus Sinus), near Naples, have unique aluminum-rich and silica-poor compositions relative to hydrothermal geological occurrences. In relict lime clasts, the crystals have calcium contents that are similar to ideal tobermorite, 33 to 35 wt%, but the low-silica contents, 39 to 40 wt%, reflect Al3+ substitution for Si4+ in Q 2(1Al), Q3(1Al), and Q3(2 Al) tetrahedral chain and branching sites. The Al-tobermorite has a double silicate chain structure with long chain lengths in the b [020] crystallographic direction, and wide interlayer spacing, 11.49 Å. Na+ and K+ partially balance Al3+ substitution for Si4+. Poorly crystalline calcium-aluminum-silicate-hydrate (C-A-S-H) cementitious binder in the dissolved perimeter of relict lime clasts has Ca/(Si+Al) = 0.79, nearly identical to the Al-tobermorite, but nanoscale heterogeneities with aluminum in both tetrahedral and octahedral coordination. The concrete is about 45 vol% glassy zeolitic tuff and 55 vol% hydrated lime-volcanic ash mortar; lime formed <10 wt% of the mix. Trace element studies confirm that the pyroclastic rock comes from Flegrean Fields volcanic district, as described in ancient Roman texts. An adiabatic thermal model of the 10 m2 by 5.7 m thick Baianus Sinus breakwater from heat evolved through hydration of lime and formation of C-A-S-H suggests maximum temperatures of 85 to 97 °C. Cooling to seawater temperatures occurred in two years. These elevated temperatures and the mineralizing effects of sea-water and alkali- and alumina-rich volcanic ash appear to be critical to Al-tobermorite crystallization. The long-term stability of the Al-tobermorite provides a valuable context to improve future syntheses in innovative concretes with advanced properties using volcanic pozzolans.

Unlocking the secrets of Al-tobermorite in Roman seawater concrete

KAUST Repository

Jackson, Marie D.

2013-10-01

Ancient Roman syntheses of Al-tobermorite in a 2000-year-old concrete block submerged in the Bay of Pozzuoli (Baianus Sinus), near Naples, have unique aluminum-rich and silica-poor compositions relative to hydrothermal geological occurrences. In relict lime clasts, the crystals have calcium contents that are similar to ideal tobermorite, 33 to 35 wt%, but the low-silica contents, 39 to 40 wt%, reflect Al3+ substitution for Si4+ in Q 2(1Al), Q3(1Al), and Q3(2 Al) tetrahedral chain and branching sites. The Al-tobermorite has a double silicate chain structure with long chain lengths in the b [020] crystallographic direction, and wide interlayer spacing, 11.49 Å. Na+ and K+ partially balance Al3+ substitution for Si4+. Poorly crystalline calcium-aluminum-silicate-hydrate (C-A-S-H) cementitious binder in the dissolved perimeter of relict lime clasts has Ca/(Si+Al) = 0.79, nearly identical to the Al-tobermorite, but nanoscale heterogeneities with aluminum in both tetrahedral and octahedral coordination. The concrete is about 45 vol% glassy zeolitic tuff and 55 vol% hydrated lime-volcanic ash mortar; lime formed <10 wt% of the mix. Trace element studies confirm that the pyroclastic rock comes from Flegrean Fields volcanic district, as described in ancient Roman texts. An adiabatic thermal model of the 10 m2 by 5.7 m thick Baianus Sinus breakwater from heat evolved through hydration of lime and formation of C-A-S-H suggests maximum temperatures of 85 to 97 °C. Cooling to seawater temperatures occurred in two years. These elevated temperatures and the mineralizing effects of sea-water and alkali- and alumina-rich volcanic ash appear to be critical to Al-tobermorite crystallization. The long-term stability of the Al-tobermorite provides a valuable context to improve future syntheses in innovative concretes with advanced properties using volcanic pozzolans.

''114''-type nitrides LnAl(Si{sub 4-x}Al{sub x})N{sub 7}O{sub δ} with unusual [AlN{sub 6}] octahedral coordination

Energy Technology Data Exchange (ETDEWEB)

Huang, Saifang; Ouyang, Xin [School of Materials Science and Technology, China University of Geosciences, Beijing (China); Department of Chemical and Materials Engineering, University of Auckland (New Zealand); Huang, Zhaohui; Fang, Minghao; Liu, Yan-gai [School of Materials Science and Technology, China University of Geosciences, Beijing (China); Cao, Peng; Gao, Wei [Department of Chemical and Materials Engineering, University of Auckland (New Zealand); Zujovic, Zoran; Soehnel, Tilo [School of Chemical Sciences, University of Auckland (New Zealand); Price, Jason R. [Australian Synchrotron, Clayton, VIC (Australia); Avdeev, Maxim [Australian Centre for Neutron Scattering, Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia); Que, Meidan [School of Electronic and Information Engineering, Xi' an Jiaotong University (China); Suzuki, Furitsu; Kido, Tsuyoshi; Kaji, Hironori [Institute for Chemical Research, Kyoto University (Japan)

2017-03-27

Aluminum-nitrogen six-fold octahedral coordination, [AlN{sub 6}], is unusual and has only been seen in the high-pressure rocksalt-type aluminum nitride or some complex compounds. Herein we report novel nitrides LnAl(Si{sub 4-x}Al{sub x})N{sub 7}O{sub δ} (Ln=La, Sm), the first inorganic compounds with [AlN{sub 6}] coordination prepared via non-high-pressure synthesis. Structure refinements of neutron powder diffraction and single-crystal X-ray diffraction data show that these compounds crystallize in the hexagonal Swedenborgite structure type with P6{sub 3}mc symmetry where Ln and Al atoms locate in anticuboctahedral and octahedral interstitials, respectively, between the triangular and Kagome layers of [SiN{sub 4}] tetrahedra. Solid-state NMR data of high-purity La-114 powders confirm the unusual [AlN{sub 6}] coordination. These compounds are the first examples of the ''33-114'' sub-type in the ''114'' family. The additional site for over-stoichiometric oxygen in the structure of 114-type compounds was also identified. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Tetrahedral gray code for visualization of genome information.

Directory of Open Access Journals (Sweden)

Natsuhiro Ichinose

Full Text Available We propose a tetrahedral Gray code that facilitates visualization of genome information on the surfaces of a tetrahedron, where the relative abundance of each [Formula: see text]-mer in the genomic sequence is represented by a color of the corresponding cell of a triangular lattice. For biological significance, the code is designed such that the [Formula: see text]-mers corresponding to any adjacent pair of cells differ from each other by only one nucleotide. We present a simple procedure to draw such a pattern on the development surfaces of a tetrahedron. The thus constructed tetrahedral Gray code can demonstrate evolutionary conservation and variation of the genome information of many organisms at a glance. We also apply the tetrahedral Gray code to the honey bee (Apis mellifera genome to analyze its methylation structure. The results indicate that the honey bee genome exhibits CpG overrepresentation in spite of its methylation ability and that two conserved motifs, CTCGAG and CGCGCG, in the unmethylated regions are responsible for the overrepresentation of CpG.

Synthesis, characterization and properties of a glycol-coordinated ε-Keggin-type Al13 chloride

KAUST Repository

Gu, Bin; Sun, Chenglin; Fettinger, James C.; Casey, William H.; Dikhtiarenko, Alla; Gascon, Jorge; Koichumanova, Kamila; Babu Sai Sankar Gupta, Karthick; Jan Heeres, Hero; He, Songbo

2018-01-01

Herein we present the first example of a glycol-coordinated ε-Keggin Al13 chloride (gl-ε-Al13), which is the first chelated version since discovery of Al13 in 1960. The molecular structure consists of [AlO4Al12(OH)12(OC2H4OH)12]Cl7·H2O units with chelating mono-anionic ethylene glycol units replacing one bridging and one terminal oxygen site.

Synthesis, characterization and properties of a glycol-coordinated ε-Keggin-type Al13 chloride

KAUST Repository

Gu, Bin

2018-03-29

Herein we present the first example of a glycol-coordinated ε-Keggin Al13 chloride (gl-ε-Al13), which is the first chelated version since discovery of Al13 in 1960. The molecular structure consists of [AlO4Al12(OH)12(OC2H4OH)12]Cl7·H2O units with chelating mono-anionic ethylene glycol units replacing one bridging and one terminal oxygen site.

A molecular dynamics study of the atomic structure of (CaO)x(Al2O3)1-x glass with x = 0.625 close to the eutectic

Science.gov (United States)

Thomas, B. W. M.; Mead, R. N.; Mountjoy, G.

2006-05-01

Aluminate glasses are difficult to prepare as they do not contain traditional network formers, but they are promising materials for optical applications. The atomic structure of calcium aluminate glasses has been studied using several experimental techniques. The current study uses molecular dynamics to obtain a model of a (CaO)0.625(Al2O3)0.375 glass close to the eutectic. The glass consists of a tetrahedral alumina network with average network polymerization \\langle Q^{n}\\rangle of n = 3.3. Ca acts as a network modifier with average coordination of 6.2. Ca is typically coordinated to three bridging oxygens (Ob) and three non-bridging oxygens (Onb), with Ca-Onb bonds noticeably shorter than the Ca-Ob bonds. A new method of analysing modifier cation coordination is presented, which specifically shows the distribution of Ca coordination NCaO in terms of combinations of NCaOb and NCaOnb. Ob is most often coordinated to two Al plus two Ca, and Onb is most often coordinated to one Al plus three Ca. The typical coordinations of Ca, Ob, and Onb all have a noticeable similarity to those for the 5CaO·3Al2O3 crystal. The Ca-Ca distribution shows a clear similarity to that for (CaO)0.5(SiO2)0.5 glass, and this is attributed to the equal atomic number densities of Ca in these glasses.

Local coordination of polyvalent metal ions in molten halide mixtures

International Nuclear Information System (INIS)

Akdeniz, Z.; Tosi, M.P.

1989-07-01

Ample experimental evidence is available in the literature on the geometry and the stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides. Recent schemes for classifying this evidence are discussed. Dissociation of tetrahedral halocomplexes in good ionic systems can be viewed as a classical Mott problem of bound-state stability in a conducting matrix. More generally, structural coordinates can be constructed from properties of the component elements, to separate out systems with long-lived fourfold or sixfold coordination and to distinguish between these. (author). 11 refs, 1 fig

Electronic structure of filled tetrahedral semiconductors

NARCIS (Netherlands)

Wood, D.M.; Zunger, Alex; Groot, R. de

1985-01-01

We discuss the susceptibility of zinc-blende semiconductors to band-structure modification by insertion of small atoms at their tetrahedral interstitial states. GaP is found to become a direct-gap semiconductor with two He atoms present at its interstitial sites; Si does not. Analysis of the factors

Synthesis and properties of γ-Ga2O3-Al2O3 solid solutions

Science.gov (United States)

Afonasenko, T. N.; Leont'eva, N. N.; Talzi, V. P.; Smirnova, N. S.; Savel'eva, G. G.; Shilova, A. V.; Tsyrul'nikov, P. G.

2017-10-01

The textural and structural properties of mixed oxides Ga2O3-Al2O3, obtained via impregnating γ-Al2O3 with a solution of Ga(NO3)3 and subsequent heat treatment, are studied. According to the results from X-ray powder diffraction, gallium ions are incorporated into the structure of aluminum oxide to form a solid solution of spinel-type γ-Ga2O3-Al2O3 up to a Ga2O3 content of 50 wt % of the total weight of the sample, accompanied by a reduction in the specific surface area, volume, and average pore diameter. It is concluded that when the Ga2O3 content exceeds 50 wt %, the β-Ga2O3 phase is observed along with γ-Ga2O3-Al2O3 solid solution. 71Ga and 27Al NMR spectroscopy shows that gallium replaces aluminum atoms from the tetrahedral position to the octahedral coordination in the structure of γ-Ga2O3-Al2O3.

Atomic Nuclei with Tetrahedral and Octahedral Symmetries

International Nuclear Information System (INIS)

Dudek, J.; Gozdz, A.; Schunck, N.

2003-01-01

We present possible manifestations of octahedral and tetrahedral symmetries in nuclei. These symmetries are associated with the O D h and T D d double point groups. Both of them have very characteristic finger-prints in terms of the nucleonic level properties - unique in the Fermionic universe. The tetrahedral symmetry leads to the four-fold degeneracies in the nucleonic spectra; it does not preserve the parity. The octahedral symmetry leads to the four-fold degeneracies in the nucleonic spectra as well but it does preserve the parity. Microscopic predictions have been obtained using mean-field theory based on the relativistic equations and confirmed by using ''traditional'' Schrodinger equation formalism. Calculations are performed in multidimensional deformation spaces using newly designed algorithms. We discuss some experimental fingerprints of the hypothetical new symmetries and possibilities of their verification through experiments. (author)

Tetrahedral meshing via maximal Poisson-disk sampling

KAUST Repository

Guo, Jianwei

2016-02-15

In this paper, we propose a simple yet effective method to generate 3D-conforming tetrahedral meshes from closed 2-manifold surfaces. Our approach is inspired by recent work on maximal Poisson-disk sampling (MPS), which can generate well-distributed point sets in arbitrary domains. We first perform MPS on the boundary of the input domain, we then sample the interior of the domain, and we finally extract the tetrahedral mesh from the samples by using 3D Delaunay or regular triangulation for uniform or adaptive sampling, respectively. We also propose an efficient optimization strategy to protect the domain boundaries and to remove slivers to improve the meshing quality. We present various experimental results to illustrate the efficiency and the robustness of our proposed approach. We demonstrate that the performance and quality (e.g., minimal dihedral angle) of our approach are superior to current state-of-the-art optimization-based approaches.

Tetrahedral meshing via maximal Poisson-disk sampling

KAUST Repository

Guo, Jianwei; Yan, Dongming; Chen, Li; Zhang, Xiaopeng; Deussen, Oliver; Wonka, Peter

2016-01-01

-distributed point sets in arbitrary domains. We first perform MPS on the boundary of the input domain, we then sample the interior of the domain, and we finally extract the tetrahedral mesh from the samples by using 3D Delaunay or regular triangulation for uniform

Interacting spin-1/2 tetrahedral system Cu2Te2O5X2 (X = Cl, Br)

DEFF Research Database (Denmark)

Jensen, Jens

2009-01-01

Magnetic ordering and excitations of Cu2Te2O5Cl2 are analyzed in terms of a tetramerized spin model for the tetrahedral Cu clusters of spin 1/2. The mean-field model is able to account for the main properties of the incommensurable magnetic structure observed by Zaharko et al. [Phys. Rev. B 73......-dimensional fashion. Preliminary model calculations for the Cu2Te2O5Br2 system lead to the same conclusion. Udgivelsesdato: 7. Januar...

Computer simulation of the structural transformation in liquid Al2O3

International Nuclear Information System (INIS)

Vo Van Hoang; Oh, Suhk Kun

2005-01-01

We investigate the pressure-induced structural transformation in liquid Al 2 O 3 by a molecular dynamics (MD) method. Simulations were done in the basic cube, under periodic boundary conditions, containing 3000 ions with Born-Mayer-type pair potentials. The structure of the liquid Al 2 O 3 model with a real density at ambient pressure is in good agreement with Landron's experiment. In order to study the structural transformation, seven models of liquid alumina at temperature 2500 K and at densities in the range 2.80-4.5 g cm -3 have been built. The microstructure of Al 2 O 3 systems has been analysed through the pair radial distribution functions, coordination number distributions, interatomic distances and bond-angle distributions. And we found clear evidence of a structural transition in liquid alumina from a tetrahedral to an octahedral network. According to our results, this transformation occurred at densities in the range 3.6-4.5 g cm -3 . We also obtained an anomalous density dependence of the self-diffusion constant in the region of the structural transformation

Controlled synthesis of concave tetrahedral palladium nanocrystals by reducing Pd(acac)2 with carbon monoxide

International Nuclear Information System (INIS)

Zhu, Hai; Chi, Quan; Zhao, Yanxi; Li, Chunya; Tang, Heqing; Li, Jinlin; Huang, Tao; Liu, Hanfan

2012-01-01

Graphical abstract: By using CO as a reducing agent, uniform and well-defined concave tetrahedral Pd nanocrystals were successfully synthesized. CO flow rate was the most essential for the formation of the concave tetrahedral nanostructures. The morphologies and sizes of the final products can be well controlled by adjusting the flow rate of CO. Highlights: ► By using CO as a reducing agent, concave tetrahedral Pd nanocrystals were obtained. ► CO flow rate is critical to the formation of concave tetrahedral Pd nanocrystals. ► The selective adsorption of CO on (1 1 0) facets is essential to concave Pd tetrahedra. -- Abstract: CO reducing strategy to control the morphologies of palladium nanocrystals was investigated. By using CO as a reducing agent, uniform and well-defined concave tetrahedral Pd nanocrystals with a mean size of about 55 ± 2 nm were readily synthesized with Pd(acac) 2 as a precursor and PVP as a stabilizer. The structures of the as-prepared Pd nanocrystals were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), ultraviolet–visible (UV–vis) absorption spectroscopy and electrochemical measurements. The results demonstrated that CO was the most essential for the formation of the concave tetrahedral Pd nanostructures. The morphologies and sizes of the final products can be well controlled by adjusting the flow rate of CO. The most appropriate CO flow rate, temperature and time for the formation of the ideal concave tetrahedral Pd nanocrystals was 0.033 mL s −1 , 100 °C and 3 h, respectively.

Symmetry and topology code of the cluster self-assembly of framework MT structures of alumophosphates AlPO4(H2O)2 (metavariscite and variscite) and Al2(PO4)2(H2O)3 (APC)

Science.gov (United States)

Ilyushin, G. D.; Blatov, V. A.

2017-03-01

The supramolecular chemistry of alumophosphates, which form framework 3D MT structures from polyhedral AlO4(H2O)2 clusters with octahedral O coordination (of M polyhedra) and PO4 and AlO4 with tetrahedral O coordination (of T polyhedra), is considered. A combinatorial-topological modeling of the formation of possible types of linear (six types) and ring (two types) tetrapolyhedral cluster precursors M2T2 from MT monomers is carried out. Different versions of chain formation from linked (MT)2 rings (six types) are considered. The model, which has a universal character, has been used to simulate the cluster selfassembly of the crystal structure of AlPO4(H2O)2 minerals (metavariscite, m-VAR, and variscite, VAR) and zeolite [Al2(PO4)2(H2O)2] · H2O (APC). A tetrapolyhedral linear precursor is established for m-VAR and a ring precursor (MT)2 is established for VAR and APC. The symmetry and topology code of the processes of crystal structure self-assembly from cluster precursors is completely reconstructed. The functional role of the O-H···O hydrogen bonds is considered for the first time. The cluster self-assembly model explains the specific features of the morphogenesis of single crystals: m-VAR prisms, flattened VAR octahedra, and needleshaped APC square-base prisms.

Synthesis and characterization of Al-TON zeolite using a dialkylimizadolium as structure-directing agent

Energy Technology Data Exchange (ETDEWEB)

Lopes, Christian Wittee; Pergher, Sibele Berenice Castella, E-mail: chriswittee@gmail.com [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Villarroel-Rocha, Jhonny [Laboratorio de Solidos Porosos, Instituto de Fisica Aplicada, Universidad Nacional de San Luis, Chacabuco, San Luis (Argentina); Silva, Bernardo Araldi Da; Mignoni, Marcelo Luis [Universidade Regional Integrada, Erechim, RS (Brazil)

2016-11-15

In this work, the synthesis of zeolites using 1-butyl-3-methylimidazolium chloride [C{sub 4}MI]Cl as a structure-directing agent was investigated. The organic cation shows effectiveness and selectivity for the syntheses of TON zeolites under different reaction conditions compared to the traditional structure directing agent, 1,8-diaminooctane. The 1-butyl-3-methylimidazolium cation lead to highly crystalline materials and its role as OSDA in our synthesis conditions has been confirmed by characterization techniques. ICP-OES confirms the presence of Al in the samples and {sup 27}Al MAS NMR analysis indicated that aluminum atoms were incorporated in tetrahedral coordination. Scanning electron microscopy indicated that changing the crystallization condition (static or stirring), zeolites with different crystal size were obtained, which consequently affects the textural properties of the zeolites. Moreover, varying some synthesis parameters MFI zeolite can also be obtained. (author)

Three-Dimensional Cadmium(II Cyanide Coordination Polymers with Ethoxy-, Butoxy- and Hexyloxy-ethanol

Directory of Open Access Journals (Sweden)

Takeshi Kawasaki

2016-08-01

Full Text Available The three novel cadmium(II cyanide coordination polymers with alkoxyethanols, [Cd(CN2(C2H5OCH2CH2OH]n (I, [{Cd(CN2(C4H9OCH2CH2OH}3{Cd(CN2}]n (II and [{Cd(CN2(H2O2}{Cd(CN2}3·2(C6H13OCH2CH2OH]n (III, were synthesized and charcterized by structural determination. Three complexes have three-dimensional Cd(CN2 frameworks; I has distorted tridymite-like structure, and, II and III have zeolite-like structures. The cavities of Cd(CN2 frameworks of the complexes are occupied by the alkoxyethanol molecules. In I and II, hydroxyl oxygen atoms of alkoxyethanol molecules coordinate to the Cd(II ions, and the Cd(II ions exhibit slightly distort trigonal-bipyramidal coordination geometry. In II, there is also tetrahedral Cd(II ion which is coordinated by only the four cyanides. The hydroxyl oxygen atoms of alkoxyethanol connects etheric oxygen atoms of the neighboring alkoxyethanol by hydrogen bond in I and II. In III, hexyloxyethanol molecules do not coordinate to the Cd(II ions, and two water molecules coordnate to the octahedral Cd(II ions. The framework in III contains octahedral Cd(II and tetrahedral Cd(II in a 1:3 ratio. The Cd(CN2 framework structures depended on the difference of alkyl chain for alkoxyethanol molecules.

Ab initio investigation of inversion in tetrahedral molecules of transition metals

International Nuclear Information System (INIS)

Musaev, D.G.; Boldyrev, A.I.

1984-01-01

Tetrahedral and plane square configurations of TiH 4 , TiF 4 , molecules and ScH 4 - , ScF 4 - anions are optimized in the frames of Hartree-Fock-Roothaan method with the bases of DZHD and DZRS type. Inversion barriers of tetrahedral molecules through plane sqUare configuration which make up 46; 70; 27 and 39 kcal/mol in TiH 4 , TiF 4 , SoH 4 - and ScF 4 - respectively are estimated. Correlation diagrams under inversion are analyzed

Three-dimensional modeling of capsule implosions in OMEGA tetrahedral hohlraums

International Nuclear Information System (INIS)

Schnittman, J. D.; Craxton, R. S.

2000-01-01

Tetrahedral hohlraums have been proposed as a means for achieving the highly uniform implosions needed for ignition with inertial confinement fusion (ICF) [J. D. Schnittman and R. S. Craxton, Phys. Plasmas 3, 3786 (1996)]. Recent experiments on the OMEGA laser system have achieved good drive uniformity consistent with theoretical predictions [J. M. Wallace et al., Phys. Rev. Lett. 82, 3807 (1999)]. To better understand these experiments and future investigations of high-convergence ICF implosions, the three-dimensional (3-D) view-factor code BUTTERCUP has been expanded to model the time-dependent radiation transport in the hohlraum and the hydrodynamic implosion of the capsule. Additionally, a 3-D postprocessor has been written to simulate x-ray images of the imploded core. Despite BUTTERCUP's relative simplicity, its predictions for radiation drive temperatures, fusion yields, and core deformation show close agreement with experiment. (c) 2000 American Institute of Physics

Direct Observation of Very Large Zero-Field Splitting in a Tetrahedral Ni(II)Se4 Coordination Complex.

Science.gov (United States)

Jiang, Shang-Da; Maganas, Dimitrios; Levesanos, Nikolaos; Ferentinos, Eleftherios; Haas, Sabrina; Thirunavukkuarasu, Komalavalli; Krzystek, J; Dressel, Martin; Bogani, Lapo; Neese, Frank; Kyritsis, Panayotis

2015-10-14

The high-spin (S = 1) tetrahedral Ni(II) complex [Ni{(i)Pr2P(Se)NP(Se)(i)Pr2}2] was investigated by magnetometry, spectroscopic, and quantum chemical methods. Angle-resolved magnetometry studies revealed the orientation of the magnetization principal axes. The very large zero-field splitting (zfs), D = 45.40(2) cm(-1), E = 1.91(2) cm(-1), of the complex was accurately determined by far-infrared magnetic spectroscopy, directly observing transitions between the spin sublevels of the triplet ground state. These are the largest zfs values ever determined--directly--for a high-spin Ni(II) complex. Ab initio calculations further probed the electronic structure of the system, elucidating the factors controlling the sign and magnitude of D. The latter is dominated by spin-orbit coupling contributions of the Ni ions, whereas the corresponding effects of the Se atoms are remarkably smaller.

Theory and X-ray Absorption Spectroscopy for Aluminum Coordination Complexes – Al K-Edge Studies of Charge and Bonding in (BDI)Al, (BDI)AlR2, and (BDI)AlX2 Complexes.

Science.gov (United States)

Altman, Alison B; Pemmaraju, C D; Camp, Clément; Arnold, John; Minasian, Stefan G; Prendergast, David; Shuh, David K; Tyliszczak, Tolek

2015-08-19

Polarized aluminum K-edge X-ray absorption near edge structure (XANES) spectroscopy and first-principles calculations were used to probe electronic structure in a series of (BDI)Al, (BDI)AlX2, and (BDI)AlR2 coordination compounds (X = F, Cl, I; R = H, Me; BDI = 2,6-diisopropylphenyl-β-diketiminate). Spectral interpretations were guided by examination of the calculated transition energies and polarization-dependent oscillator strengths, which agreed well with the XANES spectroscopy measurements. Pre-edge features were assigned to transitions associated with the Al 3p orbitals involved in metal-ligand bonding. Qualitative trends in Al 1s core energy and valence orbital occupation were established through a systematic comparison of excited states derived from Al 3p orbitals with similar symmetries in a molecular orbital framework. These trends suggested that the higher transition energies observed for (BDI)AlX2 systems with more electronegative X(1-) ligands could be ascribed to a decrease in electron density around the aluminum atom, which causes an increase in the attractive potential of the Al nucleus and concomitant increase in the binding energy of the Al 1s core orbitals. For (BDI)Al and (BDI)AlH2 the experimental Al K-edge XANES spectra and spectra calculated using the eXcited electron and Core-Hole (XCH) approach had nearly identical energies for transitions to final state orbitals of similar composition and symmetry. These results implied that the charge distributions about the aluminum atoms in (BDI)Al and (BDI)AlH2 are similar relative to the (BDI)AlX2 and (BDI)AlMe2 compounds, despite having different formal oxidation states of +1 and +3, respectively. However, (BDI)Al was unique in that it exhibited a low-energy feature that was attributed to transitions into a low-lying p-orbital of b1 symmetry that is localized on Al and orthogonal to the (BDI)Al plane. The presence of this low-energy unoccupied molecular orbital on electron-rich (BDI)Al distinguishes

DNA tetrahedral scaffolds-based platform for the construction of electrochemiluminescence biosensor.

Science.gov (United States)

Feng, Qiu-Mei; Zhou, Zhen; Li, Mei-Xing; Zhao, Wei; Xu, Jing-Juan; Chen, Hong-Yuan

2017-04-15

Proximal metallic nanoparticles (NPs) could quench the electrochemiluminescence (ECL) emission of semiconductor quantum dots (QDs) due to Förster energy transfer (FRET), but at a certain distance, the coupling of light-emission with surface plasmon resonance (SPR) result in enhanced ECL. Thus, the modification strategies and distances control between QDs and metallic NPs are critical for the ECL intensity of QDs. In this strategy, a SPR enhanced ECL sensor based on DNA tetrahedral scaffolds modified platform was reported for the detection of telomerase activity. Due to the rigid three-dimensional structure, DNA tetrahedral scaffolds grafting on the electrode surface could accurately modulate the distance between CdS QDs and luminol labelled gold nanoparticles (L-Au NPs), meanwhile provide an enhanced spatial dimension and accessibility for the assembly of multiple L-Au NPs. The ECL intensities of both CdS QDs (-1.25V vs. SCE) and luminol (+0.33V vs. SCE) gradually increased along with the formation of multiple L-Au NPs at the vertex of DNA tetrahedral scaffolds induced by telomerase, bringing in a dual-potential ECL analysis. The proposed method showed high sensitivity for the identification of telomerase and was successfully applied for the differentiation of cancer cells from normal cells. This work suggests that DNA tetrahedral scaffolds could serve as an excellent choice for the construction of SPR-ECL system. Copyright © 2016 Elsevier B.V. All rights reserved.

The effect of synthetic method and annealing temperature on metal site preference in Al(1-x)Ga(x)FeO3.

Science.gov (United States)

Walker, James D S; Grosvenor, Andrew P

2013-08-05

Magnetoelectric materials couple both magnetic and electronic properties, making them attractive for use in multifunctional devices. The magnetoelectric AFeO3 compounds (Pna2(1); A = Al, Ga) have received attention as the properties of the system depend on composition as well as the synthetic method used. Al(1-x)Ga(x)FeO3. (0 ≤ x ≤ 1) was synthesized by the sol-gel and coprecipitation methods and studied by X-ray absorption near-edge spectroscopy (XANES). Al L(2,3-), Ga K-, and Fe K-edge XANES spectra were collected to examine how the average metal coordination number (CN) changes with the synthetic method. Al and Fe were found to prefer octahedral sites, while Ga prefers the tetrahedral site. It was found that composition played a larger role in determining site occupancies than synthetic method. Samples made by the sol-gel or ceramic methods (reported previously; Walker, J. D. S.; Grosvenor, A. P. J. Solid State Chem. 2013, 197, 147-153) showed smaller spectral changes than samples made via the coprecipitation method. This is attributed to greater ion mobility in samples synthesized via coprecipitation as the reactants do not have a long-range polymeric or oxide network during synthesis like samples synthesized via the sol-gel or ceramic method. Increasing annealing temperature increases the average coordination number of Al, and to a lesser extent Ga, while the average coordination number of Fe decreases. This study indicates that greater disorder is observed when the Al(1-x)Ga(x)FeO3. compounds have high Al content, and when annealed at higher temperatures.

Chemical bonding modifications of tetrahedral amorphous carbon and nitrogenated tetrahedral amorphous carbon films induced by rapid thermal annealing

International Nuclear Information System (INIS)

McCann, R.; Roy, S.S.; Papakonstantinou, P.; Bain, M.F.; Gamble, H.S.; McLaughlin, J.A.

2005-01-01

Tetrahedral amorphous carbon (ta-C) and nitrogenated tetrahedral amorphous carbon films (ta-CN x ), deposited by double bend off plane Filtered Vacuum Cathodic Arc were annealed up to 1000 deg. C in flowing argon for 2 min. Modifications on the chemical bonding structure of the rapidly annealed films, as a function of temperature, were investigated by NEXAFS, X-ray photoelectron and Raman spectroscopies. The interpretation of these spectra is discussed. The results demonstrate that the structure of undoped ta-C films prepared at floating potential with an arc current of 80 A remains stable up to 900 deg. C, whereas that of ta-CN x containing 12 at.% nitrogen is stable up to 700 deg. C. At higher temperatures, all the spectra indicated the predominant formation of graphitic carbon. Through NEXAFS studies, we clearly observed three π* resonance peaks at the ' N K edge structure. The origin of these three peaks is not well established in the literature. However our temperature-dependant study ascertained that the first peak originates from C=N bonds and the third peak originates from the incorporation of nitrogen into the graphite like domains

A computational study of nodal-based tetrahedral element behavior.

Energy Technology Data Exchange (ETDEWEB)

Gullerud, Arne S.

2010-09-01

This report explores the behavior of nodal-based tetrahedral elements on six sample problems, and compares their solution to that of a corresponding hexahedral mesh. The problems demonstrate that while certain aspects of the solution field for the nodal-based tetrahedrons provide good quality results, the pressure field tends to be of poor quality. Results appear to be strongly affected by the connectivity of the tetrahedral elements. Simulations that rely on the pressure field, such as those which use material models that are dependent on the pressure (e.g. equation-of-state models), can generate erroneous results. Remeshing can also be strongly affected by these issues. The nodal-based test elements as they currently stand need to be used with caution to ensure that their numerical deficiencies do not adversely affect critical values of interest.

A geometric toolbox for tetrahedral finite element partitions

NARCIS (Netherlands)

Brandts, J.; Korotov, S.; Křížek, M.; Axelsson, O.; Karátson, J.

2011-01-01

In this work we present a survey of some geometric results on tetrahedral partitions and their refinements in a unified manner. They can be used for mesh generation and adaptivity in practical calculations by the finite element method (FEM), and also in theoretical finite element (FE) analysis.

Disordered crystal structure of 20H-AlON, Al10O3N8

International Nuclear Information System (INIS)

Banno, Hiroki; Funahashi, Shiro; Asaka, Toru; Hirosaki, Naoto; Fukuda, Koichiro

2015-01-01

The disordered crystal structure of 20H-AlON (Al 10 O 3 N 8 ) was determined by combined use of X-ray powder diffraction and transmission electron microscopy. The title compound is hexagonal with space group P6 3 /mmc (Z=2) and the unit-cell dimensions are a=0.307082(5) nm, c=5.29447(8) nm and V=0.432376(12) nm 3 . The structural model showed the positional disordering of three of the six Al sites in the unit cell. The reliability indices calculated from the Rietveld method were R wp =6.97%, S (=R wp /R e )=1.68, R p =5.45%, R B =5.13% and R F =4.56%. We interpreted the disordered structure of 20H-AlON as a statistical average of six different types of ordered structural configurations, which are composed of an octahedral [Al(O, N) 6 ] layer and tetrahedral [Al(O, N) 4 ] layers. We demonstrated the high correlations between the hexagonal unit-cell dimensions and the octahedral layer concentrations for AlON and SiAlON polytypoids. - Graphical abstract: Variations of a and c/(n O +n T ) with n O /(n O +n T ). The a and c are the hexagonal unit-cell dimensions of AlON, SiAlON and AlN. The n O and n T are, respectively, the numbers of octahedral and tetrahedral layers in the unit cells. The unit-cell dimensions in literature are plotted in black plus for AlON and black cross for SiAlON. The unit-cell dimensions of AlN are a=0.3110 nm and c=0.4980 nm. - Highlights: • Crystal structure of Al10O3N8 is determined by laboratory X-ray powder diffraction. • The atom arrangements are represented by the split-atom model. • Six types of ordered atom arrangements are derived from the disordered structure. • Hexagonal unit-cell dimensions changed systematically for AlON and SiAlON compounds

Vibrational spectra of four-coordinated random networks with periodic boundary conditions

International Nuclear Information System (INIS)

Guttman, L.

1976-01-01

Examples of perfectly four-coordinated networks satisfying periodic boundary conditions are constructed by a pseudo-random process, starting from a crystalline region. The unphysical features (high density, large deviations from the tetrahedral bond-angle) are removed by systematic modification of the bonding scheme. The vibrational spectra are calculated, using a valence-force potential, and the neutron scattering is computed by a phonon-expansion approximation

Determination of the population of octahedral and tetrahedral interstitials in zirconium hydrides

International Nuclear Information System (INIS)

Fedorov, V.M.; Gogava, V.V.; Shilo, S.I.; Biryukova, E.A.

1983-01-01

Results of neutron investigations of ZrHsub(1.66), ZrHsub(1.75) and ZrHsub(1.98) zirconium hydrides are presented. Investigations were conducted using plane polycrystal samples by multidetector system of scattered neutron detection. Neutron diffraction method was used to determine the number of interstitial hydrogen atoms in interstitials of the lattice cell in the case of statistic atom distribution. The numbers of interstitial atoms in octahedral interstitials for zirconium hydrides were determined experimentally; the difference of potential energies of hydrogen atoms in octa- and tetrahedral interstitials was determined as well. It is shown that experimentally determined difference of potential energies of hydrogen atoms, occupying octa- and tetrahedral positions in investigated zirconium hydrides results at room temperature in the pretailing occupation of tetrahedral interstitials by hydrogen atoms (85-90%); the occupation number grows with temperature decrease and the ordering of interstitial vacancies with formation of hydrogen superstructure takes place at low temperatures

Environmentally stable adsorbent of tetrahedral silica and non-tetrahedral alumina for removal and recovery of malachite green dye from aqueous solution

International Nuclear Information System (INIS)

Kannan, Chellapandian; Sundaram, Thiravium; Palvannan, Thayumanavan

2008-01-01

The conventional adsorbents like activated carbon, agricultural wastes, molecular sieves, etc., used for dye adsorption are unstable in the environment for long time, and hence the adsorbed dyes again gets liberated and pollute the environment. To avoid this problem, environmentally stable adsorbent of silica and alumina should be employed for malachite green adsorption. The adsorbents were characterized by Fourier transformed infrared spectroscopy (FT-IR) to confirm the tetrahedral framework of silica and non-tetrahedral framework of alumina. The adsorption equilibrium of dye on alumina and silica were 4 and 5 h, respectively, this less adsorption time on alumina might be due to the less activation energy on alumina (63.46 kJ mol -1 ) than silica (69.93 kJ mol -1 ). Adsorption increased with increase of temperature on silica, in alumina, adsorption increased up to 60 deg. C, and further increase of temperature decreased the adsorption due to the structural change of non-tetrahedral alumina in water. The optimum pH for dye adsorption on alumina was 5 and silica was 6. The dye adsorptions on both adsorbents followed pseudo-second-order kinetics. The adsorption well matched with Langmuir and Freundlich adsorption isotherms and found that adsorption capacity on alumina was more than silica. The thermodynamic studies proved that the adsorption was endothermic and chemisorptions (ΔH o > 40 kJ mol -1 ) on alumina and silica. Recovery of dye on alumina and silica were studied from 30 to 90 deg. C and observed that 52% of dye was recovered from alumina and only 3.5% from silica. The less recovery on silica proved the strong adsorption of dye on silica than alumina

Environmentally stable adsorbent of tetrahedral silica and non-tetrahedral alumina for removal and recovery of malachite green dye from aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Kannan, Chellapandian [Department of Chemistry, Periyar University, Salem 636011, Tamilnadu (India)], E-mail: chellapandiankannan@gmail.com; Sundaram, Thiravium [Department of Chemistry, Periyar University, Salem 636011, Tamilnadu (India); Palvannan, Thayumanavan [Department of Biochemistry, Periyar University, Salem 636011, Tamilnadu (India)

2008-08-30

The conventional adsorbents like activated carbon, agricultural wastes, molecular sieves, etc., used for dye adsorption are unstable in the environment for long time, and hence the adsorbed dyes again gets liberated and pollute the environment. To avoid this problem, environmentally stable adsorbent of silica and alumina should be employed for malachite green adsorption. The adsorbents were characterized by Fourier transformed infrared spectroscopy (FT-IR) to confirm the tetrahedral framework of silica and non-tetrahedral framework of alumina. The adsorption equilibrium of dye on alumina and silica were 4 and 5 h, respectively, this less adsorption time on alumina might be due to the less activation energy on alumina (63.46 kJ mol{sup -1}) than silica (69.93 kJ mol{sup -1}). Adsorption increased with increase of temperature on silica, in alumina, adsorption increased up to 60 deg. C, and further increase of temperature decreased the adsorption due to the structural change of non-tetrahedral alumina in water. The optimum pH for dye adsorption on alumina was 5 and silica was 6. The dye adsorptions on both adsorbents followed pseudo-second-order kinetics. The adsorption well matched with Langmuir and Freundlich adsorption isotherms and found that adsorption capacity on alumina was more than silica. The thermodynamic studies proved that the adsorption was endothermic and chemisorptions ({delta}H{sup o} > 40 kJ mol{sup -1}) on alumina and silica. Recovery of dye on alumina and silica were studied from 30 to 90 deg. C and observed that 52% of dye was recovered from alumina and only 3.5% from silica. The less recovery on silica proved the strong adsorption of dye on silica than alumina.

Practical implementation of tetrahedral mesh reconstruction in emission tomography

Science.gov (United States)

Boutchko, R.; Sitek, A.; Gullberg, G. T.

2013-05-01

This paper presents a practical implementation of image reconstruction on tetrahedral meshes optimized for emission computed tomography with parallel beam geometry. Tetrahedral mesh built on a point cloud is a convenient image representation method, intrinsically three-dimensional and with a multi-level resolution property. Image intensities are defined at the mesh nodes and linearly interpolated inside each tetrahedron. For the given mesh geometry, the intensities can be computed directly from tomographic projections using iterative reconstruction algorithms with a system matrix calculated using an exact analytical formula. The mesh geometry is optimized for a specific patient using a two stage process. First, a noisy image is reconstructed on a finely-spaced uniform cloud. Then, the geometry of the representation is adaptively transformed through boundary-preserving node motion and elimination. Nodes are removed in constant intensity regions, merged along the boundaries, and moved in the direction of the mean local intensity gradient in order to provide higher node density in the boundary regions. Attenuation correction and detector geometric response are included in the system matrix. Once the mesh geometry is optimized, it is used to generate the final system matrix for ML-EM reconstruction of node intensities and for visualization of the reconstructed images. In dynamic PET or SPECT imaging, the system matrix generation procedure is performed using a quasi-static sinogram, generated by summing projection data from multiple time frames. This system matrix is then used to reconstruct the individual time frame projections. Performance of the new method is evaluated by reconstructing simulated projections of the NCAT phantom and the method is then applied to dynamic SPECT phantom and patient studies and to a dynamic microPET rat study. Tetrahedral mesh-based images are compared to the standard voxel-based reconstruction for both high and low signal-to-noise ratio

Practical implementation of tetrahedral mesh reconstruction in emission tomography

International Nuclear Information System (INIS)

Boutchko, R; Gullberg, G T; Sitek, A

2013-01-01

This paper presents a practical implementation of image reconstruction on tetrahedral meshes optimized for emission computed tomography with parallel beam geometry. Tetrahedral mesh built on a point cloud is a convenient image representation method, intrinsically three-dimensional and with a multi-level resolution property. Image intensities are defined at the mesh nodes and linearly interpolated inside each tetrahedron. For the given mesh geometry, the intensities can be computed directly from tomographic projections using iterative reconstruction algorithms with a system matrix calculated using an exact analytical formula. The mesh geometry is optimized for a specific patient using a two stage process. First, a noisy image is reconstructed on a finely-spaced uniform cloud. Then, the geometry of the representation is adaptively transformed through boundary-preserving node motion and elimination. Nodes are removed in constant intensity regions, merged along the boundaries, and moved in the direction of the mean local intensity gradient in order to provide higher node density in the boundary regions. Attenuation correction and detector geometric response are included in the system matrix. Once the mesh geometry is optimized, it is used to generate the final system matrix for ML-EM reconstruction of node intensities and for visualization of the reconstructed images. In dynamic PET or SPECT imaging, the system matrix generation procedure is performed using a quasi-static sinogram, generated by summing projection data from multiple time frames. This system matrix is then used to reconstruct the individual time frame projections. Performance of the new method is evaluated by reconstructing simulated projections of the NCAT phantom and the method is then applied to dynamic SPECT phantom and patient studies and to a dynamic microPET rat study. Tetrahedral mesh-based images are compared to the standard voxel-based reconstruction for both high and low signal-to-noise ratio

Revisiting the polytopal rearrangements in penta-coordinate d7-metallocomplexes: modified Berry pseudorotation, octahedral switch, and butterfly isomerization.

Science.gov (United States)

Asatryan, Rubik; Ruckenstein, Eli; Hachmann, Johannes

2017-08-01

This paper provides a first-principles theoretical investigation of the polytopal rearrangements and fluxional behavior of five-coordinate d 7 -transition metal complexes. Our work is primarily based on a potential energy surface analysis of the iron tetracarbonyl hydride radical HFe˙(CO) 4 . We demonstrate the existence of distorted coordination geometries in this prototypical system and, for the first time, introduce three general rearrangement mechanisms, which account for the non-ideal coordination. The first of these mechanisms constitutes a modified version of the Berry pseudorotation via a square-based pyramidal C 4v transition state that connects two chemically identical edge-bridged tetrahedral stereoisomers of C 2v symmetry. It differs from the classical Berry mechanism, which involves two regular D 3h equilibrium structures and a C 4v transition state. The second mechanism is related to the famous "tetrahedral jump" hypothesis, postulated by Muetterties for a number of d 6 HML 4 and H 2 ML 4 complexes. Here, our study suggests two fluxional rearrangement pathways via distinct types of C 2v transition states. Both pathways of this mechanism can be described as a single-ligand migration to a vacant position of an "octahedron", thus interchanging (switching) the apical and basal ligands of the initial quasi-square pyramidal isomer, which is considered as an idealized octahedron with a vacancy. Accordingly, we call this mechanism "octahedral switch". The third mechanism follows a butterfly-type isomerization featuring a key-angle deformation, and we thus call it "butterfly isomerization". It connects the quasi-square pyramidal and edge-bridged tetrahedral isomers of HFe˙(CO) 4 through a distorted edge-bridged tetrahedral transition state of C s symmetry. Our paper discusses the overall features of the isomers and rearrangement mechanisms as well as their implications. We rationalize the existence of each stationary point through an electronic structure

Quantifying linguistic coordination

DEFF Research Database (Denmark)

Fusaroli, Riccardo; Tylén, Kristian

task (Bahrami et al 2010, Fusaroli et al. 2012) we extend to linguistic coordination dynamical measures of recurrence employed in the analysis of sensorimotor coordination (such as heart-rate (Konvalinka et al 2011), postural sway (Shockley 2005) and eye-movements (Dale, Richardson and Kirkham 2012......). We employ nominal recurrence analysis (Orsucci et al 2005, Dale et al 2011) on the decision-making conversations between the participants. We report strong correlations between various indexes of recurrence and collective performance. We argue this method allows us to quantify the qualities...

Tetrahedral hydrocarbon nanoparticles in space: X-ray spectra

Science.gov (United States)

Bilalbegović, G.; Maksimović, A.; Valencic, L. A.

2018-06-01

It has been proposed, or confirmed, that diamond nanoparticles exist in various environments in space: close to active galactic nuclei, in the vicinity of supernovae and pulsars, in the interior of several planets in the Solar system, in carbon planets, and other exoplanets, carbon-rich stars, meteorites, in X-ray active Herbig Ae/Be stars, and in the interstellar medium. Using density functional theory methods, we calculate the carbon K-edge X-ray absorption spectrum of two large tetrahedral nanodiamonds: C26H32 and C51H52. We also study and test our methods on the astrophysical molecule CH4, the smallest C-H tetrahedral structure. A possible detection of nanodiamonds from X-ray spectra by future telescopes, such as the project Arcus, is proposed. Simulated spectra of the diffuse interstellar medium using Cyg X-2 as a source show that nanodiamonds studied in this work can be detected by Arcus, a high-resolution X-ray spectrometer mission selected by NASA for a Phase A concept study.

Multinuclear (27Al, 29Si, 47,49Ti) solid-state NMR of titanium substituted zeolite USY.

Science.gov (United States)

Ganapathy, S; Gore, K U; Kumar, Rajiv; Amoureux, Jean-Paul

2003-01-01

Multinuclear solid-state NMR spectroscopy, employing 29Si MAS,27Al MAS/3Q-MAS and (47,49)Ti wide-line experiments, has been used for the structural characterization of titanium substituted ultra-stable zeolite Y (Ti-USY). 27Al MAS experiments show the presence of aluminum in four (Al(IV)), five (Al(V)), and six (Al(VI)) coordination, whereas the multiplicity within Al(IV) and Al(VI) is revealed by 27Al 3Q-MAS experiments. Two different tetrahedral and octahedral Al environments are resolved and their isotropic chemical shifts (delta(CS)) and second-order quadrupole interaction parameters (P(Q)) have been determined by a graphical analysis of the 3Q-MAS spectra. The emergence of signal with higher intensity at -101 ppm in the 29Si MAS spectrum of Ti-USY samples indicates the possible occurrence of Q4(3Si,1Ti) type silicon environments due to titanium substitution in the faujasite framework. High-field (11.74T) operation, using a probehead specially designed to handle a large sample volume, has enabled the acquisition of 47,49Ti static spectra and identification of the titanium environment in the zeolite. The chemical shielding and electric field gradient tensors for the titanium environment in the zeolite have been determined by a computer simulation of the quadrupolar broadened static 47,49Ti NMR spectra.

Kinetic Control of Intralayer Cobalt Coordination in Layered Hydroxides: CoxoctCoxtet(OH)2(Cl)x(H2O)n

International Nuclear Information System (INIS)

Neilson, James R.; Schwenzer, Birgit; Seshadri, Ram; Morse, Daniel E.

2009-01-01

We report the synthesis and characterization of new structural variants of the isotypic compound with the generic chemical formula, Co 1-0.5x oct Co x tet (OH) 2 (Cl) x (H 2 O) n , all modifications of an α-Co(OH) 2 lattice. We show that the occupancy of tetrahedrally coordinated cobalt sites and associated chloride ligands, x, is modulated by the rate of formation of the respective layered hydroxide salts from kinetically controlled aqueous hydrolysis at an air-water interface. This new level of structural control is uniquely enabled by the slow diffusion of a hydrolytic catalyst, a simple technique. Independent structural characterizations of the compounds separately describe various attributes of the materials on different length scales, revealing details hidden by the disordered average structures. The precise control over the population of distinct octahedrally and tetrahedrally coordinated cobalt ions in the lattice provides a gentle, generic method for modulating the coordination geometry of cobalt in the material without disturbing the lattice or using additional reagents. A mechanism is proposed to reconcile the observation of the kinetic control of the structure with competing interactions during the initial stages of hydrolysis and condensation.

Tetrahedral hohlraums at omega

International Nuclear Information System (INIS)

Kyrala, G.A.; Goldman, S.R.; Batha, S.H.; Wallace, J.M.; Klare, K.A.; Schappert, G.T.; Oertel, J.; Turner, R.E.

2000-01-01

We have initiated a study of the usefulness of tetrahedrally illuminated spherical hohlraums, using the Omega laser beams, to drive planar shocks in packages that require indirect drive. A first suite of experiments used spherical hohlraums with a 2-μm thick gold wall surrounded by a 100-μm thick epoxy layer and had an internal diameter of 2.8 mm. Four laser entrance holes each of diameter 700 μm, located on the tips of a regular tetrahedron were used. The shock velocities and the shock uniformities were measured using optical shock break out techniques. The hohlraum x-ray radiation spectrum was also measured using a 10-channel x-ray detector. Tentatively, peak temperatures approaching 195 eV were achieved and shock speeds of 60 μm/ns were measured, when the hohlraum was driven by 22 kJ of 3 ω radiation. (authors)

First-principles study of anharmonic phonon effects in tetrahedral semiconductors via an external electric field

Energy Technology Data Exchange (ETDEWEB)

Dabiri, Zohreh, E-mail: z.dabiri@stu.yazd.ac.ir [Physics Department, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Kazempour, Ali [Department of Physics, Payame Noor University, P.O. BOX 119395-3697, Tehran (Iran, Islamic Republic of); Nano Structured Coatings Institute of Yazd Payame Noor University, P.O. Code 89431-74559, Yazd (Iran, Islamic Republic of); Sadeghzadeh, Mohammad Ali [Physics Department, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)

2016-11-15

The strength of phonon anharmonicity is investigated in the framework of the Density Functional Perturbation Theory via an applied constant electric field. In contrast to routine approaches, we have employed the electric field as an effective probe to quest after the quasi-harmonic and anharmonic effects. Two typical tetrahedral semiconductors (diamond and silicon) have been selected to test the efficiency of this approach. In this scheme the applied field is responsible for establishing the perturbation and also inducing the anharmonicity in systems. The induced polarization is a result of changing the electronic density while ions are located at their ground state coordinates or at a specified strain. Employing this method, physical quantities of the semiconductors are calculated in presence of the electron–phonon interaction directly and, phonon–phonon interaction, indirectly. The present approach, which is in good agreement with previous theoretical and experimental studies, can be introduced as a benchmark to simply investigate the anharmonicity and pertinent consequences in materials.

SUMMARY OF 2010 DOE EM INTERNATIONAL PROGRAM STUDIES OF WASTE GLASS STRUCTURE AND PROPERTIES

Energy Technology Data Exchange (ETDEWEB)

Fox, K.; Choi, A.; Marra, J.; Billings, A.

2011-02-07

Collaborative work between the Savannah River National Laboratory (SRNL) and SIA Radon in Russia was divided among three tasks for calendar year 2010. The first task focused on the study of simplified high level waste glass compositions with the objective of identifying the compositional drivers that lead to crystallization and poor chemical durability. The second task focused on detailed characterization of more complex waste glass compositions with unexpectedly poor chemical durabilities. The third task focused on determining the structure of select high level waste glasses made with varying frit compositions in order to improve models under development for predicting the melt rate of the Defense Waste Processing Facility (DWPF) glasses. The majority of these tasks were carried out at SIA Radon. Selection and fabrication of the glass compositions, along with chemical composition measurements and evaluations of durability were carried out at SRNL and are described in this report. SIA Radon provided three summary reports based on the outcome of the three tasks. These reports are included as appendices to this document. Briefly, the result of characterization of the Task 1 glasses may indicate that glass compositions where iron is predominantly tetrahedrally coordinated have more of a tendency to crystallize nepheline or nepheline-like phases. For the Task 2 glasses, the results suggested that the relatively low fraction of tetrahedrally coordinated boron and the relatively low concentrations of Al{sub 2}O{sub 3} available to form [BO{sub 4/2}]{sup -}Me{sup +} and [AlO{sub 4/2}]{sup -}Me{sup +} tetrahedral units are not sufficient to consume all of the alkali ions, and thus these alkali ions are easily leached from the glasses. All of the twelve Task 3 glass compositions were determined to be mainly amorphous, with some minor spinel phases. Several key structural units such as metasilicate chains and rings were identified, which confirms the current modeling

Physics at low spin in the mass 160 region: the search for tetrahedral shapes

International Nuclear Information System (INIS)

Bark, R.A.; Sharpey-Schafer, J.F.; Maliage, S.M.; Madiba, T.E.; Komati, F.S.; Lawrie, E.A.; Lawrie, J.J.; Lindasy, R.; Maine, P.; Mullins, S.M.; Murray, S.H.T.; Ncapayi, N.J.; Ramashidza, T.M.; Smit, F.D.; Vymers, P.

2010-01-01

The low-lying, odd-spin negative parity bands in the mass 160 region have been identified as candidates for the rotation of a tetrahedral shape, as they have very weak in-band E2 transitions. We report the observation of such bands in 160 Yb and 154 Gd. They are crossed by 2 quasiparticle bands which allow band mixing calculations to be carried out to derive relative quadrupole moments. However, those studied are not consistent with zero, as required for tetrahedral shape. The aligned angular momenta of the bands suggest an octupole vibrational assignment.

Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

International Nuclear Information System (INIS)

Sadikin, Yolanda; Stare, Katarina; Schouwink, Pascal; Brix Ley, Morten; Jensen, Torben R.; Meden, Anton; Černý, Radovan

2015-01-01

The system Li–A–Y–BH 4 (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y 3+ is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH 4 both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A 3 Y(BH 4 ) 6 or c-A 2 LiY(BH 4 ) 6 (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH 4 ) 4 crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH 4 (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y 3+ is revealed, which can be employed to form both octahedral frameworks and tetrahedral complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH 4 ) 4 structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH 4 (A=K, Rb, Cs) contains nine compounds in total. • Y 3+ forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH 4 ) 4 crystallize with structure types analogous to metal oxides. • Double-perovskites decompose and form a novel

A tetrapyridine ligand with a rigid tetrahedral core forms metal-organic frameworks with PtS type architecture.

Science.gov (United States)

Caputo, Christopher B; Vukotic, V Nicholas; Sirizzotti, Natalie M; Loeb, Stephen J

2011-08-14

A new tetradentate, pyridine ligand with a rigid tetrahedral core can be prepared in good yield by a cross-coupling methodology. Two metal organic framework structures of Cu(II) with PtS-type topology having a carbon atom as the tetrahedral node have been characterized utilising this ligand. This journal is © The Royal Society of Chemistry 2011

Growth Mechanism and Origin of High s p3 Content in Tetrahedral Amorphous Carbon

Science.gov (United States)

Caro, Miguel A.; Deringer, Volker L.; Koskinen, Jari; Laurila, Tomi; Csányi, Gábor

2018-04-01

We study the deposition of tetrahedral amorphous carbon (ta-C) films from molecular dynamics simulations based on a machine-learned interatomic potential trained from density-functional theory data. For the first time, the high s p3 fractions in excess of 85% observed experimentally are reproduced by means of computational simulation, and the deposition energy dependence of the film's characteristics is also accurately described. High confidence in the potential and direct access to the atomic interactions allow us to infer the microscopic growth mechanism in this material. While the widespread view is that ta-C grows by "subplantation," we show that the so-called "peening" model is actually the dominant mechanism responsible for the high s p3 content. We show that pressure waves lead to bond rearrangement away from the impact site of the incident ion, and high s p3 fractions arise from a delicate balance of transitions between three- and fourfold coordinated carbon atoms. These results open the door for a microscopic understanding of carbon nanostructure formation with an unprecedented level of predictive power.

Natural gels: crystal-chemistry of short range ordered components in Al, Fe, and Si systems

International Nuclear Information System (INIS)

Ildefonse, Ph.; Calas, G.

1997-01-01

In this review, the most important inorganic natural gels are presented: opal, aluminosilicate (allophanes) and hydrous iron oxides and silicates. It is demonstrated that natural gels are ordered at the atomic scale. In allophanes, Al is distributed between octahedral and tetrahedral sites. The amount of Al increases as Al/Si ratio decreases. Si-rich allophane have a local structure around Al and Si very different of that is known in kaolinite or halloysite. Transformation of Si-rich allophanes to crystallized minerals implies dissolution-recrystallization processes. On the contrary, in iron silicate with Fe/Si = 0.72, Si and Fe environments are close to those found in nontronite. The gel transformation to Fe-smectite may occur by long range ordering during ageing. In ferric silicate gels, the similarity of local structure around Fe in poorly ordered precursors and what is known in crystallized minerals suggests a solid transformation during ageing. This difference between iron and aluminium is mainly due to the ability of Al to enter both tetrahedral and octahedral sites, while the affinity of iron for octahedral sites is higher at low temperature

Anion-Dependent Exocyclic Mercury(II) Coordination Polymers of Bis-dithiamacrocycle

Energy Technology Data Exchange (ETDEWEB)

Siewe, Arlette Deukam; Kim, Seul Gi; Choi, Kyu Seong [Kyungnam University, Changwon (Korea, Republic of); Lee, Shim Sung [Gyeongsang National University, Jinju (Korea, Republic of)

2014-09-15

Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}-Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}- macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies outside the cavity is six-coordinate with a distorted octahedral geometry, being bound to four adjacent ligands via monodentate Hg-S bonds and two remaining sites are occupied by two terminal chlorido ligands to form a fishnet-like 2D structure. When reacting with mercury(II) iodide, L afforded a 1D coordination polymer [Hg{sub 2}(L)I{sub 4}]·CHCl{sub 3}n in which each exocyclic Hg atom is four-coordinate, being bound to two sulfur donors from different ligands doubly bridging the ligand molecules in a head-to-tail mode. The coordination sphere in 3 is completed by two iodo terminal ligands, adopting a distorted tetrahedral geometry. On reacting with mercury(II) perchlorate, L forms solvent-coordinated 1D coordination polymer ([Hg{sub 2}(L)(DMF){sub 6}](ClO{sub 4}){sub 4}·2DMF)n instead of the anion-coordination. In 4, the Hg atom is five-coordinate, being bound to two sulfur donors from two different ligands doubly bridging the ligand molecules in a side-by-side mode to form a ribbon-like 1D structure.. The three remaining coordination sites in 4 are completed by three DMF molecules in a monodentate manner. Consequently, the different structures and connectivity patterns for the observed exocyclic coordination polymers depending on the anions used are influenced not only by the coordination ability of the anions but also by anion sizes macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies

Co(II) Coordination in Prokaryotic Zinc Finger Domains as Revealed by UV-Vis Spectroscopy

Science.gov (United States)

Sivo, Valeria; D'Abrosca, Gianluca; Russo, Luigi; Iacovino, Rosa; Pedone, Paolo Vincenzo; Fattorusso, Roberto

2017-01-01

Co(II) electronic configuration allows its use as a spectroscopic probe in UV-Vis experiments to characterize the metal coordination sphere that is an essential component of the functional structure of zinc-binding proteins and to evaluate the metal ion affinities of these proteins. Here, exploiting the capability of the prokaryotic zinc finger to use different combinations of residues to properly coordinate the structural metal ion, we provide the UV-Vis characterization of Co(II) addition to Ros87 and its mutant Ros87_C27D which bears an unusual CysAspHis2 coordination sphere. Zinc finger sites containing only one cysteine have been infrequently characterized. We show for the CysAspHis2 coordination an intense d-d transition band, blue-shifted with respect to the Cys2His2 sphere. These data complemented by NMR and CD data demonstrate that the tetrahedral geometry of the metal site is retained also in the case of a single-cysteine coordination sphere. PMID:29386985

Coordination Environments of Highly Charged Cations (Ti, Cr, and Light REE's) in Borosilicate Glass/Melts to 1120C

Energy Technology Data Exchange (ETDEWEB)

Farges, Francois; /Museum Natl. Hist. Natur. /Stanford U., Geo. Environ. Sci.; Brown, Gordon E., Jr.; /Stanford U., Geo. Environ Sci. /SLAC, SSRL

2007-01-02

The local environments around Ti, Cr, and several light rare-earth elements (La, Ce, and Nd) were investigated by in-situ XANES spectroscopy in a number of complex borosilicate glasses and melts (to 1120 C) that are used for nuclear waste storage. Examination of the high-resolution XANES spectra at the Ti K-edge shows that the average coordination of Ti changes from {approx}5 to {approx}4.5. Cr is dominantly trivalent in the melts studied. However, its average coordination is probably lower in the melt (tetrahedral ?) as revealed by the more intense Cr-K pre-edge feature. Ce also changes its average valence from dominantly +4 to +3.5 upon glass melting. These changes are reversible at T{sub g}, the glass transition temperature ({approx}500-550 C for these glasses). In contrast, the local environments of Nd, Pr, and La are unaffected by melting. Therefore, structural reorganization of these borosilicate glass/melts above T{sub g} is variable, not only in terms of valence (as for Ce) but also speciation (Ti and Cr). Both the ability of B to adopt various coordination geometries (triangular and tetrahedral) and the chemical complexity of the glass/melts explain these changes.

Split-Cell Exponential Characteristic Transport Method for Unstructured Tetrahedral Meshes

International Nuclear Information System (INIS)

Brennan, Charles R.; Miller, Rodney L.; Mathews, Kirk A.

2001-01-01

The nonlinear, exponential characteristic (EC) method is extended to unstructured meshes of tetrahedral cells in three-dimensional Cartesian coordinates. The split-cell approach developed for the linear characteristic (LC) method on such meshes is used. Exponential distributions of the source within a cell and of the inflow flux on upstream faces of the cell are assumed. The coefficients of these distributions are determined by nonlinear root solving so as to match the zeroth and first moments of the source or entering flux. Good conditioning is achieved by casting the formulas for the moments of the source, inflow flux, and solution flux as sums of positive functions and by using accurate and robust algorithms for evaluation of those functions. Various test problems are used to compare the performance of the EC and LC methods. The EC method is somewhat less accurate than the LC method in regions of net out leakage but is strictly positive and retains good accuracy with optically thick cells, as in shielding problems, unlike the LC method. The computational cost per cell is greater for the EC method, but the use of substantially coarser meshes can make the EC method less expensive in total cost. The EC method, unlike the LC method, may fail if negative cross sections or angular quadrature weights are used. It is concluded that the EC and LC methods should be practical, reliable, and complimentary schemes for these meshes

Synthesis and Molecular Structures of Two [1,4-bis(3-pyridyl)-2,3-diazo-1,3-butadiene]-dichloro-Zn(II) Coordination Polymers

OpenAIRE

Lee, Gene-Hsiang; Wang, Hsin-Ta

2006-01-01

Two novel coordination polymers with 3D metal-organic frameworks (MOFs) have been synthesized by reacting 1,4-bis(3-pyridyl)-2,3-diazo-1,3-butadiene (L) with zinc dichloride. Both compounds have the same repeating unit consisting of a distorted tetrahedral Zn(II) center coordinated by two chlorides and two pyridyl nitrogen atoms of two bridging bismonodentate L ligands, however, different structural conformations have been found, one forming a helical chain and the other producing a square-wa...

Simultaneous travel time tomography for updating both velocity and reflector geometry in triangular/tetrahedral cell model

Science.gov (United States)

Bai, Chao-ying; He, Lei-yu; Li, Xing-wang; Sun, Jia-yu

2018-05-01

To conduct forward and simultaneous inversion in a complex geological model, including an irregular topography (or irregular reflector or velocity anomaly), we in this paper combined our previous multiphase arrival tracking method (referred as triangular shortest-path method, TSPM) in triangular (2D) or tetrahedral (3D) cell model and a linearized inversion solver (referred to as damped minimum norms and constrained least squares problem solved using the conjugate gradient method, DMNCLS-CG) to formulate a simultaneous travel time inversion method for updating both velocity and reflector geometry by using multiphase arrival times. In the triangular/tetrahedral cells, we deduced the partial derivative of velocity variation with respective to the depth change of reflector. The numerical simulation results show that the computational accuracy can be tuned to a high precision in forward modeling and the irregular velocity anomaly and reflector geometry can be accurately captured in the simultaneous inversion, because the triangular/tetrahedral cell can be easily used to stitch the irregular topography or subsurface interface.

Tetrahedral-Mesh Simulation of Turbulent Flows with the Space-Time Conservative Schemes

Science.gov (United States)

Chang, Chau-Lyan; Venkatachari, Balaji; Cheng, Gary C.

2015-01-01

Direct numerical simulations of turbulent flows are predominantly carried out using structured, hexahedral meshes despite decades of development in unstructured mesh methods. Tetrahedral meshes offer ease of mesh generation around complex geometries and the potential of an orientation free grid that would provide un-biased small-scale dissipation and more accurate intermediate scale solutions. However, due to the lack of consistent multi-dimensional numerical formulations in conventional schemes for triangular and tetrahedral meshes at the cell interfaces, numerical issues exist when flow discontinuities or stagnation regions are present. The space-time conservative conservation element solution element (CESE) method - due to its Riemann-solver-free shock capturing capabilities, non-dissipative baseline schemes, and flux conservation in time as well as space - has the potential to more accurately simulate turbulent flows using unstructured tetrahedral meshes. To pave the way towards accurate simulation of shock/turbulent boundary-layer interaction, a series of wave and shock interaction benchmark problems that increase in complexity, are computed in this paper with triangular/tetrahedral meshes. Preliminary computations for the normal shock/turbulence interactions are carried out with a relatively coarse mesh, by direct numerical simulations standards, in order to assess other effects such as boundary conditions and the necessity of a buffer domain. The results indicate that qualitative agreement with previous studies can be obtained for flows where, strong shocks co-exist along with unsteady waves that display a broad range of scales, with a relatively compact computational domain and less stringent requirements for grid clustering near the shock. With the space-time conservation properties, stable solutions without any spurious wave reflections can be obtained without a need for buffer domains near the outflow/farfield boundaries. Computational results for the

Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

KAUST Repository

Werghi, Baraa; Pump, Eva; Tretiakov, Mykyta; Abou-Hamad, Edy; Gurinov, Andrei; Doggali, Pradeep; Anjum, Dalaver H.; Cavallo, Luigi; Bendjeriou-Sedjerari, Anissa; Basset, Jean-Marie

2018-01-01

Immobilization of the 2 generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, H and C solid state NMR, DNP-SENS, EF-TEM...). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (d = 6 nm) or KCC-1 (d = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

KAUST Repository

Werghi, Baraa

2018-03-05

Immobilization of the 2 generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, H and C solid state NMR, DNP-SENS, EF-TEM...). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (d = 6 nm) or KCC-1 (d = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

Tellurium rings as electron pair donors in cluster compounds and coordination polymers; Tellurringe als Elektronenpaardonoren in Clusterverbindungen und Koordinationspolymeren

Energy Technology Data Exchange (ETDEWEB)

Guenther, Anja

2011-11-08

In this dissertation novel and already known molecular tellurium rings are presented in cluster compounds and quasi-one-dimensional coordination polymers. The cyclic, homonuclear units are always stabilized by coordination to electron-rich transition metal atoms, with the coordinating tellurium atoms acting as two-electron donors. As a synthesis route, the solid-state reaction in quartz glass vials was used uniformly. In addition to structural determination, the focus was on the characterization of the resulting compounds. For this purpose, resistance measurements were carried out on selected compounds, the magnetic behavior and the thermal degradation reactions were investigated and accompanying quantum chemical calculations were carried out. [German] In dieser Dissertation werden neuartige sowie bereits bekannte molekulare Tellurringe in Clusterverbindungen und quasi-eindimensionalen Koordinationspolymeren vorgestellt. Die Stabilisierung der zyklischen, homonuklearen Einheiten erfolgt dabei stets durch die Koordination an elektronenreiche Uebergangsmetallatome, wobei die koordinierenden Telluratome gegenueber diesen als Zwei-Elektronendonoren fungieren. Als Syntheseroute wurde dabei einheitlich auf die Festkoerperreaktion in Quarzglasampullen zurueckgegriffen. Neben der Strukturaufklaerung stand die Charakterisierung der erhaltenden Verbindungen im Fokus der Arbeit. Dazu wurden an ausgewaehlten Verbindungen Widerstandsmessungen durchgefuehrt, das magnetische Verhalten sowie die thermischen Abbaureaktionen untersucht und begleitende quantenchemische Rechnungen durchgefuehrt.

Kinetic control of intralayer cobalt coordination in layered hydroxides: Co(1-0.5x)(oct) Co(x)(tet) (OH)2 (Cl)x (H2O)n.

Science.gov (United States)

Neilson, James R; Schwenzer, Birgit; Seshadri, Ram; Morse, Daniel E

2009-12-07

We report the synthesis and characterization of new structural variants of the isotypic compound with the generic chemical formula, Co(1-0.5x)(oct) Co(x)(tet) (OH)2 (Cl)x (H2O)n, all modifications of an alpha-Co(OH)2 lattice. We show that the occupancy of tetrahedrally coordinated cobalt sites and associated chloride ligands, x, is modulated by the rate of formation of the respective layered hydroxide salts from kinetically controlled aqueous hydrolysis at an air-water interface. This new level of structural control is uniquely enabled by the slow diffusion of a hydrolytic catalyst, a simple technique. Independent structural characterizations of the compounds separately describe various attributes of the materials on different length scales, revealing details hidden by the disordered average structures. The precise control over the population of distinct octahedrally and tetrahedrally coordinated cobalt ions in the lattice provides a gentle, generic method for modulating the coordination geometry of cobalt in the material without disturbing the lattice or using additional reagents. A mechanism is proposed to reconcile the observation of the kinetic control of the structure with competing interactions during the initial stages of hydrolysis and condensation.

Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

Energy Technology Data Exchange (ETDEWEB)

Sadikin, Yolanda [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Stare, Katarina [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana (Slovenia); Schouwink, Pascal [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Brix Ley, Morten; Jensen, Torben R. [Center for Materials Crystallography (CMC), Interdisciplinary Nanoscience Center (iNANO), and Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Århus C (Denmark); Meden, Anton [Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana (Slovenia); Černý, Radovan, E-mail: radovan.cerny@unige.ch [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland)

2015-05-15

The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y{sup 3+} is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH{sub 4} both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A{sub 3}Y(BH{sub 4}){sub 6} or c-A{sub 2}LiY(BH{sub 4}){sub 6} (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH{sub 4}){sub 4} crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y{sup 3+} is revealed, which can be employed to form both octahedral frameworks and tetrahedral complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH{sub 4}){sub 4} structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH{sub 4} (A=K, Rb, Cs) contains nine compounds in total. • Y{sup 3+} forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH{sub 4}){sub 4} crystallize with

A new titanium-bearing calcium aluminosilicate phase. 2: Crystallography and crystal chemistry of grains formed in slowly cooled melts with bulk compositions of calcium-aluminium-rich inclusions

Science.gov (United States)

Barber, David J.; Beckett, John R.; Paque, Julie M.; Stolper, Edward

1994-01-01

The crystallography and crystal chemistry of a new calcium- titanium-aluminosilicate mineral (UNK) observed in synthetic analogs to calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites was studied by electron diffraction techniques. The unit cell is primitive hexagonal or trigonal, with a = 0.790 +/- 0.02 nm and c = 0.492 +/- 0.002 nm, similar to the lattice parameters of melilite and consistent with cell dimensions for crystals in a mixer furnace slag described by Barber and Agrell (1994). The phase frequently displays an epitactic relationship in which melilite acts as the host, with (0001)(sub UNK) parallel (001)(sub mel) and zone axis group 1 0 -1 0(sub UNK) parallel zone axis group 1 0 0(sub mel). If one of the two space groups determined by Barber and Agrell (1994) for their sample of UNK is applicable (P3m1 or P31m), then the structure is probably characterized by puckered sheets of octahedra and tetrahedra perpendicular to the c-axis with successive sheets coordinated by planar arrays of Ca. In this likely structure, each unit cell contains three Ca sites located in mirror planes, one octahedrally coordinated cation located along a three-fold axis and five tetrahedrally coordinated cations, three in mirrors and two along triads. The octahedron contains Ti but, because there are 1.3-1.9 cations of Ti/formula unit, some of the Ti must also be in tetrahedral coordination, an unusual but not unprecedented situation for a silicate. Tetrahedral sites in mirror planes would contain mostly Si, with lesser amounts of Al while those along the triads correspondingly contain mostly Al with subordinate Ti. The structural formula, therefore, can be expressed as Ca(sub 3)(sup VIII)(Ti,Al)(sup VI)(Al,Ti,Si)(sub 2)(sup IV)(Si,Al)(sub 3)(sup IV)O14 with Si + Ti = 4. Compositions of meteoritic and synthetic Ti-bearing samples of the phase can be described in terms of a binary solid solution between the end-members Ca3TiAl2Si3O14 and Ca3Ti(AlTi)(AlSi2)O14. A Ti

Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis.

Science.gov (United States)

Boubnov, Alexey; Lichtenberg, Henning; Mangold, Stefan; Grunwaldt, Jan Dierk

2015-03-01

Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is

In situ structural analysis of calcium aluminosilicate glasses under high pressure.

Science.gov (United States)

Muniz, R F; de Ligny, D; Martinet, C; Sandrini, M; Medina, A N; Rohling, J H; Baesso, M L; Lima, S M; Andrade, L H C; Guyot, Y

2016-08-10

In situ micro-Raman spectroscopy was used to investigate the structural evolution of OH(-)-free calcium aluminosilicate glasses, under high pressure and at room temperature. Evaluation was made of the role of the SiO2 concentration in percalcic join systems, for Al/(Al  +  Si) in the approximate range from 0.9 to 0.2. Under high pressure, the intensity of the main band related to the bending mode of bridging oxygen ([Formula: see text][T-O-T], where T  =  Si or Al) decreased gradually, suggesting that the bonds were severely altered or even destroyed. In Si-rich glasses, compression induced a transformation of Q (n) species to Q (n-1). In the case of Al-rich glass, the Al in the smallest Q (n) units evolved from tetrahedral to higher-coordinated Al (([5])Al and ([6])Al). Permanent structural changes were observed in samples recovered from the highest pressure of around 15 GPa and, particularly for Si-rich samples, the recovered structure showed an increase of three-membered rings in the Si/Al tetrahedral network.

Modeling amorphization of tetrahedral structures under local approaches

International Nuclear Information System (INIS)

Jesurum, C.E.; Pulim, V.; Berger, B.; Hobbs, L.W.

1997-01-01

Many crystalline ceramics can be topologically disordered (amorphized) by disordering radiation events involving high-energy collision cascades or (in some cases) successive single-atom displacements. The authors are interested in both the potential for disorder and the possible aperiodic structures adopted following the disordering event. The potential for disordering is related to connectivity, and among those structures of interest are tetrahedral networks (such as SiO 2 , SiC and Si 3 N 4 ) comprising corner-shared tetrahedral units whose connectivities are easily evaluated. In order to study the response of these networks to radiation, the authors have chosen to model their assembly according to the (simple) local rules that each corner obeys in connecting to another tetrahedron; in this way they easily erect large computer models of any crystalline polymorphic form. Amorphous structures can be similarly grown by application of altered rules. They have adopted a simple model of irradiation in which all bonds in the neighborhood of a designated tetrahedron are destroyed, and they reform the bonds in this region according to a set of (possibly different) local rules appropriate to the environmental conditions. When a tetrahedron approaches the boundary of this neighborhood, it undergoes an optimization step in which a spring is inserted between two corners of compatible tetrahedra when they are within a certain distance of one another; component forces are then applied that act to minimize the distance between these corners and minimize the deviation from the rules. The resulting structure is then analyzed for the complete adjacency matrix, irreducible ring statistics, and bond angle distributions

Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

Science.gov (United States)

Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

2016-04-28

Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

Energy Technology Data Exchange (ETDEWEB)

Conrad Ingram; Mark Mitchell

2006-09-30

The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of mesoporous aluminosilicate catalyst, Al-SBA-15, containing strong Broensted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt% Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst will be evaluated for the conversion of heavy petroleum feedstocks to naphtha and middle distillates.

Cobalt Coordination and Clustering in α-Co(OH)2 Revealed by Synchrotron X-ray Total Scattering

International Nuclear Information System (INIS)

Neilson, James R.; Kurzman, Joshua A.; Seshadri, Ram; Morse, Daniel E.

2010-01-01

Structures of layered metal hydroxides are not well described by traditional crystallography. Total scattering from a synthesis-controlled subset of these materials, as described here, reveals that different cobalt coordination polyhedra cluster within each layer on short length scales, offering new insights and approaches for understanding the properties of these and related layered materials. Structures related to that of brucite (Mg(OH) 2 ) are ubiquitous in the mineral world and offer a variety of useful functions ranging from catalysis and ion-exchange to sequestration and energy transduction, including applications in batteries. However, it has been difficult to resolve the atomic structure of these layered compounds because interlayer disorder disrupts the long-range periodicity necessary for diffraction-based structure determination. For this reason, traditional unit-cell-based descriptions have remained inaccurate. Here we apply, for the first time to such layered hydroxides, synchrotron X-ray total scattering methods - analyzing both the Bragg and diffuse components - to resolve the intralayer structure of three different α-cobalt hydroxides, revealing the nature and distribution of metal site coordination. The different compounds with incorporated chloride ions have been prepared with kinetic control of hydrolysis to yield different ratios of octahedrally and tetrahedrally coordinated cobalt ions within the layers, as confirmed by total scattering. Real-space analyses indicate local clustering of polyhedra within the layers, manifested in the weighted average of different ordered phases with fixed fractions of tetrahedrally coordinated cobalt sites. These results, hidden from an averaged unit-cell description, reveal new structural characteristics that are essential to understanding the origin of fundamental material properties such as color, anion exchange capacity, and magnetic behavior. Our results also provide further insights into the detailed

Cobalt coordination and clustering in alpha-Co(OH)(2) revealed by synchrotron X-ray total scattering.

Science.gov (United States)

Neilson, James R; Kurzman, Joshua A; Seshadri, Ram; Morse, Daniel E

2010-09-03

Structures of layered metal hydroxides are not well described by traditional crystallography. Total scattering from a synthesis-controlled subset of these materials, as described here, reveals that different cobalt coordination polyhedra cluster within each layer on short length scales, offering new insights and approaches for understanding the properties of these and related layered materials. Structures related to that of brucite [Mg(OH)(2)] are ubiquitous in the mineral world and offer a variety of useful functions ranging from catalysis and ion-exchange to sequestration and energy transduction, including applications in batteries. However, it has been difficult to resolve the atomic structure of these layered compounds because interlayer disorder disrupts the long-range periodicity necessary for diffraction-based structure determination. For this reason, traditional unit-cell-based descriptions have remained inaccurate. Here we apply, for the first time to such layered hydroxides, synchrotron X-ray total scattering methods-analyzing both the Bragg and diffuse components-to resolve the intralayer structure of three different alpha-cobalt hydroxides, revealing the nature and distribution of metal site coordination. The different compounds with incorporated chloride ions have been prepared with kinetic control of hydrolysis to yield different ratios of octahedrally and tetrahedrally coordinated cobalt ions within the layers, as confirmed by total scattering. Real-space analyses indicate local clustering of polyhedra within the layers, manifested in the weighted average of different ordered phases with fixed fractions of tetrahedrally coordinated cobalt sites. These results, hidden from an averaged unit-cell description, reveal new structural characteristics that are essential to understanding the origin of fundamental material properties such as color, anion exchange capacity, and magnetic behavior. Our results also provide further insights into the detailed

Erasing no-man’s land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles

Science.gov (United States)

Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

2014-09-01

One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point located in the `no-man’s land’. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, as spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon, carbon and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

International Nuclear Information System (INIS)

Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D.

2004-01-01

X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca 2 Ge 0.8 Cr 0.2 O 4 , Ba 2 Ge 0.1 Cr 0.9 O 4 , Sr 2 CrO 4 , Ca 2 (PO 4 ) x (CrO 4 ) 1-x Cl (x=0.25,0.5), Ca 5 (CrO 4 ) 3 Cl, CrO 3 , the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3 , CrF 3 , Cr 2 O 3 , KCr(SO 4 ) 2 · 12H 2 O, CrO 2 and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code

The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

Science.gov (United States)

Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D.

2004-05-01

X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca 2Ge 0.8Cr 0.2O 4, Ba 2Ge 0.1Cr 0.9O 4, Sr 2CrO 4, Ca 2(PO 4) x(CrO 4) 1- xCl ( x=0.25,0.5), Ca 5(CrO 4) 3Cl, CrO 3, the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3, CrF 3, Cr 2O 3, KCr(SO 4) 2 · 12H 2O, CrO 2 and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code.

Erasing no-man's land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles.

Science.gov (United States)

Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

2014-09-01

One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point [1] located in the "no-man's land" [2]. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, since spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water [3, 4]. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon [5], carbon [6] and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

Urea-functionalized crystalline capsules for recognition and separation of tetrahedral oxoanions

Energy Technology Data Exchange (ETDEWEB)

Custelcean, Radu [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

2012-12-21

We reviewed the persistent ability of tripodal TREN-based tris-urea receptors (TREN = tris(2-aminoethyl)amine) to self-assemble with a variety of oxoanions into dimeric capsules upon crystallization. The capsule crystallization allows for charge-, shape-, and size-selective encapsulation of tetrahedral XO₄^n-anions (n = 2,3), and provides an effective way to separate these anions from competitive aqueous environments.

Tetrahedral mesh generation of real terrain and topography effect on ERT image in Beishan region, Gansu province

International Nuclear Information System (INIS)

Lu Debao; Zhou Qiyou; Xiao Anlin; Song Zhen

2014-01-01

The paper starts from tetrahedral meshes generation of real terrain, a detailed way of tetradralization toward complicated terrain has been proposed based on comparing of advantage and disadvantage of several methods. DEM image has been used to help to generate tetrahedral mesh of research area. And then, forward soft Gmdata is used to calculate and analyze the topography effect on ERT Image with different kinds of terrain. Meanwhile, a quantitative way to define the topography effect was presented. Based on that, the method is used to eliminate the topography effect. The results show the method is effective and useful. (authors)

Evolution of stacking fault tetrahedral and work hardening effect in copper single crystals

Science.gov (United States)

Liu, Hai Tao; Zhu, Xiu Fu; Sun, Ya Zhou; Xie, Wen Kun

2017-11-01

Stacking fault tetrahedral (SFT), generated in machining of copper single crystal as one type of subsurface defects, has significant influence on the performance of workpiece. In this study, molecular dynamics (MD) simulation is used to investigate the evolution of stacking fault tetrahedral in nano-cutting of copper single crystal. The result shows that SFT is nucleated at the intersection of differently oriented stacking fault (SF) planes and SFT evolves from the preform only containing incomplete surfaces into a solid defect. The evolution of SFT contains several stress fluctuations until the complete formation. Nano-indentation simulation is then employed on the machined workpiece from nano-cutting, through which the interaction between SFT and later-formed dislocations in subsurface is studied. In the meanwhile, force-depth curves obtained from nano-indentation on pristine and machined workpieces are compared to analyze the mechanical properties. By simulation of nano-cutting and nano-indentation, it is verified that SFT is a reason of the work hardening effect.

Cause and Cure - Deterioration in Accuracy of CFD Simulations With Use of High-Aspect-Ratio Triangular Tetrahedral Grids

Science.gov (United States)

Chang, Sin-Chung; Chang, Chau-Lyan; Venkatachari, Balaji Shankar

2017-01-01

Traditionally high-aspect ratio triangular/tetrahedral meshes are avoided by CFD re-searchers in the vicinity of a solid wall, as it is known to reduce the accuracy of gradient computations in those regions and also cause numerical instability. Although for certain complex geometries, the use of high-aspect ratio triangular/tetrahedral elements in the vicinity of a solid wall can be replaced by quadrilateral/prismatic elements, ability to use triangular/tetrahedral elements in such regions without any degradation in accuracy can be beneficial from a mesh generation point of view. The benefits also carry over to numerical frameworks such as the space-time conservation element and solution element (CESE), where triangular/tetrahedral elements are the mandatory building blocks. With the requirement of the CESE method in mind, a rigorous mathematical framework that clearly identities the reason behind the difficulties in use of such high-aspect ratio triangular/tetrahedral elements is presented here. As will be shown, it turns out that the degree of accuracy deterioration of gradient computation involving a triangular element is hinged on the value of its shape factor Gamma def = sq sin Alpha1 + sq sin Alpha2 + sq sin Alpha3, where Alpha1; Alpha2 and Alpha3 are the internal angles of the element. In fact, it is shown that the degree of accuracy deterioration increases monotonically as the value of Gamma decreases monotonically from its maximal value 9/4 (attained by an equilateral triangle only) to a value much less than 1 (associated with a highly obtuse triangle). By taking advantage of the fact that a high-aspect ratio triangle is not necessarily highly obtuse, and in fact it can have a shape factor whose value is close to the maximal value 9/4, a potential solution to avoid accuracy deterioration of gradient computation associated with a high-aspect ratio triangular grid is given. Also a brief discussion on the extension of the current mathematical framework to the

DNA-mediated self-assembly of tetrahedral plasmonic clusters for metafluids

Science.gov (United States)

Schade, Nicholas; Sun, Li; Lee, You-Jin; Fan, Jonathan; Capasso, Federico; Yi, Gi-Ra; Manoharan, Vinothan

2014-03-01

We direct the self-assembly of clusters of gold nanospheres with the goal of creating a bulk, isotropic, optical metafluid. We use spherical gold nanoparticles that are exceptionally smooth, monocrystalline, and monodisperse. These particles exhibit highly reproducible scattering spectra compared with commercially available gold colloids. We label them with DNA sequences and mix them together to self-assemble small clusters. By controlling the particle sizes and the interactions between them, we maximize the yield of tetrahedral clusters, the ideal structures for isotropic metamaterials.

High field 27Al MAS NMR and TPD studies of active sites in ethanol dehydration using thermally treated transitional aluminas as catalysts

Energy Technology Data Exchange (ETDEWEB)

Hu, Jian Zhi; Xu, Suochang; Kwak, Ja Hun; Hu, Mary Y.; Wan, Chuan; Zhao, Zhenchao; Szanyi, Janos; Bao, Xinhe; Han, Xiuwen; Wang, Yong; Peden, Charles H. F.

2016-04-01

Gamma-, sigma- and theta-Al2O3 are well known metastable “transitional” alumina structural polymorphs. Upon heating, Al2O3 transitions to the so-called and Al2O3 polymorphs and finally forms the thermally stable Al2O3. The poorly developed crystallinity and co-existence of the , , and Al2O3 prior to forming all Al2O3, making it difficult to characterize the structures as well as to quantify the various phases of the transition alumina. As a result, there are significant controversies in the literatures. In this work, a detailed NMR analysis was carried out at high magnetic field on three special aluminum oxide samples where the, , , Al2O3 phases are made dominant, respectively, by controlling the synthesis conditions. The goal is to simplify, including making unambiguous, spectral assignments in 27Al MAS NMR spectra of transition alumina that have not yet been commonly agreed previously. Specifically, quantitative 1D 27Al MAS NMR was used to quantify the ratios of the different alumina structural units, 2D MQMAS 27Al MAS was used for obtaining the highest spectral resolution to guide the analysis of the 1D spectrum, and a saturation pulse sequence was integrated into the 1D NMR to select the amorphous structures, including obtain spectra where the penta-coordinate sites are observed with enhanced relative intensity. Collectively, this study uniquely assigns Al-peaks (both octahedral and tetrahedral) to the Al2O3 and the Al2O3 phases and offers a new way of understanding, including quantifying, the different structural units and sites in transition alumina samples.

Modular construction of oxide structures--compositional control of transition metal coordination environments.

Science.gov (United States)

Tenailleau, Christophe; Allix, Mathieu; Claridge, John B; Hervieu, Maryvonne; Thomas, Michael F; Hirst, James P; Rosseinsky, Matthew J

2008-06-18

The effects of reaction temperature and pO2 were investigated on a series of (Ba,Ca,Nd)FeO3-delta perovskite systems in order to isolate phases containing ordered arrangements of the distinct vacancy and cation ordering patterns identified in less compositionally complex iron oxide systems. Initial synthesis in air at high temperature yields cubic perovskite phases (I) with average iron oxidation states higher than 3; selected area electron diffraction together with diffuse features observed in the synchrotron X-ray diffraction (SXRD) patterns of these materials show evidence of small domains of short-range cation and vacancy order. Annealing these materials in nitrogen or in a sealed tube in the presence of an NiO/Ni buffer yielded the Fe(3+) phase Ca2Ba2Nd2Fe6O16 (II), closely related to Sr2LaFe3O8 but with partial cation order as well as anion order present the larger Ba cations are largely present in the 12-coordinate site between the octahedral iron layers, and Ca is largely present in 10-coordinate sites between octahedral and tetrahedral sites. Further reduction of Ca2Ba2Nd2Fe6O16 using a Zr getter yields the mixed-valence phase Ca2Ba2Nd2Fe6O15.6 (III). The structure of III was solved by maximum entropy analysis of XRD data coupled with analysis of high-temperature neutron diffraction data and refined against combined SXRD and high-Q ambient-temperature neutron data. This material crystallizes in a 20-fold perovskite super cell (Imma, a approximately square root(2 x a(p), b approximately 10 x a(p), c approximately square root(x 2a(p)) and can be visualized as an intergrowth between brownmillerite (Ca2Fe2O5) and the YBa2Fe3O8 structure. There are three distinct iron coordination environments, octahedral (O), square-pyramidal (Sp), and trigonal planar (Tp, formed by distorting the tetrahedral site in brownmillerite), which form a Sp-O-Tp-O-Sp repeat. Bond valence calculations indicate that Tp is an Fe(2+) site, while the O and Sp sites are Fe(3+). The A

The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

Energy Technology Data Exchange (ETDEWEB)

Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D

2004-05-10

X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca{sub 2}Ge{sub 0.8}Cr{sub 0.2}O{sub 4}, Ba{sub 2}Ge{sub 0.1}Cr{sub 0.9}O{sub 4}, Sr{sub 2}CrO{sub 4}, Ca{sub 2}(PO{sub 4}){sub x}(CrO{sub 4}){sub 1-x}Cl (x=0.25,0.5), Ca{sub 5}(CrO{sub 4}){sub 3}Cl, CrO{sub 3}, the octahedrally coordinated compounds Cr(II)-acetate, CrCl{sub 3}, CrF{sub 3}, Cr{sub 2}O{sub 3}, KCr(SO{sub 4}){sub 2} {center_dot} 12H{sub 2}O, CrO{sub 2} and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code.

Shutdown dose rate analysis with CAD geometry, Cartesian/tetrahedral mesh, and advanced variance reduction

International Nuclear Information System (INIS)

Biondo, Elliott D.; Davis, Andrew; Wilson, Paul P.H.

2016-01-01

Highlights: • A CAD-based shutdown dose rate analysis workflow has been implemented. • Cartesian and superimposed tetrahedral mesh are fully supported. • Biased and unbiased photon source sampling options are available. • Hybrid Monte Carlo/deterministic techniques accelerate photon transport. • The workflow has been validated with the FNG-ITER benchmark problem. - Abstract: In fusion energy systems (FES) high-energy neutrons born from burning plasma activate system components to form radionuclides. The biological dose rate that results from photons emitted by these radionuclides after shutdown—the shutdown dose rate (SDR)—must be quantified for maintenance planning. This can be done using the Rigorous Two-Step (R2S) method, which involves separate neutron and photon transport calculations, coupled by a nuclear inventory analysis code. The geometric complexity and highly attenuating configuration of FES motivates the use of CAD geometry and advanced variance reduction for this analysis. An R2S workflow has been created with the new capability of performing SDR analysis directly from CAD geometry with Cartesian or tetrahedral meshes and with biased photon source sampling, enabling the use of the Consistent Adjoint Driven Importance Sampling (CADIS) variance reduction technique. This workflow has been validated with the Frascati Neutron Generator (FNG)-ITER SDR benchmark using both Cartesian and tetrahedral meshes and both unbiased and biased photon source sampling. All results are within 20.4% of experimental values, which constitutes satisfactory agreement. Photon transport using CADIS is demonstrated to yield speedups as high as 8.5·10"5 for problems using the FNG geometry.

Verification of the three-dimensional tetrahedral grid SN code THOR

International Nuclear Information System (INIS)

Schunert, S.; Ferrer, R.; Azmy, Y.

2013-01-01

In this work current capabilities implemented in the novel, arbitrary-order, tetrahedral-grid short characteristics S N radiation transport code THOR are verified based on four benchmark problems: (1) A one-group Method of Manufactured Solution (MMS) problem on a cuboidal domain, (2) an infinite medium eigenvalue problem with up-scattering, (3) a homogeneous torus and (4) a bare cube eigenvalue problem with anisotropic scattering up to order three. The first benchmark problem exercises the various spatial discretization options available in THOR: The short characteristics method in conjunction with polynomial expansions of the source and face fluxes either using the complete or Lagrange family of arbitrary orders. Using the numerical solution's order of convergence test in the framework of a mesh refinement study, correct implementation of a selection of spatial expansion orders is demonstrated for two meshes with tetrahedral aspect ratios close to unity and 50. The second benchmark problem exercises the implementation of angular fluxes on reflective boundary faces that are implicit within a mesh sweep, and up-scattering. The third benchmark problem comprises cyclic dependencies within the mesh sweep thus exercising the algorithm devised for 'breaking' the cyclic dependencies. Finally, the fourth benchmark problem, a simple bare cube, is used to test correct implementation of the anisotropic scattering capability. For all test problems THOR obtains solutions that converge to the reference/exact solution with the expected rate thereby contributing to our confidence in the correctness of its tested features in the present implementation. (authors)

Al and Si Influences on Hydrogen Embrittlement of Carbide-Free Bainitic Steel

Directory of Open Access Journals (Sweden)

Yanguo Li

2013-01-01

Full Text Available A first-principle method based on the density functional theory was applied to investigate the Al and Si influences on the hydrogen embrittlement of carbide-free bainitic steel. The hydrogen preference site, binding energy, diffusion behaviour, and electronic structure were calculated. The results showed that hydrogen preferred to be at the tetrahedral site. The binding energy of the cell with Si was the highest and it was decreased to be the worst by adding hydrogen. The diffusion barrier of hydrogen in the cell containing Al was the highest, so it was difficult for hydrogen to diffuse. Thus, hydrogen embrittlement can be reduced by Al rather than Si.

Artificial intelligence approach to planning the robotic assembly of large tetrahedral truss structures

Science.gov (United States)

Homemdemello, Luiz S.

1992-01-01

An assembly planner for tetrahedral truss structures is presented. To overcome the difficulties due to the large number of parts, the planner exploits the simplicity and uniformity of the shapes of the parts and the regularity of their interconnection. The planning automation is based on the computational formalism known as production system. The global data base consists of a hexagonal grid representation of the truss structure. This representation captures the regularity of tetrahedral truss structures and their multiple hierarchies. It maps into quadratic grids and can be implemented in a computer by using a two-dimensional array data structure. By maintaining the multiple hierarchies explicitly in the model, the choice of a particular hierarchy is only made when needed, thus allowing a more informed decision. Furthermore, testing the preconditions of the production rules is simple because the patterned way in which the struts are interconnected is incorporated into the topology of the hexagonal grid. A directed graph representation of assembly sequences allows the use of both graph search and backtracking control strategies.

Nuclear tetrahedral symmetry: possibly present throughout the periodic table.

Science.gov (United States)

Dudek, J; Goźdź, A; Schunck, N; Miśkiewicz, M

2002-06-24

More than half a century after the fundamental, spherical shell structure in nuclei had been established, theoretical predictions indicated that the shell gaps comparable or even stronger than those at spherical shapes may exist. Group-theoretical analysis supported by realistic mean-field calculations indicate that the corresponding nuclei are characterized by the TD(d) ("double-tetrahedral") symmetry group. Strong shell-gap structure is enhanced by the existence of the four-dimensional irreducible representations of TD(d); it can be seen as a geometrical effect that does not depend on a particular realization of the mean field. Possibilities of discovering the TD(d) symmetry in experiment are discussed.

Tracking the Chemical Transformations at the Brønsted Acid Site upon Water-Induced Deprotonation in a Zeolite Pore

Energy Technology Data Exchange (ETDEWEB)

Vjunov, Aleksei; Wang, Meng; Govind, Niranjan; Huthwelker, Thomas; Shi, Hui; Mei, Donghai; Fulton, John L.; Lercher, Johannes A.

2017-10-23

We report the structural changes induced by Brønsted acidic site deprotonation in a zeolite with MFI structure as a function of temperature up to 430°C using in situ Al K-edge X-ray absorption fine structure spectroscopy (XAFS). At ambient conditions, the protons are present as hydrated hydronium ions (H3O+(H2O)n) that are ion-paired to the anionic, Al tetrahedral (T) site. At elevated temperatures, loss of water molecules hydrating the hydronium ions leads to an unstable free hydronium ion that disso-ciates to form the hydroxylated T-site. The formation of this (-O3)-Al-(OH-) species leads to the elongation of one of the four Al-O bonds and causes significant distortion of the tetrahedral symmetry about the Al atom. This distortion leads to the appearance of new pre-edge features in the Al K-edge X-ray absorption near edge structure (XANES) spectra. The pre-edge peak assignment is confirmed by time-dependent density functional theory calculation of the XANES spectrum. The XANES spectra are also sensitive to solutes or solvent that are in proximity to the T-site. A second structural transition occurs at about the same temperature, namely the conversion of a minor fraction of extra-framework octahedral Al present in the sample at ambient conditions to a tetrahedral species through the de-coordination of H2O-ligands. Both IR spectroscopy and thermogravimetric analysis (TGA) are further used to confirm the overall chemical transformation of the T-site.

Cause and Cure-Deterioration in Accuracy of CFD Simulations with Use of High-Aspect-Ratio Triangular/Tetrahedral Grids

Science.gov (United States)

Chang, Sin-Chung; Chang, Chau-Lyan; Venkatachari, Balaji

2017-01-01

In the multi-dimensional space-time conservation element and solution element16 (CESE) method, triangles and tetrahedral mesh elements turn out to be the most natural building blocks for 2D and 3D spatial grids, respectively. As such, the CESE method is naturally compatible with the simplest 2D and 3D unstructured grids and thus can be easily applied to solve problems with complex geometries. However, because (a) accurate solution of a high-Reynolds number flow field near a solid wall requires that the grid intervals along the direction normal to the wall be much finer than those in a direction parallel to the wall and, as such, the use of grid cells with extremely high aspect ratio (103 to 106) may become mandatory, and (b) unlike quadrilateral hexahedral grids, it is well-known that accuracy of gradient computations involving triangular tetrahedral grids tends to deteriorate rapidly as cell aspect ratio increases. As a result, the use of triangular tetrahedral grid cells near a solid wall has long been deemed impractical by CFD researchers. In view of (a) the critical role played by triangular tetrahedral grids in the CESE development, and (b) the importance of accurate resolution of high-Reynolds number flow field near a solid wall, as will be presented in the main paper, a comprehensive and rigorous mathematical framework that clearly identifies the reasons behind the accuracy deterioration as described above has been developed for the 2D case involving triangular cells. By avoiding the pitfalls identified by the 2D framework, and its 3D extension, it has been shown numerically.

Electromagnetic forward modelling for realistic Earth models using unstructured tetrahedral meshes and a meshfree approach

Science.gov (United States)

Farquharson, C.; Long, J.; Lu, X.; Lelievre, P. G.

2017-12-01

Real-life geology is complex, and so, even when allowing for the diffusive, low resolution nature of geophysical electromagnetic methods, we need Earth models that can accurately represent this complexity when modelling and inverting electromagnetic data. This is particularly the case for the scales, detail and conductivity contrasts involved in mineral and hydrocarbon exploration and development, but also for the larger scale of lithospheric studies. Unstructured tetrahedral meshes provide a flexible means of discretizing a general, arbitrary Earth model. This is important when wanting to integrate a geophysical Earth model with a geological Earth model parameterized in terms of surfaces. Finite-element and finite-volume methods can be derived for computing the electric and magnetic fields in a model parameterized using an unstructured tetrahedral mesh. A number of such variants have been proposed and have proven successful. However, the efficiency and accuracy of these methods can be affected by the "quality" of the tetrahedral discretization, that is, how many of the tetrahedral cells in the mesh are long, narrow and pointy. This is particularly the case if one wants to use an iterative technique to solve the resulting linear system of equations. One approach to deal with this issue is to develop sophisticated model and mesh building and manipulation capabilities in order to ensure that any mesh built from geological information is of sufficient quality for the electromagnetic modelling. Another approach is to investigate other methods of synthesizing the electromagnetic fields. One such example is a "meshfree" approach in which the electromagnetic fields are synthesized using a mesh that is distinct from the mesh used to parameterized the Earth model. There are then two meshes, one describing the Earth model and one used for the numerical mathematics of computing the fields. This means that there are no longer any quality requirements on the model mesh, which

Atomic Scale Picture of the Ion Conduction Mechanism in Tetrahedral Network of Lanthanum Barium Gallate

Energy Technology Data Exchange (ETDEWEB)

Jalarvo, Niina H [ORNL; Gourdon, Olivier [ORNL; Bi, Zhonghe [ORNL; Gout, Delphine J [ORNL; Ohl, Michael E [ORNL; Paranthaman, Mariappan Parans [ORNL

2013-01-01

Combined experimental study of impedance spectroscopy, neutron powder diffraction and quasielastic neutron scattering was performed to shed light into the atomic scale ion migration processes in proton and oxide ion conductor; La0.8Ba1.2GaO3.9 . This material consist of tetrahedral GaO4 units, which are rather flexible and rocking motion of these units promotes the ionic migration process. The oxide ion (vacancy) conduction takes place on channels along c axis, involving a single elementary step, which occurs between adjacent tetrahedron (inter-tetrahedron jump). The proton conduction mechanism consists of intra-tetrahedron and inter-tetrahedron elementary processes. The intra-tetrahedron proton transport is the rate-limiting process, with activation energy of 0.44 eV. The rocking motion of the GaO4 tetrahedron aids the inter-tetrahedral proton transport, which has the activation energy of 0.068 eV.

Controllable synthesis and tunable luminescence of glass ceramic containing Mn2+:ZnAl2O4 and Pr3+:YF3 nano-crystals

International Nuclear Information System (INIS)

Yu, Yunlong; Li, Xiaoyan

2016-01-01

Highlights: • Glass ceramic containing ZnAl 2 O 4 and YF 3 nano-crystals is fabricated. • Mn 2+ and Pr 3+ are selectively incorporated into ZnAl 2 O 4 and YF 3 , respectively. • The luminescence color can be tuned by adjusting the excitation wavelength. - Abstract: Glass ceramic containing spinel ZnAl 2 O 4 :Mn 2+ and orthorhombic YF 3 :Pr 3+ nano-crystals has been successfully prepared by a melt-quenching technique. X-ray diffraction and transmission electron microscopy demonstrated that two nano-phases, i.e. ZnAl 2 O 4 and YF 3 , were homogeneously distributed among the glass matrix. Importantly, the selective incorporation of Pr 3+ ions into the Y 3+ nine-fold coordinated sites of YF 3 and the segregation of Mn 2+ dopants in the Zn 2+ tetrahedral sites of ZnAl 2 O 4 were confirmed based on the excitation/emission spectra and the crystal field calculation. Under blue light excitation, both Pr 3+ and Mn 2+ in the glass ceramic can be simultaneously excited, and emit red and green luminescence, respectively, owing to the suppression of energy transfer between them. The luminescence color of the obtained glass ceramic can be easily tuned by adjusting the excitation wavelength. These results indicate the potential application of the glass ceramic as converting phosphor to generate white-light after coupling with the blue LED chip.

Reversible hydrogen storage by NaAlH4 confined within a titanium-functionalized MOF-74(Mg) nanoreactor.

Science.gov (United States)

Stavila, Vitalie; Bhakta, Raghunandan K; Alam, Todd M; Majzoub, Eric H; Allendorf, Mark D

2012-11-27

We demonstrate that NaAlH(4) confined within the nanopores of a titanium-functionalized metal-organic framework (MOF) template MOF-74(Mg) can reversibly store hydrogen with minimal loss of capacity. Hydride-infiltrated samples were synthesized by melt infiltration, achieving loadings up to 21 wt %. MOF-74(Mg) possesses one-dimensional, 12 Å channels lined with Mg atoms having open coordination sites, which can serve as sites for Ti catalyst stabilization. MOF-74(Mg) is stable under repeated hydrogen desorption and hydride regeneration cycles, allowing it to serve as a "nanoreactor". Confining NaAlH(4) within these pores alters the decomposition pathway by eliminating the stable intermediate Na(3)AlH(6) phase observed during bulk decomposition and proceeding directly to NaH, Al, and H(2), in agreement with theory. The onset of hydrogen desorption for both Ti-doped and undoped nano-NaAlH(4)@MOF-74(Mg) is ∼50 °C, nearly 100 °C lower than bulk NaAlH(4). However, the presence of titanium is not necessary for this increase in desorption kinetics but enables rehydriding to be almost fully reversible. Isothermal kinetic studies indicate that the activation energy for H(2) desorption is reduced from 79.5 kJ mol(-1) in bulk Ti-doped NaAlH(4) to 57.4 kJ mol(-1) for nanoconfined NaAlH(4). The structural properties of nano-NaAlH(4)@MOF-74(Mg) were probed using (23)Na and (27)Al solid-state MAS NMR, which indicates that the hydride is not decomposed during infiltration and that Al is present as tetrahedral AlH(4)(-) anions prior to desorption and as Al metal after desorption. Because of the highly ordered MOF structure and monodisperse pore dimensions, our results allow key template features to be identified to ensure reversible, low-temperature hydrogen storage.

EPR study of the coordination sphere of Mo5+ ions in UV-irradiated silica-supported molybdenum catalysts

International Nuclear Information System (INIS)

Canose, B.; Gonzalez-Elipe, A.R.; Che, M.

1991-01-01

The determination of the number of coordination vacancies existing at transition metal cations at the surface of bulk or supported oxides is of greater interest in relation to the adsorption and catalytic properties of such systems. In the case of paramagnetic cations, the authors have developed a method consisting of the recording of their first and third derivative EPR spectra after adsorption of 13 CO, ( 13 C, I = 1/2). In this way, the 13 C superhyperfine structure which is normally observed permits the determination of the number of CO molecules bonded to the metal center. In a recent EPR work published in this journal, Seyedmonir and Howe have reported the formation of a CO adduct of the tetrahedral Mo 5+ -OH - species formed by UV-irradiation at 20 K of a MoO 3 /SiO 2 catalyst in the presence of H 2 . In that work, although the structure of such an adduct could not be derived unambiguously on the basis of the g tensor values, the coordination of the Mo 5+ ion by two CO molecules was suggested. This would be in agreement with the previous results with thermally reduced V 2 O 5 /SiO 2 and MoO 3 /SiO 2 catalysts, where the coordination of, respectively, V 4+ and Mo 5+ tetrahedral centers by two CO molecules was proven by means of the combined use of 13 CO and third derivative EPR spectra. In the present work, using this approach, they have studied the structure of these Mo 5+ ions photochemically generated on MoO 3 /SiO 2 catalysts and concluded that only one CO molecule is bonded to the paramagnetic ion

Synthesis of mesoporous aluminophosphate and silicoaluminophosphate in the presence of nonionic poly(ethylene oxide) surfactant

International Nuclear Information System (INIS)

Zhao, G.L.; Zhang, X.J.; Chen, T.H.; Yuan, Z.Y.

2006-01-01

Thermally stable mesoporous aluminophosphate and silicoaluminophosphate materials have been synthesized by using nonionic PEO-surfactant C 16 H 33 (PEO) 10 OH as a structure-directing agent. The synthesized aluminophosphate and silicoaluminophosphate possess disordered wormhole-like mesostructures with pore sizes of 3.8 and 5 nm, respectively. BET surface areas of 376-412 m 2 /g are obtained. Both four- and six-coordinate Al and tetrahedrally coordinated P were observed. It is believed that these materials may find potential applications in the fields of catalysis and material sciences

H2O-induced trigonal-to-tetrahedral transition in boron zeolites

International Nuclear Information System (INIS)

Fois, E.; Gamba, A.; Trudu, F.; Tabacchi, G.

2008-01-01

The behaviour of a protonated boron-containing zeolite at intermediate hydration degree has been investigated by means of periodic DFT approaches. Results of a combined room-temperature Car-Parrinello molecular dynamics blue-moon path sampling simulation indicate that, in the line with experimental findings, the BO 3 /Si-OH acid site typical of dry samples is converted to a hydrated H 3 O + hydrogen bonded to tetrahedral BO 4 - at moderate water content (four H 2 O per B site) with an activation free barrier of the order of few k T.

Single walled carbon nanotube network—Tetrahedral amorphous carbon composite film

Energy Technology Data Exchange (ETDEWEB)

Iyer, Ajai, E-mail: ajai.iyer@aalto.fi; Liu, Xuwen; Koskinen, Jari [Department of Materials Science and Engineering, School of Chemical Technology, Aalto University, POB 16200, 00076 Espoo (Finland); Kaskela, Antti; Kauppinen, Esko I. [NanoMaterials Group, Department of Applied Physics, School of Science, Aalto University, POB 15100, 00076 Espoo (Finland); Johansson, Leena-Sisko [Department of Forest Products Technology, School of Chemical Technology, Aalto University, POB 16400, 00076 Espoo (Finland)

2015-06-14

Single walled carbon nanotube network (SWCNTN) was coated by tetrahedral amorphous carbon (ta-C) using a pulsed Filtered Cathodic Vacuum Arc system to form a SWCNTN—ta-C composite film. The effects of SWCNTN areal coverage density and ta-C coating thickness on the composite film properties were investigated. X-Ray photoelectron spectroscopy measurements prove the presence of high quality sp{sup 3} bonded ta-C coating on the SWCNTN. Raman spectroscopy suggests that the single wall carbon nanotubes (SWCNTs) forming the network survived encapsulation in the ta-C coating. Nano-mechanical testing suggests that the ta-C coated SWCNTN has superior wear performance compared to uncoated SWCNTN.

Impact of local symmetry breaking on the physical properties of tetrahedral liquids.

Science.gov (United States)

Shi, Rui; Tanaka, Hajime

2018-02-27

Water and silica are the most important materials with local tetrahedral symmetry. They have similar crystalline polymorphs and exhibit anomalous density maximum in the liquid state. However, water and silica also show very different characteristics. For instance, the density of water varies much more sharply than that of liquid silica near the maximum as temperature changes. More notably, silica is a very good glass-former, but water is an extremely poor one. The physical origins of these similarities and differences still remain elusive, due to the lack of a microscopic understanding of the structural ordering in these two important liquids. Here, by accessing microscopic structural information by computer simulations, we reveal that local translational symmetry breaking is responsible for the density anomalies. On the other hand, the difference in the degree of local orientational symmetry breaking between water and silica, which originates from the difference in their bonding nature, causes not only the difference in the sharpness of density anomalies, but also their distinct glass-forming abilities. Our work not only shows the crucial roles of local translational and orientational symmetry breaking in the physical properties of the two extremely important materials, water and silica, but also provides a unified scenario applicable for other tetrahedral liquids such as Si, Ge, C, BeF 2 , and GeO 2 .

The effect of gamma-Al{sub 2}O{sub 3} support on the NO adsorption on Pd{sub 4} cluster

Energy Technology Data Exchange (ETDEWEB)

Prates, Letícia M.; Cruz, Maurício T.M., E-mail: cruzmtm@uerj.br [Universidade do Estado do Rio de Janeiro (UERJ), RJ (Brazil). Departamento de Química Geral e Inorgânica; Ferreira, Glaucio B.; Carneiro, José W.M.; Almeida, Wagner B. de [Universidade Federal Fluminense (UFF), Niterói, RJ (Brazil). Departamento de Química Inorgânica; Carauta, Alexandre N.M. [Fundação Técnico-Educacional Souza Marques, Rio de Janeiro, RJ (Brazil); Correia, Julio C.G. [Centro de Tecnologia Mineral (CETEM), Rio de Janeiro, RJ (Brazil)

2016-07-01

The effect of γ-Al{sub 2}O{sub 3} support on the NO adsorption on Pd{sub 4} clusters was investigated by means of density functional theory (DFT) calculations. Pd4 adsorbed on γ-Al{sub 2}O{sub 3} (represented by a Al{sub 14}O{sub 24}H{sub 6} cluster) changes its preferential geometry from tetrahedral to a distorted planar structure. The alumina support promotes a higher dispersion in the palladium catalyst and reduces the NO adsorption energy to - 25.6 kcal mol{sup -1} (computed at B3LYP/LANL2DZ/6-311+G(d)), in close agreement with the experimental value of - 27.2 kcal mol{sup -1}. On the bare planar Pd{sub 4} cluster the NO molecule adsorbs in a bridge arrangement, with adsorption energy of - 41.2 kcal mol{sup -1}. Adsorption on the tetrahedral Pd{sub 4} cluster occur preferentially in an atop mode, with adsorption energy of - 30.6 kcal mol{sup -1}. Charge density analysis show that the electron flux between the NO molecule and Pd{sub 4} depends on the adsorption form, with back-donation being stronger in the bridge adsorption mode. (author)

Finite-element design and optimization of a three-dimensional tetrahedral porous titanium scaffold for the reconstruction of mandibular defects.

Science.gov (United States)

Luo, Danmei; Rong, Qiguo; Chen, Quan

2017-09-01

Reconstruction of segmental defects in the mandible remains a challenge for maxillofacial surgery. The use of porous scaffolds is a potential method for repairing these defects. Now, additive manufacturing techniques provide a solution for the fabrication of porous scaffolds with specific geometrical shapes and complex structures. The goal of this study was to design and optimize a three-dimensional tetrahedral titanium scaffold for the reconstruction of mandibular defects. With a fixed strut diameter of 0.45mm and a mean cell size of 2.2mm, a tetrahedral structural porous scaffold was designed for a simulated anatomical defect derived from computed tomography (CT) data of a human mandible. An optimization method based on the concept of uniform stress was performed on the initial scaffold to realize a minimal-weight design. Geometric and mechanical comparisons between the initial and optimized scaffold show that the optimized scaffold exhibits a larger porosity, 81.90%, as well as a more homogeneous stress distribution. These results demonstrate that tetrahedral structural titanium scaffolds are feasible structures for repairing mandibular defects, and that the proposed optimization scheme has the ability to produce superior scaffolds for mandibular reconstruction with better stability, higher porosity, and less weight. Copyright © 2017 IPEM. Published by Elsevier Ltd. All rights reserved.

Magnetic Grüneisen parameter and magnetocaloric properties of a coupled spin–electron double-tetrahedral chain

International Nuclear Information System (INIS)

Gálisová, Lucia; Strečka, Jozef

2015-01-01

Magnetocaloric effect in a double-tetrahedral chain, in which nodal lattice sites occupied by the localized Ising spins regularly alternate with three equivalent lattice sites available for mobile electrons, is exactly investigated by considering the one-third electron filling and the ferromagnetic Ising exchange interaction between the mobile electrons and their nearest Ising neighbours. The entropy and the magnetic Grüneisen parameter, which closely relate to the magnetocaloric effect, are exactly calculated in order to investigate the relation between the ground-state degeneracy and the cooling efficiency of the hybrid spin–electron system during the adiabatic demagnetization. - Highlights: • A double-tetrahedral chain of mobile electrons and localized Ising spins is studied. • Magnetic Grüneisen parameter for the system is exactly derived. • Macroscopically degenerate phases FRU and FM constitute the ground state. • MCE is three times higher nearby FRU–FM transition than in FRU phase at small fields

Cluster-spin dynamics in a GaMo{sub 4}S{sub 8}-type compound: {sup 27}Al nuclear magnetic resonance study of AlMo{sub 4}S{sub 8}

Energy Technology Data Exchange (ETDEWEB)

Ikeno, R; Nakamura, H; Kohara, T [Graduate School of Material Science, University of Hyogo, Kamigori, Ako-gun, Hyogo 678-1297 (Japan)

2007-01-31

The cluster-spin dynamics of the tetrahedral Mo{sub 4} cluster, involved in AlMo{sub 4}S{sub 8} with a cubic GaMo{sub 4}S{sub 8} type structure, was investigated by NMR of the nonmagnetic {sup 27}Al site located outside the cluster. The nuclear spin-lattice relaxation is described well by the conventional local moment model assuming the presence of S=1/2 at each cluster, indicating that each Mo{sub 4} cluster behaves like a local spin with rigid magnitude. This behaviour is in contrast to the in-cluster relaxation, which reflects the spin-density fluctuations inside the cluster as a small unit of metal.

Efficient KF loaded on MgCaAl hydrotalcite-like compounds in the transesterification of Jatropha curcas oil

International Nuclear Information System (INIS)

Guzmán-Vargas, Ariel; Santos-Gutiérrez, Teresa; Lima, Enrique; Flores-Moreno, Jorge L.; Oliver-Tolentino, Miguel A.; Martínez-Ortiz, María de J.

2015-01-01

Highlights: • MgCaAl hydrotalcite-like compounds were synthetized. • After KF impregnation and calcination fluorinated species were detected. • Fluorinated species were stables and actives. • LDH composition and KF load effect were evaluated in biodiesel production. - Abstract: In this work a series of MgCaAl hydrotalcite-like compounds were synthetized by coprecipitation method at constant pH. In order to obtain the catalysts, the samples were modified with KF by incipient wetness impregnation at different wt%, after that, they were dried and calcined to obtain the mixed oxides. The effect of divalent cations ratio and KF load were studied in the transesterification reaction of Jatropha curcas oil to obtain biodiesel employing an inedible oil. XRD analysis showed typical diffraction patterns of LDH, by nitrogen physisorption the LDH mesoporous structure was also confirmed, 27 Al NMR spectra showed bands at 10 and 88 ppm attributed to the Al coordination before and after thermal treatment. While for the impregnated samples after calcination the profiles exhibited the mixed oxide formation, in addition, another peaks appeared associated to the formation of various fluorinated species as shown by XRD, additionally, 19 F NMR showed a main signal at −180 ppm indicating the presence of active tetrahedral aluminum fluoride species. The reaction evolution was monitoring calculating the oil conversion to biodiesel by integration of the signal spectra using 1 H NMR spectroscopy. The results of catalytic tests in transesterification reaction showed a direct correlation between Mg/Ca ratio and KF content in the oil conversion to biodiesel, the higher conversion was achieved (90%) when Mg/Ca = 1 and KF load was 30 wt%

Efficient KF loaded on MgCaAl hydrotalcite-like compounds in the transesterification of Jatropha curcas oil

Energy Technology Data Exchange (ETDEWEB)

Guzmán-Vargas, Ariel, E-mail: aguzmanv@ipn.mx [ESIQIE-IPN, Departamento de Ingeniería Química, Laboratorio de Investigación en Materiales Porosos, Catálisis Ambiental y Química Fina, UPALM Edif.7 P.B. Zacatenco, México D.F. 07738 (Mexico); Santos-Gutiérrez, Teresa [ESIQIE-IPN, Departamento de Ingeniería Química, Laboratorio de Investigación en Materiales Porosos, Catálisis Ambiental y Química Fina, UPALM Edif.7 P.B. Zacatenco, México D.F. 07738 (Mexico); Lima, Enrique [IIM-Universidad Nacional Autónoma de México, Circuito exterior s/n, Cd. Universitaria, 04510 México DF (Mexico); Flores-Moreno, Jorge L. [UAM-Azcapotzalco, Área de Química de Materiales, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200 México DF (Mexico); Oliver-Tolentino, Miguel A.; Martínez-Ortiz, María de J. [ESIQIE-IPN, Departamento de Ingeniería Química, Laboratorio de Investigación en Materiales Porosos, Catálisis Ambiental y Química Fina, UPALM Edif.7 P.B. Zacatenco, México D.F. 07738 (Mexico)

2015-09-15

Highlights: • MgCaAl hydrotalcite-like compounds were synthetized. • After KF impregnation and calcination fluorinated species were detected. • Fluorinated species were stables and actives. • LDH composition and KF load effect were evaluated in biodiesel production. - Abstract: In this work a series of MgCaAl hydrotalcite-like compounds were synthetized by coprecipitation method at constant pH. In order to obtain the catalysts, the samples were modified with KF by incipient wetness impregnation at different wt%, after that, they were dried and calcined to obtain the mixed oxides. The effect of divalent cations ratio and KF load were studied in the transesterification reaction of Jatropha curcas oil to obtain biodiesel employing an inedible oil. XRD analysis showed typical diffraction patterns of LDH, by nitrogen physisorption the LDH mesoporous structure was also confirmed, {sup 27}Al NMR spectra showed bands at 10 and 88 ppm attributed to the Al coordination before and after thermal treatment. While for the impregnated samples after calcination the profiles exhibited the mixed oxide formation, in addition, another peaks appeared associated to the formation of various fluorinated species as shown by XRD, additionally, {sup 19}F NMR showed a main signal at −180 ppm indicating the presence of active tetrahedral aluminum fluoride species. The reaction evolution was monitoring calculating the oil conversion to biodiesel by integration of the signal spectra using {sup 1}H NMR spectroscopy. The results of catalytic tests in transesterification reaction showed a direct correlation between Mg/Ca ratio and KF content in the oil conversion to biodiesel, the higher conversion was achieved (90%) when Mg/Ca = 1 and KF load was 30 wt%.

Tetrahedral 1B4Sb nanoclusters in GaP:(B, Sb)

Energy Technology Data Exchange (ETDEWEB)

Elyukhin, V A, E-mail: elyukhin@cinvestav.m [Departamento de Ingenieria Electrica-SEES, CINVESTAV-IPN, Avenida IPN 2508, Col. San Pedro Zacatenco, C. P. 07360, Mexico, D. F. (Mexico)

2009-05-01

Self-assembling conditions of 1B4Sb tetrahedral nanoclusters in GaP doped with boron and Sb isoelectronic impurities are represented in the ultradilute and dilute limits of the boron and Sb contents, respectively. The fulfilled estimates demonstrated the preferential complete or almost complete allocation of boron atoms in 1B4Sb nanoclusters at temperatures of 500 {sup 0}C and 900 {sup 0}C, respectively. The significant decrease of the sum of the free energies of the constituent compounds is the main origin of self-assembling. The reduction of the strain energy is the additional cause of this phenomenon.

Photoluminescence of the Mg2Al4Si5O18-Al2O3-MgAl2O4-SiO2 ceramic system containing Fe3+ and Cr3+ as impurity ions

Science.gov (United States)

Sosman, L. P.; López, A.; Pedro, S. S.; Papa, A. R. R.

2018-02-01

This work presents the results of photoluminescence, excitation and radiative decay time for a ceramic system containing Mg2Al4Si5O18-Al2O3-MgAl2O4-SiO2 with Fe3+ and Cr3+ as impurity ions. Emission data were obtained using several excitation wavelengths and the excitation data were acquired for the most intense emission bands. The optical results were analyzed according to the Tanabe-Sugano (TS) theory from which the crystalline field parameter Dq and Racah parameters B and C were obtained for the Fe3+ and Cr3+ sites. The results indicate that the Fe3+ and Cr3+ ions occupy tetrahedral and octahedral sites, respectively. The emission from Fe3+ and Cr3+ ions causes an intense and broad band ranging between 350 nm and 850 nm, showing that this material is a potential tunable radiation source at room temperature.

3He/4He production ratios by tetrahedral symmetric condensation

International Nuclear Information System (INIS)

Takahashi, Akito

2006-01-01

The present paper treats application of the Electronic Quasi-Particle Expansion Theory (EQPET) model for Tetrahedral Symmetric Condensate (TSC) of H/D mixed systems for Pd host metal. Production ratios of 3 He/ 4 He for multi-body fusion reactions in H/D mixed TSC systems are calculated as a function of H/D mixing ratio. The model is further extended to treat direct nuclear interactions between host-metal nucleus and TSC of pure four protons (or four deuterons), since TSC can become very small (far less than 1 pm radius) charge-neutral pseudo-particle. Results for the case of Ni + 4p/TSC are discussed with Ni + p capture reactions and Ni + 4p fission reactions. (authors)

Cd(II) and Zn(II) thiocyanate coordination compounds with 3-ethylpyridine. Synthesis, crystal structures and properties

Energy Technology Data Exchange (ETDEWEB)

Neumann, Tristan; Jess, Inke; Dos Santos Cunha, Cesar; Terraschke, Huayna; Naether, Christian [Kiel Univ. (Germany). Inst. fuer Anorganische Chemie

2018-04-01

Reaction of Cd(NCS){sub 2} and Zn(NCS){sub 2} with 3-ethylpyridine leads to the formation of compounds of compositions M(NCS){sub 2}(3-ethylpyridine){sub 4} (M=Cd, 1-Cd; Zn, 1-Zn) and M(NCS){sub 2}(3-ethylpyridine){sub 2} (M=Cd, 2-Cd; Zn, 2-Zn). 1-Cd and 1-Zn are isotypic and form discrete complexes in which the metal cations are octahedrally coordinated by two trans-coordinating N-bonded thiocyanate anions and four 3-ethylpyridine co-ligands. In 2-Cd the cations are also octahedrally coordinated but linked into chains by pairs of μ-1,3-bridging anionic ligands. 2-Zn is built up of discrete complexes, in which the Zn cation is tetrahedrally coordinated by two N-bonded thiocyanate anions and two 3-ethylpyridine co-ligands. Compounds 1-Cd, 2-Cd and 2-Zn can be prepared in a pure state, whereas 1-Zn is unstable and transforms on storage into 2-Zn. If 1-Cd and 1-Zn are heated, a transformation into 2-Cd, respectively 2-Zn is observed. Luminescence measurements reveal that 1-Cd, 2-Cd and 2-Zn emit light in the blue spectral range with maxima at, respectively, 21724, 21654 and 22055 cm{sup -1}, assigned to ligand-based luminescence.

Triangles and squares for a unique molecular crystal structure. Unsupported two-coordinate lithium cations and CC agostic interactions in cyclopropyllithium derivatives

Energy Technology Data Exchange (ETDEWEB)

Dufrois, Quentin; Daran, Jean-Claude; Vendier, Laure; Dinoi, Chiara; Etienne, Michel [Laboratoire de Chimie de Coordination du CNRS (LCC), Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, Toulouse (France)

2018-02-12

Understanding and controlling the aggregation state is germane to alkyllithium chemistry. Lewis base-free alkyllithium compounds normally form tetrahedral tetramers or octahedral hexamers in the solid state with the lithium cations being three-coordinate. We report that the unsupported cyclopropyl derivative 1-(trimethylsilyl)cyclopropyllithium [{μ-c-C(SiMe_3)C_2H_4}Li]{sub 4} (1), synthesized by the reduction of 1-(phenylthio)-1-(trimethylsilyl)cyclopropane, crystallizes as a tetramer in the space group I-4 with the two-coordinate lithium atoms forming a square. CC agostic interactions complete the coordination sphere around each lithium. The aggregate is preserved in hydrocarbon solution. Furthermore, CC agostic interactions compete intra- and intermolecularly with Lewis base donation as in the unsaturated dimer of 1-(phenylthio)cyclopropyllithium [Li(thf){sub 2}{μ-c-C(SPh)C_2H_4}{sub 2}Li (thf)] (3) which is also fully characterized. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

A three-dimensional tetrahedral-shaped conjugated small molecule for organic solar cells

Directory of Open Access Journals (Sweden)

QIN Yang

2014-04-01

Full Text Available We report the synthesis of a novel three-dimensional tetrahedral-shaped small molecule,SO,containing a tetraphenylsilane core and cyanoester functionalized terthiophene arms.A deep lying HOMO energy level of -5.3 eV and a narrow bandgap of 1.9 eV were obtained from cyclic voltammetry measurements.Absorption,X-ray scattering and differential scanning calorimetry experiments all indicate high crystallinity of this compound.Solar cells employing SO were fabricated and evaluated.The relatively low performance was mainly ascribed to lack of appreciable phase separation,which is confirmed by optical microscopy.

Tetrahedral ↔ octahedral network structure transition in simulated vitreous SiO2

International Nuclear Information System (INIS)

Vo Van Hoang; Nguyen Trung Hai; Hoang Zung

2006-01-01

By using molecular dynamics (MD) simulations we found a transition from a tetrahedral to an octahedral network structure in an amorphous SiO 2 model under compression from 2.20 to 5.35 g/cm 3 . And on heating of a high density amorphous (hda) model of 5.35 g/cm 3 at zero pressure, the structure transforms to a low density amorphous (lda) form. Simulations were done in a model containing 3000 particles under periodic boundary conditions with interatomic potentials which have a weak Coulomb interaction and a Morse type short-range interaction

XAS study of V2O5/Al2O3 catalysts doped with rare earth oxides

International Nuclear Information System (INIS)

Centeno, M.A.; Malet, P.; Capitan, M.J.; Benitez, J.J.; Carrizosa, I.; Odriozola, J.A.

1995-01-01

This paper reports on XAS studies of well dispersed V 2 O 5 /Al 2 O 3 and V 2 O 5 /Sm 2 O 3 /Al 2 O 3 samples. XAS spectra at V-K and Sm-L III edges show that the rare earth oxide favours the formation of regular tetrahedral units, [VO 4 ], over the surface of the support. Positions of the preedge peak at the V-K edge, and intensities of the white line at the Sm-L III edge also suggest modifications in the electronic density around V and Sm atoms when they are simultaneously supported over Al 2 O 3 . ((orig.))

Evaluation of a 3D point cloud tetrahedral tomographic reconstruction method

Science.gov (United States)

Pereira, N. F.; Sitek, A.

2010-09-01

Tomographic reconstruction on an irregular grid may be superior to reconstruction on a regular grid. This is achieved through an appropriate choice of the image space model, the selection of an optimal set of points and the use of any available prior information during the reconstruction process. Accordingly, a number of reconstruction-related parameters must be optimized for best performance. In this work, a 3D point cloud tetrahedral mesh reconstruction method is evaluated for quantitative tasks. A linear image model is employed to obtain the reconstruction system matrix and five point generation strategies are studied. The evaluation is performed using the recovery coefficient, as well as voxel- and template-based estimates of bias and variance measures, computed over specific regions in the reconstructed image. A similar analysis is performed for regular grid reconstructions that use voxel basis functions. The maximum likelihood expectation maximization reconstruction algorithm is used. For the tetrahedral reconstructions, of the five point generation methods that are evaluated, three use image priors. For evaluation purposes, an object consisting of overlapping spheres with varying activity is simulated. The exact parallel projection data of this object are obtained analytically using a parallel projector, and multiple Poisson noise realizations of these exact data are generated and reconstructed using the different point generation strategies. The unconstrained nature of point placement in some of the irregular mesh-based reconstruction strategies has superior activity recovery for small, low-contrast image regions. The results show that, with an appropriately generated set of mesh points, the irregular grid reconstruction methods can out-perform reconstructions on a regular grid for mathematical phantoms, in terms of the performance measures evaluated.

Evaluation of a 3D point cloud tetrahedral tomographic reconstruction method

International Nuclear Information System (INIS)

Pereira, N F; Sitek, A

2010-01-01

Tomographic reconstruction on an irregular grid may be superior to reconstruction on a regular grid. This is achieved through an appropriate choice of the image space model, the selection of an optimal set of points and the use of any available prior information during the reconstruction process. Accordingly, a number of reconstruction-related parameters must be optimized for best performance. In this work, a 3D point cloud tetrahedral mesh reconstruction method is evaluated for quantitative tasks. A linear image model is employed to obtain the reconstruction system matrix and five point generation strategies are studied. The evaluation is performed using the recovery coefficient, as well as voxel- and template-based estimates of bias and variance measures, computed over specific regions in the reconstructed image. A similar analysis is performed for regular grid reconstructions that use voxel basis functions. The maximum likelihood expectation maximization reconstruction algorithm is used. For the tetrahedral reconstructions, of the five point generation methods that are evaluated, three use image priors. For evaluation purposes, an object consisting of overlapping spheres with varying activity is simulated. The exact parallel projection data of this object are obtained analytically using a parallel projector, and multiple Poisson noise realizations of these exact data are generated and reconstructed using the different point generation strategies. The unconstrained nature of point placement in some of the irregular mesh-based reconstruction strategies has superior activity recovery for small, low-contrast image regions. The results show that, with an appropriately generated set of mesh points, the irregular grid reconstruction methods can out-perform reconstructions on a regular grid for mathematical phantoms, in terms of the performance measures evaluated.

Evaluation of a 3D point cloud tetrahedral tomographic reconstruction method

Energy Technology Data Exchange (ETDEWEB)

Pereira, N F; Sitek, A, E-mail: nfp4@bwh.harvard.ed, E-mail: asitek@bwh.harvard.ed [Department of Radiology, Brigham and Women' s Hospital-Harvard Medical School Boston, MA (United States)

2010-09-21

Tomographic reconstruction on an irregular grid may be superior to reconstruction on a regular grid. This is achieved through an appropriate choice of the image space model, the selection of an optimal set of points and the use of any available prior information during the reconstruction process. Accordingly, a number of reconstruction-related parameters must be optimized for best performance. In this work, a 3D point cloud tetrahedral mesh reconstruction method is evaluated for quantitative tasks. A linear image model is employed to obtain the reconstruction system matrix and five point generation strategies are studied. The evaluation is performed using the recovery coefficient, as well as voxel- and template-based estimates of bias and variance measures, computed over specific regions in the reconstructed image. A similar analysis is performed for regular grid reconstructions that use voxel basis functions. The maximum likelihood expectation maximization reconstruction algorithm is used. For the tetrahedral reconstructions, of the five point generation methods that are evaluated, three use image priors. For evaluation purposes, an object consisting of overlapping spheres with varying activity is simulated. The exact parallel projection data of this object are obtained analytically using a parallel projector, and multiple Poisson noise realizations of these exact data are generated and reconstructed using the different point generation strategies. The unconstrained nature of point placement in some of the irregular mesh-based reconstruction strategies has superior activity recovery for small, low-contrast image regions. The results show that, with an appropriately generated set of mesh points, the irregular grid reconstruction methods can out-perform reconstructions on a regular grid for mathematical phantoms, in terms of the performance measures evaluated.

Influence of Al doping on optical properties of CdS/PVA nanocomposites: Theory and experiment

Energy Technology Data Exchange (ETDEWEB)

Bala, Vaneeta, E-mail: vaneetabala@yahoo.com; Tripathi, S. K., E-mail: vaneetabala@yahoo.com; Kumar, Ranjan, E-mail: vaneetabala@yahoo.com [Department of Physics, Panjab University, Chandigarh (India)

2014-04-24

In the present work theoretical and experimental studies of aluminium doped cadmium sulphide polyvinyl alcohol (Al:CdS/PVA) nanocomposites have been carried out. Tetrahedral cluster AlCd{sub 9}S{sub 2}(SH){sub 18}]{sup 1−} has been encapsulated by small segments of polyvinyl alcohol (PVA) chains in order to simulate experimental environment of nanocomposites. Density functional theory (DFT) using local density approximation (LDA) functionals is employed to study the broadening of band gap upon ligation of nanoclusters. We have used in situ chemical route to synthesize nanocomposites. Optical band gap has been calculated from both experimental and theoretical approach.

Adsorption of oxygen on low-index surfaces of the TiAl{sub 3} alloy

Energy Technology Data Exchange (ETDEWEB)

Latyshev, A. M.; Bakulin, A. V.; Kulkova, S. E., E-mail: kulkova@ms.tsc.ru [National Research Tomsk State University (Russian Federation); Hu, Q. M.; Yang, R. [Chinese Academy of Sciences, Shenyang National Laboratory for Materials Science, Institute of Metal Research (China)

2016-12-15

Method of the projector augmented waves in the plane-wave basis within the generalized-gradient approximation for the exchange-correlation functional has been used to study oxygen adsorption on (001), (100), and (110) low-index surfaces of the TiAl{sub 3} alloy. It has been established that the sites that are most energetically preferred for the adsorption of oxygen are hollow (H) positions on the (001) surface and bridge (B) positions on the (110) and (100) surfaces. Structural and electronic factors that define their energy preference have been discussed. Changes in the atomic and electronic structure of subsurface layers that occur as the oxygen concentration increases to three monolayers have been analyzed. It has been shown that the formation of chemical bonds of oxygen with both components of the alloy leads to the appearance of states that are split-off from the bottoms of their valence bands, which is accompanied by the formation of a forbidden gap at the Fermi level and by a weakening of the Ti–Al metallic bonds in the alloy. On the Al-terminated (001) and (110) surfaces, the oxidation of aluminum dominates over that of titanium. On the whole, the binding energy of oxygen on the low-index surfaces with a mixed termination is higher than that at the aluminum-terminated surface. The calculation of the diffusion of oxygen in the TiAl{sub 3} alloy has shown that the lowest barriers correspond to the diffusion between tetrahedral positions in the (001) plane; the diffusion of oxygen in the [001] direction occurs through octahedral and tetrahedral positions. An increase in the concentration of aluminum in the alloy favors a reduction in the height of the energy barriers as compared to the corresponding barriers in the γ-TiAl alloy.

Modeling the neuroanatomic propagation of ALS in the spinal cord

Science.gov (United States)

Drawert, Brian; Thakore, Nimish; Mitchell, Brian; Pioro, Erik; Ravits, John; Petzold, Linda R.

2017-07-01

Recent hypotheses of amyotrophic lateral sclerosis (ALS) progression have posited a point-source origin of motor neuron death with neuroanatomic propagation either contiguously to adjacent regions, or along networks via axonal and synaptic connections. Although the molecular mechanisms of propagation are unknown, one leading hypothesis is a "prion-like" spread of misfolded and aggregated proteins, including SOD1 and TDP-43. We have developed a mathematical model representing cellular and molecular spread of ALS in the human spinal cord. Our model is based on the stochastic reaction-diffusion master equation approach using a tetrahedral discretized space to capture the complex geometry of the spinal cord. Domain dimension and shape was obtained by reconstructing human spinal cord from high-resolution magnetic resonance (MR) images and known gross and histological neuroanatomy. Our preliminary results qualitatively recapitulate the clinically observed pattern of spread of ALS thorough the spinal cord.

Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

Energy Technology Data Exchange (ETDEWEB)

Conrad Ingram; Mark Mitchell

2007-03-31

The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of a mesoporous aluminosilicate catalyst, AlSBA-15. The Al-SBA-15 mesoporous catalyst contains strong Br{umlt o}nsted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt % Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at a temperature of 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into a psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst is being evaluated for the conversion of a heavy petroleum feedstock to naphtha and middle distillates. This phase was significantly delayed during the past six months due to a serious malfunction of the fume hoods in the Clark Atlanta University's Research Center for Science and Technology, where the project is being conducted. The fume hood system was repaired and the catalyst evaluation is now underway.

Verification of the three-dimensional tetrahedral grid S{sub N} code THOR

Energy Technology Data Exchange (ETDEWEB)

Schunert, S. [Department of Nuclear Engineering, North Carolina State University (United States); Ferrer, R. [Studsvik Scandpower, Idaho Falls, ID (United States); Azmy, Y. [Department of Nuclear Engineering, North Carolina State University (United States)

2013-07-01

In this work current capabilities implemented in the novel, arbitrary-order, tetrahedral-grid short characteristics S{sub N} radiation transport code THOR are verified based on four benchmark problems: (1) A one-group Method of Manufactured Solution (MMS) problem on a cuboidal domain, (2) an infinite medium eigenvalue problem with up-scattering, (3) a homogeneous torus and (4) a bare cube eigenvalue problem with anisotropic scattering up to order three. The first benchmark problem exercises the various spatial discretization options available in THOR: The short characteristics method in conjunction with polynomial expansions of the source and face fluxes either using the complete or Lagrange family of arbitrary orders. Using the numerical solution's order of convergence test in the framework of a mesh refinement study, correct implementation of a selection of spatial expansion orders is demonstrated for two meshes with tetrahedral aspect ratios close to unity and 50. The second benchmark problem exercises the implementation of angular fluxes on reflective boundary faces that are implicit within a mesh sweep, and up-scattering. The third benchmark problem comprises cyclic dependencies within the mesh sweep thus exercising the algorithm devised for 'breaking' the cyclic dependencies. Finally, the fourth benchmark problem, a simple bare cube, is used to test correct implementation of the anisotropic scattering capability. For all test problems THOR obtains solutions that converge to the reference/exact solution with the expected rate thereby contributing to our confidence in the correctness of its tested features in the present implementation. (authors)

Binding of anions in triply interlocked coordination catenanes and dynamic allostery for dehalogenation reactions.

Science.gov (United States)

Yang, Linlin; Jing, Xu; An, Bowen; He, Cheng; Yang, Yang; Duan, Chunying

2018-01-28

By synergistic combination of multicomponent self-assembly and template-directed approaches, triply interlocked metal organic catenanes that consist of two isolated chirally identical tetrahedrons were constructed and stabilized as thermodynamic minima. In the presence of suitable template anions, the structural conversion from the isolated tetrahedral conformers into locked catenanes occurred via the cleavage of an intrinsically reversible coordination bond in each of the tetrahedrons, followed by the reengineering and interlocking of two fragments with the regeneration of the broken coordination bonds. The presence of several kinds of individual pocket that were attributed to the triply interlocked patterns enabled the possibility of encapsulating different anions, allowing the dynamic allostery between the unlocked/locked conformers to promote the dehalogenation reaction of 3-bromo-cyclohexene efficiently, as with the use of dehalogenase enzymes. The interlocked structures could be unlocked into two individual tetrahedrons through removal of the well-matched anion templates. The stability and reversibility of the locked/unlocked structures were further confirmed by the catching/releasing process that accompanied emission switching, providing opportunities for the system to be a dynamic molecular logic system.

The asc trinodal platform: Two-step assembly of triangular, tetrahedral, and trigonal-prismatic molecular building blocks

KAUST Repository

Schoedel, Alexander; Cairns, Amy; Belmabkhout, Youssef; Wojtas, Łukasz; Mohamed, Mona Hassan; Zhang, ZhenJie; Proserpio, Davide Maria; Eddaoudi, Mohamed; Zaworotko, Michael J.

2013-01-01

The self-assembly of triangular, tetrahedral, and trigonal-prismatic molecular building blocks affords the first example of a trinodal family of metal-organic materials. Four examples of isoreticular expanded and functionalized frameworks are detailed. Gas adsorption experiments validated the permanent porosity of the parent structure. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The asc trinodal platform: Two-step assembly of triangular, tetrahedral, and trigonal-prismatic molecular building blocks

KAUST Repository

Schoedel, Alexander

2013-02-10

The self-assembly of triangular, tetrahedral, and trigonal-prismatic molecular building blocks affords the first example of a trinodal family of metal-organic materials. Four examples of isoreticular expanded and functionalized frameworks are detailed. Gas adsorption experiments validated the permanent porosity of the parent structure. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Characterization of the Quaternary Thio-aluminogermanates A(AlS2)(GeS2) (A = Na, K)

KAUST Repository

Al-Bloushi, Mohammed

2015-05-27

The quaternary thioaluminogermanates Na(AlS2)(GeS2) (1) and K(AlS2)(GeS2) (2) crystallize in the tetragonal space group I4/mcm (no. 140) with unit cell parameters a = 7.4274(11) Å, c = 5.8560(12) Å for Na(AlS2)(GeS2) and a = 7.8826(2) Å, c = 5.8642(4) Å for K(AlS2)(GeS2). The crystal structure comprises of one-dimensional [(AlS2)(GeS2)]- anionic chains with Al and Ge sharing the tetrahedral site. The alkali metal cations fill the square antiprismatic voids between chains. Both 1 and 2 are semiconductors with bandgap of around 3.6 eV and 3.5 eV, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Site occupancy and magnetic study of Al3+ and Cr3+ co-substituted Y3Fe5O12

International Nuclear Information System (INIS)

Bouziane, K.; Yousif, A.; Widatallah, H.M.; Amighian, J.

2008-01-01

Single-phased polycrystalline Y 3 Fe 5-2x Al x Cr x O 12 garnet samples (x=0, 0.2, 0.4 and 0.6) have been prepared by the conventional ceramic technique. Rietveld refinement of X-ray diffraction patterns of the samples shows them to crystallize in the Ia3d space group and the corresponding lattice constant to decrease with increasing Al 3+ and Cr 3+ contents (x). Moessbauer results indicate that Cr 3+ substitutes for Fe 3+ at the octahedral sites whilst Al 3+ essentially replaces Fe 3+ at the tetrahedral sites. This result indicates that co-doping of Y 3 Fe 5 O 12 does not affect the preferential site occupancy for separate individual substitution of either Cr 3+ or Al 3+ . The magnetization measurements reveal that the Curie temperature (T c ) monotonically decreases with increasing x while the magnetic moment per unit formula decreases up to x=0.4 and then slightly increases for x=0.6. This reflects a progressive weakening of the ferrimagnetic exchange interaction between the Fe 3+ ions at octahedral and tetrahedral sites due to co-substitution. The magnetic moment was calculated using the cations distribution inferred from the Moessbauer data and the collinear ferrimagnetic model, and was found to agree reasonably with the experimentally measured value. The phenomenological amplitude crossover, characterized by the temperature T*, has also been observed in the doped YIG and briefly discussed

Effects of Composition and Structure of Mg/Al Oxides on Their Activity and Selectivity for the Condensation of Methyl Ketones

KAUST Repository

Shylesh, Sankaranarayanapillai

2016-09-22

The effects of chemical composition and pretreatment on Mg–Al hydrotalcites and alumina-supported MgO were evaluated for the gas-phase, self-condensation reaction of C3–C5 biomass-derived methyl ketones. We show that the selectivity toward the acyclic dimer enone and the cyclic enone trimer can be tuned by controlling the temperature of hydrotalcite calcination. Methyl ketone cyclization is promoted by Lewis acidic sites present on the hydrotalcite catalysts. XRD and thermal decomposition analysis reveal that the formation of periclase MgO starts above 623 K accompanied by complete disappearance of the hydrotalcite structure and is accompanied by an increase in hydroxyl condensation as the formation of well-crystallized periclase. 27Al MQMAS and 25Mg MAS NMR show that at progressively higher temperatures, Al3+ cations diffuses out of the octahedral brucite layers and incorporate into the tetrahedral and octahedral sites of the MgO matrix thereby creating defects to compensate the excess positive charge generated. The oxygen anions adjacent to the Mg2+/Al3+ defects become coordinatively unsaturated, leading to the formation of new basic sites. A kinetic isotope effect, kH/kD = 0.96, is observed at 473 K for the reaction of (CH3)2CO versus (CD3)2CO, which suggests that carbon–carbon bond formation leading to the dimer aldol product is the rate-determining step in the condensation reaction of methyl ketones. We also show that acid–base catalysts having similar reactivity and higher hydrothermal stability to that of calcined hydrotalcites can be achieved by creating defects in MgO crystallites supported alumina as a consequence of the diffusion of Al3+ cations into MgO. The physical properties of these materials are shown to be very similar to those of hydrotalcite calcined at 823 K.

Effects of Composition and Structure of Mg/Al Oxides on Their Activity and Selectivity for the Condensation of Methyl Ketones

KAUST Repository

Shylesh, Sankaranarayanapillai; Kim, Daeyoup; Gokhale, Amit A.; Canlas, Christian; Struppe, Jochem O.; Ho, Christopher R.; Jadhav, Deepak; Yeh, Alice; Bell, Alexis T.

2016-01-01

The effects of chemical composition and pretreatment on Mg–Al hydrotalcites and alumina-supported MgO were evaluated for the gas-phase, self-condensation reaction of C3–C5 biomass-derived methyl ketones. We show that the selectivity toward the acyclic dimer enone and the cyclic enone trimer can be tuned by controlling the temperature of hydrotalcite calcination. Methyl ketone cyclization is promoted by Lewis acidic sites present on the hydrotalcite catalysts. XRD and thermal decomposition analysis reveal that the formation of periclase MgO starts above 623 K accompanied by complete disappearance of the hydrotalcite structure and is accompanied by an increase in hydroxyl condensation as the formation of well-crystallized periclase. 27Al MQMAS and 25Mg MAS NMR show that at progressively higher temperatures, Al3+ cations diffuses out of the octahedral brucite layers and incorporate into the tetrahedral and octahedral sites of the MgO matrix thereby creating defects to compensate the excess positive charge generated. The oxygen anions adjacent to the Mg2+/Al3+ defects become coordinatively unsaturated, leading to the formation of new basic sites. A kinetic isotope effect, kH/kD = 0.96, is observed at 473 K for the reaction of (CH3)2CO versus (CD3)2CO, which suggests that carbon–carbon bond formation leading to the dimer aldol product is the rate-determining step in the condensation reaction of methyl ketones. We also show that acid–base catalysts having similar reactivity and higher hydrothermal stability to that of calcined hydrotalcites can be achieved by creating defects in MgO crystallites supported alumina as a consequence of the diffusion of Al3+ cations into MgO. The physical properties of these materials are shown to be very similar to those of hydrotalcite calcined at 823 K.

A composite of complex and chemical hydrides yields the first Al-based amidoborane with improved hydrogen storage properties.

Science.gov (United States)

Dovgaliuk, Iurii; Jepsen, Lars H; Safin, Damir A; Łodziana, Zbigniew; Dyadkin, Vadim; Jensen, Torben R; Devillers, Michel; Filinchuk, Yaroslav

2015-10-05

The first Al-based amidoborane Na[Al(NH2 BH3 )4 ] was obtained through a mechanochemical treatment of the NaAlH4 -4 AB (AB=NH3 BH3 ) composite releasing 4.5 wt % of pure hydrogen. The same amidoborane was also produced upon heating the composite at 70 °C. The crystal structure of Na[Al(NH2 BH3 )4 ], elucidated from synchrotron X-ray powder diffraction and confirmed by DFT calculations, contains the previously unknown tetrahedral ion [Al(NH2 BH3 )4 ](-) , with every NH2 BH3 (-) ligand coordinated to aluminum through nitrogen atoms. Combination of complex and chemical hydrides in the same compound was possible due to both the lower stability of the AlH bonds compared to the BH ones in borohydride, and due to the strong Lewis acidity of Al(3+) . According to the thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) studies, Na[Al(NH2 BH3 )4 ] releases in two steps 9 wt % of pure hydrogen. As a result of this decomposition, which was also supported by volumetric studies, the formation of NaBH4 and amorphous product(s) of the surmised composition AlN4 B3 H(0-3.6) were observed. Furthermore, volumetric experiments have also shown that the final residue can reversibly absorb about 27 % of the released hydrogen at 250 °C and p(H2 )=150 bar. Hydrogen re-absorption does not regenerate neither Na[Al(NH2 BH3 )4 ] nor starting materials, NaAlH4 and AB, but rather occurs within amorphous product(s). Detailed studies of the latter one(s) can open an avenue for a new family of reversible hydrogen storage materials. Finally, the NaAlH4 -4 AB composite might become a starting point towards a new series of aluminum-based tetraamidoboranes with improved hydrogen storage properties such as hydrogen storage density, hydrogen purity, and reversibility. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Motion Intention Analysis-Based Coordinated Control for Amputee-Prosthesis Interaction

Directory of Open Access Journals (Sweden)

Fei Wang

2010-01-01

Full Text Available To study amputee-prosthesis (AP interaction, a novel reconfigurable biped robot was designed and fabricated. In homogeneous configuration, two identical artificial legs (ALs were used to simulate the symmetrical lower limbs of a healthy person. Linear inverted pendulum model combining with ZMP stability criterion was used to generate the gait trajectories of ALs. To acquire interjoint coordination for healthy gait, rate gyroscopes were mounted on CoGs of thigh and shank of both legs. By employing principal component analysis, the measured angular velocities were processed and the motion synergy was obtained in the final. Then, one of two ALs was replaced by a bionic leg (BL, and the biped robot was changed into heterogeneous configuration to simulate the AP coupling system. To realize symmetrical stable walking, master/slave coordinated control strategy is proposed. According to information acquired by gyroscopes, BL recognized the motion intention of AL and reconstructed its kinematic variables based on interjoint coordination. By employing iterative learning control, gait tracking of BL to AL was archived. Real environment robot walking experiments validated the correctness and effectiveness of the proposed scheme.

Al-Shebab: An Al-Qaeda Affiliate Case Study (2Rev)

Science.gov (United States)

2017-10-01

deputies responsible for finance , administration, and security. Coordination among regional groups is common.10 The deputy leader of al-Shebab, Mukhtar...Maaliya (Ministry of Finance ) controlled taxation. A complex court system also emerged. Multiple training camps were built that focused on hand-to-hand...Nathan Chandler, Counterterrorism and Counterinsurgency in Somalia: Assessing the Campaign Against Al Shabaab, Rand Corporation , 2016, accessed 6/5

Brønsted acid sites based on penta-coordinated aluminum species

Science.gov (United States)

Wang, Zichun; Jiang, Yijiao; Lafon, Olivier; Trébosc, Julien; Duk Kim, Kyung; Stampfl, Catherine; Baiker, Alfons; Amoureux, Jean-Paul; Huang, Jun

2016-12-01

Zeolites and amorphous silica-alumina (ASA), which both provide Brønsted acid sites (BASs), are the most extensively used solid acid catalysts in the chemical industry. It is widely believed that BASs consist only of tetra-coordinated aluminum sites (AlIV) with bridging OH groups in zeolites or nearby silanols on ASA surfaces. Here we report the direct observation in ASA of a new type of BAS based on penta-coordinated aluminum species (AlV) by 27Al-{1H} dipolar-mediated correlation two-dimensional NMR experiments at high magnetic field under magic-angle spinning. Both BAS-AlIV and -AlV show a similar acidity to protonate probe molecular ammonia. The quantitative evaluation of 1H and 27Al sites demonstrates that BAS-AlV co-exists with BAS-AlIV rather than replaces it, which opens new avenues for strongly enhancing the acidity of these popular solid acids.

The Case for Tetrahedral Oxy-subhydride (TOSH Structures in the Exclusion Zones of Anchored Polar Solvents Including Water

Directory of Open Access Journals (Sweden)

Klaus Oehr

2014-11-01

Full Text Available We hypothesize a mechanistic model of how negatively-charged exclusion zones (EZs are created. While the growth of EZs is known to be associated with the absorption of ambient photonic energy, the molecular dynamics giving rise to this process need greater elucidation. We believe they arise due to the formation of oxy-subhydride structures (OH−(H2O4 with a tetrahedral (sp3 (OH−(H2O3 core. Five experimental data sets derived by previous researchers were assessed in this regard: (1 water-derived EZ light absorbance at specific infrared wavelengths, (2 EZ negative potential in water and ethanol, (3 maximum EZ light absorbance at 270 nm ultraviolet wavelength, (4 ability of dimethyl sulphoxide but not ether to form an EZ, and (5 transitory nature of melting ice derived EZs. The proposed tetrahedral oxy-subhydride structures (TOSH appear to adequately account for all of the experimental evidence derived from water or other polar solvents.

Anion effect on the retention of recoil atom of coordination crystalline compounds

International Nuclear Information System (INIS)

Dimotakis, P.N.; Papadopoulos, B.P.

1980-01-01

The anion effect of various cobaltic crystalline compounds - having the same cation and differing in anion -on the retention of neutron activated central cobalt atom has been studied. The cation was trans-dichloro(bis)ethylenediamine cobalt(III) and the anions were simple spherical anions (Cl - , Br - , I - ), planar anions (NO 3 - ), trigonal pyramidal anions (ClO 3 - , BrO 3 - ), tetrahedral anions (SO 4 2- , CrO 4 2- , MnO 4 - ) and linear anions (SCN - ). The cobalt-60 activity after reactor irradiation either in simple Co 2+ cation or in cobaltic complex cation determined the retention values. In all irradiations at ordinary temperature and at liquid nitrogen temperature the results showed an effect of the different anions, depending on the geometry, volume and charge, on the recombination of the recoil cobalt with the ligands in the coordination sphere. (author)

Spectroscopic criteria for identification of nuclear tetrahedral and octahedral symmetries: Illustration on a rare earth nucleus

Science.gov (United States)

Dudek, J.; Curien, D.; Dedes, I.; Mazurek, K.; Tagami, S.; Shimizu, Y. R.; Bhattacharjee, T.

2018-02-01

We formulate criteria for identification of the nuclear tetrahedral and octahedral symmetries and illustrate for the first time their possible realization in a rare earth nucleus 152Sm. We use realistic nuclear mean-field theory calculations with the phenomenological macroscopic-microscopic method, the Gogny-Hartree-Fock-Bogoliubov approach, and general point-group theory considerations to guide the experimental identification method as illustrated on published experimental data. Following group theory the examined symmetries imply the existence of exotic rotational bands on whose properties the spectroscopic identification criteria are based. These bands may contain simultaneously states of even and odd spins, of both parities and parity doublets at well-defined spins. In the exact-symmetry limit those bands involve no E 2 transitions. We show that coexistence of tetrahedral and octahedral deformations is essential when calculating the corresponding energy minima and surrounding barriers, and that it has a characteristic impact on the rotational bands. The symmetries in question imply the existence of long-lived shape isomers and, possibly, new waiting point nuclei—impacting the nucleosynthesis processes in astrophysics—and an existence of 16-fold degenerate particle-hole excitations. Specifically designed experiments which aim at strengthening the identification arguments are briefly discussed.

Highly active sulfided CoMo catalysts supported on (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxides

Energy Technology Data Exchange (ETDEWEB)

Escobar, José, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, Col. San Bartolo Atepehuacan, Gustavo A. Madero, México, D.F. 07730 (Mexico); De Los Reyes, José A., E-mail: jarh@xanum.uam.mx [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Ulín, Carlos A. [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Barrera, María C., E-mail: mcbdgavilan@gmail.com [Facultad de Ciencias Químicas, Universidad Veracruzana, Av. Universidad km. 7.5, Col. Santa Isabel, Coatzacoalcos, Veracruz, México, D.F. 96538 (Mexico)

2013-12-16

(ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxide at 20 mol% Al{sub 2}O{sub 3} (80% ZrO{sub 2}–TiO{sub 2}, in turn at 40–60 mol ratio) prepared by controlled co-precipitation (by urea thermal decomposition) of zirconium (ZrOCl{sub 2}·8H{sub 2}O) and titanium (TiCl{sub 4}) chlorides over a ground alumina substrate constitutes a promising material to be used as carrier of sulfided hydrodesulfurization (HDS) catalysts. After calcining (at 500 °C), the ternary oxide presented textural properties (S{sub g} = 387 m{sup 2} g{sup −1}, V{sub p} = 0.74 ml g{sup −1}, mean pore diameter = 7.6 nm) suitable to its utilization as carrier of catalysts applied in the oil-derived middle distillates HDS. As determined by temperature programmed-reduction and Raman and UV–vis spectroscopies ZrO{sub 2}–TiO{sub 2} deposition over alumina substrate resulted in decreased proportion of Mo{sup 6+} species in tetrahedral coordination on the oxidic impregnated material. As those species constitute hardly reducible precursors, their diminished concentration could be reflected in enhanced amount of Mo species susceptible of activation by sulfiding (H{sub 2}S/H{sub 2} at 400 °C) over our ternary carrier. Limiting the concentration of zirconia-titania (at 40–60 mol ratio) to 20 mol% in the mixed oxides support allowed the preparation of highly active promoted (by cobalt, at Co/(Co + Mo) = 0.3) MoS{sub 2} phase (at 2.8 atoms/nm{sup 2}), that formulation showing excellent properties in hydrodesulfurization (HDS) of both dibenzothiophene and highly-refractory 4,6-dimethyl-dibenzothiophene. Due to alike yields to various HDS products over CoMo/(ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} and the corresponding Al{sub 2}O{sub 3}-supported formulation, presence of similar actives sites over those catalysts was strongly suggested. It seemed that enhanced concentration of octahedral Mo{sup 6+} over the oxidic impregnated precursor with (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3

Cu and Al co-substituted cobalt ferrite: structural analysis ...

Indian Academy of Sciences (India)

... 400 cm−1 (v2). They are attributed to the tetrahedral and octahedral group complexes of the spinel .... Intensity (a.u.). 2 (degree) ... Heating iron-hydroxides in air is known to yield haematite ... M–O distance in tetrahedral and octahedral sites.

Ionizing radiation effects in MgAl sub 2 O sub 4. Efecto de la radiacion ionizante en MgAl2 O4

Energy Technology Data Exchange (ETDEWEB)

Ibarra, A.

1990-11-01

The effect of ionizing radiation in MgAl{sub 2}O{sub 4} has been studied, paying special interest to the influence of the high concentration of intrinsic defects of this material. Optical absorption, ESR, photoluminescence, radioluminescence, and thermoluminescence are the main techniques used. The ionizing radiation induces formation of V centres. During the work its characteristics (structure, thermal stability, absorption spectra, etc.) has been studied. The thermoluminescence spectra allowed the discovery of several charge release processes between 85 and 650 K, all of them associated to electron release. The V-centres and several impurities (Cr, Mn,...) appear as recombination centres. The obtained data show that the kinetic of these charge release processes is regulated by the presence of a point defect with a very high concentration. This defect is an electron trap and its structure is an Al ion in a lattice site of tetrahedral symmetry. (Author)

Structural evolution in nanoporous anodic aluminium oxide

International Nuclear Information System (INIS)

Rocca, Emmanuel; Vantelon, Delphine; Reguer, Solenn; Mirambet, François

2012-01-01

Nanoporous and self-organized layers of aluminium alloys are used in many applications as membranes, templates for nanometric objects or corrosion protection for aluminium alloys. The use of this nanometric structure widely remains empirical, especially in the case of very small pores ( 4 into AlO 6 cluster and a partial release of sulphate ions are an important chemical transformation of the amorphous structure. This structural transformation defines the chemistry (pH and surface charge) inside the nanopores, the ageing behaviour and the possible incorporation or diffusion of chemical species in the nanostructure. Highlights: ► Investigations of local chemical environment of aluminium atoms in anodic aluminium oxide. ► The oxide structure is constituted by 2/3 of aluminium in tetrahedral coordination 1/3 in octahedral coordination. ► In contact with water, AlO 4 clusters are transformed into AlO 6 cluster and the aluminium sulphate bonds are hydrolysed. ► These transformations induce a pH decrease inside the nanostructure.

Amorphous-tetrahedral diamondlike carbon layered structures resulting from film growth energetics

Science.gov (United States)

Siegal, M. P.; Barbour, J. C.; Provencio, P. N.; Tallant, D. R.; Friedmann, T. A.

1998-08-01

High-resolution transmission electron microscopy (HRTEM) shows that amorphous-tetrahedral diamondlike carbon (a-tC) films grown by pulsed-laser deposition on Si(100) consist of three-to-four layers, depending on the growth energetics. We estimate the density of each layer using both HRTEM image contrast and Rutherford backscattering spectrometry. The first carbon layer and final surface layer have relatively low density. The bulk of the film between these two layers has higher density. For films grown under the most energetic conditions, there exists a superdense a-tC layer between the interface and bulk layers. The density of all four layers, and the thickness of the surface and interfacial layers, correlate well with the energetics of the depositing carbon species.

Coordination Behavior of Ni2+, Cu2+, and Zn2+ in Tetrahedral 1-Methylimidazole Complexes: A DFT/CSD Study

OpenAIRE

Tetteh, Samuel

2018-01-01

The interaction between nickel (Ni2+), copper (Cu2+), and zinc (Zn2+) ions and 1-methylimidazole has been studied by exploring the geometries of eleven crystal structures in the Cambridge Structural Database (CSD). The coordination behavior of the respective ions was further investigated by means of density functional theory (DFT) methods. The gas-phase complexes were fully optimized using B3LYP/GENECP functionals with 6-31G∗ and LANL2DZ basis sets. The Ni2+ and Cu2+ complexes show distorted ...

Rietveld profile analysis of calcined AlPO/sub 4/-11 using pulsed neutron powder diffraction

Energy Technology Data Exchange (ETDEWEB)

Richardson, J.W. Jr.; Pluth, J.J.; Smith, J.V.

1988-08-01

Aluminium phosphate, AlPO/sub 4/, M/sub r/=121.95, orthorhombic, Icmm (disordered Al, P), Icm2 (ordered Al, P), a=13.5333(8), b=18.4845(10), c=8.3703(4) A, V=2094 A/sup 3/, Z=20, D/sub x/=1.93 g cm/sup -3/, T approx. = 295 K, R/sub wp/=0.031, R/sub F//sup 2/=0.109 (Icmm) and R/sub wp/=0.027, R/sub F//sup 2/=0.058 (Icm2) for 1017 independent reflections. Sample calcined at 873 K and dehydrated at 573 K. Time-of-flight neutron powder diffraction data were taken on the GPPD diffractometer at the Argonne National Laboratory Intense Pulsed Neutron Source. The structure was refined by Rietveld profile analysis in the range d=0.86-3.91 A in two space groups: Icmm assuming no ordering of Al and P, and Icm2 assuming strict alternation of Al and P on tetrahedral nodes. (orig./BHo).

Location of Framework Al Atoms in the Channels of ZSM-5: Effect of the (Hydrothermal) Synthesis.

Science.gov (United States)

Pashkova, Veronika; Sklenak, Stepan; Klein, Petr; Urbanova, Martina; Dědeček, Jiří

2016-03-14

(27) Al 3Q MAS NMR and UV/Vis spectroscopy with bare Co(II) ions as probes of Al pairs in the zeolite framework were employed to analyze the location of framework Al atoms in the channel system of zeolite ZSM-5. Furthermore, the effect of Na(+) ions together with tetrapropylammonium cation (TPA(+)) in the ZSM-5 synthesis gel on the location of Al in the channel system was investigated. Zeolites prepared using exclusively TPA(+) as a structure-directing agent (i.e., in the absence of Na(+) ions) led to 55-90% of Al atoms located at the channel intersection, regardless the presence or absence of Al pairs [Al-O-(Si-O)2 -Al sequences in one ring] in the zeolite framework. The presence of Na(+) ions in the synthesis gel did not modify the Al location at the channel intersection (55-95% of Al atoms) and led only to changes in i) the distribution of framework Al atoms between Al pairs (decrease) and single isolated Al atoms (increase), and ii) the siting of Al in distinguishable framework tetrahedral sites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rietveld refinement of the mixed boracite Fe1.59Zn1.41B7O13Br

Directory of Open Access Journals (Sweden)

Sandra Ulloa-Godínez

2009-11-01

Full Text Available The structural characterization of the new iron–zinc heptaborate bromide with composition Fe1.59Zn1.41B7O13Br, prepared by chemical transport is reported. A rigid-body model with constrained generalized coordinates was defined in order to hold the positions of the B atoms at reasonable interatomic distances that typically would reach unacceptable values because of the weak scattering power of boron. There are three independent sites for the B atoms of which two are tetrahedrally coordinated. The bond-valence sum around the third B atom, located on a threefold rotation axis, was calculated considering two cases of coordination of boron with oxygens: trigonal-planar and tetrahedral. The contribution of the fourth O atom to the bond-valence sum was found to be only 0.06 v.u., indicating the presence of a very weak bond in the right position to have a distorted tetrahedral coordination in favour of the trigonal-planar coordination for the third B atom. X-ray fluorescence (XRF was used to determinate the Fe/Zn ratio.

Rietveld refinement of the mixed boracite Fe(1.59)Zn(1.41)B(7)O(13)Br.

Science.gov (United States)

Ulloa-Godínez, Sandra; Rosales, Ivonne; Bucio, Lauro; Farías, Mario H; Campa-Molina, Jorge

2009-10-31

The structural characterization of the new iron-zinc hepta-borate bromide with composition Fe(1.59)Zn(1.41)B(7)O(13)Br, prepared by chemical transport is reported. A rigid-body model with constrained generalized coordinates was defined in order to hold the positions of the B atoms at reasonable inter-atomic distances that typically would reach unacceptable values because of the weak scattering power of boron. There are three independent sites for the B atoms of which two are tetra-hedrally coordinated. The bond-valence sum around the third B atom, located on a threefold rotation axis, was calculated considering two cases of coordination of boron with oxygens: trigonal-planar and tetrahedral. The contribution of the fourth O atom to the bond-valence sum was found to be only 0.06 v.u., indicating the presence of a very weak bond in the right position to have a distorted tetra-hedral coordination in favour of the trigonal-planar coordination for the third B atom. X-ray fluorescence (XRF) was used to determinate the Fe/Zn ratio.

The application of Car-Parrinello molecular dynamics to the study of tetrahedral amorphous carbon

International Nuclear Information System (INIS)

McKenzie, D.R.; McCulloch, D.G.; Goringe, C.M.

1998-01-01

The Car-Parrinello method for carrying out molecular dynamics enables the forces between atoms to be calculated by solving Schroedinger's equation for the valence electrons using Density Functional Theory. The method is capable of giving good structural predictions for amorphous network solids by quenching from the melt, even in situations where the bonding changes from one site to another. In amorphous carbon where, depending on its environment, carbon may show sp 2 or sp 3 bonds. The method is applied here to the study of network solids using the example of tetrahedral amorphous carbon

Coordinating Robot Teams for Disaster Relief

Science.gov (United States)

2015-05-01

eventually guide vehicles in cooperation with its Operator(s), but in this paper we assume static mission goals, a fixed number of vehicles, and a...is tedious and error prone. Kress-Gazit et al. (2009) instead synthesize an FSA from an LTL specification using a game theory approach (Bloem et al...helping an Operator coordinate a team of vehicles in Disaster Relief. Acknowledgements Thanks to OSD ASD (R&E) for sponsoring this research. The

Analytical investigation of AlCl[3]/SO[2]Cl[2] catholyte materials for secondary fuze reserve batteries.

Energy Technology Data Exchange (ETDEWEB)

Butler, Paul Charles; Rodriguez, Mark Andrew; Segall, Judith M.; Malizia, Louis A., Jr.; Cherry, Brian Ray; Andrews, Nicholas L.; Clark, Nancy H.; Alam, Todd Michael; Ingersoll, David T.; Tallant, David Robert; Simpson, Regina Lynn; Boyle, Timothy J.; Garcia, Manuel Joseph

2004-05-01

Exploration of the fundamental chemical behavior of the AlCl{sub 3}/SO{sub 2}Cl{sub 2} catholyte system for the ARDEC Self-Destruct Fuze Reserve Battery Project under accelerated aging conditions was completed using a variety of analytical tools. Four different molecular species were identified in this solution, three of which are major. The relative concentrations of the molecular species formed were found to depend on aging time, initial concentrations, and storage temperature, with each variable affecting the kinetics and thermodynamics of this complex reaction system. We also evaluated the effect of water on the system, and determined that it does not play a role in dictating the observed molecular species present in solution. The first Al-containing species formed was identified as the dimer [Al({mu}-Cl)Cl{sub 2}]{sub 2}, and was found to be in equilibrium with the monomer, AlCl{sub 3}. The second species formed in the reaction scheme was identified by single crystal X-ray diffraction studies as [Cl{sub 2}Al({mu}-O{sub 2}SCl)]{sub 2} (I), a scrambled AlCl{sub 3}{center_dot}SO{sub 2} adduct. The SO{sub 2}(g) present, as well as CL{sub 2}(g), was formed through decomposition of SO{sub 2}CL{sub 2}. The SO{sub 2}(g) generated was readily consumed by AlCl{sub 3} to form the adduct 1 which was experimentally verified when 1 was also isolated from the reaction of SO{sub 2}(g) and AlCl {sub 3}. The third species found was tentatively identified as a compound having the general formula {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n}. This was based on {sup 27}Al NMR data that revealed a species with tetrahedrally coordinated Al metal centers with increased oxygen coordination and the fact that the precipitate, or gel, that forms over time was shown by Raman spectroscopic studies to possess a component that is consistent with SOCl{sub 2}. The precursor to the precipitate should have similar constituents, thus the assignment of {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2

Polarity Control in Group-III Nitrides beyond Pragmatism

Science.gov (United States)

Mohn, Stefan; Stolyarchuk, Natalia; Markurt, Toni; Kirste, Ronny; Hoffmann, Marc P.; Collazo, Ramón; Courville, Aimeric; Di Felice, Rosa; Sitar, Zlatko; Vennéguès, Philippe; Albrecht, Martin

2016-05-01

Controlling the polarity of polar semiconductors on nonpolar substrates offers a wealth of device concepts in the form of heteropolar junctions. A key to realize such structures is an appropriate buffer-layer design that, in the past, has been developed by empiricism. GaN or ZnO on sapphire are prominent examples for that. Understanding the basic processes that mediate polarity, however, is still an unsolved problem. In this work, we study the structure of buffer layers for group-III nitrides on sapphire by transmission electron microscopy as an example. We show that it is the conversion of the sapphire surface into a rhombohedral aluminum-oxynitride layer that converts the initial N-polar surface to Al polarity. With the various AlxOyNz phases of the pseudobinary Al2O3 -AlN system and their tolerance against intrinsic defects, typical for oxides, a smooth transition between the octahedrally coordinated Al in the sapphire and the tetrahedrally coordinated Al in AlN becomes feasible. Based on these results, we discuss the consequences for achieving either polarity and shed light on widely applied concepts in the field of group-III nitrides like nitridation and low-temperature buffer layers.

Self-assembly of a tetrahedral 58-nuclear barium vanadium oxide cluster.

Science.gov (United States)

Kastner, Katharina; Puscher, Bianka; Streb, Carsten

2013-01-07

We report the synthesis and characterization of a molecular barium vanadium oxide cluster featuring high nuclearity and high symmetry. The tetrameric, 2.3 nm cluster H(5)[Ba(10)(NMP)(14)(H(2)O)(8)[V(12)O(33)](4)Br] is based on a bromide-centred, octahedral barium scaffold which is capped by four previously unknown [V(12)O(33)](6-) clusters in a tetrahedral fashion. The compound represents the largest polyoxovanadate-based heterometallic cluster known to date. The cluster is formed in organic solution and it is suggested that the bulky N-methyl-2-pyrrolidone (NMP) solvent ligands allow the isolation of this giant molecule and prevent further condensation to a solid-state metal oxide. The cluster is fully characterized using single-crystal XRD, elemental analysis, ESI mass spectrometry and other spectroscopic techniques.

A Deep Penetration Problem Calculation Using AETIUS:An Easy Modeling Discrete Ordinates Transport Code UsIng Unstructured Tetrahedral Mesh, Shared Memory Parallel

Science.gov (United States)

KIM, Jong Woon; LEE, Young-Ouk

2017-09-01

As computing power gets better and better, computer codes that use a deterministic method seem to be less useful than those using the Monte Carlo method. In addition, users do not like to think about space, angles, and energy discretization for deterministic codes. However, a deterministic method is still powerful in that we can obtain a solution of the flux throughout the problem, particularly as when particles can barely penetrate, such as in a deep penetration problem with small detection volumes. Recently, a new state-of-the-art discrete-ordinates code, ATTILA, was developed and has been widely used in several applications. ATTILA provides the capabilities to solve geometrically complex 3-D transport problems by using an unstructured tetrahedral mesh. Since 2009, we have been developing our own code by benchmarking ATTILA. AETIUS is a discrete ordinates code that uses an unstructured tetrahedral mesh such as ATTILA. For pre- and post- processing, Gmsh is used to generate an unstructured tetrahedral mesh by importing a CAD file (*.step) and visualizing the calculation results of AETIUS. Using a CAD tool, the geometry can be modeled very easily. In this paper, we describe a brief overview of AETIUS and provide numerical results from both AETIUS and a Monte Carlo code, MCNP5, in a deep penetration problem with small detection volumes. The results demonstrate the effectiveness and efficiency of AETIUS for such calculations.

Irradiation-induced changes in the local environment of Si and Al in LnSiAlON glasses as probed by {sup 27}Al and {sup 29}Si NMR

Energy Technology Data Exchange (ETDEWEB)

Sangleboeuf, J.C. [Univ Rennes 1, CNRS, FRE 2717, LARMAUR, F-35042 Rennes (France); Dauce, R.; Le Floch, M.; Verdier, P. [Univ Rennes 1, Inst Chem, UMR 6512, CNRS, F-35042 Rennes (France); Dauce, R. [CE Cadarache, DEC/SESC, F-13018 St Paul Les Durance (France)

2007-03-15

Two compounds have been studied: an oxide glass from the Y-Si-Al-O system and an oxynitride glass from the Y-Si-Al-O-N system, both bombarded with Sn-ions (975 MeV, fluences ranging from 10{sup 12} to 2.7 * 10{sup 13} Sn/cm{sup 2}). The changes in the environment of the silicon and the aluminium were investigated using NMR spectroscopy. Irradiation by Sn ions leads to a loss of nitrogen in the silicon and probably the aluminium environments. Part of the aluminium changes from a network former coordination to a network modifier coordination while the oxide silicate network exhibits a higher cross-linking due to an increase of the population of bridging oxygen. Part of the aluminium in five-fold coordination is formed at the expense of aluminium in six-fold coordination in the case of the oxynitride glass and the changes in the silicon environment occur at lower fluences than for the oxide glass. (authors)

Control Coordination of Large Scale Hereditary Systems.

Science.gov (United States)

1985-07-01

Theory - A Hilbert Space Approach, (Academic Press, New York, 1982). [4] W. Findeisen , F. N. Bailey, M. Brdys, K Malinowski, P. Tatjewski and A. Wozniak... Findeisen et al. (1980), in the sense that local models are used in the design of component control laws and a higher level coordination problem is...Vol. 1, pp. 590-591, 1985. 3. W. Findeisen , F.N. Bailley, M. Brdys, K. Malinowski, P. Tatjewski and A. Wozniak, Control Coordination in Hierarchical

Smart Sensing Methodology for Object Identification Using Circularly Polarized Luminescence from Coordination-Driven Self-Assembly.

Science.gov (United States)

Imai, Yuki; Nakano, Yuka; Kawai, Tsuyoshi; Yuasa, Junpei

2018-05-21

This work demonstrates a potential use of circularly polarized luminescence for object identification methodology in a sensor application. Towards this aim, we have developed new luminescence probes using pyrene derivatives as sensor luminophores. The probes [(R,R)- and (S,S)-Im2Py] contain two chiral imidazole moieties at 1,6-positions through ethynyl spacers (the angle between the spacers is close to 180°). The probe molecules spontaneously self-assemble into chiral stacks (P or M helicity) upon coordination to metal ions with tetrahedral coordination preference (e.g., Zn2+). The chiral probes display neither circular dichroism (CD) nor circularly polarized luminescence (CPL) in the absence of metal ions. However, [(R,R)- and (S,S)-Im2Py] begins to exhibit intense chiroptical activity (CD and CPL) upon self-assembly with Zn2+ ions. The unique chiroptical properties of [(R,R)- and (S,S)-Im2Py] with chemical stimuli-responsibility are capable of demonstrating the new sensing methodology using the CPL signal as detection output, enabling us to discriminate between a signal from the target analyte and that from non-target species. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Delaunay Tetrahedralization of the Heart Based on Integration of Open Source Codes

International Nuclear Information System (INIS)

Pavarino, E; Neves, L A; Machado, J M; Momente, J C; Zafalon, G F D; Pinto, A R; Valêncio, C R; Godoy, M F de; Shiyou, Y; Nascimento, M Z do

2014-01-01

The Finite Element Method (FEM) is a way of numerical solution applied in different areas, as simulations used in studies to improve cardiac ablation procedures. For this purpose, the meshes should have the same size and histological features of the focused structures. Some methods and tools used to generate tetrahedral meshes are limited mainly by the use conditions. In this paper, the integration of Open Source Softwares is presented as an alternative to solid modeling and automatic mesh generation. To demonstrate its efficiency, the cardiac structures were considered as a first application context: atriums, ventricles, valves, arteries and pericardium. The proposed method is feasible to obtain refined meshes in an acceptable time and with the required quality for simulations using FEM

Interpolation Error Estimates for Mean Value Coordinates over Convex Polygons.

Science.gov (United States)

Rand, Alexander; Gillette, Andrew; Bajaj, Chandrajit

2013-08-01

In a similar fashion to estimates shown for Harmonic, Wachspress, and Sibson coordinates in [Gillette et al., AiCM, to appear], we prove interpolation error estimates for the mean value coordinates on convex polygons suitable for standard finite element analysis. Our analysis is based on providing a uniform bound on the gradient of the mean value functions for all convex polygons of diameter one satisfying certain simple geometric restrictions. This work makes rigorous an observed practical advantage of the mean value coordinates: unlike Wachspress coordinates, the gradient of the mean value coordinates does not become large as interior angles of the polygon approach π.

Malamih al-Ashwat al-'Arabiyyah wa Makharijaha

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Amrah Muhammad Kasim

2015-12-01

Full Text Available This writing discusses on al-ashwat al-‘arabiyyah that is known with “phonetic” term. It talks and interprets makharij al-huruf or place for producing sounds and also processing production of sounds by parts of mouth in Arabic language. The problems of sounds and its systems in Arabic language have been conducted by the scholars of al-ashwat al-‘arabiyyah attractively, neatly, and detail and gotten ahead the phonetic western scholars. Part of their analysis results formulate the study about al-ashwat al-sakinah (al-Shamit is known with vocal and consonant sounds in research questions shawait – shawamit. Ibnu Jinni has formulated “harakat”(wowel in Arabic language and dimension of letter  mad and liyn on alif  letter - waw - ya’ (ا و ي, from these letters create  harakat fathah, dammah, and kasrah. Moreover, in this writing also exist the description of hija’i letters and its makhraj that are correct from parts of mouth and the unity of coordinative sounds that produce sounds in morphemes arrangement, in one word that produces meaning. The result of phonological study has divided al-ashwat to be kinds of sound like the pronounced sounds, produced sounds from mouth, and heard sound.

Synthesis, characterization and crystal structure of a 2-(diethylaminomethylindole ligated dimethylaluminium complex

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Logan E. Shephard

2015-10-01

Full Text Available The title compound, [Al(CH32(C13H17N2] (systematic name; {2-[(diethylaminomethyl]indol-1-yl-κ2N,N′}dimethylaluminium, was prepared by methane elimination from the reaction of 2-(diethylaminomethylindole and trimethylaluminium. The complex crystallizes readily from a concentrated toluene solution in high yield. The asymmetric unit contains two crystallographically independent molecules. Each molecule has a four-coordinate aluminium atom that has pseudo-tetrahedral geometry. C—H...π interactions link the independent molecules into chains extending along the b-axis direction.

Coordination diversity of new mononucleating hydrazone in 3d metal complexes: Synthesis, characterization and structural studies

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RAJESH S. BALIGAR

2006-12-01

Full Text Available The mononucleating hydrazone ligand LH3, a condensation product of salicyloylhydrazine and (2-formylphenoxyacetic acid, was synthesized and its coordination behavior with first row transition metal(II ions was investigated by isolating and elucidating the structure of the complexes using elemental analysis, conductivity and magnetic susceptibility measurements, as well as IR, 1H-NMR, electronic and EPR spectral techniques. The ligand forms mononuclear metal(II complexes of the type [CoLH(H2O2], [NiLH(H2O2, [CuLH] and [ZnLH]. The ligand field parameters, Dq, B and b values, in the case of the cobalt and nickel complexes support not only the octahedral geometry around the metal ion, but also imply the covalent nature of the bonding in the complexes. The EPR study revealed the presence of a spin exchange interaction in the solid copper complex and the covalent nature of the bonding. The 1H-NMR study of the zinc(II complex indicated the non-involvement of the COOH group in the coordination. The physico-chemical study supports for the presence of octahedral geometry around cobalt(II, nickel(II and tetrahedral geometry around copper(II and zinc(II ions.

Influence of aluminum addition in the framework of MCM-41 mesoporous molecular sieve synthesized by non-hydrothermal method in an alkali-free system

International Nuclear Information System (INIS)

La-Salvia, Nathália; Lovón-Quintana, Juan José; Lovón, Adriana Siviero Pagani; Valença, Gustavo Paim

2017-01-01

Purely siliceous MCM-41 and Al-containing MCM-41 (Al-MCM-41) mesoporous materials were synthesized by non-hydrothermal method in alkali-free ions medium at room temperature and short reaction times. Under these synthesis conditions, it was also investigated the influence of Al incorporation in the crystal structure of MCM-41. The solids were characterized by ICP-OES, AAS, N 2 adsorption at 77 K, XRD, TEM, NH3 -TPD, 27 Al and 29 Si-MAS-NMR, FT-IR and TGA. The resulting mesoporous materials showed a well-defined hexagonally ordered pore geometry maintaining a uniform and unimodal pore size distribution with high specific surface areas (1000-1400 m 2 g -1 ). The Al +3 ions were introduced successfully in the structure of the purely siliceous MCM-41 expanding the unit cell parameter and forming four-coordinated Al species, and in a less extent, forming six-coordinated Al species. In addition, the surface acidity of the MCM-41 increased with Al loading. Contrary, the presence of Al in the MCM-41 mesoporous structure resulted in a decrease of the crystallinity and specific surface area possibly due to the presence of Al species in highly distorted tetrahedral structures and Al extra-framework or amorphous alumina occluded in the pores. The MCM-41 type mesoporous materials obtained in this work show similar characteristics of those synthesized by conventional hydrothermal methods. (author)

Polyamorphism in tetrahedral substances: Similarities between silicon and ice

Science.gov (United States)

Garcez, K. M. S.; Antonelli, A.

2015-07-01

Tetrahedral substances, such as silicon, water, germanium, and silica, share various unusual phase behaviors. Among them, the so-called polyamorphism, i.e., the existence of more than one amorphous form, has been intensively investigated in the last three decades. In this work, we study the metastable relations between amorphous states of silicon in a wide range of pressures, using Monte Carlo simulations. Our results indicate that the two amorphous forms of silicon at high pressures, the high density amorphous (HDA) and the very high density amorphous (VHDA), can be decompressed from high pressure (˜20 GPa) down to the tensile regime, where both convert into the same low density amorphous. Such behavior is also observed in ice. While at high pressure (˜20 GPa), HDA is less stable than VHDA, at the pressure of 10 GPa both forms exhibit similar stability. On the other hand, at much lower pressure (˜5 GPa), HDA and VHDA are no longer the most stable forms, and, upon isobaric annealing, an even less dense form of amorphous silicon emerges, the expanded high density amorphous, again in close similarity to what occurs in ice.

Hydroxyapatite/MCM-41 and SBA-15 Nano-Composites: Preparation, Characterization and Applications

Science.gov (United States)

Anunziata, Oscar A.; Martínez, Maria L.; Beltramone, Andrea R.

2009-01-01

Composites of hydroxyapatite (HaP) and highly ordered large pore mesoporous silica molecular sieves such as, Al-SBA-15 and Al-MCM-41 (denoted as SBA-15 and MCM-41, respectively) were developed, characterized by XRD, BET, FTIR, HRTEM and NMR-MAS, and applied to fluoride retention from contaminated water. The proposed procedure by a new route to prepare the HaP/SBA-15 and HaP/MCM-41, composites generates materials with aluminum only in tetrahedral coordination, according to the 27Al NMR-MAS results. Free OH- groups of HaP nanocrystals, within the hosts, allowed high capacity fluoride retention. The activity of fluoride retention using HaP/MCM-41 or HaP/SBA-15 was 1-2 orders of magnitude greater, respectively, than with pure HaP.

Site occupancy and magnetic study of Al{sup 3+} and Cr{sup 3+} co-substituted Y{sub 3}Fe{sub 5}O{sub 12}

Energy Technology Data Exchange (ETDEWEB)

Bouziane, K. [Department of Physics, College of Science, Sultan Qaboos University, P.O. Box 36, PC 123, Muscat, Sultanate of Oman (Oman)], E-mail: bouzi@squ.edu.om; Yousif, A.; Widatallah, H.M. [Department of Physics, College of Science, Sultan Qaboos University, P.O. Box 36, PC 123, Muscat, Sultanate of Oman (Oman); Amighian, J. [Department of Physics, University of Isfahan, Isfahan (Iran, Islamic Republic of)

2008-10-15

Single-phased polycrystalline Y{sub 3}Fe{sub 5-2x}Al{sub x}Cr{sub x}O{sub 12} garnet samples (x=0, 0.2, 0.4 and 0.6) have been prepared by the conventional ceramic technique. Rietveld refinement of X-ray diffraction patterns of the samples shows them to crystallize in the Ia3d space group and the corresponding lattice constant to decrease with increasing Al{sup 3+} and Cr{sup 3+} contents (x). Moessbauer results indicate that Cr{sup 3+} substitutes for Fe{sup 3+} at the octahedral sites whilst Al{sup 3+} essentially replaces Fe{sup 3+} at the tetrahedral sites. This result indicates that co-doping of Y{sub 3}Fe{sub 5}O{sub 12} does not affect the preferential site occupancy for separate individual substitution of either Cr{sup 3+} or Al{sup 3+}. The magnetization measurements reveal that the Curie temperature (T{sub c}) monotonically decreases with increasing x while the magnetic moment per unit formula decreases up to x=0.4 and then slightly increases for x=0.6. This reflects a progressive weakening of the ferrimagnetic exchange interaction between the Fe{sup 3+} ions at octahedral and tetrahedral sites due to co-substitution. The magnetic moment was calculated using the cations distribution inferred from the Moessbauer data and the collinear ferrimagnetic model, and was found to agree reasonably with the experimentally measured value. The phenomenological amplitude crossover, characterized by the temperature T*, has also been observed in the doped YIG and briefly discussed.

On the origin of the giant magnetic moment of the Al-Mn quasicrystals

Directory of Open Access Journals (Sweden)

Bocharov P.V.

2011-05-01

Full Text Available Ab initio calculations of magnetic moments for icosahedral clusters contained in crystal structures Al10Mn3, Al5Co2, Al17Mn4 (Al13Cr4Si4-type fulfilled in the framework of Density Functional Theory. The AlMn cluster having the trigonal D3h symmetry with the triangle of Mn ions in the interior has the moment being equal to three magnetic moments of a single manganese ion (4.4 μB, the moment of the tetrahedral Td cluster with the Mn tetrahedron in the interior is equal approximately to twelve magnetic moments of the single manganese ion (15.5 μB. The magnetic moment of icosahedral Al-Co clusters having the same configuration is equal to zero. The magnetic moments of the rod assembled from the icosahedral clusters with the sequence Td D3h - Td was found to be 20.5 μB. This value permits to explain the giant magnetic moment of icosahedral and decagonal Al-Mn quasicrystals and gives the indirect evidence to the hierarchical model of the quasicrystals structure proposed by the authors recently. An arrangement of magnetic moment carriers in the interior of the aluminum shell of icosahedral clusters permits to suggest the interaction between contacting manganese ions as the main origin of the giant magnetic moment of the Al-Mn quasicrystals.

Potential of AlN nanostructures as hydrogen storage materials.

Science.gov (United States)

Wang, Qian; Sun, Qiang; Jena, Puru; Kawazoe, Yoshiyuki

2009-03-24

The capability of AlN nanostructures (nanocages, nanocones, nanotubes, and nanowires) to store hydrogen has been studied using gradient-corrected density functional theory. In contrast to bulk AlN, which has the wurtzite structure and four-fold coordination, the Al sites in AlN nanostructures are unsaturated and have two- and three-fold coordination. Each Al atom is capable of binding one H(2) molecule in quasi-molecular form, leading to 4.7 wt % hydrogen, irrespective of the topology of the nanostructures. With the exception of AlN nanotubes, energetics does not support the adsorption of additional hydrogen. The binding energies of hydrogen to these unsaturated metal sites lie in the range of 0.1-0.2 eV/H(2) and are ideal for applications under ambient thermodynamic conditions. Furthermore, these materials do not suffer from the clustering problem that often plagues metal-coated carbon nanostructures.

Comprehensive understanding of mole concept subject matter according to the tetrahedral chemistry education (empirical study on the first-year chemistry students of Technische Universität Dresden)

Science.gov (United States)

Prabowo, D. W.; Mulyani, S.; van Pée, K.-H.; Indriyanti, N. Y.

2018-05-01

This research aims to apprehend: (1) the shape of tetrahedral chemistry education which is called the future of chemistry education, (2) comprehensive understanding of chemistry first-year students of Technische Universität Dresden according to the chemistry education’s tetrahedral shape on mole concept subject matter. This research used quantitative and qualitative; paper and pencil test and interview. The former was conducted in the form of test containing objective test instrument. The results of this study are (1) learning based on tetrahedral shape of chemistry education put the chemical substance (macroscopic), symbolic representation (symbol), and its process (molecular) in the context of human beings (human element) by integrating content and context, without emphasis on one thing and weaken another, (2) first-year chemistry students of Technische Universität Dresden have comprehensively understood the mole concept associated with the context of everyday life, whereby students are able to find out macroscopic information from statements that are contextual to human life and then by using symbols and formulas are able to comprehend the molecular components as well as to interpret and analyse problems effectively.

Synthesis, coordination and biological aspects of organotin(IV derivatives of 4-[(2,4-dinitrophenylamino]-4-oxo-2-butenoic acid and 2-{[(2,4-dinitrophenylamino]carbonyl}benzoic acid

Directory of Open Access Journals (Sweden)

KHADIJA SHAHID

2009-02-01

Full Text Available New series of organotin(IV complexes of aniline derivatives, R2SnL2 and R3SnL [where R = Me, n-Bu, Ph, n-Oct] have been synthesized by the reaction of HL1 and HL2 with respective organotin halides or oxides. Experimental details for the preparation and characterization (including elemental analysis, IR and multinuclear NMR (1H-, 13C- and 119Sn- spectra in CDCl3 and EI mass spectra of both series are provided. The binding sites of the ligands were identified by means of FTIR spectroscopic measurements. It was found that in all cases the organotin(IV moiety reacts with the oxygen of COO– group to form new complexes. In the diorganotin complexes, the COO– group is coordinated to the organotin(IV centres in a bidentate manner in the solid state. The 119Sn NMR data and the nJ(13C‑119/117Sn coupling constant support the tetrahedral coordination geometry of the organotin complexes in non-coordinating solvents. Biological activities (antibacterial, antifungal, cytotoxicity, antileishmanial and insecticidal of these compounds are also reported.

Atomic structures of a monolayer of AlAs, GaAs, and InAs on Si(111)

International Nuclear Information System (INIS)

Lee, Geunjung; Yoon, Younggui

2010-01-01

We study atomic structures of a monolayer of AlAs, GaAs, and InAs on a Si(111) substrate from first-principles. The surface with the stacking sequence of ...SiSiMAsSiAs is energetically more stable than the surface with the stacking sequence of ...SiSiSiAsMAs, where M is Al, Ga, or In. The atomic structure of the three top layers of the low-energy surfaces are quite robust, irrespective of M, and the atomic structure of the AlAsSiAs terminated surface and that of the GaAsSiAs terminated surface are very similar. For the high-energy AsMAs terminated surfaces, the broken local tetrahedral symmetry plays an important role in the atomic structures. The calculated atomic structures of InAs on the Si(111) substrate depart most from the structure of crystalline Si.

Ultrafast carrier dynamics in tetrahedral amorphous carbon: carrier trapping versus electron-hole recombination

International Nuclear Information System (INIS)

Carpene, E; Mancini, E; Dallera, C; Schwen, D; Ronning, C; Silvestri, S De

2007-01-01

We report the investigation of the ultrafast carrier dynamics in thin tetrahedral amorphous carbon films by means of femtosecond time-resolved reflectivity. We estimated the electron-phonon relaxation time of a few hundred femtoseconds and we observed that under low optical excitation photo-generated carriers decay according to two distinct mechanisms attributed to trapping by defect states and direct electron-hole recombination. With high excitation, when photo-carrier and trap densities are comparable, a unique temporal evolution develops, as the time dependence of the trapping process becomes degenerate with the electron-hole recombination. This experimental evidence highlights the role of defects in the ultrafast electronic dynamics and is not specific to this particular form of carbon, but has general validity for amorphous and disordered semiconductors

Environmentally Sustainable Aluminum-Coordinated Poly(tetrahydroxybenzoquinone) as a Promising Cathode for Sodium Ion Batteries.

Science.gov (United States)

Kim, Hee Joong; Kim, Youngjin; Shim, Jimin; Jung, Kyung Hwa; Jung, Min Soo; Kim, Hanseul; Lee, Jong-Chan; Lee, Kyu Tae

2018-01-31

Na-ion batteries are attractive as an alternative to Li-ion batteries because of their lower cost. Organic compounds have been considered as promising electrode materials due to their environmental friendliness and molecular diversity. Herein, aluminum-coordinated poly(tetrahydroxybenzoquinone) (P(THBQ-Al)), one of the coordination polymers, is introduced for the first time as a promising cathode for Na-ion batteries. P(THBQ-Al) is synthesized through a facile coordination reaction between benzoquinonedihydroxydiolate (C 6 O 6 H 2 2- ) and Al 3+ as ligands and complex metal ions, respectively. Tetrahydroxybenzoquinone is environmentally sustainable, because it can be obtained from natural resources such as orange peels. Benzoquinonedihydroxydiolate also contributes to delivering high reversible capacity, because each benzoquinonedihydroxydiolate unit is capable of two electron reactions through the sodiation of its conjugated carbonyl groups. Electrochemically inactive Al 3+ improves the structural stability of P(THBQ-Al) during cycling because of a lack of a change in its oxidation state. Moreover, P(THBQ-Al) is thermally stable and insoluble in nonaqueous electrolytes. These result in excellent electrochemical performance including a high reversible capacity of 113 mA h g -1 and stable cycle performance with negligible capacity fading over 100 cycles. Moreover, the reaction mechanism of P(THBQ-Al) is clarified through ex situ XPS and IR analyses, in which the reversible sodiation of C═O into C-O-Na is observed.

The architecture of metal coordination groups in proteins.

Science.gov (United States)

Harding, Marjorie M

2004-05-01

A set of tables is presented and a survey given of the architecture of metal coordination groups in a representative set of protein structures from the Protein Data Bank [Bernstein et al. (1977), J. Mol. Biol. 112, 535-542; Berman et al. (2000), Nucleic Acids Res. 28, 235-242]. The structures have been determined to a resolution of 2.5 A or better; the metals considered are Ca, Mg, Mn, Fe, Cu, Zn, Na and K, with particular emphasis on Ca and Zn and the exclusion of haem groups and Fe/S clusters; the proteins are a representative set in which none has more than 30% sequence identity with any other. In them the metal is coordinated by several donor groups from different amino-acid residues in the protein chain and often also by water or other small molecules. The tables, for approximately 600 metal coordination groups, include information on the conformations of the protein chain in the region around the metal and reliability indicators. They illustrate the wide variety of coordination numbers, chelate-loop sizes and other properties and the different characteristics of different metals. They show that glycine has a particular significance in the position adjacent to a donor residue, especially in Ca coordination groups. They also show that metal coordination does not appear to lead to significant distortions of the torsion angles phi, psi from their normally allowed values. Very few metal coordination groups occur more than once in the representative set and when they do they are usually related in fold and function; they have similar but not necessarily identical conformations. However, individual chelate loops, for example Zn(-C-X-X'-C-), in which both cysteines are coordinated to Zn through S, and X and X' are any amino acids, are repeated frequently in many different and unrelated proteins. Not all chelate loops with the same composition have the same conformation, but for smaller loops there are usually one or two strongly preferred and well defined

Molecular dinamics of tetrahedral clelate compounds of Cd(2) in solutions

International Nuclear Information System (INIS)

Nivorozhkin, L.E.; Minkin, V.I.; Borisenko, N.I.; Konstantinovskij, L.E.; Korobov, M.S.; Olekhnovich, R.Ya.

1981-01-01

Interconversion kinetics of enantiomers of tetrahedral intracomplex compounds of metals (ICM) on the base of unsymmetric ligands in solu-- tions is studied for several series of compounds according to the temperature dependence of the shape of line of prochiral substituents using the methods of the dynamic NMR (DNMR). The use of tetracoordinated ICM in the solutions of synthesized compounds of Cd(2) with the inclusion of magnetic isotope 111 Cd(S=1/2) to study molecular dynamics and the application of the corresponding methods of calculation of the DNMR signal forms permitted to clearly separate the mechanisms of digonal twist and degenerated ligand exchange. In ICM solutions the low-barrier transformations, connected with intramolecular digonal twist, take place as well as high-barrier processes of degenerated ligand exchange. The technique suggested can be applied to the studies of ICM molecular dynamics with other magnetic isotopes of metals ( 207 Pb, 199 Hg, etc.) and rapid non-degenerated ligand exchanges [ru

About the coordinate time for photons in Lifshitz space-times

International Nuclear Information System (INIS)

Villanueva, J.R.; Vasquez, Yerko

2013-01-01

In this paper we studied the behavior of radial photons from the point of view of the coordinate time in (asymptotically) Lifshitz space-times, and we found a generalization to the result reported in previous works by Cruz et al. (Eur. Phys. J. C 73:7, 2013), Olivares et al. (Astrophys. Space Sci. 347:83-89, 2013), and Olivares et al. arXiv:1306.5285. We demonstrate that all asymptotically Lifshitz space-times characterized by a lapse function f(r) which tends to one when r→∞, present the same behavior, in the sense that an external observer will see that photons arrive at spatial infinity in a finite coordinate time. Also, we show that radial photons in the proper system cannot determine the presence of the black hole in the region r + < r<∞, because the proper time as a result is independent of the lapse function f(r). (orig.)

High-Temperature Decomposition of Brønsted Acid Sites in Gallium-Substituted Zeolites

Energy Technology Data Exchange (ETDEWEB)

K Al-majnouni; N Hould; W Lonergan; D Vlachos; R Lobo

2011-12-31

The dehydroxylation of Broensted acid sites (BAS) in Ga-substituted zeolites was investigated at temperatures up to 850 C using X-ray absorption spectroscopy (XAS), Fourier transform infrared spectroscopy (FTIR), and mass spectrometry-temperature programmed desorption (MS-TPD). X-ray absorption near-edge spectroscopy (XANES) revealed that the majority of gallium has tetrahedral coordination even after complete dehydroxylation. The interatomic gallium-oxygen distance and gallium coordination number determined by extended X-ray absorption fine structure (EXAFS) are consistent with gallium in tetrahedral coordination at low T (< 550 C). Upon heating Ga-Beta and Ga-ZSM5 to 850 C, analysis of the EXAFS showed that 70 and 80% of the gallium was still in tetrahedral coordination. The remainder of the gallium was found to be in octahedral coordination. No trigonal Ga atoms were observed. FTIR measurements carried out at similar temperatures show that the intensity of the OH vibration due to BAS has been eliminated. MS-TPD revealed that hydrogen in addition to water evolved from the samples during dehydroxylation. This shows that dehydrogenation in addition to dehydration is a mechanism that contributes to BAS decomposition. Dehydrogenation was further confirmed by exposing the sample to hydrogen to regenerate some of the BAS as monitored by FTIR and MS-TPD.

Structure of high alumina content Al2O3-SiO2 composition glasses.

Science.gov (United States)

Weber, Richard; Sen, Sabyasachi; Youngman, Randall E; Hart, Robert T; Benmore, Chris J

2008-12-25

The structure of binary aluminosilicate glasses containing 60-67 mol % Al2O3 were investigated using high-resolution 27Al NMR and X-ray and neutron diffraction. The glasses were made by aerodynamic levitation of molten oxides. The 67% alumina composition required a cooling rate of approximately 1600 degrees C s(1-) to form glass from submillimeter sized samples. NMR results show that the glasses contain aluminum in 4-, 5-, and 6-fold coordination in the approximate ratio 4:5:1. The average Al coordination increases from 4.57 to 4.73 as the fraction of octahedral Al increases with alumina content. The diffraction results on the 67% composition are consistent with a disordered Al framework with Al ions in a range of coordination environments that are substantially different from those found in the equilibrium crystalline phases. Analysis of the neutron and X-ray structure factors yields an average bond angle of 125 +/- 4 degrees between an Al ion and the adjoining cation via a bridging oxygen. We propose that the structure of the glass is a "transition state" between the alumina-rich liquid and the equilibrium mullite phase that are dominated by 4- and 6-coordinated aluminum ions, respectively.

Raman scattering and lattice stability of NaAlH{sub 4} and Na{sub 3}AlH{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Yukawa, H. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan)], E-mail: hiroshi@numse.nagoya-u.ac.jp; Morisaku, N.; Li, Y.; Komiya, K.; Rong, R.; Shinzato, Y. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan); Sekine, R. [Department of Chemistry, Faculty of Science, Shizuoka University, 836 Ohya, Shizuoka 422-8529 (Japan); Morinaga, M. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan)

2007-10-31

In situ Raman spectroscopy measurements have been performed during the decomposition of NaAlH{sub 4} in order to investigate the transition from the four-coordinated complex anion, [AlH{sub 4}]{sup -}, in NaAlH{sub 4} to the six-coordinated complex anion, [AlH{sub 6}]{sup 3-}, in Na{sub 3}AlH{sub 6}. Also, the local geometry and the Al-H vibrations are analyzed theoretically by the first-principle calculations of the electronic structures. It is found that the Raman sift at 1765 cm{sup -1} for the Al-H stretching vibration in NaAlH{sub 4} shifts towards the higher frequency side, 1801 cm{sup -1} upon melting. This Raman spectrum for the liquid phase recovers to the original position when it is cooled down to room temperature before Na{sub 3}AlH{sub 6} start to appear. The Raman peak around 1800 cm{sup -1} is still observed after the decomposition of NaAlH{sub 4} occurs to precipitate Na{sub 3}AlH{sub 6}. However, this peak does not recover to its original position by cooling, but still persists in the sample cooled down to room temperature. From these results, the intermediate transition state during the decomposition of NaAlH{sub 4} into Na{sub 3}AlH{sub 6} is discussed. In addition, it is shown from a series of calculation that the highest frequency of the Al-H vibration correlates with the shortest Al-H bond length in the MAlH{sub 4}-type and its derivative complex hydrides.

Soft Chemistry, Coloring and Polytypism in Filled Tetrahedral Semiconductors: Toward Enhanced Thermoelectric and Battery Materials.

Science.gov (United States)

White, Miles A; Medina-Gonzalez, Alan M; Vela, Javier

2018-03-12

Filled tetrahedral semiconductors are a rich family of compounds with tunable electronic structure, making them ideal for applications in thermoelectrics, photovoltaics, and battery anodes. Furthermore, these materials crystallize in a plethora of related structures that are very close in energy, giving rise to polytypism through the manipulation of synthetic parameters. This Minireview highlights recent advances in the solution-phase synthesis and nanostructuring of these materials. These methods enable the synthesis of metastable phases and polytypes that were previously unobtainable. Additionally, samples synthesized in solution phase have enhanced thermoelectric performance due to their decreased grain size. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Site-specific local structure of Mn in artificial manganese ferrite films

International Nuclear Information System (INIS)

Kravtsov, E.; Haskel, D.; Cady, A.; Yang, A.; Vittoria, C.; Harris, V. G.; Zuo, X.

2006-01-01

Diffraction anomalous fine structure (DAFS) spectroscopy has been applied to resolve site-specific Mn local structure in manganese ferrite films grown under nonequilibrium conditions. The DAFS spectra were measured at a number of Bragg reflections in the vicinity of the Mn absorption K edge. The DAFS data analysis done with an iterative Kramers-Kroenig algorithm made it possible to solve separately the local structure around crystallographically inequivalent Mn sites in the unit cell with nominal octahedral and tetrahedral coordination. The strong preference for Mn to be tetrahedrally coordinated in this compound is not only manifested in the relative site occupancies but also in a strong reduction in coordination number for Mn ions at nominal octahedral sites

About the coordinate time for photons in Lifshitz space-times

Energy Technology Data Exchange (ETDEWEB)

Villanueva, J.R. [Universidad de Valparaiso, Departamento de Fisica y Astronomia, Facultad de Ciencias, Valparaiso (Chile); Centro de Astrofisica de Valparaiso, Valparaiso (Chile); Vasquez, Yerko [Universidad de La Frontera, Departamento de Ciencias Fisicas, Facultad de Ingenieria, Ciencias y Administracion, Temuco (Chile); Universidad de La Serena, Departamento de Fisicas, Facultad de Ciencias, La Serena (Chile)

2013-10-15

In this paper we studied the behavior of radial photons from the point of view of the coordinate time in (asymptotically) Lifshitz space-times, and we found a generalization to the result reported in previous works by Cruz et al. (Eur. Phys. J. C 73:7, 2013), Olivares et al. (Astrophys. Space Sci. 347:83-89, 2013), and Olivares et al. arXiv:1306.5285. We demonstrate that all asymptotically Lifshitz space-times characterized by a lapse function f(r) which tends to one when r{yields}{infinity}, present the same behavior, in the sense that an external observer will see that photons arrive at spatial infinity in a finite coordinate time. Also, we show that radial photons in the proper system cannot determine the presence of the black hole in the region r{sub +}

Synthesis and Molecular Structures of Two [1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene]-dichloro-Zn(II Coordination Polymers

Directory of Open Access Journals (Sweden)

Hsin-Ta Wang

2006-08-01

Full Text Available Two novel coordination polymers with 3D metal-organic frameworks (MOFs have been synthesized by reacting 1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene (L with zinc dichloride. Both compounds have the same repeating unit consisting of a distorted tetrahedral Zn(II center coordinated by two chlorides and two pyridyl nitrogen atoms of two bridging bismonodentate L ligands, however, different structural conformations have been found, one forming a helical chain and the other producing a square-wave chain. The intermolecular C−H···Cl hydrogen bonds in 1 and 2 play important roles in the formation of three-dimensional coordination polymers. Compound 1 crystallized in an orthorhombic space group Pna21 with a = 7.9652(3, b = 21.4716(7, c = 8.2491(3Å, V = 1410.81(9 Å 3 and Z = 4. Compound 2 crystallized in a monoclinic space group P21/n with a = 9.1752(3, b = 14.5976(4, c = 10.3666(3 Å , β = 98.231(2°, V = 1374.16(7 Å 3 and Z = 4.

Adsorption of Zn(II) on the kaolinite(001) surfaces in aqueous environment: A combined DFT and molecular dynamics study

Energy Technology Data Exchange (ETDEWEB)

Wang, Qiang; Kong, Xiang-Ping; Zhang, Bao-Hua; Wang, Juan, E-mail: juaner80@163.com

2017-08-31

Highlights: • Zn(II) adsorption on two types of neutral kaolinite(001) surfaces is investigated. • Surface “Ou” is found the preferred site for mono- and bi-dentate complexes. • Both Zn(II) and surface oxygen accept electrons from aqua oxygens. • Coupling of O 2p with Zn sp{sup 3}d{sup 2} (or sp{sup 3}) hybridization states is the bonding nature. - Abstract: Adsorption of Zn(II) on two types of neutral (001) surfaces of kaolinite, tetrahedral Si(t) and octahedral Al(o), was studied by means of DFT calculations and classical molecular dynamics simulations. The position and structure for both outer-sphere and mono-/bi-dentate inner-sphere complexes of Zn(II) in aqueous environment were examined, with binding energy and radial distribution function calculated. Outer-sphere complex on the Si(t) surface, monodentate inner-sphere complex of “O{sub u}” (surface oxygen with “upright” hydrogen) site and bidentate complex of “O{sub u}-O{sub u}” site of neighboring Al centers on the Al(o) surface are considered to be the dominant adsorption species. The outer-sphere complex is found six-coordinated with distorted octahedral geometry, while both the inner-sphere complexes exhibit the tetrahedral structure with coordination number of four. Hydrogen bonding interactions between oxygen or hydrogen of the kaolinite(001) surfaces and the aqua ligands of Zn(II) act as the key role for the structure and stability of adsorption complexes. Upon the Mulliken population analysis and partial density of states, both Zn(II) and surface oxygen accept electrons from aqua oxygens, and coupling of O 2p with the sp{sup 3}d{sup 2} or sp{sup 3} hybridization states of Zn(II) is the primary bonding nature of Zn(II) with oxygen in outer- and inner-sphere complexes, respectively.

In situ dehydration of yugawaralite

DEFF Research Database (Denmark)

Artioli, G.; Ståhl, Kenny; Cruciani, G.

2001-01-01

The structural response of the natural zeolite yugawaralite (CaAl2Si6O16. 4H(2)O) upon thermally induced dehydration has been studied by Rietveld analysis of temperature-resolved powder diffraction data collected in situ in the temperature range 315-791 K using synchrotron radiation. The room...... progressively disappearing as the dehydration proceeds. The yugawaralite structure reacts to the release of water molecules with small changes in the Ca-O bond distances and minor distortions of the tetrahedral framework up to about 695 K. Above this temperature the Ca coordination falls below 7 (four framework...

Influence of aluminum addition in the framework of MCM-41 mesoporous molecular sieve synthesized by non-hydrothermal method in an alkali-free system

Energy Technology Data Exchange (ETDEWEB)

La-Salvia, Nathália; Lovón-Quintana, Juan José; Lovón, Adriana Siviero Pagani; Valença, Gustavo Paim, E-mail: nathalialasalvia@gmail.com [Laboratório para o Estudo de Processos de Adsorção e Catálise - LEPAC, Faculdade de Engenharia Química, Universidade Estadual de Campinas - UNICAMP, Campinas, SP (Brazil)

2017-11-15

Purely siliceous MCM-41 and Al-containing MCM-41 (Al-MCM-41) mesoporous materials were synthesized by non-hydrothermal method in alkali-free ions medium at room temperature and short reaction times. Under these synthesis conditions, it was also investigated the influence of Al incorporation in the crystal structure of MCM-41. The solids were characterized by ICP-OES, AAS, N{sub 2} adsorption at 77 K, XRD, TEM, NH3 -TPD, {sup 27}Al and {sup 29}Si-MAS-NMR, FT-IR and TGA. The resulting mesoporous materials showed a well-defined hexagonally ordered pore geometry maintaining a uniform and unimodal pore size distribution with high specific surface areas (1000-1400 m{sup 2} g{sup -1}). The Al{sup +3} ions were introduced successfully in the structure of the purely siliceous MCM-41 expanding the unit cell parameter and forming four-coordinated Al species, and in a less extent, forming six-coordinated Al species. In addition, the surface acidity of the MCM-41 increased with Al loading. Contrary, the presence of Al in the MCM-41 mesoporous structure resulted in a decrease of the crystallinity and specific surface area possibly due to the presence of Al species in highly distorted tetrahedral structures and Al extra-framework or amorphous alumina occluded in the pores. The MCM-41 type mesoporous materials obtained in this work show similar characteristics of those synthesized by conventional hydrothermal methods. (author)

Evolution of structural and optical properties in the course of thermal evolution of sol-gel derived cobalt-doped gahnite

International Nuclear Information System (INIS)

Kurajica, S.; Tkalcec, E.; Grzeta, B.; Ivekovic, D.; Mandic, V.; Popovic, J.; Kranzelic, D.

2011-01-01

Research highlights: → Distribution of Co 2+ ions in zinc cobalt aluminate lattice seats depend on Co loading. The green color of samples at lower temperatures is a consequence of partial oxidation of Co 2+ ions and their accommodation in octahedral sites. Thermal treatment at higher temperatures promotes gradual change of color to blue, characteristic for tetrahedrally coordinated Co 2+ ions. The spectra evolution could be interpreted as a progressive reduction of Co 3+ to Co 2+ ions at higher temperatures. - Abstract: Thermal evolution of sol-gel derived gahnite (ZnAl 2 O 4 ) with 4, 8 and 12 at.% of Zn replaced with Co was studied by thermal analysis techniques (DTA/TGA), X-ray diffraction (XRD) and UV-vis diffuse reflectance spectroscopy (DRS). Zinc-cobalt spinel powders were produced by gel heat treatment at temperatures as low as 400 o C. Crystal structure was characterized using Rietveld refinement of X-ray diffraction patterns for the samples annealed at 800 o C, simultaneously with the analysis of diffraction line broadening. It was found out that the distribution of Co 2+ ions in tetrahedral and octahedral sites of zinc cobalt aluminate crystal lattice, crystallite size and lattice strain depend on Co loading. The green color of samples thermally treated at T 2+ ions at lower temperatures and accommodation of Co 3+ ions in octahedral sites. Thermal treatment at higher temperatures promote gradual change of color from green to blue, characteristic for tetrahedrally coordinated Co 2+ ions. The spectra evolution could be interpreted as a progressive reduction of Co 3+ to Co 2+ ions at higher temperatures.

Copper(II) and zinc(II) as metal-carboxylate coordination complexes based on (1-methyl-1H-benzo[d]imidazol-2-yl) methanol derivative: Synthesis, crystal structure, spectroscopy, DFT calculations and antioxidant activity

Science.gov (United States)

Benhassine, Anfel; Boulebd, Houssem; Anak, Barkahem; Bouraiou, Abdelmalek; Bouacida, Sofiane; Bencharif, Mustapha; Belfaitah, Ali

2018-05-01

This work presents a combined experimental and theoretical study of two new metal-carboxylate coordination compounds. These complexes were prepared from (1-methyl-1H-benzimidazol-2-yl)methanol under mild conditions. The structures of the prepared compounds were characterized by single-crystal X-ray analysis, FTIR and UV-Vis spectroscopy. In the Cupper complex, the Cu(II) ion is coordinated by two ligands, which act as bidentate chelator through the non-substituted N and O atoms, and two carboxylicg oxygen atoms, displaying a hexa-coordinated compound in a distorted octahedral geometry, while in the Zinc complex the ligand is ligated to the Zn(II) ion in monodentate fashion through the N atom, and the metal ion is also bonded to carboxylic oxygen atoms. The tetra-coordinated compound displays a distorted tetrahedral shape. The density functional theory calculations are carried out for the determination of the optimized structures. The electronic transitions and fundamental vibrational wave numbers are calculated and are in good agreement with experimental. In addition, the ligand and its Cu(II) and Zn(II) complexes were screened and evaluated for their potential as DPPH radical scavenger.

LiBSi2: a tetrahedral semiconductor framework from boron and silicon atoms bearing lithium atoms in the channels.

Science.gov (United States)

Zeilinger, Michael; van Wüllen, Leo; Benson, Daryn; Kranak, Verina F; Konar, Sumit; Fässler, Thomas F; Häussermann, Ulrich

2013-06-03

Silicon swallows up boron: The novel open tetrahedral framework structure (OTF) of the Zintl phase LiBSi2 was made by applying high pressure to a mixture of LiB and elemental silicon. The compound represents a new topology in the B-Si net (called tum), which hosts Li atoms in the channels (see picture). LiBSi2 is the first example where B and Si atoms form an ordered common framework structure with B engaged exclusively in heteronuclear B-Si contacts.

Origin of 6-fold coordinated aluminum at (010-type pyrophyllite edges

Directory of Open Access Journals (Sweden)

M. Okumura

2017-05-01

Full Text Available To better understand the aqueous chemical reactivity of clay mineral edges we explored the relationships between hydration and the structure of (010-type edges of pyrophyllite. In particular, we used density functional theory and the quantum theory of atoms in molecules to evaluate the stability of 6-fold coordinated hydrated aluminum at the edge in terms of the electron density distribution. Geometrical optimization revealed an intra-edge hydrogen bond network between aluminol hydroxyls and water ligands completing the aluminum coordination shell. From the electron density isosurfaces one water ligand is not covalently bonded to aluminum. Bader charge analysis revealed that OH2 ligands have small negative charge. In addition, it is also found that the charge of the 6-fold coordinated aluminum is larger than one of the 5-fold aluminum. From these results, the charging of the OH2 ligands is interpreted as charge transfer originated from the formation of the hydrogen bond network and not from Al-OH2 interaction per se. This suggests that the weakly bound water ligand in question, and more generally 6-fold hydrated edge Al coordination, is stabilized primarily by the hydrogen bond network which in turn leads to weak ionic attraction to the aluminum center itself. The finding highlights the importance of cooperative effects between solvent structure and the coordination of metal cations exposed at clay mineral edges.

Results and simulations on γ-spectroscopy of deformed nuclei: cases of isomers and tetrahedral nuclei

International Nuclear Information System (INIS)

Vancraeyenest, A.

2010-10-01

The major part of this work is about the realization and complete analysis of an experiment for studying isomeric states in 138,139,140 Nd nuclei. This was performed at Jyvaeskylae laboratory (Finland) using a fusion-evaporation reaction with 48 Ca beam on a thin 96 Zr target. Experimental setup consisted in the target position gamma ray detector Jurogam II which was coupled with the RITU recoil separator and the GREAT focal plane detector array. This particularly well adapted setup permit to manage γ spectroscopy of the interest nuclei around isomeric states. Indeed, we used prompt-delayed matrices to separate rays that come onto isomeric states and these who decay from them. Then, the correlations between the two components permit to establish feeding transitions of isomeric states. Thanks to this experiment, a new isomeric state was also highlighted in 139 Nd with spin 23/2+, which was predicted and interpreted in Cranked-Nilsson-Strutinsky calculation. Finally, very clean time spectra allow to determine precisely life-time of four states in four nuclei. This Ph.d. is also made of a part of the analysis of the first experimental search for fingerprints of tetrahedral symmetry in 156 Gd using high fold gamma ray spectroscopy. Thanks to a large number of triple coincidence events, we managed a detailed spectroscopy of this nucleus. Particularly, we found out 13 new transitions in positive parity bands. As a complement of this work, we have done GEANT4 simulations about the detection limits of low intensity transitions by Agata multidetector. Indeed, tetrahedral symmetry predicts vanishing of E2 transitions at lower spin states and simulations permit to determine observation limit of these transitions with different version of Agata. (author)

Three-dimensional dynamic rupture simulation with a high-order discontinuous Galerkin method on unstructured tetrahedral meshes

KAUST Repository

Pelties, Christian

2012-02-18

Accurate and efficient numerical methods to simulate dynamic earthquake rupture and wave propagation in complex media and complex fault geometries are needed to address fundamental questions in earthquake dynamics, to integrate seismic and geodetic data into emerging approaches for dynamic source inversion, and to generate realistic physics-based earthquake scenarios for hazard assessment. Modeling of spontaneous earthquake rupture and seismic wave propagation by a high-order discontinuous Galerkin (DG) method combined with an arbitrarily high-order derivatives (ADER) time integration method was introduced in two dimensions by de la Puente et al. (2009). The ADER-DG method enables high accuracy in space and time and discretization by unstructured meshes. Here we extend this method to three-dimensional dynamic rupture problems. The high geometrical flexibility provided by the usage of tetrahedral elements and the lack of spurious mesh reflections in the ADER-DG method allows the refinement of the mesh close to the fault to model the rupture dynamics adequately while concentrating computational resources only where needed. Moreover, ADER-DG does not generate spurious high-frequency perturbations on the fault and hence does not require artificial Kelvin-Voigt damping. We verify our three-dimensional implementation by comparing results of the SCEC TPV3 test problem with two well-established numerical methods, finite differences, and spectral boundary integral. Furthermore, a convergence study is presented to demonstrate the systematic consistency of the method. To illustrate the capabilities of the high-order accurate ADER-DG scheme on unstructured meshes, we simulate an earthquake scenario, inspired by the 1992 Landers earthquake, that includes curved faults, fault branches, and surface topography. Copyright 2012 by the American Geophysical Union.

First-principles molecular dynamics investigation of thermal and mechanical stability of the TiN(001)/AlN and ZrN(001)/AlN heterostructures

International Nuclear Information System (INIS)

Ivashchenko, V.I.; Veprek, S.; Turchi, P.E.A.; Shevchenko, V.I.; Leszczynski, J.; Gorb, L.; Hill, F.

2014-01-01

First-principles quantum molecular dynamics investigations of TiN(001)/AlN and ZrN(001)/AlN heterostructures with one and two monolayers (1 ML and 2 ML) of AlN interfacial layers were carried out in the temperature range of 0–1400 K with subsequent static relaxation. It is shown that the epitaxially stabilized cubic B1-AlN interfacial layers are preserved in all TiN(001)/AlN heterostructures over the whole temperature range. In the ZrN(001)/AlN heterostructures, the B1-AlN(001) interfacial layer exists at 0 K, but it transforms into a distorted one at 10 K consisting of tetrahedral AlN 4 , octahedral AlN 6 , and AlN 5 units. The thermal stability of the interfaces was investigated by studying the phonon dynamic stability of the B1-AlN phase with different lattice parameters. The calculations showed that the B1-AlN interface should be unstable in ZrN(001)/AlN heterostructures and nanocomposites, and in those based on transition metal nitrides with lattice parameters larger than 4.4 Å. Electronic band structure calculations showed that energy gap forms around the Fermi energy for all interfaces. The formation of the interfacial AlN layer in TiN and ZrN crystals reduces their ideal tensile and shear strengths. Upon tensile load, decohesion occurs between Ti (Zr) and N atoms adjacent to the 1 ML AlN interfacial layer, whereas in the case of 2 ML AlN it occurs inside the TiN and ZrN slabs. The experimentally reported strength enhancement in the TiN/AlN and ZrN/AlN heterostructures is attributed to impeding effect of the interfacial layer on the plastic flow. - Highlights: • First-principles quantum molecular dynamics studies were conducted. • TiN- and ZrN-based heterostructures with one and two AlN interfacial layers. • Stability and structural transformation between 0 and 1400 K have been calculated. • Stress–strain relationships and ideal strengths determined. • Systems which may form stable superhard heterostructures are identified

First-principles molecular dynamics investigation of thermal and mechanical stability of the TiN(001)/AlN and ZrN(001)/AlN heterostructures

Energy Technology Data Exchange (ETDEWEB)

Ivashchenko, V.I., E-mail: ivash@ipms.kiev.ua [Institute of Problems of Material Science, National Academy of Science of Ukraine, Krzhyzhanosky str. 3, 03142 Kyiv (Ukraine); Veprek, S., E-mail: stan.veprek@lrz.tum.de [Department of Chemistry, Technical University Munich, Lichtenbergstrasse 4, D-85747 Garching (Germany); Turchi, P.E.A. [Lawrence Livermore National Laboratory (L-352), P.O. Box 808, Livermore, CA 94551 (United States); Shevchenko, V.I. [Institute of Problems of Material Science, National Academy of Science of Ukraine, Krzhyzhanosky str. 3, 03142 Kyiv (Ukraine); Leszczynski, J. [Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, MS 39217 (United States); Gorb, L. [Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, MS 39217 (United States); U.S. Army ERDC, Vicksburg, MS 39180 (United States); Hill, F. [U.S. Army ERDC, Vicksburg, MS 39180 (United States)

2014-08-01

First-principles quantum molecular dynamics investigations of TiN(001)/AlN and ZrN(001)/AlN heterostructures with one and two monolayers (1 ML and 2 ML) of AlN interfacial layers were carried out in the temperature range of 0–1400 K with subsequent static relaxation. It is shown that the epitaxially stabilized cubic B1-AlN interfacial layers are preserved in all TiN(001)/AlN heterostructures over the whole temperature range. In the ZrN(001)/AlN heterostructures, the B1-AlN(001) interfacial layer exists at 0 K, but it transforms into a distorted one at 10 K consisting of tetrahedral AlN{sub 4}, octahedral AlN{sub 6}, and AlN{sub 5} units. The thermal stability of the interfaces was investigated by studying the phonon dynamic stability of the B1-AlN phase with different lattice parameters. The calculations showed that the B1-AlN interface should be unstable in ZrN(001)/AlN heterostructures and nanocomposites, and in those based on transition metal nitrides with lattice parameters larger than 4.4 Å. Electronic band structure calculations showed that energy gap forms around the Fermi energy for all interfaces. The formation of the interfacial AlN layer in TiN and ZrN crystals reduces their ideal tensile and shear strengths. Upon tensile load, decohesion occurs between Ti (Zr) and N atoms adjacent to the 1 ML AlN interfacial layer, whereas in the case of 2 ML AlN it occurs inside the TiN and ZrN slabs. The experimentally reported strength enhancement in the TiN/AlN and ZrN/AlN heterostructures is attributed to impeding effect of the interfacial layer on the plastic flow. - Highlights: • First-principles quantum molecular dynamics studies were conducted. • TiN- and ZrN-based heterostructures with one and two AlN interfacial layers. • Stability and structural transformation between 0 and 1400 K have been calculated. • Stress–strain relationships and ideal strengths determined. • Systems which may form stable superhard heterostructures are identified.

Silver(I) complexes of the weakly coordinating solvents SO(2) and CH(2)Cl(2): crystal structures, bonding, and energetics of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)].

Science.gov (United States)

Decken, Andreas; Knapp, Carsten; Nikiforov, Grigori B; Passmore, Jack; Rautiainen, J Mikko; Wang, Xinping; Zeng, Xiaoqing

2009-06-22

Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand

Decoration of the Truncated Tetrahedron—An Archimedean Polyhedron—To Produce a New Class of Convex Equilateral Polyhedra with Tetrahedral Symmetry

Directory of Open Access Journals (Sweden)

Stan Schein

2016-08-01

Full Text Available The Goldberg construction of symmetric cages involves pasting a patch cut out of a regular tiling onto the faces of a Platonic host polyhedron, resulting in a cage with the same symmetry as the host. For example, cutting equilateral triangular patches from a 6.6.6 tiling of hexagons and pasting them onto the full triangular faces of an icosahedron produces icosahedral fullerene cages. Here we show that pasting cutouts from a 6.6.6 tiling onto the full hexagonal and triangular faces of an Archimedean host polyhedron, the truncated tetrahedron, produces two series of tetrahedral (Td fullerene cages. Cages in the first series have 28n2 vertices (n ≥ 1. Cages in the second (leapfrog series have 3 × 28n2. We can transform all of the cages of the first series and the smallest cage of the second series into geometrically convex equilateral polyhedra. With tetrahedral (Td symmetry, these new polyhedra constitute a new class of “convex equilateral polyhedra with polyhedral symmetry”. We also show that none of the other Archimedean polyhedra, six with octahedral symmetry and six with icosahedral, can host full-face cutouts from regular tilings to produce cages with the host’s polyhedral symmetry.

Highly parallel demagnetization field calculation using the fast multipole method on tetrahedral meshes with continuous sources

Science.gov (United States)

Palmesi, P.; Exl, L.; Bruckner, F.; Abert, C.; Suess, D.

2017-11-01

The long-range magnetic field is the most time-consuming part in micromagnetic simulations. Computational improvements can relieve problems related to this bottleneck. This work presents an efficient implementation of the Fast Multipole Method [FMM] for the magnetic scalar potential as used in micromagnetics. The novelty lies in extending FMM to linearly magnetized tetrahedral sources making it interesting also for other areas of computational physics. We treat the near field directly and in use (exact) numerical integration on the multipole expansion in the far field. This approach tackles important issues like the vectorial and continuous nature of the magnetic field. By using FMM the calculations scale linearly in time and memory.

Calculation of fluctuations and photoemission properties in a tetrahedral-cluster model for an intermediate-valence system

International Nuclear Information System (INIS)

Reich, A.; Falicov, L.M.

1986-01-01

An exact solution of a four-site tetrahedral-crystal model, the smallest face-centered-cubic crystal, is presented in the case of an intermediate-valence system. The model consists of the following: (a) one extended orbital and one localized orbital per atom, (b) an interatomic transfer term between extended orbitals, (c) an interatomic hybridization between the localized and extended orbitals, (d) strong intra-atomic Coulomb repulsion between opposite-spin localized states, and (e) intermediate-strength intra-atomic Coulomb repulsion between the localized and extended states. These competing effects are examined as they manifest themselves in the intermediate-valence, photoemission, inverse-photoemission, and thermodynamic properties

Spectroscopic and dielectric properties of titanium doped MgO-Al{sub 2}O{sub 3}-B{sub 2}O{sub 3} glass system

Energy Technology Data Exchange (ETDEWEB)

Raju, G Naga; Ramesh, N Ch; Naresh, P; Krishna, T L; Srinivasulu, K; Sudhkar, K S V; Rao, P Venkateswara, E-mail: gnag_9@rediffmail.com [Department of Physics, Acharya Nagarjuna University-Nuzvid Campus, Nuzvid - 521 201 (India)

2009-07-15

In this paper we have reported the influence of titanium ions on different spectroscopic and dielectric properties of MgO-Al{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses. The analysis of result of all these studies has indicated that as the concentration of TiO{sub 2} increased in the glass matrix, there is a gradual transformation of titanium ions from octahedral position to tetrahedral positions and cause to increase the rigidity of glass network.

Selective high capacity adsorption of Congo red, luminescence and antibacterial assessment of two new cadmium(II) coordination polymers

Science.gov (United States)

Beheshti, Azizolla; Nozarian, Kimia; Ghamari, Narges; Mayer, Peter; Motamedi, Hossein

2018-02-01

Coordination polymers [CdCl(NCS)L]n (1) and {[Cd2I4(L)2]·H2O·DMF}n (2) (where L = 1, 1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione)) were synthesized and structurally characterized. Compounds 1 and 2 both possess a tetrahedral arrangement with CdS2NCl and CdS2I2 cores, respectively. In these structures, the flexible thione ligands adopt a μ- bridging coordination mode to form 1D chains along the b-axis. The 1D chains are join together by C-H--Cl hydrogen bonds (in 1) and water molecules (in 2) to create a 2D supramolecular framework with an ABAB…packing mode. Remarkably, compounds 1 and 2 in particular polymer 1 exhibit excellent capacity to adsorb Congo red (CR) with high selectivity. The experimental data demonstrate that the mechanism of sorption process can be described by the Elovich and pseudo second order kinetic models for 1 and 2, respectively. Furthermore, the possible mechanism of CR absorption was investigated by UV-Vis and solid state fluorescence spectra for the title polymers. In addition, the antibacterial assessment of these compounds have also been studied.

The formation mechanism of mechanically alloyed Fe-20 at% Al powder

Energy Technology Data Exchange (ETDEWEB)

Hadef, F., E-mail: hadef77@yahoo.fr [Laboratoire de Recherche sur la Physico-Chimie des Surfaces et Interfaces, LRPCSI, Universite 20 Aout 1955, BP 26, Route d' El-Hadaiek, Skikda 21000 (Algeria); Otmani, A. [Laboratoire de Recherche sur la Physico-Chimie des Surfaces et Interfaces, LRPCSI, Universite 20 Aout 1955, BP 26, Route d' El-Hadaiek, Skikda 21000 (Algeria); Djekoun, A. [Laboratoire de Magnetisme et Spectroscopie des Solides, LM2S, Universite Badji Mokhtar, BP 12 Annaba 23000 (Algeria); Greneche, J.M. [LUNAM, Universite du Maine, Institut des Molecules et Materiaux du Mans, UMR CNRS 6283, 72085 Le Mans (France)

2013-01-15

The formation mechanism of the mechanically alloyed Fe-20 at% Al, from elemental Fe and Al powders, has been investigated. The experimental results indicate the formation of a nanocrystalline bcc {alpha}-Fe(Al) solid solution with a lattice parameter close to a{sub {alpha}-Fe(Al)}=0.2890 nm, where each Fe atom is surrounded by (6Fe+2Al) in the first coordination sphere. The reaction mechanism of MA process seems to be controlled by a diffusion phenomenon. Aluminum particles undergo an important refinement to the nanometer scale and then they stick on Fe particles of large sizes. A large number of clear Al/Fe interface areas were generated. The short diffusion path and the presence of high concentration of defects accelerated the solid state reaction. - Highlights: Black-Right-Pointing-Pointer A nanocrystalline bcc {alpha}-Fe(Al) solid solution is formed from elemental Fe and Al powders. Black-Right-Pointing-Pointer The reaction mechanism of MA process seems to be controlled by a diffusion phenomenon. Black-Right-Pointing-Pointer Each Fe atom is surrounded by (6Fe+2Al) in the first coordination sphere.

Three series of quaternary rare-earth transition-metal pnictides with CaAl{sub 2}Si{sub 2}-type structures: RECuZnAs{sub 2}, REAgZnP{sub 2}, and REAgZnAs{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Stoyko, Stanislav S.; Ramachandran, Krishna K.; Blanchard, Peter E.R. [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2 (Canada); Rosmus, Kimberly A.; Aitken, Jennifer A. [Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282 (United States); Mar, Arthur, E-mail: arthur.mar@ualberta.ca [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2 (Canada)

2014-05-01

Three series of quaternary rare-earth transition-metal pnictides REMM′Pn{sub 2} (M=Cu, Ag; M′=Zn; Pn=P, As) have been prepared by reaction of the elements at 800 °C, with crystal growth promoted through the addition of iodine. The extent of RE substitution is broad in these series: RECuZnAs{sub 2} (RE=Y, La-Nd, Sm, Gd–Lu), REAgZnP{sub 2} (RE=La–Nd, Sm, Gd–Dy), and REAgZnAs{sub 2} (RE=La-Nd, Sm, Gd-Dy). Powder and single-crystal X-ray diffraction analysis revealed that they adopt the trigonal CaAl{sub 2}Si{sub 2}-type structure (space group P3{sup ¯}m1, Z=1), in which Cu or Ag atoms are disordered with Zn atoms over the unique tetrahedrally coordinated transition-metal site. Magnetic measurements indicated Curie–Weiss behavior for several members of the RECuZnAs{sub 2} and REAgZnP{sub 2} series. Core-line X-ray photoelectron spectra (XPS) collected on some RECuZnAs{sub 2} members corroborate the charge assignment deduced by the Zintl concept for these compounds, (RE{sup 3+})(M{sup 1+})(Zn{sup 2+})(Pn{sup 3−}){sub 2}. Optical diffuse reflectance spectra and valence band XPS spectra established that these compounds are small band-gap semiconductors (up to ∼0.8 eV in REAgZnP{sub 2}) or semimetals (RECuZnAs{sub 2}). Band structure calculations also support this electronic structure and indicate that the band gap can be narrowed through appropriate chemical substitution (RE=smaller atoms, M=Cu, and Pn=As). - Graphical abstract: Cu or Ag atoms are disordered with Zn atoms over the tetrahedral site within relatively rigid [M{sub 2}Pn{sub 2}] slabs in three series of quaternary pnictides adopting the CaAl{sub 2}Si{sub 2}-type structure. - Highlights: • Three series (comprising 25 compounds) of pnictides REMM'Pn{sub 2} were prepared. • Cu or Ag atoms are disordered with Zn atoms within relatively rigid [M{sub 2}Pn{sub 2}] slabs. • They are semimetals or small band-gap semiconductors. • RECuZnAs{sub 2} and REAgZnP{sub 2} are generally

Numerical construction of the p(fold) (committor) reaction coordinate for a Markov process.

Science.gov (United States)

Krivov, Sergei V

2011-10-06

To simplify the description of a complex multidimensional dynamical process, one often projects it onto a single reaction coordinate. In protein folding studies, the folding probability p(fold) is an optimal reaction coordinate which preserves many important properties of the dynamics. The construction of the coordinate is difficult. Here, an efficient numerical approach to construct the p(fold) reaction coordinate for a Markov process (satisfying the detailed balance) is described. The coordinate is obtained by optimizing parameters of a chosen functional form to make a generalized cut-based free energy profile the highest. The approach is illustrated by constructing the p(fold) reaction coordinate for the equilibrium folding simulation of FIP35 protein reported by Shaw et al. (Science 2010, 330, 341-346). © 2011 American Chemical Society

Syntheses, spectroscopic and magnetic properties of polystyrene-anchored coordination compounds of thiazolidinone

Directory of Open Access Journals (Sweden)

D. Kumar

2014-01-01

Full Text Available The reaction between polystyrene 3-formylsalicylate and furoic acid hydrazide in DMF in the presence of ethyl acetate results in the formation of polystyrene N-(2-carbamoylfuranyl-3'-carboxy-2'-hydroxybenzylideneimine (I. A benzene suspension of I reacts with mercaptoacetic acid and forms the polystyrene N-(2-carbamoylfuranyl-C-(3'-carboxy-2'-hydroxyphenylthiazolidin-4-one, PSCH2–LH2 (II. A DMF suspension of II reacts with Mn(II, Ni(II, Cd(II, Fe(III and UO2(VI ions and forms the polystyrene-anchored coordination compounds of the types, [PSCH2–LMn(DMF3], [PSCH2–LNi(DMF3], [PSCH2–LCd(DMF], [PSCH2–LH2FeCl3] and [PSCH2–LHUO2(NO3(DMF]. The polystyrene-anchored coordination compounds have been characterized on the basis of elemental analyses, spectral (IR, reflectance studies and magnetic susceptibility measurements. II acts as a neutral tridentate ONO donor ligand in [PSCH2–LH2FeCl3], a monobasic tridentate ONO donor ligand in [PSCH2–LHUO2(NO3(DMF], a dibasic tridentate ONO donor ligand in [PSCH2–LMn(DMF3], [PSCH2–LNi(DMF3] and [PSCH2–LCd(DMF]. A tetrahedral structure for Cd(II and an octahedral structure for Mn(II, Ni(II, Fe(III and a square-antiprism geometry for UO2(VI complex are suggested. DOI: http://dx.doi.org/10.4314/bcse.v28i1.4

Fast and Exact Fiber Surfaces for Tetrahedral Meshes.

Science.gov (United States)

Klacansky, Pavol; Tierny, Julien; Carr, Hamish; Zhao Geng

2017-07-01

Isosurfaces are fundamental geometrical objects for the analysis and visualization of volumetric scalar fields. Recent work has generalized them to bivariate volumetric fields with fiber surfaces, the pre-image of polygons in range space. However, the existing algorithm for their computation is approximate, and is limited to closed polygons. Moreover, its runtime performance does not allow instantaneous updates of the fiber surfaces upon user edits of the polygons. Overall, these limitations prevent a reliable and interactive exploration of the space of fiber surfaces. This paper introduces the first algorithm for the exact computation of fiber surfaces in tetrahedral meshes. It assumes no restriction on the topology of the input polygon, handles degenerate cases and better captures sharp features induced by polygon bends. The algorithm also allows visualization of individual fibers on the output surface, better illustrating their relationship with data features in range space. To enable truly interactive exploration sessions, we further improve the runtime performance of this algorithm. In particular, we show that it is trivially parallelizable and that it scales nearly linearly with the number of cores. Further, we study acceleration data-structures both in geometrical domain and range space and we show how to generalize interval trees used in isosurface extraction to fiber surface extraction. Experiments demonstrate the superiority of our algorithm over previous work, both in terms of accuracy and running time, with up to two orders of magnitude speedups. This improvement enables interactive edits of range polygons with instantaneous updates of the fiber surface for exploration purpose. A VTK-based reference implementation is provided as additional material to reproduce our results.

Thermodynamics of CoAl2O4-CoGa2O4 solid solutions

International Nuclear Information System (INIS)

Lilova, Kristina I.; Navrotsky, Alexandra; Melot, Brent C.; Seshadri, Ram

2010-01-01

CoAl 2 O 4 , CoGa 2 O 4 , and their solid solution Co(Ga z Al 1-z ) 2 O 4 have been studied using high temperature oxide melt solution calorimetry in molten 2PbO.B 2 O 3 at 973 K. There is an approximately linear correlation between lattice parameters, enthalpy of formation from oxides, and the Ga content. The experimental enthalpy of mixing is zero within experimental error. The cation distribution parameters are calculated using the O'Neill and Navrotsky thermodynamic model. The enthalpies of mixing calculated from these parameters are small and consistent with the calorimetric data. The entropies of mixing are calculated from site occupancies and compared to those for a random mixture of Ga and Al ions on octahedral site with all Co tetrahedral and for a completely random mixture of all cations on both sites. Despite a zero heat of mixing, the solid solution is not ideal in that activities do not obey Raoult's Law because of the more complex entropy of mixing. - Graphical abstract: Measured enthalpies of mixing of CoAl 2 O 4 -CoGa 2 O 4 solid solutions are close to zero but entropies of mixing reflect the complex cation distribution, so the system is not an ideal solution.

AlN and Al oxy-nitride gate dielectrics for reliable gate stacks on Ge and InGaAs channels

Energy Technology Data Exchange (ETDEWEB)

Guo, Y.; Li, H.; Robertson, J. [Engineering Department, Cambridge University, Cambridge CB2 1PZ (United Kingdom)

2016-05-28

AlN and Al oxy-nitride dielectric layers are proposed instead of Al{sub 2}O{sub 3} as a component of the gate dielectric stacks on higher mobility channels in metal oxide field effect transistors to improve their positive bias stress instability reliability. It is calculated that the gap states of nitrogen vacancies in AlN lie further away in energy from the semiconductor band gap than those of oxygen vacancies in Al{sub 2}O{sub 3}, and thus AlN might be less susceptible to charge trapping and have a better reliability performance. The unfavourable defect energy level distribution in amorphous Al{sub 2}O{sub 3} is attributed to its larger coordination disorder compared to the more symmetrically bonded AlN. Al oxy-nitride is also predicted to have less tendency for charge trapping.

Co3(PO42·4H2O

Directory of Open Access Journals (Sweden)

Yang Kim

2008-10-01

Full Text Available Single crystals of Co3(PO42·4H2O, tricobalt(II bis[orthophosphate(V] tetrahydrate, were obtained under hydrothermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO42·4H2O (mineral name hopeite and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetrahedral coordination, while the second, located on a mirror plane, has a distorted octahedral coordination environment. The tetrahedrally coordinated Co2+ is bonded to four O atoms of four PO43− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water molecules (two of which are located on mirror planes, forming a framework structure. In addition, hydrogen bonds of the type O—H...O are present throughout the crystal structure.

Local structure and disorder in crystalline Pb9Al8O21

International Nuclear Information System (INIS)

Hannon, Alex C.; Barney, Emma R.; Holland, Diane; Knight, Kevin S.

2008-01-01

Crystalline Pb 9 Al 8 O 21 is a model compound for the structure of non-linear optical glasses containing lone-pair ions, and its structure has been investigated by neutron powder diffraction and total scattering, and 27 Al magic angle spinning NMR. Rietveld analysis (space group Pa3-bar (No. 205), a=13.25221(4) A) shows that some of the Pb and O sites have partial occupancies, due to lead volatilisation during sample preparation, and the non-stoichiometric sample composition is Pb 9-δ Al 8 O 21-δ with δ=0.54. The NMR measurements show evidence for a correlation between the chemical shift and the variance of the bond angles at the aluminium sites. The neutron total correlation function shows that the true average Al-O bond length is 0.8% longer than the apparent bond length determined by Rietveld refinement. The thermal variation in bond length is much smaller than the thermal variation in longer interatomic distances determined by Rietveld refinement. The total correlation function is consistent with an interpretation in which AlO 3 groups with an Al-O bond length of 1.651 A occur as a result of the oxygen vacancies in the structure. The width of the tetrahedral Al-O peak in the correlation function for the crystal is very similar to that for lead aluminate glass, indicating that the extent of static disorder is very similar in the two phases. - Graphical abstract: Combined neutron powder diffraction and total scattering, and 27 Al NMR on crystalline Pb 9 Al 8 O 21 shows it to be a non-stoichiometric compound with vacancies due to PbO volatilisation. A detailed consideration of the thermal and static disorder is given, showing that glass and crystal phases have very similar disorder at short range

Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations

Energy Technology Data Exchange (ETDEWEB)

Flank, A-M; Trcera, N; Itie, J-P; Lagarde, P [Synchrotron Soleil, L' Orme des Merisiers, BP 48, 91192 Gif sur Yvette (France); Brunet, F [Laboratoire de Geologie, CNRS-ENS-UMR8538, 24 rue Lhommond, 75005 Paris (France); Irifune, T [Geodynamics Research Center, Ehime University, Matsuyama 790-8577 (Japan)

2009-11-15

Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO{sub 4} groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO{sub 6} groups). This new coordination was achieved in AlPO{sub 4} doped SiO{sub 2} stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100{mu}m diameter) were embedded in the back-transformation products of high pressure form of AlPO{sub 4} matrix. They were identified by elemental mapping ({mu}-XRF). {mu}-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations

Science.gov (United States)

Flank, A.-M.; Trcera, N.; Brunet, F.; Itié, J.-P.; Irifune, T.; Lagarde, P.

2009-11-01

Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO6 groups). This new coordination was achieved in AlPO4 doped SiO2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations

International Nuclear Information System (INIS)

Flank, A-M; Trcera, N; Itie, J-P; Lagarde, P; Brunet, F; Irifune, T

2009-01-01

Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO 4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO 6 groups). This new coordination was achieved in AlPO 4 doped SiO 2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO 4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

LiBSi{sub 2}: a tetrahedral semiconductor framework from boron and silicon atoms bearing lithium atoms in the channels

Energy Technology Data Exchange (ETDEWEB)

Zeilinger, Michael; Faessler, Thomas F. [Department of Chemistry, Technische Universitaet Muenchen, Garching (Germany); Wuellen, Leo van [Department of Physics, University of Augsburg (Germany); Benson, Daryn [Department of Physics, Arizona State University, Tempe, AZ (United States); Kranak, Verina F.; Konar, Sumit; Haeussermann, Ulrich [Department of Materials and Environmental Chemistry, Stockholm University (Sweden)

2013-06-03

Silicon swallows up boron. The novel open tetrahedral framework structure (OTF) of the Zintl phase LiBSi{sub 2} was made by applying high pressure to a mixture of LiB and elemental silicon. The compound represents a new topology in the B-Si net (called tum), which hosts Li atoms in the channels. LiBSi{sub 2} is the first example where B and Si atoms form an ordered common framework structure with B engaged exclusively in heteronuclear B-Si contacts. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Longitudinal momentum distributions in transverse coordinate space

International Nuclear Information System (INIS)

Kumar, Narinder; Mondal, Chandan

2016-01-01

In the present work, we study the longitudinal momentum distributions in the transverse coordinate space in a light-front quark-diquark model inspired by soft-wall AdS/QCD. We take the phenomenological light-front quark-diquark model proposed by Gutsche et. al. In this model, the light-front wave functions (LFWFs) for the proton are constructed from the two particle wave functions obtained in soft-wall AdS/QCD

Luminescence properties of copper(I), zinc(II) and cadmium(II) coordination compounds with picoline ligands

Energy Technology Data Exchange (ETDEWEB)

Małecki, Jan Grzegorz, E-mail: gmalecki@us.edu.pl; Maroń, Anna

2017-06-15

Mononuclear coordination compounds of copper(I) – [Cu(PPh{sub 3}){sub 2}(picoline)(NO{sub 3})], zinc(II) – [ZnCl{sub 2}(picoline){sub 2}] (picoline=3– and 4–methylpyridine) and polymeric cadmium(II) – [CdCl{sub 2}(β-picoline){sub 2}]{sub n} were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. Single crystal X-ray crystallography revealed distorted tetrahedral geometry around the central ions of the compounds. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. The emission of copper(I) compounds originated from metal-to-ligand charge transfer state combined with nitrato-to-picoline charge transfer state i.e. ({sup 1}(M+X)LCT). The presence of nitrato ligand in the coordination sphere of copper(I) compounds quenches the emission. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution). - Graphical abstract: Coordination compounds of copper(I), zinc(II) and polymeric cadmium(II) with picoline ligands were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. Emission of copper(I) compounds originated from {sup 1}(M+X)LCT state. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution).

Tetrahedral silsesquioxane-C2H2Ti complex for hydrogen storage

Science.gov (United States)

Konda, Ravinder; Tavhare, Priyanka; Ingale, Nilesh; Chaudhari, Ajay

2018-04-01

The interaction of molecular hydrogen with tetrahedral silsesquioxane (T4)-C2H2Ti complex has been studied using Density Functional Theory with M06-2X functional and MP2 method with 6-311++G** basis set. T4-C2H2Ti complex can absorb maximum five hydrogen molecules with the gravimetric hydrogen storage capacity of 3.4 wt %. Adsorption energy calculations show that H2 adsorption on T4-C2H2Ti complex is favorable at room temperature by both the methods. We have studied the effect of temperature and pressure on Gibbs free energy corrected adsorption energies. Molecular dynamics simulations for H2 adsorbed T4-C2H2Ti complex have also been performed at 300K and show that loosely bonded H2 molecule flies away within 1fs. Various interaction energies within the complex are studied. Stability of a complex is predicted by means of a gap between Highest Occupied Molecular Orbital (HUMO) and Lowest Unoccupied Molecular Orbital (LUMO). The H2 desorption temperature for T4-C2H2Ti complex is calculated with Van't Hoff equation and it is found to be 229K.

Martinandresite, Ba2(Al4Si12O32)·10H2O, a new zeolite from Wasenalp, Switzerland

Science.gov (United States)

Chukanov, Nikita V.; Zubkova, Natalia V.; Meisser, Nicolas; Ansermet, Stefan; Weiss, Stefan; Pekov, Igor V.; Belakovskiy, Dmitriy I.; Vozchikova, Svetlana A.; Britvin, Sergey N.; Pushcharovsky, Dmitry Yu.

2018-06-01

The new zeolite martinandresite, ideally Ba2(Al4Si12O32)·10H2O, was discovered in the armenite locality of Wasenalp near the Isenwegg peak, Ganter valley, Simplon region, Switzerland. The associated minerals are armenite, quartz, dickite, and chlorite. Martinandresite forms tan-coloured blocky crystals up to 8 × 5 × 3.5 mm, their aggregates up to 6 cm across, as well as cruciform twins up to 3.5 mm. The major form is {010}; the subordinate forms are {100} and {001}. Indistinct cleavage is observed, presumably on (010) and in a direction across (010). The Mohs' hardness is 4½. Density measured by flotation in heavy liquids is 2.482(5) g/cm3. Density calculated using the empirical formula is equal to 2.495 g/cm3. Martinandresite is optically biaxial, negative, α = 1.500(2), β = 1.512(2), γ = 1.515(2) ( λ = 589 nm). 2 V (meas.) = 55(10)°. The IR spectrum is given. The chemical composition of martinandresite is (wt%; electron microprobe, H2O determined by the modified Penfield method): Na2O 0.37, K2O 0.12, BaO 21.55, Al2O3 15.03, SiO2 49.86, H2O 12.57, total 99.50. The empirical formula based on 16 atoms Si + Al pfu is Na0.17K0.04Ba2.00(Al4.19Si11.81O32)H19.85O9.93. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is orthorhombic, space group Pmmn, with a = 9.4640(5), b = 14.2288(6), c = 6.9940(4) Å, V = 941.82(8) Å3 and Z = 1. The crystal structure of martinandresite is unique and is based on the Al-Si-O tetrahedral framework containing four-, six- and eight-membered rings of tetrahedra. Si and Al are disordered between the two independent tetrahedral sites. The strongest lines of the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are: 6.98 (74) (001), 6.26 (83) (011), 5.61 (100) (101), 3.933 (60) (220, 031), 3.191 (50) (112), 3.170 (62) (041), 3.005 (79) (231, 141). Martinandresite is named after Martin Andres (b. 1965), the discoverer of the armenite locality of Wasenalp.

Martinandresite, Ba2(Al4Si12O32)·10H2O, a new zeolite from Wasenalp, Switzerland

Science.gov (United States)

Chukanov, Nikita V.; Zubkova, Natalia V.; Meisser, Nicolas; Ansermet, Stefan; Weiss, Stefan; Pekov, Igor V.; Belakovskiy, Dmitriy I.; Vozchikova, Svetlana A.; Britvin, Sergey N.; Pushcharovsky, Dmitry Yu.

2017-12-01

The new zeolite martinandresite, ideally Ba2(Al4Si12O32)·10H2O, was discovered in the armenite locality of Wasenalp near the Isenwegg peak, Ganter valley, Simplon region, Switzerland. The associated minerals are armenite, quartz, dickite, and chlorite. Martinandresite forms tan-coloured blocky crystals up to 8 × 5 × 3.5 mm, their aggregates up to 6 cm across, as well as cruciform twins up to 3.5 mm. The major form is {010}; the subordinate forms are {100} and {001}. Indistinct cleavage is observed, presumably on (010) and in a direction across (010). The Mohs' hardness is 4½. Density measured by flotation in heavy liquids is 2.482(5) g/cm3. Density calculated using the empirical formula is equal to 2.495 g/cm3. Martinandresite is optically biaxial, negative, α = 1.500(2), β = 1.512(2), γ = 1.515(2) (λ = 589 nm). 2V (meas.) = 55(10)°. The IR spectrum is given. The chemical composition of martinandresite is (wt%; electron microprobe, H2O determined by the modified Penfield method): Na2O 0.37, K2O 0.12, BaO 21.55, Al2O3 15.03, SiO2 49.86, H2O 12.57, total 99.50. The empirical formula based on 16 atoms Si + Al pfu is Na0.17K0.04Ba2.00(Al4.19Si11.81O32)H19.85O9.93. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is orthorhombic, space group Pmmn, with a = 9.4640(5), b = 14.2288(6), c = 6.9940(4) Å, V = 941.82(8) Å3 and Z = 1. The crystal structure of martinandresite is unique and is based on the Al-Si-O tetrahedral framework containing four-, six- and eight-membered rings of tetrahedra. Si and Al are disordered between the two independent tetrahedral sites. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.98 (74) (001), 6.26 (83) (011), 5.61 (100) (101), 3.933 (60) (220, 031), 3.191 (50) (112), 3.170 (62) (041), 3.005 (79) (231, 141). Martinandresite is named after Martin Andres (b. 1965), the discoverer of the armenite locality of Wasenalp.

Sonochemical synthesis and characterization of nano-sized zinc(II coordination complex as a precursor for the preparation of pure-phase zinc(II oxide nanoparticles

Directory of Open Access Journals (Sweden)

Maryam Ranjbar

2017-01-01

Full Text Available In current study, nanoparticles and single crystals of a Zn(II coordination complex, [Zn(dmphI2](1, {dmph=2,9-dimethyl-1,10-phenanthroline(neocuproine}, have been synthesized by the reaction of zinc(II acetate, KI and neocuproine as ligand in methanol using sonochemical and heat gradient methods, respectively. The nanostructure of 1 was characterized by scanning electron microscopy (SEM, X-ray powder diffraction (XRD, FT-IR spectroscopy and elemental analyses, and the structure of compound 1 was determined by single-crystal X-ray diffraction. The thermal stability of nano-sized 1 has been studied by thermogravimetric (TG and differential thermal analyses (DTA. Structural determination of compound 1 reveals the Zn(II ion is four-coordinated in a distorted tetrahedral configuration by two N atoms from a 2,9-dimethyl-1,10-Phenanthroline ligand and two terminal I atoms. The effect of supercritical condition on stability, size and morphology of nano-structured compound 1 has also been studied. The XRD pattern of the residue obtained from thermal decomposition of nano-sized compound 1 at 600 °C under air atmosphere provided pure phase of ZnO with the average particles size of about 31 nm.

The Crystal Structure of Cu4Bi4Se9

DEFF Research Database (Denmark)

Makovicky, E.; Søtofte, Inger; Karup-Møller, S.

2002-01-01

contains three square pyramidal Bi sites, an octahedrally coordinated Bi site as well as two tetrahedrally and two irregularly coordinated Cu sites. The structure is an intergrowth of PbS-like slabs with irregularly configured slabs of Bi pyramids and Cu tetrahedra. It contains covalently bonded Se-2...

The Space-Time Conservative Schemes for Large-Scale, Time-Accurate Flow Simulations with Tetrahedral Meshes

Science.gov (United States)

Venkatachari, Balaji Shankar; Streett, Craig L.; Chang, Chau-Lyan; Friedlander, David J.; Wang, Xiao-Yen; Chang, Sin-Chung

2016-01-01

Despite decades of development of unstructured mesh methods, high-fidelity time-accurate simulations are still predominantly carried out on structured, or unstructured hexahedral meshes by using high-order finite-difference, weighted essentially non-oscillatory (WENO), or hybrid schemes formed by their combinations. In this work, the space-time conservation element solution element (CESE) method is used to simulate several flow problems including supersonic jet/shock interaction and its impact on launch vehicle acoustics, and direct numerical simulations of turbulent flows using tetrahedral meshes. This paper provides a status report for the continuing development of the space-time conservation element solution element (CESE) numerical and software framework under the Revolutionary Computational Aerosciences (RCA) project. Solution accuracy and large-scale parallel performance of the numerical framework is assessed with the goal of providing a viable paradigm for future high-fidelity flow physics simulations.

Luminescence of Eu:Y3Al5O12, Eu:Lu3Al5O12, and Eu:GdAlO3 Nanocrystals Synthesized by Solution Combustion

Science.gov (United States)

Vilejshikova, E. V.; Khort, A. A.; Podbolotov, K. B.; Loiko, P. A.; Shimanski, V. I.; Shashkov, S. N.; Yumashev, K. V.

2017-11-01

Nanocrystals of rare-earth garnets Y3Al5O12 and Lu3Al5O12 and perovskite GdAlO3 highly doped (10-20 at%) with Eu3+ are synthesized by the solution combustion technique and subsequent annealing in air at 800 and 1300oC. Their structure, morphology, and phase composition are studied. These materials exhibit intense red luminescence under UV excitation. Eu:GdAlO3 luminescence has CIE 1931 color coordinates (0.632, 0.368); dominant wavelength, 599.6 nm; and color purity, >99%. Judd-Ofelt parameters, luminescence branching ratios, and lifetimes of the Eu3+ 5D0 state are determined. The luminescence quantum yield for Eu:GdAlO3 (10 at%) reaches 74% with a lifetime of 1.4 ms for the 5D0 state. The synthesized materials are promising for red ceramic phosphors.

Insights into Substrate Specificity and Metal Activation of Mammalian Tetrahedral Aspartyl Aminopeptidase

Energy Technology Data Exchange (ETDEWEB)

Chen, Yuanyuan; Farquhar, Erik R.; Chance, Mark R.; Palczewski, Krzysztof; Kiser, Philip D. (Case Western)

2012-07-11

Aminopeptidases are key enzymes involved in the regulation of signaling peptide activity. Here, we present a detailed biochemical and structural analysis of an evolutionary highly conserved aspartyl aminopeptidase called DNPEP. We show that this peptidase can cleave multiple physiologically relevant substrates, including angiotensins, and thus may play a key role in regulating neuron function. Using a combination of x-ray crystallography, x-ray absorption spectroscopy, and single particle electron microscopy analysis, we provide the first detailed structural analysis of DNPEP. We show that this enzyme possesses a binuclear zinc-active site in which one of the zinc ions is readily exchangeable with other divalent cations such as manganese, which strongly stimulates the enzymatic activity of the protein. The plasticity of this metal-binding site suggests a mechanism for regulation of DNPEP activity. We also demonstrate that DNPEP assembles into a functionally relevant tetrahedral complex that restricts access of peptide substrates to the active site. These structural data allow rationalization of the enzyme's preference for short peptide substrates with N-terminal acidic residues. This study provides a structural basis for understanding the physiology and bioinorganic chemistry of DNPEP and other M18 family aminopeptidases.

Syntheses, Magnetic and Spectral Studies on the Coordination Compounds of the Polystyrene-anchored Thiazolidin-4-one

Directory of Open Access Journals (Sweden)

Dinesh Kumar

2012-01-01

Full Text Available The reaction between polystyrene 3-formylsalicylate and thiophene-2-carboxylic acid hydrazide in DMF in the presence of ethyl acetate results in the formation of polystyrene N-(2-carbamoylthienyl-3'-carboxy-2'-hydroxybenzylideneimine (I. A benzene suspension of I reacts with mercaptoacetic acid and forms the polystyrene N-(2-carbamoylthienyl-C-(3'-carboxy-2'-hydroxyphenyl thiazolidin-4-one, PSCH2–LH2 (II. A DMF suspension of II reacts with Zn(II, Co(II, Cu(II, Zr(OH2(IV and MoO2(VI ions and forms the corresponding polystyrene-anchored coordination compounds, [PSCH2–LZn(DMF] (III, [PSCH2–LCo(DMF3] (IV, [PSCH2–LHCu(OAc] (V, [PSCH2–LH2Zr(OH2(OAc2] (VI and [PSCH2–LHMoO2(acac] (VII respectively. The polystyrene-anchored coordination compounds have been characterized on the basis of elemental analyses, spectral (IR, reflectance, ESR studies and magnetic susceptibility measurements. II acts as a neutral tridentate ONS donor ligand in VI, a monobasic bidentate OS donor ligand in VII, a monobasic tridentate ONS donor ligand in V and a dibasic tridentate ONO donor ligand in III and IV. The acetato groups behave as monodentate ligands in V and VI. A square-planar structure for V, a tetrahedral structure for III, an octahedral structure for IV and VII and a pentagonal-bipyramidal structure for VI are suggested.

TU-AB-202-05: GPU-Based 4D Deformable Image Registration Using Adaptive Tetrahedral Mesh Modeling

International Nuclear Information System (INIS)

Zhong, Z; Zhuang, L; Gu, X; Wang, J; Chen, H; Zhen, X

2016-01-01

Purpose: Deformable image registration (DIR) has been employed today as an automated and effective segmentation method to transfer tumor or organ contours from the planning image to daily images, instead of manual segmentation. However, the computational time and accuracy of current DIR approaches are still insufficient for online adaptive radiation therapy (ART), which requires real-time and high-quality image segmentation, especially in a large datasets of 4D-CT images. The objective of this work is to propose a new DIR algorithm, with fast computational speed and high accuracy, by using adaptive feature-based tetrahedral meshing and GPU-based parallelization. Methods: The first step is to generate the adaptive tetrahedral mesh based on the image features of a reference phase of 4D-CT, so that the deformation can be well captured and accurately diffused from the mesh vertices to voxels of the image volume. Subsequently, the deformation vector fields (DVF) and other phases of 4D-CT can be obtained by matching each phase of the target 4D-CT images with the corresponding deformed reference phase. The proposed 4D DIR method is implemented on GPU, resulting in significantly increasing the computational efficiency due to its parallel computing ability. Results: A 4D NCAT digital phantom was used to test the efficiency and accuracy of our method. Both the image and DVF results show that the fine structures and shapes of lung are well preserved, and the tumor position is well captured, i.e., 3D distance error is 1.14 mm. Compared to the previous voxel-based CPU implementation of DIR, such as demons, the proposed method is about 160x faster for registering a 10-phase 4D-CT with a phase dimension of 256×256×150. Conclusion: The proposed 4D DIR method uses feature-based mesh and GPU-based parallelism, which demonstrates the capability to compute both high-quality image and motion results, with significant improvement on the computational speed.

TU-AB-202-05: GPU-Based 4D Deformable Image Registration Using Adaptive Tetrahedral Mesh Modeling

Energy Technology Data Exchange (ETDEWEB)

Zhong, Z; Zhuang, L [Wayne State University, Detroit, MI (United States); Gu, X; Wang, J [UT Southwestern Medical Center, Dallas, TX (United States); Chen, H; Zhen, X [Southern Medical University, Guangzhou, Guangdong (China)

2016-06-15

Purpose: Deformable image registration (DIR) has been employed today as an automated and effective segmentation method to transfer tumor or organ contours from the planning image to daily images, instead of manual segmentation. However, the computational time and accuracy of current DIR approaches are still insufficient for online adaptive radiation therapy (ART), which requires real-time and high-quality image segmentation, especially in a large datasets of 4D-CT images. The objective of this work is to propose a new DIR algorithm, with fast computational speed and high accuracy, by using adaptive feature-based tetrahedral meshing and GPU-based parallelization. Methods: The first step is to generate the adaptive tetrahedral mesh based on the image features of a reference phase of 4D-CT, so that the deformation can be well captured and accurately diffused from the mesh vertices to voxels of the image volume. Subsequently, the deformation vector fields (DVF) and other phases of 4D-CT can be obtained by matching each phase of the target 4D-CT images with the corresponding deformed reference phase. The proposed 4D DIR method is implemented on GPU, resulting in significantly increasing the computational efficiency due to its parallel computing ability. Results: A 4D NCAT digital phantom was used to test the efficiency and accuracy of our method. Both the image and DVF results show that the fine structures and shapes of lung are well preserved, and the tumor position is well captured, i.e., 3D distance error is 1.14 mm. Compared to the previous voxel-based CPU implementation of DIR, such as demons, the proposed method is about 160x faster for registering a 10-phase 4D-CT with a phase dimension of 256×256×150. Conclusion: The proposed 4D DIR method uses feature-based mesh and GPU-based parallelism, which demonstrates the capability to compute both high-quality image and motion results, with significant improvement on the computational speed.

Multi-particle three-dimensional coordinate estimation in real-time optical manipulation

DEFF Research Database (Denmark)

Dam, Jeppe Seidelin; Perch-Nielsen, Ivan R.; Palima, Darwin

2009-01-01

We have previously shown how stereoscopic images can be obtained in our three-dimensional optical micromanipulation system [J. S. Dam et al, Opt. Express 16, 7244 (2008)]. Here, we present an extension and application of this principle to automatically gather the three-dimensional coordinates for...

MCrAlY bond coat with enhanced yttrium

Science.gov (United States)

Jablonski, Paul D.; Hawk, Jeffrey A.

2016-08-30

One or more embodiments relates to a method of producing an MCrAlY bond coat comprising an MCrAlY layer in contact with a Y--Al.sub.2O.sub.3 layer. The MCrAlY layer is comprised of a .gamma.-M solid solution, a .beta.-MAl intermetallic phase, and Y-type intermetallics. The Y--Al.sub.2O.sub.3 layer is comprised of Yttrium atoms coordinated with oxygen atoms comprising the Al.sub.2O.sub.3 lattice. The method comprises depositing an MCrAlY material on a substrate, applying an Y.sub.2O.sub.3 paste, and heating the substrate in a non-oxidizing atmosphere at a temperature between 400-1300.degree. C. for a time sufficient to generate the Y--Al.sub.2O.sub.3 layer. Both the MCrAlY layer and the Y--Al.sub.2O.sub.3 layer have a substantial absence of Y.sub.2O.sub.3, YAG, and YAP phases.

Implementation of an integrated primary care cardiometabolic risk prevention and management network in Montréal: does greater coordination of care with primary care physicians have an impact on health outcomes?

Directory of Open Access Journals (Sweden)

Sylvie Provost

2017-04-01

Full Text Available Introduction: Chronic disease management requires substantial services integration. A cardiometabolic risk management program inspired by the Chronic Care Model was implemented in Montréal for patients with diabetes or hypertension. One of this study's objectives was to assess the impact of care coordination between the interdisciplinary teams and physicians on patient participation in the program, lifestyle improvements and disease control. Methods: We obtained data on health outcomes from a register of clinical data, questionnaires completed by patients upon entry into the program and at the 12-month mark, and we drew information on the program's characteristics from the implementation analysis. We conducted multiple regression analyses, controlling for patient sociodemographic and health characteristics to measure the association between interdisciplinary team coordination with primary care physicians and various health outcomes. Results: A total of 1689 patients took part in the study (60.1% participation rate. Approximately 40% of patients withdrew from the program during the first year. At the 12-month follow-up (n = 992, we observed a significant increase in the proportion of patients achieving the various clinical targets. The perception by the interdisciplinary team of greater care coordination with primary care physicians was associated with increased participation in the program and the achievement of better clinical results. Conclusion: Greater coordination of patient services between interdisciplinary teams and primary care physicians translates into benefits for patients.

Implementation of an integrated primary care cardiometabolic risk prevention and management network in Montréal: does greater coordination of care with primary care physicians have an impact on health outcomes?

Science.gov (United States)

Provost, Sylvie; Pineault, Raynald; Grimard, Dominique; Pérez, José; Fournier, Michel; Lévesque, Yves; Desforges, Johanne; Tousignant, Pierre; Borgès Da Silva, Roxane

2017-04-01

Chronic disease management requires substantial services integration. A cardiometabolic risk management program inspired by the Chronic Care Model was implemented in Montréal for patients with diabetes or hypertension. One of this study's objectives was to assess the impact of care coordination between the interdisciplinary teams and physicians on patient participation in the program, lifestyle improvements and disease control. We obtained data on health outcomes from a register of clinical data, questionnaires completed by patients upon entry into the program and at the 12-month mark, and we drew information on the program's characteristics from the implementation analysis. We conducted multiple regression analyses, controlling for patient sociodemographic and health characteristics, to measure the association between interdisciplinary team coordination with primary care physicians and various health outcomes. A total of 1689 patients took part in the study (60.1% participation rate). Approximately 40% of patients withdrew from the program during the first year. At the 12-month follow-up (n = 992), we observed a significant increase in the proportion of patients achieving the various clinical targets. The perception by the interdisciplinary team of greater care coordination with primary care physicians was associated with increased participation in the program and the achievement of better clinical results. Greater coordination of patient services between interdisciplinary teams and primary care physicians translates into benefits for patients.

21 January 2008 - Vice-President of the Human Rights Commission Z. Muhsin Al Hussein, Ambassador to United Nations A. Attar and their delegation from Saudi Arabia, visiting the ATLAS experimental cavern with Collaboration Spokesperson P. Jenni and Technical Coordinator M. Nessi.

CERN Multimedia

Claudia Marcelloni

2008-01-01

21 January 2008 - Vice-President of the Human Rights Commission Z. Muhsin Al Hussein, Ambassador to United Nations A. Attar and their delegation from Saudi Arabia, visiting the ATLAS experimental cavern with Collaboration Spokesperson P. Jenni and Technical Coordinator M. Nessi.

The AgMIP Coordinated Climate-Crop Modeling Project (C3MP): Methods and Protocols

Science.gov (United States)

Shukla, Sonali P.; Ruane, Alexander Clark

2014-01-01

Climate change is expected to alter a multitude of factors important to agricultural systems, including pests, diseases, weeds, extreme climate events, water resources, soil degradation, and socio-economic pressures. Changes to carbon dioxide concentration ([CO2]), temperature, and water (CTW) will be the primary drivers of change in crop growth and agricultural systems. Therefore, establishing the CTW-change sensitivity of crop yields is an urgent research need and warrants diverse methods of investigation. Crop models provide a biophysical, process-based tool to investigate crop responses across varying environmental conditions and farm management techniques, and have been applied in climate impact assessment by using a variety of methods (White et al., 2011, and references therein). However, there is a significant amount of divergence between various crop models' responses to CTW changes (Rotter et al., 2011). While the application of a site-based crop model is relatively simple, the coordination of such agricultural impact assessments on larger scales requires consistent and timely contributions from a large number of crop modelers, each time a new global climate model (GCM) scenario or downscaling technique is created. A coordinated, global effort to rapidly examine CTW sensitivity across multiple crops, crop models, and sites is needed to aid model development and enhance the assessment of climate impacts (Deser et al., 2012). To fulfill this need, the Coordinated Climate-Crop Modeling Project (C3MP) (Ruane et al., 2014) was initiated within the Agricultural Model Intercomparison and Improvement Project (AgMIP; Rosenzweig et al., 2013). The submitted results from C3MP Phase 1 (February 15, 2013-December 31, 2013) are currently being analyzed. This chapter serves to present and update the C3MP protocols, discuss the initial participation and general findings, comment on needed adjustments, and describe continued and future development. AgMIP aims to improve

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100- x Al x Metallic Glasses

Science.gov (United States)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-06-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated and 13-coordinated ) and by playing a main role in the structure stability of the Ti-Al MGs.

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100-x Al x Metallic Glasses

Science.gov (United States)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-03-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated and 13-coordinated ) and by playing a main role in the structure stability of the Ti-Al MGs.

Magnesium doping on brownmillerite Ca2FeAlO5

International Nuclear Information System (INIS)

Malveiro, J.; Ramos, T.; Ferreira, L.P.; Waerenborgh, J.C.; Nunes, M.R.; Godinho, M.; Carvalho, M.D.

2007-01-01

Ca 2 FeAl 1- x Mg x O 5 (x=0, 0.05 and 0.1) compounds adopting the brownmillerite-type structure were prepared by a self-combustion route using two different fuels. Characterisation was performed using X-ray powder diffraction, Moessbauer spectroscopy, magnetisation measurements, chemical analysis, scanning electron microscopy and 4-point dc conductivity measurements. Global results indicate that the solubility limit was reached for x=0.1. An antiferromagnetic behaviour was detected for all studied compositions, with magnetic ordering temperatures of 340 and 290 K for x=0 and 0.05, respectively. Mg doping increases the number of iron cations in tetrahedral sites, which induces magnetisation enhancement at low temperatures through the coupling between octahedral iron cations in different octahedral planes. The compounds exhibit semiconductor behaviour and Mg 2+ doping yields a significant enhancement of the total conductivity, which can be essentially attributed to the presence of Fe 4+ ions. - Graphical abstract: Ca 2 FeAl 1- x Mg x O 5 (x=0, 0.05, 0.1) compounds with the brownmillerite structure were prepared and characterised. The paramagnetic Moessbauer spectra presented were obtained at T=363 K (x=0); T=297 K (x=0.05) and T=353 K (x=0.1)

Superstructure formation in PrNi_2Al_3 and ErPd_2Al_3

International Nuclear Information System (INIS)

Eustermann, Fabian; Hoffmann, Rolf-Dieter; Janka, Oliver; Oldenburg Univ.

2017-01-01

The intermetallic phase ErPd_2Al_3 was obtained by arc-melting of the elements and subsequent annealing for crystal growth. The sample was studied by X-ray diffraction on powders and single crystals. The structure of ErPd_2Al_3 was refined from X-ray diffraction data and revealed a superstructure of PrNi_2Al_3 - a CaCu_5 derivative (P6/m, a=1414.3(1), c=418.87(3) pm wR=0.0820, 1060 F"2 values, 48 variables). The same superstructure was subsequently found for PrNi_2Al_3 (P6/m, a=1407.87(4), c=406.19(2) pm, wR=0.0499, 904 F"2 values, 47 variables). In the crystal structure, the aluminium and transition metal atoms form a polyanionic network according to [T_2Al_3]"δ"-, while rare earth atoms fill cavities within the networks. They are coordinated by six transition metal and twelve aluminum atoms. In contrast to the PrNi_2Al_3 type structure reported so far, two crystallographic independent rare-earth sites are found of which one (1b) is shifted by 1/2 z, causing a distortion in the structure along with a recoloring of the T and Al atoms in the network.

Algebraic and coordinate space potentials from heavy ion scattering

International Nuclear Information System (INIS)

Amos, K.; Berge, L.; Allen, L.J.; Fiedeldey, H.

1993-01-01

An inversion scheme is presented to derive the potentials of algebraic scattering theory from the corresponding S-functions. Representative heavy ion scattering data of 12 C, 14 N and 16 O ions on 208 Pb, accurately fitted by McIntyre strong absorption type S-functions, are employed to obtain exact algebraic potentials and to generalize the analytical shapes proposed previously by Alhassid et al. The coordinate space potentials corresponding to a number of S-functions are also obtained via semiclassical inversion. The major advantage of the algebraic potentials is that, at a theoretical level they are more directly related to the S-functions than are coordinate space potentials. 16 refs., 1 tab., 9 figs

Automated Support for Rapid Coordination of Joint UUV Operation

Science.gov (United States)

2015-03-01

Figure 20. MOOS -IvP Simulation Test Run Using the pMarineViewer Graphical User Interface, from [9...Global Positioning System ISR intelligence, surveillance and reconnaissance MAUV multiple AUVs Mbps megabits per second MOOS -IvP mission oriented...it to UUV coordination. D. Jiang et al. used the mission-oriented operating suite interval programming ( MOOS -IvP) architecture (open source) and a

Mo-containing tetrahedral amorphous carbon deposited by dual filtered cathodic vacuum arc with selective pulsed bias voltage

International Nuclear Information System (INIS)

Pasaja, Nitisak; Sansongsiri, Sakon; Intarasiri, Saweat; Vilaithong, Thiraphat; Anders, Andre

2007-01-01

Metal-containing tetrahedral amorphous carbon films were produced by dual filtered cathodic vacuum arc plasma sources operated in sequentially pulsed mode. Negatively pulsed bias was applied to the substrate when carbon plasma was generated, whereas it was absent when the molybdenum plasma was presented. Film thickness was measured after deposition by profilometry. Glass slides with silver pads were used as substrates for the measurement of the sheet resistance. The microstructure and composition of the films were characterized by Raman spectroscopy and Rutherford backscattering, respectively. It was found that the electrical resistivity decreases with an increase of the Mo content, which can be ascribed to an increase of the sp 2 content and an increase of the sp 2 cluster size

Co2+ ion exchange with NaY

International Nuclear Information System (INIS)

Garcia, I.; Solache-Rios, M.; Bulbulian, S.; Bosch, P.

1993-01-01

Co 2+ ion exchange from aqueous cobalt chloride-sodium chloride solutions with NaY zeolite has been investigated. The effect of contact time on the sorption of Co 2+ by dehydrated Y zeolite at 150 degrees C is unusual. A fast sorption uptake is observed in which 1.73 mequiv/g of zeolite of Na + ions is replaced by cobalt ions, followed by a desorption process where the uptake decreases to 1.56 mequiv/g of zeolite. This behavior is explained by the location and coordination of cobalt in Y zeolite sites. It is suggested that the maximum uptake corresponds to cobalt ions being simultaneously in two sites; tetrahedrally coordinated in the sodalite units and octahedrally coordinated in the large cavities. It is also suggested that the desorption process is a consequence of a reaction between Cl - ions and the tetrahedral species. 20 refs., 4 figs

Reaction mechanisms of phosphate with Al(OH)3 and a sandy soil

NARCIS (Netherlands)

Riemsdijk, van W.H.

1979-01-01

Al(OH) ₃ is a very effective sorbent for orthophosphate especially at low pH. At low phosphate concentration c _p , phosphate is adsorbed by an exchange mechanism with singly coordinated OH(H) groups residing on the surface of the Al(OH)

MCrAlY bond coat with enhanced Yttrium layer

Science.gov (United States)

Jablonski, Paul D; Hawk, Jeffrey A

2015-04-21

One or more embodiments relates to an MCrAlY bond coat comprising an MCrAlY layer in contact with a Y--Al.sub.2O.sub.3 layer. The MCrAlY layer is comprised of a .gamma.-M solid solution, a .beta.-MAl intermetallic phase, and Y-type intermetallics. The Y--Al.sub.2O.sub.3 layer is comprised of Yttrium atoms coordinated with oxygen atoms comprising the Al.sub.2O.sub.3 lattice. Both the MCrAlY layer and the Y--Al.sub.2O.sub.3 layer have a substantial absence of Y--Al oxides, providing advantage in the maintainability of the Yttrium reservoir within the MCrAlY bulk. The MCrAlY bond coat may be fabricated through application of a Y.sub.2O.sub.3 paste to an MCrAlY material, followed by heating in a non-oxidizing environment.

Ligand design for alkali-metal-templated self-assembly of unique high-nuclearity CuII aggregates with diverse coordination cage units: crystal structures and properties.

Science.gov (United States)

Du, Miao; Bu, Xian-He; Guo, Ya-Mei; Ribas, Joan

2004-03-19

The construction of two unique, high-nuclearity Cu(II) supramolecular aggregates with tetrahedral or octahedral cage units, [(mu(3)-Cl)[Li subset Cu(4)(mu-L(1))(3)](3)](ClO(4))(8)(H(2)O)(4.5) (1) and [[Na(2) subset Cu(12)(mu-L(2))(8)(mu-Cl)(4)](ClO(4))(8)(H(2)O)(10)(H(3)O(+))(2)](infinity) (2) by alkali-metal-templated (Li(+) or Na(+)) self-assembly, was achieved by the use of two newly designed carboxylic-functionalized diazamesocyclic ligands, N,N'-bis(3-propionyloxy)-1,4-diazacycloheptane (H(2)L(1)) or 1,5-diazacyclooctane-N,N'-diacetate acid (H(2)L(2)). Complex 1 crystallizes in the trigonal R3c space group (a = b = 20.866(3), c = 126.26(4) A and Z = 12), and 2 in the triclinic P1 space group (a = 13.632(4), b = 14.754(4), c = 19.517(6) A, alpha = 99.836(6), beta = 95.793(5), gamma = 116.124(5) degrees and Z = 1). By subtle variation of the ligand structures and the alkali-metal templates, different polymeric motifs were obtained: a dodecanuclear architecture 1 consisting of three Cu(4) tetrahedral cage units with a Li(+) template, and a supramolecular chain 2 consisting of two crystallographically nonequivalent octahedral Cu(6) polyhedra with a Na(+) template. The effects of ligand functionality and alkali metal template ions on the self-assembly processes of both coordination supramolecular aggregates, and their magnetic behaviors are discussed in detail.

Luminescent properties of Y3Al5−xGaxO12:Ce crystals

International Nuclear Information System (INIS)

Zorenko, Yu.; Zorenko, T.; Malinowski, P.; Sidletskiy, O.; Neicheva, S.

2014-01-01

Absorption, luminescent and scintillation properties of Ce 3+ doped Y 3 Al 5−x Ga x O 12 crystals with Ga content in the x=1–5 range were investigated in this work and compared with the properties of YAG:Ce crystals. Apart from the traditional spectral methods (absorption, cathodoluminescence and light yield measurements), the intrinsic and Ce 3+ related luminescence of Y 3 Al 5−x Ga x O 12 :Ce solid-solution were also investigated using the luminescent spectroscopy under excitation by synchrotron radiation in the 3.7–25 eV range. We show that the optical properties Y 3 Al 5−x Ga x O 12 :Ce garnets monotonically change with increasing the Ga content in the x=0–3 range due to preferable localization of Ga ions in the tetrahedral position of the garnet lattice. At the highest Ga concentration (x>3) the deviation of the optical properties of Y 3 Al 5−x Ga x O 12 :Ce garnets is observed from the respective properties of these crystals with Ga content in the x=0–3 range due to occupation by Ga ions of the octahedral position in the garnet host. - Highlights: • Different dependence of optical properties of Y 3 Al 5−x Ga x O 12 :Ce crystals on Ga content in x=0–3 and 3–5 ranges. • Elimination of the luminescence of Y Al antisite defects in Y 3 Al 5−x Ga x O 12 :Ce crystals at x>2. • Significant improvement of the scintillation properties of Y 3 Al 5−x Ga x O 12 :Ce crystals at x=2 and 3 in comparison with YAG:Ce

Solid-state nuclear magnetic resonance studies of phosphorus and boron in coals and combustion residues

Energy Technology Data Exchange (ETDEWEB)

Burchill, P.; Howarth, O.W.; Richards, D.G.; Sword, B.J. (British Coal Corporation, Stoke Orchard (UK). Coal Research Establishment)

1990-04-01

Solid-state nuclear magnetic resonance spectroscopy with magic angle spinning (MAS-n.m.r.) was used to study the occurrence of phosphorus and boron in coal, and their fate on combustion. These elements are only minor components of coal, but may significantly influence the utilization properties. {sup 31} P MAS-n.m.r. spectroscopy has confirmed that phosphorus is present in coal predominantly as apatite. This mineral is thermally stable under oxidizing conditions, and survives largely unaltered in high temperature ashes. However, under the semi-reducing bed conditions of certain stoker-fired boilers, it may be decomposed, volatilizing the phosphorus. The {sup 31}P MAS-n.m.r. spectra of bonded deposits show phosphorus in a markedly different coordination environment to that in apatite, the chemical shift suggesting aluminium phosphate or boron phosphate. {sup 11}B MAS-n.m.r. spectra of coals exhibit resonances due to both trigonal and tetrahedrally coordinated boron. Trigonal boron is probably present as tourmaline, but the nature of the tetrahedral boron is less certain; it may be held in tetrahedral sites within certain clay minerals. In common with phosphorus, boron may be volatilized during combustion. The {sup 11}B MAS-n.m.r. spectra of bonded deposits show a tetrahedral resonance with a chemical shift quite consistent with that of boron phosphate. 39 refs., 9 figs., 5 tabs.

Synthesis and structure of Li{sub 4}GeS{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Matsushita, Y [National Inst. of Materials and Chemical Research, Tsukuba (Japan). High Pressure Lab.; Kanatzidis, M G [Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry

1998-01-01

The compound Li{sub 4}GeS{sub 4} has been prepared as transparent, light yellow moisture-sensitive crystals. Li{sub 4}GeS{sub 4} belongs to the space group Pnma with a = 14.107(6) A, b = 7.770(3) A and c = 6.162(2) A. The crystal structure was solved by direct-methods. The final R and R{sub w}-values are 1.85 and 1.65% for 866 observed reflections. The Li{sub 4}GeS{sub 4} structure has three crystallographically independent lithium sites and one germanium site. The lithium atoms adopt two different coordination types. The Li1 atom is coordinated to five sulfur atoms in a square pyramidal geometry, while the Li2 and Li3 atoms have distorted tetrahedral coordination. The Ge atom is tetrahedrally coordinated by four sulfur atoms and is found as [GeS{sub 4}]{sup 4-} units. The anisotropic three-dimensional crystal structure of Li{sub 4}GeS{sub 4} is described. (orig.) 57 refs.

High field 27Al MAS NMR and TPD studies of active sites in ethanol dehydration using thermally treated transitional aluminas as catalysts

Energy Technology Data Exchange (ETDEWEB)

Hu, Jian Zhi; Xu, Suochang; Kwak, Ja Hun; Hu, Mary Y.; Wan, Chuan; Zhao, Zhenchao; Szanyi, Janos; Bao, Xinhe; Han, Xiuwen; Wang, Yong; Peden, Charles H. F.

2016-04-01

High field quantitative 27Al MAS NMR and temperature programmed desorption (TPD) of ethanol are used to study the surface and phase transformation of gamma-Al2O3 during calcination in the temperature range of 500 to 1300 degrees C. Following ethanol adsorption, ethylene is generated during TPD with a desorption temperature > 200 degrees C. With increasing calcination temperature prior to TPD, the amount of ethylene produced decreases monotonically. Significantly, 27Al MAS NMR reveals that the amount of penta-coordinate Al3+ ions (Lewis acid sites) also decreases with increasing calcination temperature. In fact, a strong correlation between the amount of penta-coordinate Al3+ ions and the amount of strongly adsorbed ethanol molecules (i.e., the ones that convert to ethylene during TPD) is obtained. This result indicates that the penta-coordinate aluminum sites are the catalytic active sites on alumina surfaces during ethanol dehydration reaction across the entire course of gamma- to alpha-Al2O3 phase transformations.

Synthesis and characterization of the mixed ligand coordination polymer CPO-5

International Nuclear Information System (INIS)

Kongshaug, K.O.; FjellvAg, Helmer

2003-01-01

The synthesis and crystal structures of a novel coordination polymer and its high-temperature variant are described. The as-synthesized material (CPO-5-as), of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate)·3H 2 O, crystallizes in the triclinic space group P-1 (No. 2) with a=11.0197(2), b=14.2975(3), c=7.6586(1) A, α=95.9760(9) deg. , β=108.026(1) deg. , γ=91.373(1) deg. and V=1139.16(4) A 3 . CPO-5-as is composed of tetrahedral zinc centers that are connected by the organic linkers to give five independent, interpenetrating diamond networks. In the structure, there is additional space for channels that are filled with three water molecules. These water molecules can be removed, leading to an anhydrous variant at 130 o C. CPO-5-130, of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate), crystallizes in the triclinic space group P-1 (No. 2) with a=11.1844(6), b=14.0497(7), c=7.7198(3) A, α=96.917(2) deg. , β=109.527(2) deg. , γ=89.115(3) deg. and V=1134.6(1) A 3 . The structure of the five interpenetrating networks is virtually unchanged after the dehydration resulting in CPO-5-130 being a porous structure with an estimated free volume of 19.8%

27Al nuclear magnetic resonance of glassy and crystalline Zr(1-x)AlxO(2-x/2) materials prepared from solution precursors

International Nuclear Information System (INIS)

Balmer, M.L.; Eckert, H.; Das, N.; Lange, F.F.

1996-01-01

The local environment of the aluminum atoms in a series of metastable Zr (1-x) Al x O (2-x/2) crystalline materials (0.08 ≤ x ≤ 0.57), prepared by diffusion-limited crystallization of amorphous precursors, has been determined by 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR). Results show the existence of aluminum in 4-, 5-, and 6-fold coordination in both the amorphous and crystalline states. Although the relative amounts of each type of coordination show no compositional dependence in the amorphous state, the results for the crystalline materials show a systematic decrease in the average aluminum coordination number with increasing aluminum content. Comparisons of MAS NMR results between pure Al 2 O 3 precursors and Zr (1-x) Al x O (2-x/2) crystalline materials processed under similar conditions show a profound effect of ZrO 2 on the coordination environment of the aluminum atom. Both a random distribution model and a model that assumes small-scale clustering of aluminum ions are considered to explain the trends in the type of aluminum coordination as a function of composition

Vibrational spectroscopy of the phosphate mineral lazulite--(Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil.

Science.gov (United States)

Frost, Ray L; Xi, Yunfei; Beganovic, Martina; Belotti, Fernanda Maria; Scholz, Ricardo

2013-04-15

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm(-1) assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO4(2-) units. Two Raman bands at 1102 and 1137 cm(-1) are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm(-1) are attributed to the ν1PO4(3-) symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm(-1) are assigned to the ν3PO4(3-) antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm(-1) are attributed to the ν2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm(-1) are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood. Copyright © 2013 Elsevier B.V. All rights reserved.

Poisson Coordinates.

Science.gov (United States)

Li, Xian-Ying; Hu, Shi-Min

2013-02-01

Harmonic functions are the critical points of a Dirichlet energy functional, the linear projections of conformal maps. They play an important role in computer graphics, particularly for gradient-domain image processing and shape-preserving geometric computation. We propose Poisson coordinates, a novel transfinite interpolation scheme based on the Poisson integral formula, as a rapid way to estimate a harmonic function on a certain domain with desired boundary values. Poisson coordinates are an extension of the Mean Value coordinates (MVCs) which inherit their linear precision, smoothness, and kernel positivity. We give explicit formulas for Poisson coordinates in both continuous and 2D discrete forms. Superior to MVCs, Poisson coordinates are proved to be pseudoharmonic (i.e., they reproduce harmonic functions on n-dimensional balls). Our experimental results show that Poisson coordinates have lower Dirichlet energies than MVCs on a number of typical 2D domains (particularly convex domains). As well as presenting a formula, our approach provides useful insights for further studies on coordinates-based interpolation and fast estimation of harmonic functions.

Kinetics of dissolution of sapphire in melts in the CaO-Al2O3-SiO2 system

Science.gov (United States)

Shaw, Cliff S. J.; Klausen, Kim B.; Mao, Huahai

2018-05-01

The dissolution rate of sapphire in melts in the CAS system of varying silica activity, viscosity and degree of alumina saturation has been determined at 1600 °C and 1.5 GPa. After an initiation period of up to 1800 s, dissolution is controlled by diffusion of cations through the boundary layer adjacent to the dissolving sapphire. The dissolution rate decreases with increasing silica activity, viscosity and molar Al2O3/CaO. The calculated diffusion matrix for each solvent melt shows that CAS 1 and 9 which have molar Al2O3/CaO of 0.33 and 0.6 and dissolution rate constants of 0.65 × 10-6 and 0.59 × 10-6 m/s0.5 have similar directions and magnitudes of diffusive coupling: DCaO-Al2O3 and DAl2O3-CaO are both negative are approximately equal. The solvent with the fastest dissolution rate: CAS 4, which has a rate constant of 1.5 × 10-6 m/s0.5 and Al2O3/CaO of 0.31 has positive DCaO-Al2O3 and negative DAl2O3-CaO and the absolute values vary by a factor of 4. Although many studies show that aluminium is added to the melts via the reaction: Si4+ =Al3+ + 0.5Ca2+ the compositional profiles show that this reaction is not the only one involved in accommodating the aluminium added during sapphire dissolution. Rather, aluminium is incorporated as both tetrahedrally coordinated Al charge balanced by Ca and as aluminium not charge balanced by Ca (termed Alxs). This reaction: AlIV -Ca =Alxs +CaNBO where CaNBO is a non-bridging oxygen associated with calcium, may involve the formation of aluminium triclusters. The shape of the compositional profiles and oxide-oxide composition paths is controlled by the aluminium addition reaction. When Alxs exceeds 2%, CaO diffusion becomes increasingly anomalous and since the bond strength of Alxs correlates with CaO/CaO + Al2O3, the presence of more than 2% Alxs leads to significantly slower dissolution than when Alxs is absent or at low concentration. Thus, dissolution is controlled by diffusion of cations through the boundary layer, but this

COMPUTATIONAL EFFICIENCY OF A MODIFIED SCATTERING KERNEL FOR FULL-COUPLED PHOTON-ELECTRON TRANSPORT PARALLEL COMPUTING WITH UNSTRUCTURED TETRAHEDRAL MESHES

Directory of Open Access Journals (Sweden)

JONG WOON KIM

2014-04-01

In this paper, we introduce a modified scattering kernel approach to avoid the unnecessarily repeated calculations involved with the scattering source calculation, and used it with parallel computing to effectively reduce the computation time. Its computational efficiency was tested for three-dimensional full-coupled photon-electron transport problems using our computer program which solves the multi-group discrete ordinates transport equation by using the discontinuous finite element method with unstructured tetrahedral meshes for complicated geometrical problems. The numerical tests show that we can improve speed up to 17∼42 times for the elapsed time per iteration using the modified scattering kernel, not only in the single CPU calculation but also in the parallel computing with several CPUs.

Local atomic structure of Zr-Cu and Zr-Cu-Al amorphous alloys investigated by EXAFS method

International Nuclear Information System (INIS)

Antonowicz, J.; Pietnoczka, A.; Zalewski, W.; Bacewicz, R.; Stoica, M.; Georgarakis, K.; Yavari, A.R.

2011-01-01

Research highlights: → Coordination number, interatomic distances and mean square atomic displacement in Zr-Cu and Zr-Cu-Al glasses. → Icosahedral symmetry in local atomic structure. → Deviation from random mixing behavior resulting from Al addition. - Abstract: We report on extended X-ray absorption fine structure (EXAFS) study of rapidly quenched Zr-Cu and Zr-Cu-Al glassy alloys. The local atomic order around Zr and Cu atoms was investigated. From the EXAFS data fitting the values of coordination number, interatomic distances and mean square atomic displacement were obtained for wide range of compositions. It was found that icosahedral symmetry rather than that of corresponding crystalline analogs dominates in the local atomic structure of Zr-Cu and Zr-Cu-Al amorphous alloys. Judging from bonding preferences we conclude that addition of Al as an alloying element results in considerable deviation from random mixing behavior observed in binary Zr-Cu alloys.

Material and elastic properties of Al-tobermorite in ancient roman seawater concrete

KAUST Repository

Jackson, Marie D.

2013-05-28

The material characteristics and elastic properties of aluminum-substituted 11 Å tobermorite in the relict lime clasts of 2000-year-old Roman seawater harbor concrete are described with TG-DSC and 29Si MAS NMR studies, along with nanoscale tomography, X-ray microdiffraction, and high-pressure X-ray diffraction synchrotron radiation applications. The crystals have aluminum substitution for silicon in tetrahedral bridging and branching sites and 11.49(3) Å interlayer (002) spacing. With prolonged heating to 350°C, the crystals exhibit normal behavior. The experimentally measured isothermal bulk modulus at zero pressure, K0, 55 ±5 GPa, is less than ab initio and molecular dynamics models for ideal tobermorite with a double-silicate chain structure. Even so, K0, is substantially higher than calcium-aluminum-silicate-hydrate binder (C-A-S-H) in slag concrete. Based on nanoscale tomographic study, the crystal clusters form a well connected solid, despite having about 52% porosity. In the pumiceous cementitious matrix, Al-tobermorite with 11.27 Å interlayer spacing is locally associated with phillipsite, similar to geologic occurrences in basaltic tephra. The ancient concretes provide a sustainable prototype for producing Al-tobermorite in high-performance concretes with natural volcanic pozzolans. © 2013 The American Ceramic Society.

Lagrangian finite element method for 3D time-dependent non-isothermal flow of K-BKZ fluids

DEFF Research Database (Denmark)

Román Marín, José Manuel; Rasmussen, Henrik K.

2009-01-01

equation is replaced with a temperature dependent pseudo time. The spatial coordinate system attached to the particles is discretized by 10-node quadratic tetrahedral elements using Cartesian coordinates. The temperature and the pressure are discretized by 10-node quadratic and linear interpolation...... utilizing an implicit variable step backwards differencing (BDF2) scheme, obtaining second order convergence of the temperature in time. A quadratic interpolation in time is applied to approximate the time integral in the K-BKZ equation. This type of scheme ensures third order accuracy with respect......, respectively, in the tetrahedral particle elements. The spatial discretization of the governing equations follows a mixed Galerkin finite element method. This type of scheme ensures third order accuracy with respect to the discretization of spatial dimension. The temperature equation is solved in time...

Theoretical insight into Cobalt subnano-clusters adsorption on α-Al{sub 2}O{sub 3} (0001)

Energy Technology Data Exchange (ETDEWEB)

Gao, Fen-e [College of Chemical Engineering and Environment, North University of China, 030051 Taiyuan (China); Ren, Jun, E-mail: jun.ren@nuc.edu.cn [College of Chemical Engineering and Environment, North University of China, 030051 Taiyuan (China); Wang, Qiang [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 030001 Taiyuan (China); Li, Debao, E-mail: dbli@sxicc.ac.cn [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 030001 Taiyuan (China); Hou, Bo; Jia, Litao [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 030001 Taiyuan (China); Cao, Duanlin [College of Chemical Engineering and Environment, North University of China, 030051 Taiyuan (China)

2017-02-15

The investigation on the structural stability, nucleation, growth and interaction of cobalt cluster Con(n=2–7) on the α-Al{sub 2}O{sub 3}(0001) surface by using density functional theory methods has been reported. Energetically, the most favorable adsorption sites were identified and the strongest adsorption energy cluster is the tetrahedral Co{sub 4} cluster. On the other hand, the nucleation of Con(n=2–7) clusters on the surface is exothermic and thermodynamically favorable. Moreover, even-odd alternation was found with respect to clusters nucleation as a function of the number of cobalt atoms (for n=1–7). Meanwhile, the Co{sub n} clusters can be adsorbed on the surface stably owing to the charge transfer from Co atoms to Al and O atoms of the Al{sub 2}O{sub 3} substrate. In addition, we establish the crucial importance of monomer, dimer and trimer diffusion on the surface. The diffusion of the monomer cobalt from Al{sup (3)} to O{sup (5)} or O{sup (5)} to Al{sup (4)} site is quite easy on the Al{sub 2}O{sub 3}(0001) surface, whereas the diffusion of the Co{sub 2} dimer is thermodynamically unfavorable by compared with that of the Co adatom and Co{sub 3} trimer. - Graphical abstract: Diffusion process of Co adatom on the α-Al{sub 2}O{sub 3} (0001) surface, Al{sup (3)} site→O{sup (5)} site→Al{sup (4)} site. Potential energy surface for diffusion of a single Co atom from Al{sup (3)} to O{sup (5)} site, and from O{sup (5)} to Al{sup (4)} site on the surface. The activation energy of the two migration processes from Al{sup (3)} to O{sup (5)} and O{sup (5)} to Al{sup (4)} are 0.06 and 0.09 eV, respectively. This implies the monomer is quite mobile on the surface under typical growth conditions.

Tetrahedral node for Transmission-Line Modeling (TLM) applied to Bio-heat Transfer.

Science.gov (United States)

Milan, Hugo F M; Gebremedhin, Kifle G

2016-12-01

Transmission-Line Modeling (TLM) is a numerical method used to solve complex and time-domain bio-heat transfer problems. In TLM, parallelepipeds are used to discretize three-dimensional problems. The drawback in using parallelepiped shapes is that instead of refining only the domain of interest, a large additional domain would also have to be refined, which results in increased computational time and memory space. In this paper, we developed a tetrahedral node for TLM applied to bio-heat transfer that does not have the drawback associated with the parallelepiped node. The model includes heat source, blood perfusion, boundary conditions and initial conditions. The boundary conditions could be adiabatic, temperature, heat flux, or convection. The predicted temperature and heat flux were compared against results from an analytical solution and the results agreed within 2% for a mesh size of 69,941 nodes and a time step of 5ms. The method was further validated against published results of maximum skin-surface temperature difference in a breast with and without tumor and the results agreed within 6%. The published results were obtained from a model that used parallelepiped TLM node. An open source software, TLMBHT, was written using the theory developed herein and is available for download free-of-charge. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantitative assessment of Al-to-N bonding in dilute Al0.33Ga0.67As1-yNy

International Nuclear Information System (INIS)

Wagner, J.; Geppert, T.; Koehler, K.; Ganser, P.; Maier, M.

2003-01-01

A quantitative assessment of the group III-nitrogen bonding in low N-content Al 0.33 Ga 0.67 As 1-y N y with y≤0.04 has been performed, using vibrational mode Raman spectroscopy for the quantitative analysis of local bond formation in combination with energy dispersive x-ray analysis and secondary ion mass spectrometry for chemical analysis. Clear evidence is obtained for the preferential bonding of nitrogen to Al with one nitrogen atom being coordinated to, at the average, 3.4 Al neighbors. This strong preference for Al-to-N bond formation can be understood in terms of the much larger cohesive energy of the Al-N bond compared to the Ga-N chemical bond. In spite of this phase-separation-like formation of local Al-N complexes, the fundamental band gap and the E 1 /E 1 +Δ 1 band gaps show a continuous low-energy and high-energy shift, respectively, upon the addition of nitrogen as already known from dilute GaAsN

The influence of coordinated defects on inhomogeneous broadening in cubic lattices

Energy Technology Data Exchange (ETDEWEB)

Matheson, P. L., E-mail: phil.matheson@uvu.edu; Sullivan, Francis P.; Evenson, William E. [Utah Valley University, Department of Physics (United States)

2016-12-15

The joint probability distribution function (JPDF) of electric field gradient (EFG) tensor components in cubic materials is dominated by coordinated pairings of defects in shells near probe nuclei. The contributions from these inner shell combinations and their surrounding structures contain the essential physics that determine the PAC-relevant quantities derived from them. The JPDF can be used to predict the nature of inhomogeneous broadening (IHB) in perturbed angular correlation (PAC) experiments by modeling the G{sub 2} spectrum and finding expectation values for V{sub zz} and η. The ease with which this can be done depends upon the representation of the JPDF. Expanding on an earlier work by Czjzek et al. (Hyperfine Interact. 14, 189–194, 1983), Evenson et al. (Hyperfine Interact. 237, 119, 2016) provide a set of coordinates constructed from the EFG tensor invariants they named W{sub 1} and W{sub 2}. Using this parameterization, the JPDF in cubic structures was constructed using a point charge model in which a single trapped defect (TD) is the nearest neighbor to a probe nucleus. Individual defects on nearby lattice sites pair with the TD to provide a locus of points in the W{sub 1}−W{sub 2} plane around which an amorphous-like distribution of probability density grows. Interestingly, however, marginal, separable PDFs appear adequate to model IHB relevant cases. We present cases from simulations in cubic materials illustrating the importance of these near-shell coordinations.

A generic coordinate system and a set of generic variables for MFE database

International Nuclear Information System (INIS)

Miner, W.H. Jr.; Ross, D.W.; Solano, E.R.; Valanju, P.M.; Wiley, J.C.

1993-01-01

Over the last several years, profile data from nine different tokamaks have been stored in the magnetic fusion energy database (MFEDB). These data sets have come from a variety of sources and most are given in different coordinate systems. In order to attempt any intermachine analysis, it is convenient to transform these data sets into one generic coordinate system and to choose a uniform set of variable names. The authors describe the data sets from each tokamak indicating the source of the data and the coordinate system in which it is given. Next, they discuss the generic coordinate that has been adopted and show how it is implemented for each tokamak. Finally, the generic naming convention that has been adopted is discussed. It follows closely that which was used by Christiansen et al. for the ITER Global Energy Confinement H-Mode Database. For further clarification, they discuss the characteristics of the magnetic geometry given a Fourier representation of the magnetic equilibria

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

Energy Technology Data Exchange (ETDEWEB)

Keates, Adam C. [School of Chemistry, University of Southampton, Southampton, Hampshire SO17 1B,. UK (United Kingdom); Wang, Qianlong [Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY (United Kingdom); Weller, Mark T., E-mail: m.t.weller@bath.ac.uk [Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY (United Kingdom)

2014-02-15

Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen, as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

International Nuclear Information System (INIS)

Keates, Adam C.; Wang, Qianlong; Weller, Mark T.

2014-01-01

Single crystal and bulk polycrystalline forms of K 2 MP 2 O 7 (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42 1 m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP 2 O 7 ] 2− with potassium cations situated between the layers. The MO 4 tetrahedra share oxygen atoms with [P 2 O 7 ] 4− diphosphate groups and the potassium ions have KO 8 square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen, as a result of the Jahn–Teller (JT) effect for the high spin d 6 Fe(II) and p-orbital mixing or a second order JT effect for d 9 Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K 2 MP 2 O 7 , M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP 2 O 7 ] 2− , formed from linked pyrophosphate groups and MO 4 tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d 6 Fe(II) and p-orbital mixing and second-order JT effects for d 9 Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d 10 distorted coordinations

Characterization of local chemistry and disorder in synthetic and natural α-Al2O3 materials by X-ray absorption near edge structure spectroscopy

International Nuclear Information System (INIS)

Mottana, A.; Murata, T.

1997-11-01

X-ray absorption fine spectra at the Al K-edge were measured experimentally on and calculated theoretically via the multiple-scattering formalism for a chemically pure and physically perfect synthetic α-Al 2 O 3 (α-alumina), a natural 'ruby/sapphire' (corundum) and a series of artificial 'corundum' produced for technical purposes and used as geochemical standards. The Al K-edge spectra differ despite of the identical coordination (short-range arrangement) assumed by O around Al, and vary slightly in relation to the slightly different chemistries of the materials (substitutional defects) as well as on account of the location taken by foreign atoms in the structural lattices (positional defects). A quantitative treatment of the observed changes is made in terms of short-range modification of the coordination polyhedron and of medium- to long-range modifications in the overall structure; both of them induced by substitutions. In some technical 'corundums', the impurities of admixed 'β-alumina', where Al is both in four- and six-fold coordination, produce another small but detectable effect on Al K-edges. Therefore, XAFS spectroscopy proves its potentials for both measuring a light element such as Al, and detecting minor coordination changes and substitutions (ca. 1∼3 wt.% as oxide) of the absorber by dilute other atoms, at least under favorable conditions as those occurring in this system are

Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation

KAUST Repository

Zhang, Zailei; Zhu, Yihan; Asakura, Hiroyuki; Zhang, Bin; Zhang, Jiaguang; Zhou, Maoxiang; Han, Yu; Tanaka, Tsunehiro; Wang, Aiqin; Zhang, Tao; Yan, Ning

2017-01-01

with outstanding stability in several reactions under demanding conditions. The Pt atoms are firmly anchored in the internal surface of mesoporous Al2O3, likely stabilized by coordinatively unsaturated pentahedral Al3+ centres. The catalyst keeps its structural

Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties

International Nuclear Information System (INIS)

Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; Wood, Max; Drtina, Thomas; Bud’ko, Sergey L.; Canfield, Paul C.; Miller, Gordon J.

2015-01-01

Single crystals of Nd 4 FeOS 6 were grown from an Fe–S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd 4 MnOSe 6 -type structure (P6 3 mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å 3 , Z=2), featuring parallel chains of face-sharing [FeS 6×1/2 ] 4− trigonal antiprisms and interlinked [Nd 4 OS 3 ] 4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd 4 clusters in the [Nd 4 OS 3 ] 4 + chains. Structural differences among Nd 4 MnOSe 6 -type Nd 4 FeOS 6 and the related La 3 CuSiS 7 − and Pr 8 CoGa 3 -type structures have been described. Magnetic susceptibility measurements on Nd 4 FeOS 6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions. - Graphical abstract: Trapping of oxygen in Nd 4 tetrahedral clusters results in the formation of the Nd 4 MnOSe 6 -type Nd 4 FeOS 6 , in contrast to the La 3 CuSiS 7 -type oxygen-free Nd 4 FeS 7 and related Pr 8 CoGa 3 -type structures. Complex magnetic frustration inhibits magnetic ordering at low temperature. - Highlights: • Single crystals of Nd 4 FeOS 6 were grown using self-flux method. • Oxygen was found trapped by Nd 4 tetrahedral clusters. • Comparison with two closely related structural types were discussed. • Magnetic measurements revealed antiferromagnetic (AFM) interaction. • VASP calculations confirmed strong magnetic frustration in AFM model

Structural characterization of rondorfite, calcium silica chlorine mineral containing magnesium in tetrahedral position [MgO4]6-, with the aid of the vibrational spectroscopies and fluorescence.

Science.gov (United States)

Dulski, M; Bulou, A; Marzec, K M; Galuskin, E V; Wrzalik, R

2013-01-15

Raman and infrared spectra of rondorfite Ca8Mg(SiO4)4Cl2, a calcium chlorosilica mineral containing magnesium in tetrahedral position, has been studied in terms of spectra-structure relations. Raman spectra have been measured at different excited laser lines: 780 nm, 532 nm, 488 nm and 457 nm. This mineral is characterized by a single sharp intense Raman band at 863 cm(-1) assigned to the ν1 [SiO4]4- (Ag) symmetric stretching mode in the magnesiosilicate pentamer. Due to symmetry restriction the other Raman bands have a small intensity. Two Raman bands observed at 564 cm(-1) and 526 cm(-1) are associated simultaneously with ν4 [MgO4]6- and ν4 [SiO4]4- symmetric and antisymmetric modes where magnesium occurs in the tetrahedral configuration. The weak bands at 422 cm(-1) and 386 cm(-1) are associated with the ν2 bending mode of CaO6 in octahedral configuration, respectively. Moreover the infrared spectrum shows very weak bands associated with the hydroxyl group and/or water molecule. Additionally, the strong fluorescence phenomenon was observed and related to the presence of chlorine atoms, magnesium Mg2+ ions in atypical configuration or point defects. Copyright © 2012 Elsevier B.V. All rights reserved.

Crystal structure of Helicobacter pylori neutrophil-activating protein with a di-nuclear ferroxidase center in a zinc or cadmium-bound form

Energy Technology Data Exchange (ETDEWEB)

Yokoyama, Hideshi, E-mail: h-yokoya@u-shizuoka-ken.ac.jp [School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526 (Japan); Tsuruta, Osamu; Akao, Naoya; Fujii, Satoshi [School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526 (Japan)

2012-06-15

Highlights: Black-Right-Pointing-Pointer Structures of a metal-bound Helicobacter pylori neutrophil-activating protein were determined. Black-Right-Pointing-Pointer Two zinc ions were tetrahedrally coordinated by ferroxidase center (FOC) residues. Black-Right-Pointing-Pointer Two cadmium ions were coordinated in a trigonal-bipyramidal and octahedral manner. Black-Right-Pointing-Pointer The second metal ion was more weakly coordinated than the first at the FOC. Black-Right-Pointing-Pointer A zinc ion was found in one negatively-charged pore suitable as an ion path. -- Abstract: Helicobacter pylori neutrophil-activating protein (HP-NAP) is a Dps-like iron storage protein forming a dodecameric shell, and promotes adhesion of neutrophils to endothelial cells. The crystal structure of HP-NAP in a Zn{sup 2+}- or Cd{sup 2+}-bound form reveals the binding of two zinc or two cadmium ions and their bridged water molecule at the ferroxidase center (FOC). The two zinc ions are coordinated in a tetrahedral manner to the conserved residues among HP-NAP and Dps proteins. The two cadmium ions are coordinated in a trigonal-bipyramidal and distorted octahedral manner. In both structures, the second ion is more weakly coordinated than the first. Another zinc ion is found inside of the negatively-charged threefold-related pore, which is suitable for metal ions to pass through.

WOx supported on γ-Al2O3 with different morphologies as model catalysts for alkanol dehydration

Energy Technology Data Exchange (ETDEWEB)

Shi, Dachuan; Wang, Huamin; Kovarik, Libor; Gao, Feng; Wan, Chuan; Hu, Jian Z.; Wang, Yong

2018-04-21

The distinctive morphological and surface characteristics of platelet-like γ-Al2O3 were compared to a regular, commercial γ-Al2O3. γ-Al2O3 platelets display dominant (110) surface facets and higher densities of coordinative unsaturated penta-coordinate Al3+ (Al3+penta) sites than regular γ-Al2O3, as measured by solid-state magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). Such Al3+penta sites are also the preferred surface anchoring sites for tungsten oxide (WOx) species consistent with NMR analysis indicating that these sites are consumed upon WOx adsorption. The higher Al3+penta density on γ-Al2O3 platelets leads to greater WOx dispersion (or smaller WOx clusters), as demonstrated by scanning transmission electron microscopy and ultraviolet–visible spectroscopy, and WOx species at intermediate WOx surface concentration are the most active for the probe reaction of 2-butanol dehydration. WOx on γ-Al2O3 platelets approaches the highest turnover rates at higher surface densities than WOx on regular γ-Al2O3, yet with similar highest rate values for both series of catalysts. This indicates that different Al2O3 supports mainly affect the dispersion of supported WOx rather than the intrinsic reactivity of individual WOx clusters with similar size.

Elastic properties and structural studies on some zinc-borate glasses derived from ultrasonic, FT-IR and X-ray techniques

International Nuclear Information System (INIS)

Gaafar, M.S.; El-Aal, N.S. Abd; Gerges, O.W.; El-Amir, G.

2009-01-01

Glasses in the system (1 - x) [29Na 2 O- 4Al 2 O 3 - 67B 2 O 3 ]- xZnO (0 ≤ x ≤ 35 mol%), have been prepared by the melt quenching technique. Elastic properties, X-ray and FT-IR spectroscopic studies have been employed to study the role of ZnO on the structure of the investigated glass system. Elastic properties and Debye temperature have been investigated using sound wave velocity measurements at 4 MHz at room temperature. The results showed that the density increases and the molar volume decreases while both sound velocities and the determined glass transition temperatures decrease with increase in x. X-ray and infrared spectra of the glasses reveal that the borate network consists of diborate units and is affected by the increase in the concentration of ZnO content. These results are interpreted in terms of the decrease in the N 4 values (fraction of tetrahedral coordinated boron atoms), and substitution of longer bond lengths of Zn-O in place of shorter B-O bond. The results indicate that Zinc ions have been substituted for boron ions as tetrahedral network former ions. The elastic moduli are observed to increase with the increase of ZnO content.

Atomic-Scale Structure of Al2O3-ZrO2 Mixed Oxides Prepared by Laser Ablation

International Nuclear Information System (INIS)

Yang Xiuchun; Dubiel, M.; Hofmeister, H.; Riehemann, W.

2007-01-01

By means of x-ray diffractometry (XRD) and X-ray absorption fine structure spectroscopy, the phase composition and atomic structure of laser evaporated ZrO2 and ZrO2-Al2O3 nanopowders have been studied. The results indicate that pure ZrO2 exists in the form of tetragonal structure, Al2O3 doped ZrO2 nanoparticles, however, have cubic structure. Compared to bulk tetragonal ZrO2, pure tetragonal ZrO2 nanoparticles have a shorter Zr-O- and Zr-Zr shell, indicating that the lattice contracts with decreasing particle size. For Al2O3 doped ZrO2 solid solution, the distances of first Zr-O and Zr-Zr (Al) coordination decrease with increasing solid solubility. The disorder degree of the ZrO2 lattice increases with increasing solid solubility. The coevaporated ZrO2-Al2O3 is quickly solidified into amorphous phase when it is ablated in a higher pressure. The amorphous phase contains Zr-O-Zr (Al) clusters and has shorter Zr-O distance and tower Zr-O coordination number

Ordering principles for tetrahedral chains in Ga- and Co-substituted YBCO intergrowths

International Nuclear Information System (INIS)

Milat, O.; Krekels, T.; Tendeloo, G. van; Amelinckx, S.

1993-01-01

A model for superstructure ordering in the ''chain'' layers of Ga (Co) substituted YBCO intergrowths with general formula (REO 2 ) N Sr 2 MCu 2 O 5 (M Co, Ga; n = 1, 2, ..) is proposed. By Ga or Co substitution for Cu, the structure of the ''chain'' layer changes: instead of the CuO 4 planar squares, the chains consist of MO 4 tetrahedra (M = Ga, Co) running along the [110] perovskite direction. The existing model for the Ga substituted ''123'' implies that all the chains are the same. Our new model is based on the results of Electron diffraction and High-resolution electron microscopy investigations. The model reveals the occurene of two types of chains as a consequence of ''opposite'' ordering between neighbouring tetrahedra. The corner linked tetrahedra in each chain appear as alternatingly rotated in opposite sense, and a chain itself, as being displaced with respect to the underlying structure in one of two senses; either forth (right) or back (left) along the chain direction. The regular alternation of chains of opposite type doubles the periodicity within a layer and induces the possibility for intrinsic disorder in the chain layer stacking sequence. The planar superstructure and a staggered stacking of the tetrahedral chain layers is found irrespective of the rest of the intergrowth structure. Superstructure ordering in the case of Co substitution is more perfect than for the Ga substitution. (orig.)

Principal component analysis of NEXAFS spectra for molybdenum speciation in hydrotreating catalysts

International Nuclear Information System (INIS)

Faro Junior, Arnaldo da C.; Rodrigues, Victor de O.; Eon, Jean-G.; Rocha, Angela S.

2010-01-01

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination. (author)

Scaling Up Coordinate Descent Algorithms for Large ℓ1 Regularization Problems

Energy Technology Data Exchange (ETDEWEB)

Scherrer, Chad; Halappanavar, Mahantesh; Tewari, Ambuj; Haglin, David J.

2012-07-03

We present a generic framework for parallel coordinate descent (CD) algorithms that has as special cases the original sequential algorithms of Cyclic CD and Stochastic CD, as well as the recent parallel Shotgun algorithm of Bradley et al. We introduce two novel parallel algorithms that are also special cases---Thread-Greedy CD and Coloring-Based CD---and give performance measurements for an OpenMP implementation of these.

Refinement of the Fe4Al13 structure and its relationship to the quasihomological homeotypical structures

International Nuclear Information System (INIS)

Grin, J.; Burkhardt, U.; Ellner, M.; Peters, K.

1994-01-01

The crystal structure of Fe 4 Al 13 was refined using single crystal diffractometer data: pearson symbol mC102, space group C2/m; a=15.492(2) A, b=8.078(2) A, c=12.471(1) A, β=107.69(1) ; R F =0.053, R F (w)=0.044 for 1127 reflections and 137 refined parameters. The coordination numbers of atoms are 9, 10, 11 for iron and 10, 12, 13, 14 for aluminium. The shortest interatomic distances are: Fe-Fe - 2.902 A, Fe-Al - 2.374 A, Al-Al - 2.533 A. A preferred occupation of pentagonal prismatic coordinated positions by aluminium was found. The structural relationship between the Fe 4 Al 13 structure and chemically homologous and homeotypical structures of aluminium and gallium containing systems with the 3d transition metals is discussed. The greatest similarity was found concerning the coordination polyhedra, especially that of transition metal atoms. The main common feature of these homeotypical structures is the presence of pentagonal ''channels'', which is strongly dependent on the chemical composition. With increasing atomic number of the 3d transition metal, the stability range of these structures shifts to the transition metal-rich concentration. It is concluded that there is a connection between the occurrence of aluminium and gallium-containing decagonal and icosahedral phases and the existence of the infinite one-dimensional pentagonal channels in the intermetallic compounds showing a similar chemical composition. (orig.)

Order-disorder transition and electrical conductivity of the brownmillerite solid-solutions system Ba2(In, M)2O5 (M=Ga, Al)

International Nuclear Information System (INIS)

Yamamura, Hiroshi; Hamazaki, Hirohumi; Kakinuma, Katsuyoshi; Mori, Toshiyuki; Haneda, Hajime

1999-01-01

The brownmillerite solid-solution systems Ba 2 (In 1-x M x ) 2 O 5 (M=Ga, Al) were investigated by means of high-temperature X-ray diffraction (XRD), dilatometry, and electrical-conductivity measurements. XRD showed that the Ba 2 (In 1-x Ga x ) 2 O 5 system had orthorhombic symmetry in the composition range 0.0≤x≤0.2 and cubic symmetry in the range 0.3≤x. The Al system also changed to cubic symmetry from orthorhombic symmetry in the range 0.2≤x. While the orthorhombic phase showed an order-disorder transition in the electrical conductivity measurements, the transition temperature decreased with increasing the M content. The order-disorder transition temperature and the crystal-structure transition temperature were very different. Such a transition was not observed in the cubic phases, and their electrical conductivity were fairly low compared to those of the disordered cubic phase after the transition due to the heating process. These phenomena are discussed in terms of disordering of the tetrahedral site in the brownmillerite structure, which is occupied by the smaller Ga 3+ or Al 3+ rather than ny In 3+

Fundamentals of semiconductors physics and materials properties

CERN Document Server

Yu, Peter Y

2005-01-01

Provides detailed explanations of the electronic, vibrational, transport, and optical properties of semiconductors. This textbook emphasizes understanding the physical properties of Si and similar tetrahedrally coordinated semiconductors and features an extensive collection of tables of material parameters, figures, and problems.

Synthesis and characterization of two new zinc(II) coordination polymers with bidentate flexible ligands: Formation of a 2D structure with (44.62)-sql topology

Science.gov (United States)

Lalegani, Arash; Khaledi Sardashti, Mohammad; Gajda, Roman; Woźniak, Krzysztof

2017-12-01

Zinc(II) coordination polymers [Zn(bip)2(NCS)2]n (1) and [Zn(μ-bbd)(N3)2]n (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd) and 1,3-bis(imidazolyl)propane (bip), mono-anionic NCS- or N3-ligand and zinc(II) chloride salts. The results of the X-ray analyses demonstrate that in the structure of 1, the zinc(II) ion is located on an inversion center and exhibits an ZnN6 octahedral arrangement while, in the structure of 2, the zinc(II) ion adopts an ZnN4 tetrahedral geometry. In the polymer 1, the NCS groups are terminally N-bonded to the metal center and the each bip with anti-gauche conformation acts as bridging connecting four zinc(II) ions to form a two-dimensional network with a sql [point symbol (44.62)] topology while, in the polymer 1, the N3 groups are terminally bonded to the metal center and each bbd with anti-anti-anti conformation acts as bridging ligand connecting two zinc(II) ions to form a one-dimensional zig-zag chain. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analyses of polymers were also presented.

Hermite-Hadamard Type Integral Inequalities for Functions Whose Second-Order Mixed Derivatives Are Coordinated (s,m-P-Convex

Directory of Open Access Journals (Sweden)

Yu-Mei Bai

2018-01-01

Full Text Available We establish some new Hermite-Hadamard type integral inequalities for functions whose second-order mixed derivatives are coordinated (s,m-P-convex. An expression form of Hermite-Hadamard type integral inequalities via the beta function and the hypergeometric function is also presented. Our results provide a significant complement to the work of Wu et al. involving the Hermite-Hadamard type inequalities for coordinated (s,m-P-convex functions in an earlier article.

Superstructure formation in PrNi{sub 2}Al{sub 3} and ErPd{sub 2}Al{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Eustermann, Fabian; Hoffmann, Rolf-Dieter [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Oldenburg Univ. (Germany). Inst. fuer Chemie

2017-09-01

The intermetallic phase ErPd{sub 2}Al{sub 3} was obtained by arc-melting of the elements and subsequent annealing for crystal growth. The sample was studied by X-ray diffraction on powders and single crystals. The structure of ErPd{sub 2}Al{sub 3} was refined from X-ray diffraction data and revealed a superstructure of PrNi{sub 2}Al{sub 3} - a CaCu{sub 5} derivative (P6/m, a=1414.3(1), c=418.87(3) pm wR=0.0820, 1060 F{sup 2} values, 48 variables). The same superstructure was subsequently found for PrNi{sub 2}Al{sub 3} (P6/m, a=1407.87(4), c=406.19(2) pm, wR=0.0499, 904 F{sup 2} values, 47 variables). In the crystal structure, the aluminium and transition metal atoms form a polyanionic network according to [T{sub 2}Al{sub 3}]{sup δ-}, while rare earth atoms fill cavities within the networks. They are coordinated by six transition metal and twelve aluminum atoms. In contrast to the PrNi{sub 2}Al{sub 3} type structure reported so far, two crystallographic independent rare-earth sites are found of which one (1b) is shifted by 1/2 z, causing a distortion in the structure along with a recoloring of the T and Al atoms in the network.

Coordinate measuring machines

DEFF Research Database (Denmark)

De Chiffre, Leonardo

This document is used in connection with three exercises of 2 hours duration as a part of the course GEOMETRICAL METROLOGY AND MACHINE TESTING. The exercises concern three aspects of coordinate measuring: 1) Measuring and verification of tolerances on coordinate measuring machines, 2) Traceabilit...... and uncertainty during coordinate measurements, 3) Digitalisation and Reverse Engineering. This document contains a short description of each step in the exercise and schemes with room for taking notes of the results.......This document is used in connection with three exercises of 2 hours duration as a part of the course GEOMETRICAL METROLOGY AND MACHINE TESTING. The exercises concern three aspects of coordinate measuring: 1) Measuring and verification of tolerances on coordinate measuring machines, 2) Traceability...

Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation.

Science.gov (United States)

Crossley, Daniel L; Cid, Jessica; Curless, Liam D; Turner, Michael L; Ingleson, Michael J

2015-12-28

The addition of AlCl 3 to four-coordinate boranes of the general formula (C-N-chelate)BCl 2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl] + . The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl 3 were sufficient to effect high-yielding arylation of (C-N-chelate)BCl 2 . Boro-destannylation is more rapid than boro-desilylation and leads to double arylation at the boron center, whereas in reactions with arylsilanes either single or double arylation occurs dependent on the nucleophilicity of the arylsilane and on the electrophilicity of the borenium cation. The electrophilicity of the borenium cation derived from 2-phenylpyridine was greater than that of the benzothiadiazole analogues, enabling the boro-desilyation of less nucleophilic silanes and the direct electrophilic borylation of 2-methylthiophene.

ALS and other motor neuron diseases.

Science.gov (United States)

Tiryaki, Ezgi; Horak, Holli A

2014-10-01

This review describes the most common motor neuron disease, ALS. It discusses the diagnosis and evaluation of ALS and the current understanding of its pathophysiology, including new genetic underpinnings of the disease. This article also covers other motor neuron diseases, reviews how to distinguish them from ALS, and discusses their pathophysiology. In this article, the spectrum of cognitive involvement in ALS, new concepts about protein synthesis pathology in the etiology of ALS, and new genetic associations will be covered. This concept has changed over the past 3 to 4 years with the discovery of new genes and genetic processes that may trigger the disease. As of 2014, two-thirds of familial ALS and 10% of sporadic ALS can be explained by genetics. TAR DNA binding protein 43 kDa (TDP-43), for instance, has been shown to cause frontotemporal dementia as well as some cases of familial ALS, and is associated with frontotemporal dysfunction in ALS. The anterior horn cells control all voluntary movement: motor activity, respiratory, speech, and swallowing functions are dependent upon signals from the anterior horn cells. Diseases that damage the anterior horn cells, therefore, have a profound impact. Symptoms of anterior horn cell loss (weakness, falling, choking) lead patients to seek medical attention. Neurologists are the most likely practitioners to recognize and diagnose damage or loss of anterior horn cells. ALS, the prototypical motor neuron disease, demonstrates the impact of this class of disorders. ALS and other motor neuron diseases can represent diagnostic challenges. Neurologists are often called upon to serve as a "medical home" for these patients: coordinating care, arranging for durable medical equipment, and leading discussions about end-of-life care with patients and caregivers. It is important for neurologists to be able to identify motor neuron diseases and to evaluate and treat patients affected by them.

Convergence of Wachspress coordinates: from polygons to curved domains

KAUST Repository

Kosinka, Jiří

2014-08-08

Given a smooth, strictly convex planar domain, we investigate point-wise convergence of the sequence of Wachspress coordinates defined over finer and finer inscribed polygonal approximations of the domain. Based on a relation between the discrete Wachspress case and the limit smooth case given by the Wachspress kernel defined by Warren et al., we show that the corresponding sequences of Wachspress interpolants and mappings converge as 𝓞(h2) for a sampling step size h of the boundary curve of the domain as h → 0. Several examples are shown to numerically validate the results and to visualise the behaviour of discrete interpolants and mappings as they converge to their smooth counterparts. Empirically, the same convergence order is observed also for mean value coordinates. Moreover, our numerical tests suggest that the convergence of interpolants and mappings is uniform both in the Wachspress and mean value cases. © 2014 Springer Science+Business Media New York.

Convergence of Wachspress coordinates: from polygons to curved domains

KAUST Repository

Kosinka, Jiří ; Barton, Michael

2014-01-01

Given a smooth, strictly convex planar domain, we investigate point-wise convergence of the sequence of Wachspress coordinates defined over finer and finer inscribed polygonal approximations of the domain. Based on a relation between the discrete Wachspress case and the limit smooth case given by the Wachspress kernel defined by Warren et al., we show that the corresponding sequences of Wachspress interpolants and mappings converge as 𝓞(h2) for a sampling step size h of the boundary curve of the domain as h → 0. Several examples are shown to numerically validate the results and to visualise the behaviour of discrete interpolants and mappings as they converge to their smooth counterparts. Empirically, the same convergence order is observed also for mean value coordinates. Moreover, our numerical tests suggest that the convergence of interpolants and mappings is uniform both in the Wachspress and mean value cases. © 2014 Springer Science+Business Media New York.

Coordinated Hard Sphere Mixture (CHaSM): A fast approximate model for oxide and silicate melts at extreme conditions

Science.gov (United States)

Wolf, A. S.; Asimow, P. D.; Stevenson, D. J.

2015-12-01

Recent first-principles calculations (e.g. Stixrude, 2009; de Koker, 2013), shock-wave experiments (Mosenfelder, 2009), and diamond-anvil cell investigations (Sanloup, 2013) indicate that silicate melts undergo complex structural evolution at high pressure. The observed increase in cation-coordination (e.g. Karki, 2006; 2007) induces higher compressibilities and lower adiabatic thermal gradients in melts as compared with their solid counterparts. These properties are crucial for understanding the evolution of impact-generated magma oceans, which are dominated by the poorly understood behavior of silicates at mantle pressures and temperatures (e.g. Stixrude et al. 2009). Probing these conditions is difficult for both theory and experiment, especially given the large compositional space (MgO-SiO2-FeO-Al2O3-etc). We develop a new model to understand and predict the behavior of oxide and silicate melts at extreme P-T conditions (Wolf et al., 2015). The Coordinated Hard Sphere Mixture (CHaSM) extends the Hard Sphere mixture model, accounting for the range of coordination states for each cation in the liquid. Using approximate analytic expressions for the hard sphere model, this fast statistical method compliments classical and first-principles methods, providing accurate thermodynamic and structural property predictions for melts. This framework is applied to the MgO system, where model parameters are trained on a collection of crystal polymorphs, producing realistic predictions of coordination evolution and the equation of state of MgO melt over a wide P-T range. Typical Mg-coordination numbers are predicted to evolve continuously from 5.25 (0 GPa) to 8.5 (250 GPa), comparing favorably with first-principles Molecular Dynamics (MD) simulations. We begin extending the model to a simplified mantle chemistry using empirical potentials (generally accurate over moderate pressure ranges, consuming classical MD calculations. This approach also sheds light on the universality

Coordinated School Health and the Contribution of a District Wellness Coordinator

Science.gov (United States)

Westrich, Lisa; Sanchez, Monika; Strobel, Karen

2015-01-01

Background: A San Francisco Bay Area school health initiative was established in fall 2010 to improve wellness programs in 4 local school districts using the Coordinated School Health (CSH) model. This study examines the role of district-wide wellness coordinators and the ways in which they contribute to intentional coordination of health and…

Tetrahedral cluster and pseudo molecule: New approaches to Calculate Absolute Surface Energy of Zinc Blende (111)/(-1-1-1) Surface

Science.gov (United States)

Zhang, Yiou; Zhang, Jingzhao; Tse, Kinfai; Wong, Lun; Chan, Chunkai; Deng, Bei; Zhu, Junyi

Determining accurate absolute surface energies for polar surfaces of semiconductors has been a great challenge in decades. Here, we propose pseudo-hydrogen passivation to calculate them, using density functional theory approaches. By calculating the energy contribution from pseudo-hydrogen using either a pseudo molecule method or a tetrahedral cluster method, we obtained (111)/(-1-1-1) surfaces energies of Si, GaP, GaAs, and ZnS with high self-consistency. Our findings may greatly enhance the basic understandings of different surfaces and lead to novel strategies in the crystal growth. We would like to thank Su-huai Wei for helpful discussions. Computing resources were provided by the High Performance Cluster Computing Centre, Hong Kong Baptist University. This work was supported by the start-up funding and direct Grant with the Project.

Luminescent and scintillation properties of the Pr"3"+ doped single crystalline films of Lu_3Al_5_−_xGa_xO_1_2 garnet

International Nuclear Information System (INIS)

Gorbenko, V.; Zorenko, Yu; Zorenko, T.; Voznyak, T.; Paprocki, K.; Fabisiak, K.; Fedorov, A.; Bilski, P.; Twardak, A.; Zhusupkalieva, G.

2016-01-01

The Pr"3"+ d–f luminescence was investigated in the single crystalline films (SCF) of Lu_3Al_5_−_xGa_xO_1_2:Pr garnet solid solution at x = 1–3, grown by the liquid phase epitaxy (LPE) method from the melt-solution based on the PbO–B_2O_3 flux. The shape of CL spectra and decay kinetics of Pr"3"+ ions in Lu_3Al_5_−_xGa_xO_1_2 SCFs strongly depend on the total gallium concentration x and distribution of Ga"3"+ ions between the tetrahedral and octahedral position of the garnet host. The best scintillation properties of Lu_3Al_5_−_xGa_xO_1_2:Pr SCF are achieved at the nominal Ga content in melt-solution in the x = 2–2.5 range. - Highlights: • Single crystalline films of Lu_3Al_5_−_x Ga_xO_1_2:Pr garnet at x = 1–3 were grown by the LPE method. • Pr"3"+ emission spectra, light yield and decay time of films show strong dependence on Ga content. • The maximal light yield of Lu_3Al_5_−_x Ga_xO_1_2:Pr film is observed at Ga content x = 2.0–2.5.

Coordination behaviour of some f-block elements with o-vanillin and its derivatives (Paper No. AL-09)

International Nuclear Information System (INIS)

Agarwala, B.V.; Shukla, M.K.; Hingorani, S.

1990-02-01

Five new complexes of La(III), Ce(III) and UO 2 have been prepared with o-vanillin and its derivatives. Their coordination behaviour and structural elucidation have been described by elemental, magnetic moments, IR, electronic spectral and thermal studies. (author). 1 tab

On the ground-state degeneracy and entropy in a double-tetrahedral chain formed by the localized Ising spins and mobile electrons

Science.gov (United States)

Gálisová, Lucia

2018-05-01

Ground-state properties of a hybrid double-tetrahedral chain, in which the localized Ising spins regularly alternate with triangular plaquettes occupied by a variable number of mobile electrons, are exactly investigated. We demonstrate that the zero-temperature phase diagram of the model involves several non-degenerate, two-fold degenerate and macroscopically degenerate chiral phases. Low-temperature dependencies of the entropy and specific heat are also examined in order to gain a deeper insight into the degeneracy of individual ground-state phases and phase transitions. It is shown that a diversity of the ground-state degeneracy manifests itself in multiple-peak structures of both thermodynamic quantities. A remarkable temperature dependencies of the specific heat with two and three Schottky-type maxima are discussed in detail.

The synthesis and complex anion-vacancy ordered structure of La0.33Sr0.67MnO2.42

International Nuclear Information System (INIS)

Dixon, Edward; Hadermann, Joke; Hayward, Michael A.

2011-01-01

The low-temperature topotactic reduction of La 0.33 Sr 0.67 MnO 3 with NaH results in the formation of La 0.33 Sr 0.67 MnO 2.42 . A combination of neutron powder and electron diffraction data show that La 0.33 Sr 0.67 MnO 2.42 adopts a novel anion-vacancy ordered structure with a 6-layer OOTOOT' stacking sequence of the 'octahedral' and tetrahedral layers (Pcmb, a=5.5804(1) A, b=23.4104(7) A, c=11.2441(3) A). A significant concentration of anion vacancies at the anion site, which links neighbouring 'octahedral' layers means that only 25% of the 'octahedral' manganese coordination sites actually have 6-fold MnO 6 coordination, the remainder being MnO 5 square-based pyramidal sites. The chains of cooperatively twisted apex-linked MnO 4 tetrahedra adopt an ordered -L-R-L-R- arrangement within each tetrahedral layer. This is the first published example of a fully refined structure of this type which exhibits such intralayer ordering of the twisted tetrahedral chains. The rationale behind the contrasting structures of La 0.33 Sr 0.67 MnO 2.42 and other previously reported reduced La 1-x Sr x MnO 3-y phases is discussed. - Graphical Abstract: The topotactic reduction of the perovskite phase La 0.33 Sr 0.67 MnO 3 with NaH yields La 0.33 Sr 0.67 MnO 2.42(3) , which adopts a novel anion vacancy ordered structure with a 6-layer OOTOOT' stacking sequence of the 'octahedral' and tetrahedral layers. The anion site that links the neighbouring octahedral layers is partially occupied so only 25% of the 'octahedral' manganese sites actually have 6-fold MnO 6 coordination. Highlights: → Topotactic reduction with NaH to form a mixed valent Mn 2+ /Mn 3+ phase. → Novel layered anion-vacancy ordered structure. → Comparison to related brownmillerite structure types.

DAFS study of site-specific local structure of Mn in manganese ferrite films

International Nuclear Information System (INIS)

Kravtsov, E.; Haskel, D.; Cady, A.; Yang, A.; Vittoria, C.; Zuo, X.; Harris, V.G.

2006-01-01

Manganese ferrite (MnFe 2 O 4 ) is a well-known magnetic material widely used in electronics for many years. It is well established that its magnetic behavior is strongly influenced by local structural properties of Mn ions, which are distributed between crystallographically inequivalent tetrahedral and octahedral sites in the unit cell. In order to understand and be able to tune properties of these structures, it is necessary to have detailed site-specific structural information on the system. Here we report on the application of diffraction-anomalous fine structure (DAFS) spectroscopy to resolve site-specific Mn local structures in manganese ferrite films. The DAFS measurements were done at undulator beamline 4-ID-D of the Advanced Photon Source at Argonne National Laboratory. The DAFS spectra (Fig. 1) were measured at several Bragg reflections in the vicinity of the Mn absorption K-edge, having probed separately contributions from tetrahedrally and octahedrally coordinated Mn sites. The DAFS data analysis done with an iterative Kramers-Kroenig algorithm made it possible to solve separately the local structure around different inequivalent Mn sites in the unit cell. The reliability of the data treatment was checked carefully, and it was showed that the site-specific structural parameters obtained with DAFS allow us to describe fluorescence EXAFS spectrum measured independently. Fig. 2 shows individual site contributions to the imaginary part of the resonant scattering amplitude obtained from the treatment of the data of Fig. 1. The analysis of the refined site-specific absorption spectra was done using EXAFS methods based on theoretical standards. We provided direct evidence for the tetrahedral Mn-O bond distance being increased relative to the corresponding Fe-O distance in bulk manganese ferrites. The first coordination shell number was found to be reduced significantly for Mn atoms at these sites. This finding is consistent with the well-known tendency of Mn

Is there an ordered tetragonal phase in the Ti3Al-Nb system?

International Nuclear Information System (INIS)

Banerjee, D.

1994-01-01

In a recent series of papers, describing aging transformations in plasma sprayed Ti-24Al-11Nb, Hsiung and co-workers proposed a new ordered tetragonal structure as the first metastable phase to form in a series of transformations from quenched-in B2 to the equilibrium phase. They describe this new phase as a ''DO 3 like tetragonal structure'' with a composition Ti 5 Al 2 Nb, and lattice parameters, a = 0.65 nm and c/a ≅ 1.02. Their unit cell is constituted by 8 bcc unit cells, and the atomic coordinates of their structure are given in Table 1 on this basis. The symmetry of this structure is P4/mm. Though it is not the smallest possible unit cell for the structure, comparison with other bcc binary derivative structures is easily possible on this basis. The atomic coordinates for the latter, for a ternary composition Ti 2 AlNb, are also given. They note that the site occupation for the Hsiung et al. structure is quite distinct from that for a ternary DO 3 phase or any of the other possible bcc derivative structures (neglecting 2 possibilities with 128 or 432 atoms per unit cell(8) and interstitial ordering)

Stem cells therapy for ALS.

Science.gov (United States)

Mazzini, Letizia; Vescovi, Angelo; Cantello, Roberto; Gelati, Maurizio; Vercelli, Alessandro

2016-01-01

Despite knowledge on the molecular basis of amyotrophic lateral sclerosis (ALS) having quickly progressed over the last few years, such discoveries have not yet translated into new therapeutics. With the advancement of stem cell technologies there is hope for stem cell therapeutics as novel treatments for ALS. We discuss in detail the therapeutic potential of different types of stem cells in preclinical and clinical works. Moreover, we address many open questions in clinical translation. SC therapy is a potentially promising new treatment for ALS and the need to better understand how to develop cell-based experimental treatments, and how to implement them in clinical trials, becomes more pressing. Mesenchymal stem cells and neural fetal stem cells have emerged as safe and potentially effective cell types, but there is a need to carry out appropriately designed experimental studies to verify their long-term safety and possibly efficacy. Moreover, the cost-benefit analysis of the results must take into account the quality of life of the patients as a major end point. It is our opinion that a multicenter international clinical program aime d at fine-tuning and coordinating transplantation procedures and protocols is mandatory.

Copper(II) manganese(II) orthophosphate, Cu_0.5Mn_2.5(PO₄)₂

DEFF Research Database (Denmark)

Warner, Terence Edwin; Bond, Andrew; Foghmoes, Søren Preben Vagn

2011-01-01

The title compound, Cu0.5Mn2.5(PO4)2, is a copper-manganese phosphate solid solution with the graftonite-type structure, (Mn,Fe,Ca,Mg)3(PO4)2. The structure has three distinct metal cation sites, two of which are occupied exclusively by MnII, and one of which accommodates CuII. Incorporation of C......II into the structure distorts the coordination geometry of the metal cation site from 5-coordinate square-pyramidal towards 4-coordinate flattened tetrahedral, and serves to contract the structure principally along the c axis....

Fe K-EDGE X-RAY ABSORPTION SPECTROSCOPY OF SILICATE MINERALS AND GLASSES

OpenAIRE

Binsted , N.; Greaves , G.; Henderson , C.

1986-01-01

Structural parameters determined for crystalline iron, fayalite and aegirine agree closely with X-ray crystallograhic data. A glass of NaFeSi2O6 composition has Fe predominantly present as Fe3+ in tetrahedral coordination i.e. as a network former. CaFeSiO4 and CaFeSi2O6 glasses have about 1/3 of the total Fe in octahedral coordination i.e. as a network modifier.

Variationally optimal selection of slow coordinates and reaction coordinates in macromolecular systems

Science.gov (United States)

Noe, Frank

To efficiently simulate and generate understanding from simulations of complex macromolecular systems, the concept of slow collective coordinates or reaction coordinates is of fundamental importance. Here we will introduce variational approaches to approximate the slow coordinates and the reaction coordinates between selected end-states given MD simulations of the macromolecular system and a (possibly large) basis set of candidate coordinates. We will then discuss how to select physically intuitive order paremeters that are good surrogates of this variationally optimal result. These result can be used in order to construct Markov state models or other models of the stationary and kinetics properties, in order to parametrize low-dimensional / coarse-grained model of the dynamics. Deutsche Forschungsgemeinschaft, European Research Council.

The Partial Molar Volume and Compressibility of the FeO Component in Model Basalts (Mixed CaAl2Si2O8-CaMgSi2O6-CaFeSi2O6 Liquids) at 0 GPa: evidence of Fe2+ in 6-fold coordination

Science.gov (United States)

Guo, X.; Lange, R. A.; Ai, Y.

2010-12-01

FeO is an important component in magmatic liquids and yet its partial molar volume at one bar is not as well known as that for Fe2O3 because of the difficulty of performing double-bob density measurements under reducing conditions. Moreover, there is growing evidence from spectroscopic studies that Fe2+ occurs in 4, 5, and 6-fold coordination in silicate melts, and it is expected that the partial molar volume and compressibility of the FeO component will vary accordingly. We have conducted both density and relaxed sound speed measurements on four liquids in the An-Di-Hd (CaAl2Si2O8-CaMgSi2O6-CaFeSi2O6) system: (1) Di-Hd (50:50), (2) An-Hd (50:50), (3) An-Di-Hd (33:33:33) and (4) Hd (100). Densities were measured between 1573 and 1838 K at one bar with the double-bob Archimedean method using molybdenum bobs and crucibles in a reducing gas (1%CO-99%Ar) environment. The sound speeds were measured under similar conditions with a frequency-sweep acoustic interferometer, and used to calculate isothermal compressibility. All the density data for the three multi-component (model basalt) liquids were combined with density data on SiO2-Al2O3-CaO-MgO-K2O-Na2O liquids (Lange, 1997) in a fit to a linear volume equation; the results lead to a partial molar volume (±1σ) for FeO =11.7 ± 0.3(±1σ) cm3/mol at 1723 K. This value is similar to that for crystalline FeO at 298 K (halite structure; 12.06 cm3/mol), which suggests an average Fe2+ coordination of ~6 in these model basalt compositions. In contrast, the fitted partial molar volume of FeO in pure hedenbergite liquid is 14.6 ± 0.3 at 1723 K, which is consistent with an average Fe2+ coordination of 4.3 derived from EXAFS spectroscopy (Rossano, 2000). Similarly, all the compressibility data for the three multi-component liquids were combined with compressibility data on SiO2-Al2O3-CaO-MgO liquids (Ai and Lange, 2008) in a fit to an ideal mixing model for melt compressibility; the results lead to a partial molar

Surface charges and Np(V) sorption on amorphous Al- and Fe- silicates

International Nuclear Information System (INIS)

Del Nero, M.; Assada, A.; Barillon, R.; Duplatre, G.; Made, B.

2005-01-01

Full text of publication follows: Sorption onto Si-rich alteration layers of crystalline minerals and nuclear glasses, and onto amorphous secondary silicates of rocks and soils, are expected to retard the migration of actinides in the near- and far-field of HLW repositories. We present experimental and modeling studies on the effects of silicate structure and bulk chemistry, and of solution chemistry, on charges and adsorption of neptunyl ions at surfaces of synthetic, amorphous or poorly ordered silica, Al-silicates and Fe-silicates. The Al-silicates display similar pH-dependent surface charges characterized by predominant Si-O - Si sites, and similar surface affinities for neptunyl ions, irrespective to their Si/Al molar ratio (varying from 10 to 4.3). Such experimental features are explained by incorporation of Al atoms in tetrahedral position in the silicate lattice, leading to only trace amounts of high-affinity Al-OH surface groups due to octahedral Al. By contrast, the structure of the Fe-silicates ensures the occurrence of high-affinity Fe-OH surface groups, whose concentration is shown by proton adsorption measurements to increase with decreasing of the silicate Si/Fe molar ratio (from 10 to 2.3). Nevertheless, experimental data of the adsorption of neptunyl and electrolyte ions show unexpectedly weak effect of the Si/Fe ratio, and suggest predominant Si-OH surface groups. A possible explanation is that aqueous silicate anions, released by dissolution, adsorb at OH Fe - surface groups and / or precipitate as silica gel coatings, because experimental solutions were found at near-equilibrium with respect to amorphous silica. Therefore, the environmental sorption of Np(V) onto Si-rich, amorphous or poorly ordered Al-silicates may primarily depend on pH and silicate specific surface areas, given the low overall chemical affinity of such phases for dissolved metals. By contrast, the sorption of Np(V) on natural, amorphous or poorly ordered Fe-silicates may be a

Near-Horizon Geodesics for Astrophysical and Idealised Black Holes: Coordinate Velocity and Coordinate Acceleration

Directory of Open Access Journals (Sweden)

Petarpa Boonserm

2018-05-01

Full Text Available Geodesics (by definition have an intrinsic 4-acceleration zero. However, when expressed in terms of coordinates, the coordinate acceleration d 2 x i / d t 2 can very easily be non-zero, and the coordinate velocity d x i / d t can behave unexpectedly. The situation becomes extremely delicate in the near-horizon limit—for both astrophysical and idealised black holes—where an inappropriate choice of coordinates can quite easily lead to significant confusion. We shall carefully explore the relative merits of horizon-penetrating versus horizon-non-penetrating coordinates, arguing that in the near-horizon limit the coordinate acceleration d 2 x i / d t 2 is best interpreted in terms of horizon-penetrating coordinates.

Behaviour of Co-Mo-Al/sub 2/O/sub 3/ catalysts in the hydrogenation of phenols

Energy Technology Data Exchange (ETDEWEB)

Weigold, H.

1982-10-01

The activity of a number of ring alkyl-substituted phenols in the direct hydrodeoxygenation reaction (i.e. C-O bond scission without prior ring hydrogenation) in the presence of a commercial Co-Mo-Al/sub 2/O/sub 3/ catalyst has been investigated. The results indicate that the catalytically active site is stereochemically demanding. It is proposed that the phenol ring hydrogenation and the direct hydrodeoxygenation reaction proceed on the same catalytic site. The ease of the direct hydrodeoxygenation reaction is retarded mainly when transfer of the substrate hydroxyl group onto a co-ordinatively unsaturated metal site on the catalyst is inhibited. This occurs when the catalyst hydroxyl group receptor site is occupied by a co-ordinating ligand (poison) or when substituents on the substrate direct the phenolic hydroxyl group away from this metal site. The catalytic behaviour of Co-Mo-Al/sub 2/O/sub 3/ can be 'transformed' to resemble more closely that of Ni-Mo-Al/sub 2/O/sub 3/ (high reductive capacity) when the reaction medium contains both excess H/sub 2/S and a co-ordinating ligand. It is proposed that this 'transformed' species is of importance in hydrodenitrogenation reactions in an H/sub 2/S-rich environment.

New intermetallic compounds Ln(Ag, AL)4 (Ln-Y, Gd, Tb, Dy) and their structure

International Nuclear Information System (INIS)

Kuz'ma, Yu.B.; Stel'makhovich, B.M.

1990-01-01

By the methods of X-ray analysis crystal structure of compounds Ln(Ag,Al) 4 , where Ln-Y, Gd, Tb, Dy, posessing rhombic structure, is determined. The intermetallics have been prepared for the first time. Ways of atom distribution and their coordinates in DyAg 0.55 Al 3.45 structure (a=0.4296(1), b=04179(1), c=0.9995(3), R=0.093) are specified. Other compounds are formed in case of LnAgAl 3 compositions. Interatomic distances in Dy(Ag,Al) 4 structure are considered. A supposition is made on the formation in Ln-Ag-Al systems of a greater number of intermetallic compounds

Poly[μ-aqua-diaqua(μ2-pyrazine-2,3-dicarboxylatodilithium(I

Directory of Open Access Journals (Sweden)

Kutalmis Guven

2009-12-01

Full Text Available The asymmetric unit of the title compound, [Li2(C6H2N2O4(H2O3]n, consists of two independent Li+ cations, one pyrazine-2,3-dicarboxylate dianion and three water molecules. One of the Li+ cations has a distorted tetrahedral geometry, coordinated by one of the carboxylate O atoms of the pyrazine-2,3-dicarboxylate ligand and three O atoms from three water molecules, whereas the other Li+ cation has a distorted trigonal-bipyramidal geometry, coordinated by a carboxylate O atom of a symmetry-related pyrazine-2,3-dicarboxylate ligand, two water molecules and a chelating pyrazine-2,3-dicarboxylate ligand (by utilizing both N and O atoms of an adjacent molecule. The synthesis of a hydrated polymeric dinuclear lithium complex formed with two pyrazine-2,3-dicarboxylic acid ligands has been reported previously [Tombul et al. (2008a. Acta Cryst. E64, m491–m492]. By comparision to the complex reported here, the dinuclear complex formed with two pyrazine-2,3-dicarboxylic acid ligands differs in the coordination geometry of both Li atoms. The crystal structure further features O—H...O and O—H...N hydrogen-bonding interactions involving the water molecules and carboxylate O atoms.

Conductivity enhancement of ion tracks in tetrahedral amorphous carbon by doping with N, B, Cu and Fe

International Nuclear Information System (INIS)

Krauser, J.; Nix, A.-K.; Gehrke, H.-G.; Hofsäss, H.; Trautmann, C.; Weidinger, A.

2012-01-01

Conducting ion tracks are formed when high-energy heavy ions (e.g. 1 GeV Au) pass through tetrahedral amorphous carbon (ta-C). These nanowires with a diameter of about 8 nm are embedded in the insulating ta-C matrix and of interest for various nanotechnological applications. Usually the overall conductivity of the tracks and the current/voltage characteristics (Ohmic or non-Ohmic) vary strongly from track to track, even when measured on the same sample, indicating that the track formation is neither complete nor homogeneous. To improve the track conductivity, doping of ta-C with N, B, Cu, or Fe is investigated. Beneficial changes in track conductivity after doping compete with a conductivity increase of the surrounding matrix material. Best results are achieved by incorporation of 1 at.% Cu, while for different reasons, the improvement of the tracks remains moderate for N, B, and Fe doping. Conductivity enhancement of the tracks is assumed to develop during the ion track formation process by an increased number of localized states which contribute to the current transport.

Structural study of Al2O3-Na2O-CaO-P2O5 bioactive glasses as a function of aluminium content.

Science.gov (United States)

Smith, J M; King, S P; Barney, E R; Hanna, J V; Newport, R J; Pickup, D M

2013-01-21

Calcium phosphate based biomaterials are extensively used in the context of tissue engineering: small changes in composition can lead to significant changes in properties allowing their use in a wide range of applications. Samples of composition (Al(2)O(3))(x)(Na(2)O)(0.11-x)(CaO)(0.445)(P(2)O(5))(0.445), where x = 0, 0.03, 0.05, and 0.08, were prepared by melt quenching. The atomic-scale structure has been studied using neutron diffraction and solid state (27)Al MAS NMR, and these data have been rationalised with the determined density of the final glass product. With increasing aluminium concentration the density increases initially, but beyond about 3 mol. % Al(2)O(3) the density starts to decrease. Neutron diffraction data show a concomitant change in the aluminium speciation, which is confirmed by (27)Al MAS NMR studies. The NMR data reveal that aluminium is present in 4, 5, and 6-fold coordination and that the relative concentrations of these environments change with increasing aluminium concentration. Materials containing aluminium in 6-fold coordination tend to have higher densities than analogous materials with the aluminium found in 4-fold coordination. Thus, the density changes may readily be explained in terms of an increase in the relative concentration of 4-coordinated aluminium at the expense of 6-fold aluminium as the Al(2)O(3) content is increased beyond 3 mol. %.

A XANES study of cobalt speciation state in blue-and-white glazes from 16th to 17th century Chinese porcelains

Energy Technology Data Exchange (ETDEWEB)

Figueiredo, M.O., E-mail: ondina.figueiredo@lneg.pt [CENIMAT/I3N, Faculty Sciences and Technology, New University of Lisbon, Campus da Caparica, 2829-516 Caparica (Portugal); National Laboratory of Energy and Geology (LNEG), Apartado 7586, 2721-866 Alfragide (Portugal); Silva, T.P. [National Laboratory of Energy and Geology (LNEG), Apartado 7586, 2721-866 Alfragide (Portugal); CENIMAT/I3N, Faculty Sciences and Technology, New University of Lisbon, Campus da Caparica, 2829-516 Caparica (Portugal); Veiga, J.P. [CENIMAT/I3N, Faculty Sciences and Technology, New University of Lisbon, Campus da Caparica, 2829-516 Caparica (Portugal)

2012-04-15

Highlights: Black-Right-Pointing-Pointer Speciation of cobalt in ancient Chinese porcelain glazes studied by X-ray absorption near-edge spectroscopy. Black-Right-Pointing-Pointer Blue pigmenting role of tetrahedral Co{sup 2+} ions. Black-Right-Pointing-Pointer Uncertainties in deducing a formal valence state for cobalt ions from the edge energy. - Abstract: The composition of cobalt blue pigments used in ancient blue-and-white Chinese glazes is known to have changed between the 14th and the 17th century and ratios of some main chemical components plus trace elements are relevant guide-lines to establish the porcelain manufacture period. Once archaeological findings of Chinese porcelains can contribute to set up dating processes, a study of blue-and-white porcelain shards recovered during recent excavations in Lisbon Old-City was carried out by non-destructive laboratory X-ray fluorescence spectrometry for chemical characterization, combined with X-ray absorption spectroscopy (XAS) using synchrotron radiation to ascertain the formal valence and coordination of pigmenting cobalt ions. Following a preliminary extended X-ray absorption fine-structure study that revealed a coordination of divalent cobalt ions slightly above four, a detailed analysis of the near-edge region of Co 1s X-ray absorption spectra (XANES) was carried out on the blue-and-white glazes from those archaeological Chinese porcelain fragments. Pre-edge features and edge details are discussed in comparison with XANES spectra obtained from model compounds with well known crystal structure - Co{sub 3}O{sub 4}, CoAl{sub 2}O{sub 4} and Co{sub 2}SiO{sub 4}, plus a cobalt-based blue pigment (cerulean). Present chemical data validate the manufacture period of studied Chinese porcelains advanced by Art Historians on the single basis of stylistic features (late 16th and medium 17th century). Spectroscopic results confirm a coordination environment of pigmenting Co{sup 2+} ions close to tetrahedral and

A XANES study of cobalt speciation state in blue-and-white glazes from 16th to 17th century Chinese porcelains

International Nuclear Information System (INIS)

Figueiredo, M.O.; Silva, T.P.; Veiga, J.P.

2012-01-01

Highlights: ► Speciation of cobalt in ancient Chinese porcelain glazes studied by X-ray absorption near-edge spectroscopy. ► Blue pigmenting role of tetrahedral Co 2+ ions. ► Uncertainties in deducing a formal valence state for cobalt ions from the edge energy. - Abstract: The composition of cobalt blue pigments used in ancient blue-and-white Chinese glazes is known to have changed between the 14th and the 17th century and ratios of some main chemical components plus trace elements are relevant guide-lines to establish the porcelain manufacture period. Once archaeological findings of Chinese porcelains can contribute to set up dating processes, a study of blue-and-white porcelain shards recovered during recent excavations in Lisbon Old-City was carried out by non-destructive laboratory X-ray fluorescence spectrometry for chemical characterization, combined with X-ray absorption spectroscopy (XAS) using synchrotron radiation to ascertain the formal valence and coordination of pigmenting cobalt ions. Following a preliminary extended X-ray absorption fine-structure study that revealed a coordination of divalent cobalt ions slightly above four, a detailed analysis of the near-edge region of Co 1s X-ray absorption spectra (XANES) was carried out on the blue-and-white glazes from those archaeological Chinese porcelain fragments. Pre-edge features and edge details are discussed in comparison with XANES spectra obtained from model compounds with well known crystal structure – Co 3 O 4 , CoAl 2 O 4 and Co 2 SiO 4 , plus a cobalt-based blue pigment (cerulean). Present chemical data validate the manufacture period of studied Chinese porcelains advanced by Art Historians on the single basis of stylistic features (late 16th and medium 17th century). Spectroscopic results confirm a coordination environment of pigmenting Co 2+ ions close to tetrahedral and substantiate the dual role of cobalt as network former plus modifier in the glaze of ancient Chinese porcelains.

Nanodiamonds on tetrahedral amorphous carbon significantly enhance dopamine detection and cell viability.

Science.gov (United States)

Peltola, Emilia; Wester, Niklas; Holt, Katherine B; Johansson, Leena-Sisko; Koskinen, Jari; Myllymäki, Vesa; Laurila, Tomi

2017-02-15

We hypothesize that by using integrated carbon nanostructures on tetrahedral amorphous carbon (ta-C), it is possible to take the performance and characteristics of these bioelectrodes to a completely new level. The integrated carbon electrodes were realized by combining nanodiamonds (NDs) with ta-C thin films coated on Ti-coated Si-substrates. NDs were functionalized with mixture of carboxyl and amine groups ND andante or amine ND amine , carboxyl ND vox or hydroxyl groups ND H and drop-casted or spray-coated onto substrate. By utilizing these novel structures we show that (i) the detection limit for dopamine can be improved by two orders of magnitude [from 10µM to 50nM] in comparison to ta-C thin film electrodes and (ii) the coating method significantly affects electrochemical properties of NDs and (iii) the ND coatings selectively promote cell viability. ND andante and ND H showed most promising electrochemical properties. The viability of human mesenchymal stem cells and osteoblastic SaOS-2 cells was increased on all ND surfaces, whereas the viability of mouse neural stem cells and rat neuroblastic cells was improved on ND andante and ND H and reduced on ND amine and ND vox. The viability of C6 cells remained unchanged, indicating that these surfaces will not cause excess gliosis. In summary, we demonstrated here that by using functionalized NDs on ta-C thin films we can significantly improve sensitivity towards dopamine as well as selectively promote cell viability. Thus, these novel carbon nanostructures provide an interesting concept for development of various in vivo targeted sensor solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Coordination, non-coordination and semi-coordination of perchlorates in the lanthanide adducts Ln (CLO4)3. 6dmba

International Nuclear Information System (INIS)

Tfouni, E.; Giesbrecht, E.

1983-01-01

The coordination or not of the perchlorate anions in the previously reported Ln(CLO 4 ) 3 .6 dmba is discussed. The analysis of the infrared spectral data and molar conductance data indicate that they may be formulated as [Ln(dmba) 6 (CLO 4 )n] (CLO 4 ) sub(3-n), n=0,1,2. The individual compounds may be a mixture of species with different n values and/or pure compounds with semi-coordinated and non-coordinated perchlorates. (Author) [pt

Magnetic Coordinate Systems

Science.gov (United States)

Laundal, K. M.; Richmond, A. D.

2017-03-01

Geospace phenomena such as the aurora, plasma motion, ionospheric currents and associated magnetic field disturbances are highly organized by Earth's main magnetic field. This is due to the fact that the charged particles that comprise space plasma can move almost freely along magnetic field lines, but not across them. For this reason it is sensible to present such phenomena relative to Earth's magnetic field. A large variety of magnetic coordinate systems exist, designed for different purposes and regions, ranging from the magnetopause to the ionosphere. In this paper we review the most common magnetic coordinate systems and describe how they are defined, where they are used, and how to convert between them. The definitions are presented based on the spherical harmonic expansion coefficients of the International Geomagnetic Reference Field (IGRF) and, in some of the coordinate systems, the position of the Sun which we show how to calculate from the time and date. The most detailed coordinate systems take the full IGRF into account and define magnetic latitude and longitude such that they are constant along field lines. These coordinate systems, which are useful at ionospheric altitudes, are non-orthogonal. We show how to handle vectors and vector calculus in such coordinates, and discuss how systematic errors may appear if this is not done correctly.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

... two indole thiohydrazide arms forming SNONS coordinating sites. NMR and IR spectral studies show that the ligand exists in thioketo form. Each Zn ion in the dinuclear core is in tetrahedral environment with endogenous phenolate bridging and exogenous acetate bridging. The zinc complex in DMF exhibits fluorescence.

Amorphous Solid Water:

DEFF Research Database (Denmark)

Wenzel, Jack; Linderstrøm-Lang, C. U.; Rice, Stuart A.

1975-01-01

-like structure factor. The Fourier-transformed structure e factor yields a real space pair distribution function consistent with local tetrahedral coordination and hydrogen bonding, as in other condensed phases of water. The intramolecular OD separation is 1.00 angstrom; the lack of data for very large wave...

Correlation between substrate bias, growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon films

International Nuclear Information System (INIS)

Liu Aiping; Zhu Jiaqi; Han Jiecai; Wu Huaping; Jia Zechun

2007-01-01

We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH 3 as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about -80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH 3 is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp 2 sites dispersed in sp 3 skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films

Motor coordination uses external spatial coordinates independent of developmental vision.

Science.gov (United States)

Heed, Tobias; Röder, Brigitte

2014-07-01

The constraints that guide bimanual movement coordination are informative about the processing principles underlying movement planning in humans. For example, symmetry relative to the body midline benefits finger and hand movements independent of hand posture. This symmetry constraint has been interpreted to indicate that movement coordination is guided by a perceptual code. Although it has been assumed implicitly that the perceptual system at the heart of this constraint is vision, this relationship has not been tested. Here, congenitally blind and sighted participants made symmetrical and non-symmetrical (that is, parallel) bimanual tapping and finger oscillation movements. For both groups, symmetrical movements were executed more correctly than parallel movements, independent of anatomical constraints like finger homology and hand posture. For the blind, the reliance on external spatial factors in movement coordination stands in stark contrast to their use of an anatomical reference frame in perceptual processing. Thus, the externally coded symmetry constraint evident in bimanual coordination can develop in the absence of the visual system, suggesting that the visual system is not critical for the establishment of an external-spatial reference frame in movement coordination. Copyright © 2014 Elsevier B.V. All rights reserved.

First-principles study of amorphous Ga4Sb6Te3 phase-change alloys

Science.gov (United States)

Bouzid, Assil; Gabardi, Silvia; Massobrio, Carlo; Boero, Mauro; Bernasconi, Marco

2015-05-01

First-principles molecular dynamics simulations within the density functional theory framework were performed to generate amorphous models of the Ga4Sb6Te3 phase change alloy by quenching from the melt. We find that Ga-Sb and Ga-Te are the most abundant bonds with only a minor amount of Sb-Te bonds participating to the alloy network. Ga and four-coordinated Sb atoms present a tetrahedral-like geometry, whereas three-coordinated Sb atoms are in a pyramidal configuration. The tetrahedral-like geometries are similar to those of the crystalline phase of the two binary compounds GaTe and GaSb. A sizable fraction of Sb-Sb bonds is also present, indicating a partial nanoscale segregation of Sb. Despite the fact that the composition Ga4Sb6Te3 lies on the pseudobinary Ga Sb -Sb2Te3 tie line, the amorphous network can be seen as a mixture of the two binary compounds GaTe and GaSb with intertwined elemental Sb.

Synthesis, Spectral and Magnetic Studies of Newly Mixed-Ligand Complexes of 4-Formyl-Acetanilide Thiosemicarbazone and 3,4-Dihydrocinnamic Acid with Some Metal Ions

Directory of Open Access Journals (Sweden)

Shayma A. Shaker

2010-01-01

Full Text Available New complexes with thiosemicarbazone derivative and 3, 4-dihydrocinnamic acid were prepared and characterized by elemental analysis, determination of metal, IR, 1H NMR, electronic spectroscopy and magnetic measurements. The thiosemicarbazone derivative forms bidentate ligand complexes of the general formula, [M(Thz(Caf] where Thz = 4-formyl- acetanilide thiosemicarbazone, Caf = 3,4-dihydrocinnamic acid and M=Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+. The IR and 1H NMR spectra indicates that the (Thz was coordinated with the metal ions through the N and S atoms and the (Caf was negatively charged bidentat ligand and was coordinated with the metal ions through the two O atoms. Electronic spectra and magnetic susceptibility measurements of the solid complexes indicates the tetrahedral geometry around the Mn2+, Fe2+, Co2+, Ni2+, Zn2+, Cd2+ and irregular tetrahedral geometry around Pb2+ ion while the Cu2+ complex has squar planer geometry.

Investigating the Constrained Action Hypothesis: A Movement Coordination and Coordination Variability Approach.

Science.gov (United States)

Vidal, Anthony; Wu, Will; Nakajima, Mimi; Becker, James

2017-09-19

The purpose of this study was to examine the effects of focus of attention cues on movement coordination and coordination variability in the lower extremity. Twenty participants performed the standing long jump under both internal and external focus of attention conditions. A modified vector coding technique was used to evaluate the influence of attentional focus cues on lower extremity coordination patterns and coordination variability during the jumps. Participants jumped significantly further under an external focus of attention condition compared with an internal focus of attention condition (p = .035, effect size = .29). Focus of attention also influenced coordination between the ankle and knee, F(6, 19) = 2.87, p = .012, effect size = .388, with participants primarily using their knees under the internal focus of attention, and using both their ankles and knees under the external focus of attention. Attentional focus cues did not influence ankle-knee, F(1, 19) = 0.02, p = .98, effect size = .02, or hip-knee, F(1, 19) = 5.00, p = .49, effect size = .16, coordination variability. Results suggest that while attentional focus may not directly influence movement coordination condition, there is still a change in movement strategy resulting in greater jump distances following an external focus of attention.

A parallel electrostatic Particle-in-Cell method on unstructured tetrahedral grids for large-scale bounded collisionless plasma simulations

Science.gov (United States)

Averkin, Sergey N.; Gatsonis, Nikolaos A.

2018-06-01

An unstructured electrostatic Particle-In-Cell (EUPIC) method is developed on arbitrary tetrahedral grids for simulation of plasmas bounded by arbitrary geometries. The electric potential in EUPIC is obtained on cell vertices from a finite volume Multi-Point Flux Approximation of Gauss' law using the indirect dual cell with Dirichlet, Neumann and external circuit boundary conditions. The resulting matrix equation for the nodal potential is solved with a restarted generalized minimal residual method (GMRES) and an ILU(0) preconditioner algorithm, parallelized using a combination of node coloring and level scheduling approaches. The electric field on vertices is obtained using the gradient theorem applied to the indirect dual cell. The algorithms for injection, particle loading, particle motion, and particle tracking are parallelized for unstructured tetrahedral grids. The algorithms for the potential solver, electric field evaluation, loading, scatter-gather algorithms are verified using analytic solutions for test cases subject to Laplace and Poisson equations. Grid sensitivity analysis examines the L2 and L∞ norms of the relative error in potential, field, and charge density as a function of edge-averaged and volume-averaged cell size. Analysis shows second order of convergence for the potential and first order of convergence for the electric field and charge density. Temporal sensitivity analysis is performed and the momentum and energy conservation properties of the particle integrators in EUPIC are examined. The effects of cell size and timestep on heating, slowing-down and the deflection times are quantified. The heating, slowing-down and the deflection times are found to be almost linearly dependent on number of particles per cell. EUPIC simulations of current collection by cylindrical Langmuir probes in collisionless plasmas show good comparison with previous experimentally validated numerical results. These simulations were also used in a parallelization

The temperature dependence of intermediate range oxygen-oxygen correlations in liquid water

International Nuclear Information System (INIS)

Schlesinger, Daniel; Pettersson, Lars G. M.; Wikfeldt, K. Thor; Skinner, Lawrie B.; Benmore, Chris J.; Nilsson, Anders

2016-01-01

We analyze the recent temperature dependent oxygen-oxygen pair-distribution functions from experimental high-precision x-ray diffraction data of bulk water by Skinner et al. [J. Chem. Phys. 141, 214507 (2014)] with particular focus on the intermediate range where small, but significant, correlations are found out to 17 Å. The second peak in the pair-distribution function at 4.5 Å is connected to tetrahedral coordination and was shown by Skinner et al. to change behavior with temperature below the temperature of minimum isothermal compressibility. Here we show that this is associated also with a peak growing at 11 Å which strongly indicates a collective character of fluctuations leading to the enhanced compressibility at lower temperatures. We note that the peak at ∼13.2 Å exhibits a temperature dependence similar to that of the density with a maximum close to 277 K or 4 °C. We analyze simulations of the TIP4P/2005 water model in the same manner and find excellent agreement between simulations and experiment albeit with a temperature shift of ∼20 K.

The temperature dependence of intermediate range oxygen-oxygen correlations in liquid water

Energy Technology Data Exchange (ETDEWEB)

Schlesinger, Daniel; Pettersson, Lars G. M., E-mail: Lars.Pettersson@fysik.su.se [Department of Physics, AlbaNova University Center, Stockholm University, SE-106 91 Stockholm (Sweden); Wikfeldt, K. Thor [Department of Physics, AlbaNova University Center, Stockholm University, SE-106 91 Stockholm (Sweden); Science Institute, University of Iceland, VR-III, 107 Reykjavik (Iceland); Skinner, Lawrie B.; Benmore, Chris J. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Nilsson, Anders [Department of Physics, AlbaNova University Center, Stockholm University, SE-106 91 Stockholm (Sweden); Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)

2016-08-28

We analyze the recent temperature dependent oxygen-oxygen pair-distribution functions from experimental high-precision x-ray diffraction data of bulk water by Skinner et al. [J. Chem. Phys. 141, 214507 (2014)] with particular focus on the intermediate range where small, but significant, correlations are found out to 17 Å. The second peak in the pair-distribution function at 4.5 Å is connected to tetrahedral coordination and was shown by Skinner et al. to change behavior with temperature below the temperature of minimum isothermal compressibility. Here we show that this is associated also with a peak growing at 11 Å which strongly indicates a collective character of fluctuations leading to the enhanced compressibility at lower temperatures. We note that the peak at ∼13.2 Å exhibits a temperature dependence similar to that of the density with a maximum close to 277 K or 4 °C. We analyze simulations of the TIP4P/2005 water model in the same manner and find excellent agreement between simulations and experiment albeit with a temperature shift of ∼20 K.

Structure of a carbon monoxide adduct of cobalt-exchanged zeolite A (Co/sub 5.25/Na/sub 1.5/-A x 1.5CO) by neutron profile refinement

International Nuclear Information System (INIS)

Adams, J.M.; Haselden, D.A.

1984-01-01

The structure of a carbon monoxide adduct of cobalt-exchanged zeolite A, Co/sub 5.25/Na/sub 1.5/-A x 1.5CO, has been determined by Rietveld neutron profile refinement. All exchangeable cations are located in sites adjacent to the 6-ring; 3.75 of the cobalt cations sit 0.4 A inside the β-cage (Co(2)) and are arranged tetrahedrally about the eight 6-rings sites in the β-cage. The sodium cations (Na(1)) reside just inside the α-cage in sites similar to those found previously for zeolites 3A, 4A, and 5A. The remaining 1.5 cobalt cations (Co(1)) are located in sites similar to those for sodium, but they are also coordinated to the carbon monoxide molecules, which lie on, or close-to, the threefold axis which passes through the 6-ring. Inside the β-cage there is a tetrahedral aluminum complex of AlO 4 type, the oxygen atoms (O*) of which point toward six rings not occupied by cobalt cations, Co(2). Each of the oxygen atoms of this complex is involved in a hydrogen bond (2.83 A) to the 6-ring oxygen O(3). Approximately 2/3 of these bonds are of type O*-H ... O(3) and 1/3 of type O* ...H-O(3)

Paramagnetic centers in ternary coordinated oxygen in beryllium aluminosilicate glasses

International Nuclear Information System (INIS)

Blaginina, L.A.; Zatsepin, A.F.; Dmitriev, I.A.

1988-01-01

Glasses of the composition 3BeO-Al 2 O 3 -6SiO 2 containing a homogenizing additive of MgF 2 were synthesized. The ESR spectra of x-ray and gamma irradiated specimens were determined. A complex ESR spectrum arose in the original glass. The ESR spectrum of the gamma-irradiated polycrystalline Be 2 SiO 4 glass was almost identical to the crystallized glass. It was shown that the presence of beryllium atoms in the composition of silicate glasses created the conditions for the formation of structural fragments with ternary coordinated oxygen

Atomic size effects on local coordination and medium range order in molten trivalent metal chlorides

International Nuclear Information System (INIS)

Tatlipinar, H.; Akdeniz, Z.; Pastore, G.

1992-08-01

Structural correlations in molten trivalent metal chlorides are evaluated as functions of the metal ion size R M across the range from LaCl 3 (R M approx. 1.4 A) to AlCl 3 (R M approx. 0.8 A), using a charged soft-sphere model and the hypernetted chain approximation. Main attention is given to trends in the local liquid structure (partial radial distribution functions, coordination numbers and bond lengths) and in the intermediate range order (first sharp diffraction peak in the number-number and partial structure factors). The trend towards fourfold local coordination of the metal ions, the stabilization of their first-neighbour chlorine cage and the growth of medium range order are found to proceed in parallel as the size of the metal ion is allowed to decrease at constant number density and temperature. A tendency to molecular-type local structure and liquid-vapour phase separation is found within the hypernetted chain scheme at small metal ion sizes corresponding to AlCl 3 and is emphasized by decreasing the number density of the fluid. The predicted molecular units are rather strongly distorted Al 2 Cl 6 dimers, in agreement with observation. The calculated structural trends for other trichlorides are compared with diffraction and transport data. (author). 17 refs, 8 figs, 1 tab

Crystal structure of (benzenecarbothioamide-κSchloridobis(triphenylphosphane-κPsilver(I

Directory of Open Access Journals (Sweden)

Wattana Ruangwut

2014-09-01

Full Text Available In the mononuclear mixed-ligand title complex, [AgCl(C7H7NS(C18H15P2], the AgI ion is four coordinated by one S atom of a benzenecarbothioamide ligand, two P atoms of two triphenylphosphane ligands and one chloride ion, displaying a distorted tetrahedral coordination geometry. In the crystal, pairs of N—H...Cl hydrogen bonds form inversion dimers. An intramolecular N—H...Cl hydrogen bond is also observed.

Evaluation of vertical coordinate and vertical mixing algorithms in the HYbrid-Coordinate Ocean Model (HYCOM)

Science.gov (United States)

Halliwell, George R.

Vertical coordinate and vertical mixing algorithms included in the HYbrid Coordinate Ocean Model (HYCOM) are evaluated in low-resolution climatological simulations of the Atlantic Ocean. The hybrid vertical coordinates are isopycnic in the deep ocean interior, but smoothly transition to level (pressure) coordinates near the ocean surface, to sigma coordinates in shallow water regions, and back again to level coordinates in very shallow water. By comparing simulations to climatology, the best model performance is realized using hybrid coordinates in conjunction with one of the three available differential vertical mixing models: the nonlocal K-Profile Parameterization, the NASA GISS level 2 turbulence closure, and the Mellor-Yamada level 2.5 turbulence closure. Good performance is also achieved using the quasi-slab Price-Weller-Pinkel dynamical instability model. Differences among these simulations are too small relative to other errors and biases to identify the "best" vertical mixing model for low-resolution climate simulations. Model performance deteriorates slightly when the Kraus-Turner slab mixed layer model is used with hybrid coordinates. This deterioration is smallest when solar radiation penetrates beneath the mixed layer and when shear instability mixing is included. A simulation performed using isopycnic coordinates to emulate the Miami Isopycnic Coordinate Ocean Model (MICOM), which uses Kraus-Turner mixing without penetrating shortwave radiation and shear instability mixing, demonstrates that the advantages of switching from isopycnic to hybrid coordinates and including more sophisticated turbulence closures outweigh the negative numerical effects of maintaining hybrid vertical coordinates.

Preparation of PbS and PbO nanopowders from new Pb(II)(saccharine) coordination polymers

International Nuclear Information System (INIS)

Aslani, Alireza; Musevi, Seyid Javad; Şahin, Ertan; Yilmaz, Veysel T.

2014-01-01

Highlights: • The complex of compounds “[Pb(H 2 O)(μ-OAc)(μ-sac)] n ” are synthesized at nano and bulk size structurally diverse and show interesting three-dimensional coordination polymers. • Reduction of the particle size of the coordination polymers to a few dozen nanometers results in lower thermal stability when compared to the single crystalline samples. • This study demonstrates that the metal–organic framework may be suitable precursors for the preparation of nanoscale materials with interesting morphologies. - Abstract: Nanopowders and single crystal of new Pb(II) three-dimensional coordination polymer, [Pb(H 2 O)(μ-OAc)(μ-sac)] n “PASAC” were synthesized by a sonochemical and branched tube methods (Yılmaz et al., Z. Anorg. Allg. Chem. 629 (2003) 172). The new nano-structures of Pb(II) coordination polymer were characterized by X-ray crystallography analysis, scanning electron microscopy (SEM), X-ray powder diffraction (XRD), surface analysis (BET), and IR spectroscopy. The crystal structure of these compounds consists of three-dimensional polymeric units. The thermal stability of compounds was studied by thermal gravimetric analysis (TGA) and differential thermal analyses (DTA). PbS and PbO nano-structures were obtained by calcinations of the nano-structures of this coordination polymer at 600 °C

Silver Cation Coordination Study to AsW9 Ligand – A Trilacunar Arsenotungstate Compound

Directory of Open Access Journals (Sweden)

Berta Lavinia

2017-06-01

Full Text Available Objective: The main objective of this research is to find the coordination ratio between AsW9 and Ag+, as a preliminary study for synthesizing a new silver-arsenotungstate complex. Material and method: The ligand:cation molar ratio in complexes was determined by conductometric and potentiometric titrations of AsW9 with silver salts: CH3COOAg, AgNO3. Results: The ratio was obtained from the inflexion points of the curves when molar ratio was plotted versus conductivity, or from the equivalence point when silver added volume was plotted versus pH value. Each graphic shows one point of inflexion corresponding to 1:1.54 ratio of AsW9:Ag+. In the same manner, the equivalent volumes determined by graphical method gave the ratio 1:1.53. The spectral results confirmed that a AsW9:Ag+ complex was formed since the ligand absorption maxima values have been changed from 190 nm to 197 nm in the case of using AgNO3 and 196 nm for CH3COOAg corresponding to the W=Od bond, and from 246.5 nm to 274 nm (AgNO3 and 270 nm (CH3COO-Ag+ for the W-Ob,c-W bond. Conclusions: Silver cation exhibit a preference for AsW9 in a ratio of 3 to 2. This ratio can be associated to a sandwich type arrangement, with two trilacunary Keggin building blocks incorporating 3 metal cations in a tetrahedral geometry.

In situ cyclization modification in polymerization of butadiene by rare earth coordination catalyst

International Nuclear Information System (INIS)

Wang Chaoyang

2005-01-01

Butadiene was polymerized to a certain extent in the presence of a rare earth coordination catalyst, neodymium compound of neodymium chloride and i-propyl alcohol and triethyl aluminum (NdCl 3 ·3i-PrOH-AlEt 3 ) in toluene and the allyl chloride was then added to the reactive solution in order to in situ cyclize the formed polybutadiene and cyclopolymerize the unreacted butadiene monomers. Effects of molar ratio of allylchloride to AlEt 3 (Cl/Al), cyclization reaction time and temperature, butadiene and NdCl 3 ·3i-PrOH concentrations on the cyclization reaction have been investigated. The cyclization reaction is very quick, only several minutes. The cyclization reaction temperature has few effects on the properties of the cyclized product. Cl/Al is a very important condition for this reaction system. Cyclized polybutadiene has a low value of intrinsic viscosity, free gelling and high yield at high Cl/Al. The microstructures and properties of the cyclized products have been characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and gel permeation chromatography. The cyclization mechanism is put forward

Explicitly computing geodetic coordinates from Cartesian coordinates

Science.gov (United States)

Zeng, Huaien

2013-04-01

This paper presents a new form of quartic equation based on Lagrange's extremum law and a Groebner basis under the constraint that the geodetic height is the shortest distance between a given point and the reference ellipsoid. A very explicit and concise formulae of the quartic equation by Ferrari's line is found, which avoids the need of a good starting guess for iterative methods. A new explicit algorithm is then proposed to compute geodetic coordinates from Cartesian coordinates. The convergence region of the algorithm is investigated and the corresponding correct solution is given. Lastly, the algorithm is validated with numerical experiments.

Mesoporous titanium phosphate molecular sieves with ion-exchange capacity.

Science.gov (United States)

Bhaumik, A; Inagaki, S

2001-01-31

Novel open framework molecular sieves, titanium(IV) phosphates named, i.e., TCM-7 and -8 (Toyota Composite Materials, numbers 7 and 8), with new mesoporous cationic framework topologies obtained by using both cationic and anionic surfactants are reported. The (31)P MAS NMR, UV-visible absorption, and XANES data suggest the tetrahedral state of P and Ti, and stabilization of the tetrahedral state of Ti in TCM-7/8 is due to the incorporation of phosphorus (at Ti/P = 1:1) vis-à-vis the most stable octahedral state of Ti in the pure mesoporous TiO(2). Mesoporous TCM-7 and -8 show anion exchange capacity due to the framework phosphonium cation and cation exchange capacity due to defective P-OH groups. The high catalytic activity in the liquid-phase partial oxidation of cyclohexene with a dilute H(2)O(2) oxidant supports the tetrahedral coordination of Ti in these materials.

Coordination failure caused by sunspots

DEFF Research Database (Denmark)

Beugnot, Julie; Gürgüç, Zeynep; Øvlisen, Frederik Roose

2012-01-01

on the efficient equilibrium, we consider sunspots as a potential reason for coordination failure. We conduct an experiment with a three player 2x2x2 game in which coordination on the efficient equilibrium is easy and should normally occur. In the control session, we find almost perfect coordination on the payoff......-dominant equilibrium, but in the sunspot treatment, dis-coordination is frequent. Sunspots lead to significant inefficiency, and we conclude that sunspots can indeed cause coordination failure....

Low pH, aluminum, and phosphorus coordinately regulate malate exudation through GmALMT1 to improve soybean adaptation to acid soils.

Science.gov (United States)

Liang, Cuiyue; Piñeros, Miguel A; Tian, Jiang; Yao, Zhufang; Sun, Lili; Liu, Jiping; Shaff, Jon; Coluccio, Alison; Kochian, Leon V; Liao, Hong

2013-03-01

Low pH, aluminum (Al) toxicity, and low phosphorus (P) often coexist and are heterogeneously distributed in acid soils. To date, the underlying mechanisms of crop adaptation to these multiple factors on acid soils remain poorly understood. In this study, we found that P addition to acid soils could stimulate Al tolerance, especially for the P-efficient genotype HN89. Subsequent hydroponic studies demonstrated that solution pH, Al, and P levels coordinately altered soybean (Glycine max) root growth and malate exudation. Interestingly, HN89 released more malate under conditions mimicking acid soils (low pH, +P, and +Al), suggesting that root malate exudation might be critical for soybean adaptation to both Al toxicity and P deficiency on acid soils. GmALMT1, a soybean malate transporter gene, was cloned from the Al-treated root tips of HN89. Like root malate exudation, GmALMT1 expression was also pH dependent, being suppressed by low pH but enhanced by Al plus P addition in roots of HN89. Quantitative real-time PCR, transient expression of a GmALMT1-yellow fluorescent protein chimera in Arabidopsis protoplasts, and electrophysiological analysis of Xenopus laevis oocytes expressing GmALMT1 demonstrated that GmALMT1 encodes a root cell plasma membrane transporter that mediates malate efflux in an extracellular pH-dependent and Al-independent manner. Overexpression of GmALMT1 in transgenic Arabidopsis, as well as overexpression and knockdown of GmALMT1 in transgenic soybean hairy roots, indicated that GmALMT1-mediated root malate efflux does underlie soybean Al tolerance. Taken together, our results suggest that malate exudation is an important component of soybean adaptation to acid soils and is coordinately regulated by three factors, pH, Al, and P, through the regulation of GmALMT1 expression and GmALMT1 function.

Simple shearing flow of dry soap foams with tetrahedrally close-packed structure

Energy Technology Data Exchange (ETDEWEB)

Reinelt, Douglas A. [Department of Mathematics, Southern Methodist University, Dallas, Texas 75275-0156 (United States); Kraynik, Andrew M. [Engineering Sciences Center, Sandia National Laboratories, Albuquerque, New Mexico 87185-0834 (United States)

2000-05-01

The microrheology of dry soap foams subjected to quasistatic, simple shearing flow is analyzed. Two different monodisperse foams with tetrahedrally close-packed (TCP) structure are examined: Weaire-Phelan (A15) and Friauf-Laves (C15). The elastic-plastic response is evaluated by using the Surface Evolver to calculate foam structures that minimize total surface area at each value of strain. The foam geometry and macroscopic stress are piecewise continuous functions of strain. The stress scales as T/V{sup 1/3}, where T is surface tension and V is cell volume. Each discontinuity corresponds to large changes in foam geometry and topology that restore equilibrium to unstable configurations that violate Plateau's laws. The instabilities occur when the length of an edge on a polyhedral foam cell vanishes. The length can tend to zero smoothly or abruptly with strain. The abrupt case occurs when a small increase in strain changes the energy profile in the neighborhood of a foam structure from a local minimum to a saddle point, which can lead to symmetry-breaking bifurcations. In general, the new structure associated with each stable solution branch results from an avalanche of local topology changes called T1 transitions. Each T1 cascade produces different cell neighbors, reduces surface energy, and provides an irreversible, film-level mechanism for plastic yield behavior. Stress-strain curves and average stresses are evaluated by examining foam orientations that admit strain-periodic behavior. For some orientations, the deformation cycle includes Kelvin cells instead of the original TCP structure; but the foam does not remain perfectly ordered. Bifurcations during subsequent T1 cascades lead to disorder and can even cause strain localization. (c) 2000 Society of Rheology.

Binding of anions in triply interlocked coordination catenanes and dynamic allostery for dehalogenation reactions† †Electronic supplementary information (ESI) available: Characterization data and additional tables and figures. CCDC 1515722 and 1515723. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04070a

Science.gov (United States)

Yang, Linlin; Jing, Xu; An, Bowen; Yang, Yang

2017-01-01

By synergistic combination of multicomponent self-assembly and template-directed approaches, triply interlocked metal organic catenanes that consist of two isolated chirally identical tetrahedrons were constructed and stabilized as thermodynamic minima. In the presence of suitable template anions, the structural conversion from the isolated tetrahedral conformers into locked catenanes occurred via the cleavage of an intrinsically reversible coordination bond in each of the tetrahedrons, followed by the reengineering and interlocking of two fragments with the regeneration of the broken coordination bonds. The presence of several kinds of individual pocket that were attributed to the triply interlocked patterns enabled the possibility of encapsulating different anions, allowing the dynamic allostery between the unlocked/locked conformers to promote the dehalogenation reaction of 3-bromo-cyclohexene efficiently, as with the use of dehalogenase enzymes. The interlocked structures could be unlocked into two individual tetrahedrons through removal of the well-matched anion templates. The stability and reversibility of the locked/unlocked structures were further confirmed by the catching/releasing process that accompanied emission switching, providing opportunities for the system to be a dynamic molecular logic system. PMID:29675152

NMR and NQR study of the electronic and structural properties of Al-Cu-Fe and Al-Cu-Ru quasicrystals

International Nuclear Information System (INIS)

Shastri, A.; Borsa, F.; Torgeson, D.R.; Shield, J.E.; Goldman, A.I.

1994-01-01

27 Al and 63,65 Cu NMR is reported for powdered stable Al-Cu-Fe and Al-Cu-Ru icosahedral quasicrystals and crystalline approximants, and for an Al-Pd-Mn single-grain quasicrystal. 27 Al NQR spectra at 4.2 K were observed in Al-Cu-Fe and Al-Cu-Ru samples. From quadrupole-perturbed NMR spectra at different magnetic fields, and from zero-field NQR spectra, a wide distribution of local electric-field gradient (EFG) tensor components and principal-axis-system orientations was found at the Al site. A model EFG calculation based on a 1/1 Al-Cu-Fe approximant successfully explained the observed NQR spectra. The average local gradient is largely determined by the p-electron wave function at the Al site, while the width of the distribution is due to EFG lattice contribution. Comparison of 63 Cu and 27 Al NMR shows the EFG distribution at the two sites is similar, but the electronic contribution to the EFG is considerably smaller at the Cu site, in agreement with a more s-type wave function of the conduction electrons. Overall spread of EFG values is well reproduced by calculation based on the approximant. However, the experimental spectra indicate a much larger number of nonequivalent sites when compared with the simulated NQR spectra based on the 1/1 approximant. The short-range, local chemical order is well represented by the approximant, but differences in coordination must be included at intermediate range in the quasicrystal. Measured 27 Al Knight shift, magnetic susceptibility, and nuclear spin-lattice relaxation time as a function of temperature indicate reduced density of states at the Fermi level by a factor of 7 or 8 from the value in Al metal, consistent with the notion of a pseudogap for these quasicrystals. No differences in measured parameters were detected as a function of composition of the quasicrystalline alloys

Coordination between Fault-Ride-Through Capability and Over-current Protection of DFIG Generators for Wind Farms

DEFF Research Database (Denmark)

Bak-Jensen, Birgitte; Kawady, T.A.; Abdel-Rahman, Mansour Hassan

2010-01-01

is investigated. Simulation test cases using MATLAB-Simulink are implemented on a 365-MW wind farm in AL-Zaafarana, Egypt. The simulation results show the influence of the FRT capability on the protective relaying coordination in wind farms, showing that the FRT may work in situations where is were expected......Fault Ride-Through (FRT) capabilities set up according to the grid codes may affect the performance of related protective elements during fault periods. Therefore, in this paper the coordination between the FRT capability and over-current protection of DFIG Wind Generators in MV networks...... not to work, and then disabling the over-current protection, which should have worked in this situation....

Cation disorder in high-dose, neutron-irradiated spinel

International Nuclear Information System (INIS)

Sickafus, K.E.; Larson, A.C.; Yu, N.; Nastasi, M.; Hollenberg, G.W.; Garner, F.A.; Bradt, R.C.

1994-08-01

The objective of this effort is to determine whether MgAl 2 O 4 spinel is a suitable ceramic for fusion applications. Here, the crystal structures of MgAl 2 O 4 spinel single crystals irradiated to high neutron fluences [>5·10 26 n/m 2 (E n > 0.1 MeV)] were examined by neutron diffraction. Crystal structure refinement of the highest dose sample indicated that the average scattering strength of the tetrahedral crystal sites decreased by ∼ 20% while increasing by ∼ 8% on octahedral sites. Since the neutron scattering length for Mg is considerably larger than for Al, this results is consistent with site exchange between Mg 2+ ions on tetrahedral sites and Al 3+ ions on octahedral sites. Least-squares refinements also indicated that, in all irradiated samples, at least 35% of Mg 2+ and Al 3+ ions in the crystal experienced disordering replacements. This retained dpa on the cation sublattices is the largest retained damage ever measured in an irradiated spinel material

Luminescent properties of Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12}:Ce crystals

Energy Technology Data Exchange (ETDEWEB)

Zorenko, Yu., E-mail: zorenko@ukw.edu.pl [Institute of Physics, Kazimierz Wielki University in Bydgoszcz, Powstańców Wielkopolskich No 2, 85-090 Bydgoszcz (Poland); Zorenko, T. [Institute of Physics, Kazimierz Wielki University in Bydgoszcz, Powstańców Wielkopolskich No 2, 85-090 Bydgoszcz (Poland); Department of Electronics, Ivan Franko National University of Lviv, Gen. Tarnavskyj str. 107, 70017 Lviv (Ukraine); Malinowski, P. [Institute of Physics, Kazimierz Wielki University in Bydgoszcz, Powstańców Wielkopolskich No 2, 85-090 Bydgoszcz (Poland); Sidletskiy, O.; Neicheva, S. [Institute for Scintillation Materials, National Academy of Sciences of Ukraine, Lenina pr. 60, 61001 Kharkiv (Ukraine)

2014-12-15

Absorption, luminescent and scintillation properties of Ce{sup 3+} doped Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12} crystals with Ga content in the x=1–5 range were investigated in this work and compared with the properties of YAG:Ce crystals. Apart from the traditional spectral methods (absorption, cathodoluminescence and light yield measurements), the intrinsic and Ce{sup 3+} related luminescence of Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12}:Ce solid-solution were also investigated using the luminescent spectroscopy under excitation by synchrotron radiation in the 3.7–25 eV range. We show that the optical properties Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12}:Ce garnets monotonically change with increasing the Ga content in the x=0–3 range due to preferable localization of Ga ions in the tetrahedral position of the garnet lattice. At the highest Ga concentration (x>3) the deviation of the optical properties of Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12}:Ce garnets is observed from the respective properties of these crystals with Ga content in the x=0–3 range due to occupation by Ga ions of the octahedral position in the garnet host. - Highlights: • Different dependence of optical properties of Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12}:Ce crystals on Ga content in x=0–3 and 3–5 ranges. • Elimination of the luminescence of Y{sub Al} antisite defects in Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12}:Ce crystals at x>2. • Significant improvement of the scintillation properties of Y{sub 3}Al{sub 5−x}Ga{sub x}O{sub 12}:Ce crystals at x=2 and 3 in comparison with YAG:Ce.

Recent Development in the CESE Method for the Solution of the Navier-Stokes Equations Using Unstructured Triangular or Tetrahedral Meshes With High Aspect Ratio

Science.gov (United States)

Chang, Sin-Chung; Chang, Chau-Lyan; Yen, Joseph C.

2013-01-01

In the multidimensional CESE development, triangles and tetrahedra turn out to be the most natural building blocks for 2D and 3D spatial meshes. As such the CESE method is compatible with the simplest unstructured meshes and thus can be easily applied to solve problems with complex geometries. However, because the method uses space-time staggered stencils, solution decoupling may become a real nuisance in applications involving unstructured meshes. In this paper we will describe a simple and general remedy which, according to numerical experiments, has removed any possibility of solution decoupling. Moreover, in a real-world viscous flow simulation near a solid wall, one often encounters a case where a boundary with high curvature or sharp corner is surrounded by triangular/tetrahedral meshes of extremely high aspect ratio (up to 106). For such an extreme case, the spatial projection of a space-time compounded conservation element constructed using the original CESE design may become highly concave and thus its centroid (referred to as a spatial solution point) may lie far outside of the spatial projection. It could even be embedded beyond a solid wall boundary and causes serious numerical difficulties. In this paper we will also present a new procedure for constructing conservation elements and solution elements which effectively overcomes the difficulties associated with the original design. Another difficulty issue which was addressed more recently is the wellknown fact that accuracy of gradient computations involving triangular/tetrahedral grids deteriorates rapidly as the aspect ratio of grid cells increases. The root cause of this difficulty was clearly identified and several remedies to overcome it were found through a rigorous mathematical analysis. However, because of the length of the current paper and the complexity of mathematics involved, this new work will be presented in another paper.

Synthesis, crystal structure and DFT calculations of a new Hg (II) metal-organic polymer

Czech Academy of Sciences Publication Activity Database

Mirtamizdoust, B.; Roodsari, M.S.; Shaabani, B.; Dušek, Michal; Fejfarová, Karla

2016-01-01

Roč. 15, č. 3 (2016), s. 257-266 ISSN 1024-1221 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : mercury (II) iodide * coordination polymer * square planar * tetrahedral geometry * density functional calculation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.565, year: 2016

Silicon nitride gradient film as the underlayer of ultra-thin tetrahedral amorphous carbon overcoat for magnetic recording slider

Energy Technology Data Exchange (ETDEWEB)

Wang Guigen, E-mail: wanggghit@yahoo.com [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen 518055 (China); Kuang Xuping; Zhang Huayu; Zhu Can [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen 518055 (China); Han Jiecai [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen 518055 (China); Center for Composite Materials, Harbin Institute of Technology, Harbin 150080 (China); Zuo Hongbo [Center for Composite Materials, Harbin Institute of Technology, Harbin 150080 (China); Ma Hongtao [SAE Technologies Development (Dongguan) Co., Ltd., Dongguan 523087 (China)

2011-12-15

Highlights: Black-Right-Pointing-Pointer The ultra-thin carbon films with different silicon nitride (Si-N) film underlayers were prepared. Black-Right-Pointing-Pointer It highlighted the influences of Si-N underlayers. Black-Right-Pointing-Pointer The carbon films with Si-N underlayers obtained by nitriding especially at the substrate bias of -150 V, can exhibit better corrosion protection properties - Abstract: There are higher technical requirements for protection overcoat of magnetic recording slider used in high-density storage fields for the future. In this study, silicon nitride (Si-N) composition-gradient films were firstly prepared by nitriding of silicon thin films pre-sputtered on silicon wafers and magnetic recording sliders, using microwave electron cyclotron resonance plasma source. The ultra-thin tetrahedral amorphous carbon films were then deposited on the Si-N films by filtered cathodic vacuum arc method. Compared with amorphous carbon overcoats with conventional silicon underlayers, the overcoats with Si-N underlayers obtained by plasma nitriding especially at the substrate bias of -150 V, can provide better corrosion protection for high-density magnetic recording sliders.

Silicon nitride gradient film as the underlayer of ultra-thin tetrahedral amorphous carbon overcoat for magnetic recording slider

International Nuclear Information System (INIS)

Wang Guigen; Kuang Xuping; Zhang Huayu; Zhu Can; Han Jiecai; Zuo Hongbo; Ma Hongtao

2011-01-01

Highlights: ► The ultra-thin carbon films with different silicon nitride (Si-N) film underlayers were prepared. ► It highlighted the influences of Si-N underlayers. ► The carbon films with Si-N underlayers obtained by nitriding especially at the substrate bias of −150 V, can exhibit better corrosion protection properties - Abstract: There are higher technical requirements for protection overcoat of magnetic recording slider used in high-density storage fields for the future. In this study, silicon nitride (Si-N) composition-gradient films were firstly prepared by nitriding of silicon thin films pre-sputtered on silicon wafers and magnetic recording sliders, using microwave electron cyclotron resonance plasma source. The ultra-thin tetrahedral amorphous carbon films were then deposited on the Si-N films by filtered cathodic vacuum arc method. Compared with amorphous carbon overcoats with conventional silicon underlayers, the overcoats with Si-N underlayers obtained by plasma nitriding especially at the substrate bias of −150 V, can provide better corrosion protection for high-density magnetic recording sliders.

catena-Poly[[[dichloridozinc(II]-μ-1,4-bis(1H-benzimidazol-2-yl-κN3butane] 1,4-bis(1H-benzimidazol-2-ylbutane solvate

Directory of Open Access Journals (Sweden)

Yan-Ling Zhou

2010-01-01

Full Text Available In the crystal structure of the title coordination polymer/co-crystal, {[ZnCl2(C18H18N4]·C18H18N4}n, the tetrahedrally coordinated ZnII ions are linked by the N-heterocycle into a linear chain. Another N-heterocycle present is not coordinated to the metal atom but interacts with the chain through N—H...N and N—H...Cl hydrogen bonds. The butyl chain of the uncoordinated ligand is disordered over three positions in a 0.511 (4:0.289 (5:0.200 (5 ratio.

Aspartic acid interaction with cobalt(II) in dilute aqueous solution: A 57Co emission Mössbauer spectroscopic study

International Nuclear Information System (INIS)

Kamnev, Alexander A.; Tugarova, Anna V.; Kovács, Krisztina; Homonnay, Zoltan; Kuzmann, Erno; Vértes, Attila

2012-01-01

Emission ( 57 Co) Mössbauer spectra of the aspartic acid— 57 CoCl 2 system were measured at T = 80 K in frozen aqueous solution and in the form of a dried residue of this solution. The Mössbauer spectra, besides a weak contribution from after-effects, showed two Fe 2 +  /Co 2 +  components which were ascribed to octahedrally and tetrahedrally coordinated 57 Co II microenvironments in the Asp–cobalt(II) complex. This dual coordination mode may be due to the involvement of the second terminal carboxylic group of aspartic acid in the coordination sphere of Co.

Aspartic acid interaction with cobalt(II) in dilute aqueous solution: A {sup 57}Co emission Moessbauer spectroscopic study

Energy Technology Data Exchange (ETDEWEB)

Kamnev, Alexander A.; Tugarova, Anna V. [Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences (Russian Federation); Kovacs, Krisztina; Homonnay, Zoltan, E-mail: homonnay@ludens.elte.hu; Kuzmann, Erno; Vertes, Attila [Eoetvoes Lorand University, Institute of Chemistry (Hungary)

2012-03-15

Emission ({sup 57}Co) Moessbauer spectra of the aspartic acid-{sup 57}CoCl{sub 2} system were measured at T = 80 K in frozen aqueous solution and in the form of a dried residue of this solution. The Moessbauer spectra, besides a weak contribution from after-effects, showed two Fe{sup 2 + }/Co{sup 2 + } components which were ascribed to octahedrally and tetrahedrally coordinated {sup 57}Co{sup II} microenvironments in the Asp-cobalt(II) complex. This dual coordination mode may be due to the involvement of the second terminal carboxylic group of aspartic acid in the coordination sphere of Co.

Idaaratu al Wahdah al Namthiyah li at Tathwiri al Tarbiyah al Islamiyah

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Ahmad Danusiri

2016-04-01

Full Text Available Islam, through the Quran, proclaims that its mission includes the teachings to the whole universe, Everything in the universe is maintained by Islam, and none of the symptoms are ignored. The revelations also include the traditions of the Prophet that are authentic (shahih and good (hasan in quality. Both the Quran and maqbulah hadiths are accepted by Muslims on the basis of faith. When some experts of UIN Walisongo from various disciplines try to understand the sacred words of these two resources, their understanding continues, reaching the paradigm of the unity of science which essentially unites the normative, social, and natural sciences. The effect of this paradigm has brought up an issue for the author. Is there any hadiths or Prophetic traditions that can be used as a grand theory in the management disciplines of Islamic education.To address this issue, the authors conducted a literature research with the title Development of Islamic Education Management Module. Sources of data were focused on nine books of Hadiths : Sahih al-Bukhari, Sahih al-Muslim, Sunan Abu Dawud, Sunan at-Turmudzi, Sunan an-Nasai, Sunan Ibn Majah, Sunan ad-Darimi, Muwatta Malik, and Musnad Imam Ahmad bin Hanbal in the form of digital data Lidwa Reader Software Book 9 Imam Hadith. The findings of the study stated that the meaning of the word Rabb includes: creating, nurturing, maintaining, teaching, educating, and organizing. Thus, in an academic term, the word Rabb implies a manager or leader. Meanwhile, in the concept of comprehensive manager it contains at least 14 nomenclature denotations: planning, responsibility, organization, coordination, system of employee payroll, learning, resources, humanity, principle of making it easier for the manager to the employee, motivated to achieve optimal performance, preventing unproductivity, education participation, institutional costs, monitoring, and evaluation system. Each nomenclature has numerous hadiths that could serve

Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

International Nuclear Information System (INIS)

Ildefonse, P.; Calas, G.; Flank, A.M.; Lagarde, P.

1995-01-01

Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaO-MgO-2SiO 2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mg-O distances of 2.01 A. In aluminosilicate gels, Al-K XANES has been used to investigate the [4]Al/Al total ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Si-K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si=1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels. (orig.)

2-Aminopyridinium (2-aminopyridinetrichloridonickelate(II

Directory of Open Access Journals (Sweden)

T. Balasubramanian

2008-04-01

Full Text Available In the title compound, (C5H7N2[NiCl3(C5H6N2], the NiII atom is four-coordinated by three chloride anions and one N atom of a 2-aminopyridine ligand, forming a distorted tetrahedral coordination. In the crystal structure, cations and complex anions are linked into chains along the a, b and c axes by N—H...Cl hydrogen bonds, leading to the formation of a three-dimensional framework.

Preparation, structure and analysis of the bonding in the molecular entity (OSO)2Li{[AlF(ORF)3]Li[Al(ORF)4]} (RF = C(CF3)3).

Science.gov (United States)

Cameron, T Stanley; Nikiforov, Grigory B; Passmore, Jack; Rautiainen, J Mikko

2010-03-14

The (SO(2))(2)Li[AlF(OR(F))(3)]Li[Al(OR(F))(4)] (1) (R(F) = C(CF(3))(3)) molecular entity was obtained by thermal decomposition of Li[Al(OR(F))(4)] followed by crystallization from liquid SO(2). 1, containing two SO(2) molecules eta(1)-O coordinated to Li(+), was structurally characterized by single crystal X-ray diffraction and NMR spectroscopy in SO(2)(l). Bonding analyses of 1 (bond valency units, AIM analysis, atomic charges, bond orders) show that 1 can be either considered as a Li(OSO)(2)(+) complex stabilized by the large WCA [AlF(OR(F))(3)](-)Li(+)[Al(OR(F))(4)](-) or as consisting of 2 SO(2), 2 Li(+), [AlF(OR(F))(3)](-), and [Al(OR(F))(4)](-) joined by electrostatic interactions into the discrete molecular entity 1. The bonding between Li(+) and SO(2) molecules is shown to be almost completely attributable to monopole-induced dipole electrostatic interactions. Theoretical gas phase lithium ion affinity of SO(2) is determined to be stronger than its silver(I) ion affinity owing largely to the shorter lithium SO(2) contacts in the calculated structures that increase the electrostatic interaction.

Acquisition and Retention of Team Coordination in Command-and-Control

Science.gov (United States)

2007-05-15

transitioning from a trot to a gallop is identical to the transition from anti-phase to in-phase finger tapping , when considered from a dynamical systems...Team Coordination conserved and mixing taps extant information in new ways. The latter interpretation seems more plausible given that the relations of...5OC1~AA To e IoumatbJfoa ee b~ei b ROZ euuy (K(M) is t(W4 DU~ V 4W~f rQ~shI1JWIIX~rI~~al ft~l~f ~ DFMPC reiorys S-STR rrsnvukis to AVO 0 Eft twos

White-emissive tandem-type hybrid organic/polymer diodes with (0.33, 0.33) chromaticity coordinates.

Science.gov (United States)

Guo, Tzung-Fang; Wen, Ten-Chin; Huang, Yi-Shun; Lin, Ming-Wei; Tsou, Chuan-Cheng; Chung, Chia-Tin

2009-11-09

This study reports fabrication of white-emissive, tandem-type, hybrid organic/polymer light-emitting diodes (O/PLED). The tandem devices are made by stacking a blue-emissive OLED on a yellow-emissive phenyl-substituted poly(para-phenylene vinylene) copolymer-based PLED and applying an organic oxide/Al/molybdenum oxide (MoO(3)) complex structure as a connecting structure or charge-generation layer (CGL). The organic oxide/Al/MoO(3) CGL functions as an effective junction interface for the transport and injection of opposite charge carriers through the stacked configuration. The electroluminescence (EL) spectra of the tandem-type devices can be tuned by varying the intensity of the emission in each emissive component to yield the visible-range spectra from 400 to 750 nm, with Commission Internationale de l'Eclairage chromaticity coordinates of (0.33, 0.33) and a high color rendering capacity as used for illumination. The EL spectra also exhibit good color stability under various bias conditions. The tandem-type device of emission with chromaticity coordinates, (0.30, 0.31), has maximum brightness and luminous efficiency over 25,000 cd/m(2) and approximately 4.2 cd/A, respectively.

Coordination Chemistry of Linear Oligopyrrolic Fragments Inspired by Heme Metabolites

Science.gov (United States)

Gautam, Ritika

at 635 nm. This reaction also explains the antioxidant properties of the linear tripyrrin-1,14-dione ligand, which acts as a scavenger of O2•-. In Chapter 4, the zinc binding properties of the tripyrrin-1,14-dione ligand are described. The tripyrrolic ligand coordinates as a dianionic ligand with the divalent Zn(II) ion in both organic and aqueous buffered conditions. The complex formed is highly fluorescent with a long wavelength emission band at 648 nm. The X-Ray crystallography analysis indicates the existence of dinuclear complex [Zn(TD1•)(H2O)]2, featuring a distorted square planar geometry around the Zn(II) center. In Chapter 5, the coordination chemistry of the dipyrrin-1,9-dione fragment of propentdyopent ligand is shown with a series of transition metals like (e.g., Co(II), Ni(II), Cu(II) and Zn(II)), which form homoleptic tetrahedral complexes. The spectroscopic and electrochemical characterization confirms that the complexes shows ligand-based redox chemistry and acts as reservoirs for unpaired electrons. Chapter 6 describes the formation of the fluorescent BODIPY complex of propentdyopent ligand. The dipyrrin-1,9-dione scaffold of heme metabolite propendyopent undergoes a one-pot reaction with borontrifluoride etherate in toluene to form a green fluorescent [(pdp)BF2] complex. Spectroscopic studies reveal that the meso-unsubstituted [(pdp)BF2] complex is stable in tetrahydrofuran and has a quantum yield of 0.13. Electrochemical studies confirm that the complex undergoes ligand-based reduction and acts as a host for an unpaired electron.

Mesoporous titanium phosphates and related molecular sieves ...

Indian Academy of Sciences (India)

Unknown

phosphate using a dilute H2O2 oxidant supports the tetrahedral coordination of Ti in ... production of H2 by photo-reduction of water under UV light irradiation. ... have been extensively studied and used as acid catalysts, adsorbents and ion ... mesoporous silica materials is also of outstanding interest because of their ...

Order-disorder transition in the complex lithium spinel Li2CoTi3O8

International Nuclear Information System (INIS)

Reeves, Nik; Pasero, Denis; West, Anthony R.

2007-01-01

Li 2 CoTi 3 O 8 has an ordered Li 2 BB' 3 O 8 spinel structure, space group P4 3 32, at room temperature with 3:1 ordering of Ti and Li on the octahedral sites, and Li, Co disordered over the tetrahedral site. Rietveld refinement of variable temperature neutron powder diffraction data has shown an order-disorder phase transition in Li 2 CoTi 3 O 8 which commences at ∼500 deg. C with Li and Co mixing on the tetrahedral and 4-fold octahedral sites and is complete at a first order structural discontinuity at ∼915 deg. C. The fraction of Ti on the 12-fold octahedral site exhibits a small decrease with increasing temperature, which may suggest that the disordering involves all three cations. Above 930 deg. C, the structure, space group Fd3-barm, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site, although Co still exhibits a preference for tetrahedral coordination. A labelling scheme for ordered and partially ordered 3:1 spinels is devised which focuses on the occupancy of the Li,B cations. - Graphical abstract: Rietveld refinement of variable temperature neutron powder diffraction data shows an order-disorder phase transition in Li 2 CoTi 3 O 8 commencing at ∼500 deg. C with Li,Co mixing on tetrahedral and octahedral sites. This becomes complete at a first-order structural discontinuity at ∼915 deg. C. Above 930 deg. C, the structure, space group Fd3-barm, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site

A MAS NMR and DRIFT study of the Ga species in Ga/H-ZSM5 catalysts and their effect on propane ammoxidation

Energy Technology Data Exchange (ETDEWEB)

Pal, P. [Indian Inst. of Petroleum, Dehradun (India). Catalysis Division; Quartararo, J. [Liverpool Univ., Liverpool (United Kingdom). Leverhulme Centre for Innovative Catalysis, Dept. of Chemistry; Abd Hamid, S.B. [Malaya Univ., Postgraduate School, Bangunan (Malaysia); Derouane, E.G. [Algarve Univ., Faro (Portugal). Faculdade de Ciencias e Tecnologia; Vedrine, J.C. [Laboratoire de Physico-Chimie des Surface, Paris (France). Faculdade de Ciencias e Tecnologia; Magusin, P.C.M.M.; Anderson, B.G. [Eindhoven Univ. of Technology, Eindhoven (Netherlands). Schuit Institute of Catalysis

2005-07-01

This paper presents the results of a study that sought information about the nature and environment of the gallium (Ga) species in Ga/H-ZSM5 zeolites following H{sub 2}-O{sub 2} redox treatments applied during their activation by use of magic-angle spinning (MAS) {sup 71}Ga, {sup 27}Al, and {sup 29}Si NMR spectroscopy (Ga coordination) complemented by diffuse reflectance FT IR (DRIFT) spectroscopy (Bronsted acidity). This information was then correlated with their catalytic behavior for the ammoxidation of propane. Ga species were observed in several environments: octahedrally coordinated gallium in small Ga{sub 2}O{sub 3} particles at the external surface of the zeolite crystals; octahedrally coordinated gallium in GaO(OH) or related species; and tetrahedrally coordinated gallium in cationic-exchange positions inside the zeolite. Redox (H{sub 2}-O{sub 2}) cycles promote the migration of gallium from the GaO(OH) or Ga{sub 2}O{sub 3} species at the external surface of the zeolite crystals to cationic-exchange sites within the zeolite channels. It was concluded that the redox treatment had a beneficial effect on its catalytic performance for the ammoxidation of propane, which occurs via a bifunctional mechanism. The main product was acetonitrile at high gallium and aluminium contents. It was suggested that higher yields in acrylonitrile could be obtained through Ga-modified zeolites with a higher gallium and lower aluminium content. 22 refs., 1 tab., 6 figs.

Effects of higher-coordination shells in garnets detected by XAS at the Al K-edge

International Nuclear Information System (INIS)

Marcelli, A.; Wu, Z.; Mottana, A.; Giuli, G.; Paris, E.; Seifert, F.

1996-03-01

The aluminium 1 s x-ray-absorption spectra of a series of garnets, pyrope, almandine, spessartine and grossular, are compared to full multiple-scattering calculation using cluster models. An overall good agreement between experiment and calculation, extended also to the edge region,is obtained in the energy range in up to 60 e V above the threshold, provided cluster containing at least 40 atoms are used. The analysis of these garnet XAS spectra provides clear evidence on the effect of probe, XANES spectroscopy at the edge of low Z elements appears to be a perfect tool to investigate the role played by atoms located in higher-coordination shells

Effects of higher-coordination shells in garnets detected by XAS at the Al K-edge

Energy Technology Data Exchange (ETDEWEB)

Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Frascati (Italy). Lab. Nazionale di Frascati; Wu, Z. [CNRS UMR 110, Laboratoire de Chimie des Solides, Nantes Cedex (France). Institut de materiaux de Nantes; Mottana, A. [Roma III Univ., Rome (Italy). Dipartimento di Scienze Geologiche; Giuli, G.; Paris, E. [Camerino Univ., Camerino (Italy).Diparimento di Scienze della Terra; Seifert, F [Univ. Bayreuth, Bayreuth (Italy). Bayerisches Geoinstitut (Germany)

1996-03-01

The aluminium 1 s x-ray-absorption spectra of a series of garnets, pyrope, almandine, spessartine and grossular, are compared to full multiple-scattering calculation using cluster models. An overall good agreement between experiment and calculation, extended also to the edge region,is obtained in the energy range in up to 60 e V above the threshold, provided cluster containing at least 40 atoms are used. The analysis of these garnet XAS spectra provides clear evidence on the effect of probe, XANES spectroscopy at the edge of low Z elements appears to be a perfect tool to investigate the role played by atoms located in higher-coordination shells.

Optical properties of white organic light-emitting devices fabricated utilizing a mixed CaAl12O19:Mn4+ and Y3Al5O12:Ce3+ color conversion layer.

Science.gov (United States)

Jeong, H S; Kim, S H; Lee, K S; Jeong, J M; Yoo, T W; Kwon, M S; Yoo, K H; Kim, T W

2013-06-01

White organic light-emitting devices (OLEDs) were fabricated by combining a blue OLED with a color conversion layer made of mixed Y3Al5O12:Ce3+ green and Ca2AlO19:Mn4+ red phosphors. The X-ray diffraction patterns showed that Ce3+ ions in the Y3Al5O12:Ce3+ phosphors completely substituted for the Y3+ ions and the Mn4+ ions in the CaAl12O19:Mn4+ phosphors completely substituted for the Ca2+ ions. Electroluminescence spectra at 11 V for the OLEDs fabricated utilizing a color conversion layer showed that the Commission Internationale de l'Eclairage coordinates for the Y3Al5O12:Ce3+ and CaAl12O19:Mn4+ phosphors mixed at the ratio of 1:5 and 1:10 were (0.31, 0.34) and (0.32, 0.37), respectively, indicative of a good white color.

Luminescent lanthanide coordination polymers

Energy Technology Data Exchange (ETDEWEB)

Ma, L.; Evans, O.R.; Foxman, B.M.; Lin, W.

1999-12-13

One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate){sub 3}(H{sub 2}O){sub 2} (Ln = Ce, Pr, Nd, Sm, Eu, Tb; 1a-f) were synthesized by treating nitrate or perchlorate salts of Ln(III) with 4-pyridinecarboxaldehyde under hydro(solvo)thermal conditions. Single-crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate){sub 2}-Ln and Ln-(carboxylate){sub 4}-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite-chain structure with one chelating carboxylate group on each metal center. In both structures, the lanthanide centers also bind to two water molecules to yield an eight-coordinate, square antiprismatic geometry. The pyridine nitrogen atoms of the isonicotinate groups do not coordinate to the metal centers in these lanthanide(III) complexes; instead, they direct the formation of Ln(III) coordination polymers via hydrogen bonding with coordinated water molecules. Photoluminescence measurements show that Tb(isonicotinate){sub 3}(H{sub 2}O){sub 2} is highly emissive at room temperature with a quantum yield of {approximately}90%. These results indicate that highly luminescent lanthanide coordination polymers can be assembled using a combination of coordination and hydrogen bonds. Crystal data for 1a: monoclinic space group P2{sub 1}/c, a = 9.712(2) {angstrom}, b = 19.833(4) {angstrom}, c = 11.616(2) {angstrom}, {beta} = 111.89(3){degree}, Z = 4. Crystal data for 1f: monoclinic space group C2/c, a = 20.253(4) {angstrom}, b = 11.584(2) {angstrom}, c = 9.839(2) {angstrom}, {beta} = 115.64(3){degree}, Z = 8.

Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold

Energy Technology Data Exchange (ETDEWEB)

Krajčí, Marian [Institute of Physics, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84511 Bratislava (Slovakia); Kameoka, Satoshi; Tsai, An-Pang [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)

2016-08-28

We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al{sub 2}Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped (211) surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir–Hinshelwood mechanism with the activation energy of 37 kJ/mol or via the CO–OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy.

TECHNICAL COORDINATION

CERN Multimedia

A. Ball

Overview From a technical perspective, CMS has been in “beam operation” state since 6th November. The detector is fully closed with all components operational and the magnetic field is normally at the nominal 3.8T. The UXC cavern is normally closed with the radiation veto set. Access to UXC is now only possible during downtimes of LHC. Such accesses must be carefully planned, documented and carried out in agreement with CMS Technical Coordination, Experimental Area Management, LHC programme coordination and the CCC. Material flow in and out of UXC is now strictly controlled. Access to USC remains possible at any time, although, for safety reasons, it is necessary to register with the shift crew in the control room before going down.It is obligatory for all material leaving UXC to pass through the underground buffer zone for RP scanning, database entry and appropriate labeling for traceability. Technical coordination (notably Stephane Bally and Christoph Schaefer), the shift crew and run ...

Coordination of Conditional Poisson Samples

Directory of Open Access Journals (Sweden)

Grafström Anton

2015-12-01

Full Text Available Sample coordination seeks to maximize or to minimize the overlap of two or more samples. The former is known as positive coordination, and the latter as negative coordination. Positive coordination is mainly used for estimation purposes and to reduce data collection costs. Negative coordination is mainly performed to diminish the response burden of the sampled units. Poisson sampling design with permanent random numbers provides an optimum coordination degree of two or more samples. The size of a Poisson sample is, however, random. Conditional Poisson (CP sampling is a modification of the classical Poisson sampling that produces a fixed-size πps sample. We introduce two methods to coordinate Conditional Poisson samples over time or simultaneously. The first one uses permanent random numbers and the list-sequential implementation of CP sampling. The second method uses a CP sample in the first selection and provides an approximate one in the second selection because the prescribed inclusion probabilities are not respected exactly. The methods are evaluated using the size of the expected sample overlap, and are compared with their competitors using Monte Carlo simulation. The new methods provide a good coordination degree of two samples, close to the performance of Poisson sampling with permanent random numbers.

Keep Meaning in Conversational Coordination

Directory of Open Access Journals (Sweden)

Elena Clare Cuffari

2014-12-01

Full Text Available Coordination is a widely employed term across recent quantitative and qualitative approaches to intersubjectivity, particularly approaches that give embodiment and enaction central explanatory roles. With a focus on linguistic and bodily coordination in conversational contexts, I review the operational meaning of coordination in recent empirical research and related theorizing of embodied intersubjectivity. This discussion articulates what must be involved in treating linguistic meaning as dynamic processes of coordination. The coordination approach presents languaging as a set of dynamic self-organizing processes and actions on multiple timescales and across multiple modalities that come about and work in certain domains (those jointly constructed in social, interactive, high-order sense-making. These processes go beyond meaning at the level that is available to first-person experience. I take one crucial consequence of this to be the ubiquitously moral nature of languaging with others. Languaging coordinates experience, among other levels of behavior and event. Ethical effort is called for by the automatic autonomy-influencing forces of languaging as coordination.

Porphyrin coordination polymer nanospheres and nanorods

Science.gov (United States)

Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

2012-12-04

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

Optical Lattice Bose-Einstein Condensates and the dd Fusion - Iwamura Connection

Science.gov (United States)

Chubb, Talbot

2003-03-01

My conjecture: LENR dd fusion occurs in PdDx when a subset of the interstitial deuterons occupy tetrahedral sites in a PdDx crystallite. The tetrahedral deuterons(d's), which occupy shallow potential wells, behave as a superfluid, similar to ultracold Na atoms in shallow-well optical traps, as modeled by Jaksch et al.(D. Jaksch, et al, Phys. Rev. Lett., 81, 3108 (1998).) The tetrahedral d's form a deuteron (d) subsystem, which is neutralized by an electron subsystem containing an equal number of electrons. In the superfluid all the properties of each quasiparticle d are partitioned among N_s_i_te equivalent sites. The partitioning of the d point charge reduces the Coulomb self-repulsion within each quasiparticle pair, which causes wave function overlap at large N_s_i_t_e, allowing d-d fusion. Similarly, partitioning of the point charge of each single quasiparticle d reduces the Coulomb repulsion between it and an obstructing impurity atom, which causes wave function overlap between quasiparticle and atom at large N_s_i_t_e, allowing transmutation of the impurity atom. The Iwamura reaction(Y. Iwamura, et al, Japan J. of Appl. Physics, 41A, 4642 (2002).) is 4 ^2D^+_B_l_o_ch + 4 e^-_B_l_o_ch + ^1^3^3Cs arrow ^1^4^1Pr, with the reaction energy incoherently transferred to the lattice.

Crystal Structure and Ferroelectric Properties of ε-Ga2O3 Films Grown on (0001)-Sapphire.

Science.gov (United States)

Mezzadri, Francesco; Calestani, Gianluca; Boschi, Francesco; Delmonte, Davide; Bosi, Matteo; Fornari, Roberto

2016-11-21

The crystal structure and ferroelectric properties of ε-Ga 2 O 3 deposited by low-temperature MOCVD on (0001)-sapphire were investigated by single-crystal X-ray diffraction and the dynamic hysteresis measurement technique. A thorough investigation of this relatively unknown polymorph of Ga 2 O 3 showed that it is composed of layers of both octahedrally and tetrahedrally coordinated Ga 3+ sites, which appear to be occupied with a 66% probability. The refinement of the crystal structure in the noncentrosymmetric space group P6 3 mc pointed out the presence of uncompensated electrical dipoles suggesting ferroelectric properties, which were finally demonstrated by independent measurements of the ferroelectric hysteresis. A clear epitaxial relation is observed with respect to the c-oriented sapphire substrate, with the Ga 2 O 3 [10-10] direction being parallel to the Al 2 O 3 direction [11-20], yielding a lattice mismatch of about 4.1%.

Positron life time and annihilation Doppler broadening measurements on transition metal complexes

International Nuclear Information System (INIS)

Levay, B.; Burger, K.

1982-01-01

Positron life time and annihilation Doppler broadening measurements have been carried out on 44 solid coordination compounds. Several correlations have been found between the annihilation life time (tau 1 ) and line shape parameters (L) and the chemical structure of the compounds. Halide ligands were the most active towards positrons. This fact supports the assumption on the possible formation of [e + X - ] positron-halide bound state. The life time was decreasing and the annihilation energy spectra were broadening with the increasing negative character of the halides. The aromatic base ligands affected the positron-halide interaction according to their basicity and space requirement and thus they indirectly affected the annihilation parameters, too. In the planar and tetrahedral complexes the electron density on the central met--al ion affected directly the annihilation parameters, while in the octahedral mixed complexes it had only an ind--irect effect through the polarization of the halide ligands. (author)

Bimanual motor coordination controlled by cooperative interactions in intrinsic and extrinsic coordinates.

Science.gov (United States)

Sakurada, Takeshi; Ito, Koji; Gomi, Hiroaki

2016-01-01

Although strong motor coordination in intrinsic muscle coordinates has frequently been reported for bimanual movements, coordination in extrinsic visual coordinates is also crucial in various bimanual tasks. To explore the bimanual coordination mechanisms in terms of the frame of reference, here we characterized implicit bilateral interactions in visuomotor tasks. Visual perturbations (finger-cursor gain change) were applied while participants performed a rhythmic tracking task with both index fingers under an in-phase or anti-phase relationship in extrinsic coordinates. When they corrected the right finger's amplitude, the left finger's amplitude unintentionally also changed [motor interference (MI)], despite the instruction to keep its amplitude constant. Notably, we observed two specificities: one was large MI and low relative-phase variability (PV) under the intrinsic in-phase condition, and the other was large MI and high PV under the extrinsic in-phase condition. Additionally, using a multiple-interaction model, we successfully decomposed MI into intrinsic components caused by motor correction and extrinsic components caused by visual-cursor mismatch of the right finger's movements. This analysis revealed that the central nervous system facilitates MI by combining intrinsic and extrinsic components in the condition with in-phases in both intrinsic and extrinsic coordinates, and that under-additivity of the effects is explained by the brain's preference for the intrinsic interaction over extrinsic interaction. In contrast, the PV was significantly correlated with the intrinsic component, suggesting that the intrinsic interaction dominantly contributed to bimanual movement stabilization. The inconsistent features of MI and PV suggest that the central nervous system regulates multiple levels of bilateral interactions for various bimanual tasks. © 2015 The Authors. European Journal of Neuroscience published by Federation of European Neuroscience Societies and

[Civilian-military coordination].

Science.gov (United States)

de Montravel, G

2002-01-01

Current humanitarian emergencies create complex, mutidimensional situations that stimulate simultaneous responses from a wide variety of sources including governments, non-governmental organizations (NGO), United Nations agencies, and private individuals. As a result, it has become essential to establish a coherent framework in which each actor can contribute promptly and effectively to the overall effort. This is the role of the United Nations Office for the Coordination of Humanitarian Affairs. Regardless of the circumstances and level of coordination, cooperation and collaboration between humanitarian and military personnel, it is necessary to bear in mind their objectives. The purpose of humanitarian action is to reduce human suffering. The purpose of military intervention is to stop warfare. The author of this article will discuss the three major obstacles to civilian-military coordination (strategic, tactical, and operational). Operations cannot be conducted smoothly and differences cannot be ironed out without mutual respect between the two parties, an explicit definition of their respective duties and responsibilities, a clear understanding of their cultural differences, and the presence of an organization and facilities for coordination and arbitrage by a neutral referee.

Synthesis and characterisation of thorium and uranium cyanoacetates and their coordination compounds (Preprint No. AL.14)

International Nuclear Information System (INIS)

Deshpande, S.G.; Vaidya, M.A.; Jain, S.C.

1989-01-01

Tetracyanoacetates, M(NCCH 2 COO) 4 (where M=Th or U) and UO 2 (NCCH 2 COO) 2 .H 2 O and their coordination complexes with (CH 3 ) 2 S=0 (DMSO), HCOON(CH 3 ) 2 , (DMF), 1,10-Phenenthrolene (Phen) and 2,2'Bipyridine (Bipy), have been synthesised and characterised by elemental analysis, molecular weight determination, molar conductance measurements, X-ray diffraction and infrared (IR) spectroscopic studies (4000 - 200 cm -1 ). Thermogravimetric analysis of the compounds have been carried out to study the thermal decomposition mode. (author)

The effect of Li2O and LiF on structural properties of cobalt doped borate glasses

Directory of Open Access Journals (Sweden)

A.M. Abdelghany

2017-10-01

Full Text Available Two glassy (LiF–B2O3 and (Li2O–B2O3 systems containing different content of CoO dopants (0.05, 0.1, 0.15, 0.2 wt% were prepared. UV/Vis optical absorption of base glasses reveals a strong UV absorption bands attributed to unavoidable contaminated trace iron impurities. CoO-doped glasses show extra three visible bands due to both octahedral and tetrahedral Co2+ ions related to the little variation between energies of ligand field stabilization between the two coordination states. Fluoride containing glasses show limited variations in the spectral properties due to the different ligand strength of the anions (F− and O2−. FTIR spectra display characteristic modes of vibrations due to triangular and tetrahedral borate groups. It is assumed that LiF acts as Li2O in promoting the formation of tetrahedral (BO3F units which possess the same wavenumber position for vibrations of (BO4 units in the range of 800–1200 cm−1. CoO causes no distinct variations in number or position of characteristic IR vibrational bands due to their low dopant level (0.05–0.2%. A new suggested trial has been utilized to calculate the percent of four coordinated borons from both optical and FTIR spectra to give more insight on the role of CoO as dopant on these spectral properties and on the calculated parameters.

Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

Directory of Open Access Journals (Sweden)

Erik Hennings

2014-12-01

Full Text Available The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetrahedral coordination with Cl− and in an octahedral environment defined by five water molecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O5] (pentaaqua-μ-chlorido-trichloridodizinc. The trihydrate {hexaaquazinc tetrachloridozinc, [Zn(H2O6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetrahedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octahedrally surrounded by water molecules. The [ZnCl4] tetrahedra and [Zn(H2O6] octahedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexaaquazinc tetrachloridozinc trihydrate, [Zn(H2O6][ZnCl4]·3H2O}, consists of isolated octahedral [Zn(H2O6] and tetrahedral [ZnCl4] units, as well as additional lattice water molecules. O—H...O hydrogen bonds between the water molecules as donor and ZnCl4 tetrahedra and water molecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures.

Copper Coordination in the Full-Length, Recombinant Prion Protein†

Science.gov (United States)

Burns, Colin S.; Aronoff-Spencer, Eliah; Legname, Giuseppe; Prusiner, Stanley B.; Antholine, William E.; Gerfen, Gary J.; Peisach, Jack; Millhauser, Glenn L.

2010-01-01

The prion protein (PrP) binds divalent copper at physiologically relevant conditions and is believed to participate in copper regulation or act as a copper-dependent enzyme. Ongoing studies aim at determining the molecular features of the copper binding sites. The emerging consensus is that most copper binds in the octarepeat domain, which is composed of four or more copies of the fundamental sequence PHGGGWGQ. Previous work from our laboratory using PrP-derived peptides, in conjunction with EPR and X-ray crystallography, demonstrated that the HGGGW segment constitutes the fundamental binding unit in the octarepeat domain [Burns et al. (2002) Biochemistry 41, 3991–4001; Aronoff-Spencer et al. (2000) Biochemistry 39, 13760–13771]. Copper coordination arises from the His imidazole and sequential deprotonated glycine amides. In this present work, recombinant, full-length Syrian hamster PrP is investigated using EPR methodologies. Four copper ions are taken up in the octarepeat domain, which supports previous findings. However, quantification studies reveal a fifth binding site in the flexible region between the octarepeats and the PrP globular C-terminal domain. A series of PrP peptide constructs show that this site involves His96 in the PrP(92–96) segment GGGTH. Further examination by X-band EPR, S-band EPR, and electron spin–echo envelope spectroscopy, demonstrates coordination by the His96 imidazole and the glycine preceding the threonine. The copper affinity for this type of binding site is highly pH dependent, and EPR studies here show that recombinant PrP loses its affinity for copper below pH 6.0. These studies seem to provide a complete profile of the copper binding sites in PrP and support the hypothesis that PrP function is related to its ability to bind copper in a pH-dependent fashion. PMID:12779334

Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen

NARCIS (Netherlands)

Tejel, C.; Ciriano, M.A.; del Río, M.P.; van den Bruele, F.J.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; de Bruin, B.

2008-01-01

Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe))(2)] leads to unexpected and unique redox asymmetric dinuclear Rh-I, Rh+I complex [{Rh(ndb)}(2)(bpa-2H)] (2) with a pi-coordinating imine bound to a tetrahedral low valent rhodate(-I). Mono-oxygenation of the deprotonated bpa ligand in 2

Poly[μ2-benzene-1,3-dicarboxylato-κ2O:O′-μ2-1,3-di-4-pyridylpropane-κ2N:N′-zinc(II

Directory of Open Access Journals (Sweden)

En Tang

2008-02-01

Full Text Available The title compound, [Zn(C8H4O4(C13H14N2]n, was obtained by the hydrothermal reaction of Zn(OAc2·H2O with 1,3-di-4-pyridylpropane (bpp and isophthalic acid (H2ip. The ZnII ion is coordinated by two bpp and two ip ligands in a distorted tetrahedral environment. Each ligand coordinates in a bridging mode to connect ZnII ions into a three-dimensional diamondoid-type structure.

Moessbauer spectroscopy of some volcanic glasses from the Pampa Region, Cordoba, Argentina

International Nuclear Information System (INIS)

Saragovi-Badler, C.; Labenski, F.

1987-01-01

Moessbauer spectroscopy was applied to the study of volcanic glasses and closely associated clay minerals which were carefully separated from the sediments of the Pampa Region. The parameters of volcanic glass samples show the presence of a high content of Fe 2+ in octahedral coordination and some Fe 3+ in tetrahedral and octahedral coordination. No remarcable difference was found comparing with a 'pure' volcanic glass sample taken as a reference. In the clay samples the only clay mineral found was illite. (author) 7 refs

47 CFR 95.1113 - Frequency coordinator.

Science.gov (United States)

2010-10-01

... SERVICES Wireless Medical Telemetry Service (WMTS) General Provisions § 95.1113 Frequency coordinator. (a) The Commission will designate a frequency coordinator(s) to manage the usage of the frequency bands for the operation of medical telemetry devices. (b) The frequency coordinator shall (1) Review and...

Mössbauer, XRD, and Complex Thermal Analysis of the Hydration of Cement with Fly Ash

Directory of Open Access Journals (Sweden)

Vili Lilkov

2013-01-01

Full Text Available Hydration of cement with and without fly ash is studied with Mössbauer spectroscopy, XRD, and thermal analysis. Iron in cement is present as Fe3+-ions and occupies two octahedral positions, with close isomer shifts and quadrupole splittings. Iron in fly ash is present as Fe2+ and Fe3+, and the Mössbauer spectra display three doublets—two for Fe3+ in octahedral coordination and one for Fe2+. A third doublet was registered in the hydrating plain cement pastes after the 5th day, due to Fe3+ in tetrahedral coordination in the structure of the newly formed monosulphate aluminate. In cement pastes with fly ash, the doublet of tetrahedral iron is formed earlier because the quantity of ettringite and portlandite is low and more monosulphate crystallizes. No Fe(OH3 phase forms during hydration of C4AF. The fly ash displays pozzolanic properties, which lead to lowering of the portlandite quantity in the cement mixtures and increasing of the high temperature products.

Crystal structure of poly[N,N-diethyl-2-hydroxyethan-1-aminium [μ3-cyanido-κ3C:C:N-di-μ-cyanido-κ4C:N-dicuprate(I

Directory of Open Access Journals (Sweden)

Peter W. R. Corfield

2016-07-01

Full Text Available In the title compound, {(C6H16NO[Cu2(CN3]}n, the cyanide groups link the CuI atoms into an open three-dimensional anionic network, with the molecular formula Cu2(CN3−. One CuI atom is tetrahedrally bound to four CN groups, and the other CuI atom is bonded to three CN groups in an approximate trigonal-planar coordination. The tetrahedrally coordinated CuI atoms are linked into centrosymmetric dimers by the C atoms of two end-on bridging CN groups which bring the CuI atoms into close contact at 2.5171 (7 Å. Two of the cyanide groups bonded to the CuI atoms with trigonal-planar surrounding link the dimeric units into columns along the a axis, and the third links the columns together to form the network. The N,N-diethylethanolamine molecules used in the synthesis have become protonated at the N atoms and are situated in cavities in the network, providing charge neutrality, with no covalent interactions between the cations and the anionic network.

40 CFR 109.6 - Coordination.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 21 2010-07-01 2010-07-01 false Coordination. 109.6 Section 109.6 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS CRITERIA FOR STATE, LOCAL AND REGIONAL OIL REMOVAL CONTINGENCY PLANS § 109.6 Coordination. For the purposes of coordination...

Nature and structure of aluminum surface sites grafted on silica from a combination of high-field aluminum-27 solid-state NMR spectroscopy and first-principles calculations

KAUST Repository

Kerber, Rachel Nathaniel; Kermagoret, Anthony; Callens, Emmanuel; Florian, Pierre A.; Massiot, Dominique; Lesage, Anne; Copé ret, Christophe; Delbecq, Franç oise; Rozanska, Xavier; Sautet, Philippe

2012-01-01

The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studied as a model for a supported methylaluminoxane and aluminum cocatalyst. While 27Al solid-state NMR spectroscopy would be a method of choice, it has been difficult to apply this technique because of large quadrupolar broadenings. Here, from a combined use of the highest stable field NMR instruments (17.6, 20.0, and 23.5 T) and ultrafast magic angle spinning (>60 kHz), high-quality spectra were obtained, allowing isotropic chemical shifts, quadrupolar couplings, and asymmetric parameters to be extracted. Combined with first-principles calculations, these NMR signatures were then assigned to actual structures of surface aluminum sites. For silica (here SBA-15) reacted with triethylaluminum, the surface sites are in fact mainly dinuclear Al species, grafted on the silica surface via either two terminal or two bridging siloxy ligands. Tetrahedral sites, resulting from the incorporation of Al inside the silica matrix, are also seen as minor species. No evidence for putative tri-coordinated Al atoms has been found. © 2012 American Chemical Society.

Nature and structure of aluminum surface sites grafted on silica from a combination of high-field aluminum-27 solid-state NMR spectroscopy and first-principles calculations

KAUST Repository

Kerber, Rachel Nathaniel

2012-04-18

The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studied as a model for a supported methylaluminoxane and aluminum cocatalyst. While 27Al solid-state NMR spectroscopy would be a method of choice, it has been difficult to apply this technique because of large quadrupolar broadenings. Here, from a combined use of the highest stable field NMR instruments (17.6, 20.0, and 23.5 T) and ultrafast magic angle spinning (>60 kHz), high-quality spectra were obtained, allowing isotropic chemical shifts, quadrupolar couplings, and asymmetric parameters to be extracted. Combined with first-principles calculations, these NMR signatures were then assigned to actual structures of surface aluminum sites. For silica (here SBA-15) reacted with triethylaluminum, the surface sites are in fact mainly dinuclear Al species, grafted on the silica surface via either two terminal or two bridging siloxy ligands. Tetrahedral sites, resulting from the incorporation of Al inside the silica matrix, are also seen as minor species. No evidence for putative tri-coordinated Al atoms has been found. © 2012 American Chemical Society.

Multipole structure and coordinate systems

International Nuclear Information System (INIS)

Burko, Lior M

2007-01-01

Multipole expansions depend on the coordinate system, so that coefficients of multipole moments can be set equal to zero by an appropriate choice of coordinates. Therefore, it is meaningless to say that a physical system has a nonvanishing quadrupole moment, say, without specifying which coordinate system is used. (Except if this moment is the lowest non-vanishing one.) This result is demonstrated for the case of two equal like electric charges. Specifically, an adapted coordinate system in which the potential is given by a monopole term only is explicitly found, the coefficients of all higher multipoles vanish identically. It is suggested that this result can be generalized to other potential problems, by making equal coordinate surfaces adapt to the potential problem's equipotential surfaces

Possibility of extending space-time coordinates

International Nuclear Information System (INIS)

Wang Yongcheng.

1993-11-01

It has been shown that one coordinate system can describe a whole space-time region except some supersurfaces on which there are coordinate singularities. The conditions of extending a coordinate from real field to complex field are studied. It has been shown that many-valued coordinate transformations may help us to extend space-time regions and many-valued metric functions may make one coordinate region to describe more than one space-time regions. (author). 11 refs

A framework of manufacturer-retailer coordination process

DEFF Research Database (Denmark)

Wong, Chee Yew; Johansen, John

2008-01-01

Purpose - Triggered by perceived inefficiency and inequality, buyers and suppliers coordinate with each other. The purpose of this paper is to develop a framework of coordination process based on theoretical review and verifications from three case studies. Design/methodology/approach - The appro......Purpose - Triggered by perceived inefficiency and inequality, buyers and suppliers coordinate with each other. The purpose of this paper is to develop a framework of coordination process based on theoretical review and verifications from three case studies. Design...... there was disagreement. Third, closer mode of coordination, which involved joint evaluation and derivation of coordination solutions, reduced the numbers of iterative coordination cycles. These empirical findings verified the presupposed framework of coordination process. Research limitations/implications - Three...... qualitative case studies may not be highly generalisable and multiple dyadic coordination processes may occur. However, the findings form a foundation for further understanding of the coordination process. Originality/value - The proposed framework of the coordination process further expands the theories...

Effect of nanoparticles as lubricant additives on friction and wear behavior of tetrahedral amorphous carbon (ta-C coating

Directory of Open Access Journals (Sweden)

Xiang Li

2018-03-01

Full Text Available As diamond like carbon (DLC coating becomes increasingly popular in providing low friction and wear under lubricated conditions, the effect of various oil additives on tribological behavior of DLC coating is drawing more attention. Various oil additives, such as ZnDTP and MoDTC, have been widely used in automobile engine industry to pursuit excellent tribological performance in the insufficient lubrication condition. Although such commercial oil additives have been proven to reduce friction or/and wear to some extent, usage of such high -SAPS (sulphuric ash, phosphor, sulfphur conventional additives is bound to arouse concerns due to environmental reasons. In this research, we investigate the effect of two nanoparticle oil additives, which are cerium oxide (CeO2 and zirconium dioxide (ZrO2, on friction and wear of non-hydrogen tetrahedral amorphous carbon (ta-C coating. The results show that by adding ZrO2 nanoparticle, the friction of DLC coating could be reduced about 32% compared to non-additive base oil scenario, but specific wear rate increases by 40%. When CeO2 nanoparticle is used, friction increases by 22% compared to non-additive base oil scenario, however wear decreases by nearly 77%.

29 CFR 42.8 - Coordination plan.

Science.gov (United States)

2010-07-01

... 29 Labor 1 2010-07-01 2010-07-01 true Coordination plan. 42.8 Section 42.8 Labor Office of the Secretary of Labor COORDINATED ENFORCEMENT § 42.8 Coordination plan. (a) Based upon, among other things, the... coordination plan concerning farm labor-related responsibilities of the Department, including migrant housing...

Structural and vibrational study of C-type doped rare earth sesquioxide Yb2-xCoxO3

International Nuclear Information System (INIS)

Farhat, L. Ben; Amami, M.; Hlil, E.K.; Hassen, R. Ben

2009-01-01

Polycrystalline samples with general formula Yb 2-x Co x O 3 (0 2 O 3 sesquioxide. The lattice parameters are found to vary linearly with the composition x. The cationic distribution over the two non-equivalent sites 8b and 24d of the space group Ia-3 is found to be preferentially. Replacing Yb 3+ by Co 3+ introduces slight changes in the atomic coordinates leading to an increase of the mean cation-anion distances. The ability of Raman spectroscopy to detect changes in local co-ordination is utilized. A pseudo-tetrahedral coordination for the Co 3+ in the 24d site was found.

Vaidya spacetime in the diagonal coordinates

Energy Technology Data Exchange (ETDEWEB)

Berezin, V. A., E-mail: berezin@inr.ac.ru; Dokuchaev, V. I., E-mail: dokuchaev@inr.ac.ru; Eroshenko, Yu. N., E-mail: eroshenko@inr.ac.ru [Russian Academy of Sciences, Institute for Nuclear Research (Russian Federation)

2017-03-15

We have analyzed the transformation from initial coordinates (v, r) of the Vaidya metric with light coordinate v to the most physical diagonal coordinates (t, r). An exact solution has been obtained for the corresponding metric tensor in the case of a linear dependence of the mass function of the Vaidya metric on light coordinate v. In the diagonal coordinates, a narrow region (with a width proportional to the mass growth rate of a black hole) has been detected near the visibility horizon of the Vaidya accreting black hole, in which the metric differs qualitatively from the Schwarzschild metric and cannot be represented as a small perturbation. It has been shown that, in this case, a single set of diagonal coordinates (t, r) is insufficient to cover the entire range of initial coordinates (v, r) outside the visibility horizon; at least three sets of diagonal coordinates are required, the domains of which are separated by singular surfaces on which the metric components have singularities (either g{sub 00} = 0 or g{sub 00} = ∞). The energy–momentum tensor diverges on these surfaces; however, the tidal forces turn out to be finite, which follows from an analysis of the deviation equations for geodesics. Therefore, these singular surfaces are exclusively coordinate singularities that can be referred to as false fire-walls because there are no physical singularities on them. We have also considered the transformation from the initial coordinates to other diagonal coordinates (η, y), in which the solution is obtained in explicit form, and there is no energy–momentum tensor divergence.

Low pH, Aluminum, and Phosphorus Coordinately Regulate Malate Exudation through GmALMT1 to Improve Soybean Adaptation to Acid Soils1[W][OA

Science.gov (United States)

Liang, Cuiyue; Piñeros, Miguel A.; Tian, Jiang; Yao, Zhufang; Sun, Lili; Liu, Jiping; Shaff, Jon; Coluccio, Alison; Kochian, Leon V.; Liao, Hong

2013-01-01

Low pH, aluminum (Al) toxicity, and low phosphorus (P) often coexist and are heterogeneously distributed in acid soils. To date, the underlying mechanisms of crop adaptation to these multiple factors on acid soils remain poorly understood. In this study, we found that P addition to acid soils could stimulate Al tolerance, especially for the P-efficient genotype HN89. Subsequent hydroponic studies demonstrated that solution pH, Al, and P levels coordinately altered soybean (Glycine max) root growth and malate exudation. Interestingly, HN89 released more malate under conditions mimicking acid soils (low pH, +P, and +Al), suggesting that root malate exudation might be critical for soybean adaptation to both Al toxicity and P deficiency on acid soils. GmALMT1, a soybean malate transporter gene, was cloned from the Al-treated root tips of HN89. Like root malate exudation, GmALMT1 expression was also pH dependent, being suppressed by low pH but enhanced by Al plus P addition in roots of HN89. Quantitative real-time PCR, transient expression of a GmALMT1-yellow fluorescent protein chimera in Arabidopsis protoplasts, and electrophysiological analysis of Xenopus laevis oocytes expressing GmALMT1 demonstrated that GmALMT1 encodes a root cell plasma membrane transporter that mediates malate efflux in an extracellular pH-dependent and Al-independent manner. Overexpression of GmALMT1 in transgenic Arabidopsis, as well as overexpression and knockdown of GmALMT1 in transgenic soybean hairy roots, indicated that GmALMT1-mediated root malate efflux does underlie soybean Al tolerance. Taken together, our results suggest that malate exudation is an important component of soybean adaptation to acid soils and is coordinately regulated by three factors, pH, Al, and P, through the regulation of GmALMT1 expression and GmALMT1 function. PMID:23341359

Enhancement of electron injection in inverted bottom-emitting organic light-emitting diodes using Al/LiF compound thin film

Science.gov (United States)

Nie, Qu-yang; Zhang, Fang-hui

2018-05-01

The inverted bottom-emitting organic light-emitting devices (IBOLEDs) were prepared, with the structure of ITO/Al ( x nm)/LiF (1 nm)/Bphen (40 nm)/CBP: GIr1 (14%):R-4b (2%) (10 nm)/BCP (3 nm)/CBP:GIr1 (14%):R-4b (2%) (20 nm)/TCTA (10 nm)/NPB (40 nm)/MoO3 (40 nm)/Al (100 nm), where the thickness of electron injection layer Al ( x) are 0 nm, 2 nm, 3 nm, 4 nm and 5 nm, respectively. In this paper, the electron injection condition and luminance properties of inverted devices were investigated by changing the thickness of Al layer in Al/LiF compound thin film. It turns out that the introduction of Al layer can improve electron injection of the devices dramatically. Furthermore, the device exerts lower driving voltage and higher current efficiency when the thickness of electron injection Al layer is 3 nm. For example, the current efficiency of the device with 3-nm-thick Al layer reaches 19.75 cd·A-1 when driving voltage is 7 V, which is 1.24, 1.17 and 17.03 times larger than those of the devices with 2 nm, 4 nm and 5 nm Al layer, respectively. The device property reaches up to the level of corresponding conventional device. In addition, all inverted devices with electron injection Al layer show superior stability of color coordinate due to the adoption of co-evaporation emitting layer and BCP spacer-layer, and the color coordinate of the inverted device with 3-nm-thick Al layer only changes from (0.580 6, 0.405 6) to (0.532 8, 0.436 3) when driving voltage increases from 6 V to 10 V.

Selective binding of choline by a phosphate-coordination-based triple helicate featuring an aromatic box

Czech Academy of Sciences Publication Activity Database

Jia, C.; Zuo, W.; Yang, D.; Chen, Y.; Cao, L.; Custelcean, R.; Hostaš, Jiří; Hobza, Pavel; Glaser, R.; Wang, Y.-Y.; Yang, X.-J.; Wu, B.

2017-01-01

Roč. 8, Oct 16 (2017), č. článku 938. ISSN 2041-1723 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : transition metal catalysis * tetrahedral anion cage * biological recognition Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 12.124, year: 2016 https://www.nature.com/articles/s41467-017-00915-8

Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

Science.gov (United States)

Ildefonse, Ph.; Calas, G.; Flank, A. M.; Lagarde, P.

1995-05-01

Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaOsbnd MgOsbnd 2SiO2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mgsbnd O distances of 2.01Å. In aluminosilicate gels, Alsbnd K XANES has been used to investigate the [4]Al/Altotal ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Sisbnd K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si= 1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels.

Redox equilibria and the structural role of iron in alumino-silicate melts

Science.gov (United States)

Dickenson, M. P.; Hess, P. C.

1982-01-01

The relationship between the redox ratio Fe+2/(Fe+2+Fe+3) and the K2O/(K2O + Al2O3) ratio (K2O*) were experimentally investigated in silicate melts with 78 mol% SiO2 in the system SiO2-Al2O3-K2O-FeO-Fe2O3, in air at 1,400° C. Quenched glass compositions were analyzed by electron microprobe and wet chemical microtitration techniques. Minimum values of the redox ratio were obtained at K2O*≈0.5. The redox ratio in peralkaline melts (K2O*>0.5) increases slightly with K2O* whereas this ratio increases dramatically in peraluminous melts (K2O*<0.5) as K2O is replaced by Al2O3. These data indicate that all Fe+3 (and Al+3) occur as tetrahedral species charge balanced with K+ in peralkaline melts. In peraluminous melts, Fe+3 (and Al+3) probably occur as both tetrahedral species using Fe+2 as a charge-balancing cation and as network-modifying cations associated with non-bridging oxygen.

IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOST

Energy Technology Data Exchange (ETDEWEB)

Conrad Ingram; Mark Mitchell

2005-11-15

Composite materials of SBA-15/zeolite Y were synthesized from zeolite Y precursor and a synthesis mixture of mesoporous silicate SBA-15 via a hydrothermal process in the presence of a slightly acidic media of pH 4-6 with 2M H{sub 2}SO{sub 4}. The SBA-15/ZY composites showed Type IV adsorption isotherms, narrow BJH average pore size distribution of 4.9 nm, surface areas up to 800 m{sup 2}2/g and pore volumes 1.03 cm{sup 3}, all comparable to pure SBA-15 synthesized under similar conditions. Chemical analysis revealed Si/Al ratio down to 8.5 in the most aluminated sample, and {sup 27}AlSS MAS NMR confirmed aluminum was in tetrahedral coordination. This method of introduction of Al in pure T{sub d} coordination is effective in comparison to other direct and post synthesis alumination methods. Bronsted acid sites were evident from a pyridinium peak at 1544 cm-1 in the FTIR spectrum after pyridine adsorption, and from NH{sub 3} -TPD experiments. SBA-15/ZY composites showed significant catalytic activities for the dealkylation of isopropylbenzene to benzene and propene, similar to those of commercial zeolite Y. It was observed that higher conversion for catalysts synthesized with high amount of ZY precursor mixture added to the SBA-15. Over all the composites has shown good catalytic activity. Further studies will be focused on gaining a better understand the nature of the precursor, and to characterize and to locate the acid sites in the composite material. The composite will also be evaluated for heavy oil conversion to naphtha and middle distillates.

Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

Energy Technology Data Exchange (ETDEWEB)

Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Nozarian, Kimia; Babadi, Susan Soleymani; Noorizadeh, Siamak [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Motamedi, Hossein [Department of Biology, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Mayer, Peter [LMU München Department Chemie, Butenandtstr 5-13, D-81377 München (Germany); Bruno, Giuseppe [Dipartimento di Chimica Inorganica, Università di Messina, Vill. S. Agata, Salita Sperone 31, 98166 Messina (Italy); Rudbari, Hadi Amiri [Faculty of Chemistry, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of)

2017-05-15

Two new compounds namely [Cu(SCN)(µ-L)]{sub n} (1) and ([Ag (µ{sub 2}-L)](ClO{sub 4})){sub n} (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS{sub 2}N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, the adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS{sub 4} tetrahedral geometry with 4-membered Ag{sub 2}S{sub 2} rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. - Graphical abstract: Two new Cu(I) and Ag(I) coordination polymers have been have been synthesized by one-pot reactions. Copper complex has a 2D non-covalent structure, but silver compound is a 3D coordination compound. These compounds have effective antibacterial activity. - Highlights: • Cu(I) and Ag(I) based coordination polymers

Coordinate-invariant regularization

International Nuclear Information System (INIS)

Halpern, M.B.

1987-01-01

A general phase-space framework for coordinate-invariant regularization is given. The development is geometric, with all regularization contained in regularized DeWitt Superstructures on field deformations. Parallel development of invariant coordinate-space regularization is obtained by regularized functional integration of the momenta. As representative examples of the general formulation, the regularized general non-linear sigma model and regularized quantum gravity are discussed. copyright 1987 Academic Press, Inc

The coordinate transforming in geography information system

International Nuclear Information System (INIS)

Zhao Xiang; Chen Gang

2003-01-01

The coordinate transforming of geography information system includes two kinds of transforming, map projection and coordinate-transforming. This paper proposed a arithmetic of coordinate-transforming, it implement the transforming between the longitude-latitude coordinate and the screen coordinate and apply it in the GIS. The preferable effect was made. (authors)

Molecular clusters of 3D and lower magnetic dimensionality

International Nuclear Information System (INIS)

Papaefthymiou, G.C

1991-01-01

Controlled polymerization of iron leads to the synthesis of molecular clusters of ever-increasing size, tending to extended structures. Polymerization of oxo-bridged octahedrally coordinated iron leads to clusters with 3D magnetic interactions between iron ions, while sulfide- and selenide-bridged tetrahedrally coordinated iron ions produce clusters of lower magnetic dimensionality. In this paper the magnetic properties of the resulting large molecular clusters with N ≥ 17 (where N = the number of iron ions in the cluster) are investigated for the presence of collective magnetic correlations associated with the solid state

Amphiphilic carbon dots for sensitive detection, intracellular imaging of Al{sup 3+}

Energy Technology Data Exchange (ETDEWEB)

Kong, Depeng [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Yan, Fanyong, E-mail: yanfanyong@tjpu.edu.cn [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Luo, Yunmei [Department of Pharmacology/Key Laboratory for Basic Pharmacology of Ministry of Education, Zunyi Medical College, Guizhou 563000 (China); Ye, Qianghua; Zhou, Siyushan [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Chen, Li, E-mail: Chenlis@tjpu.edu.cn [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China)

2017-02-08

In this paper, a simple and effective method was designed to synthesize hydrophobic carbon dots. Subsequently, amphiphilic fluorescent carbon dots (A-CDs) were synthesized by further surface modification. The result A-CDs show excellent optical properties with a quantum yield of 16.9%. It was interestingly found that morin (MR) and its fluorescent metal-ion complex (MR-Al{sup 3+}) can successfully coordinate on the surface of A-CDs, the emission of A-CDs completely overlapped the absorption peak of MR-Al{sup 3+}. Thus, the prepared A-CDs can be used as an effective fluorescent probe for Al{sup 3+} based on a fluorescence resonance energy transfer process. The sensing platform can realize real-time detection of Al{sup 3+} within 0.5 min. The fluorescence signals of the system were linearly correlated with the concentration of Al{sup 3+} over a range of 8–20 μM, with a detection limit of 0.113 μM. The method was also successfully applied to image the distribution of Al{sup 3+} in Human Umbilical Vein Endothelial Cells. - Highlights: • Amphiphilic carbon dots were obtained by simply modifying hydrophobic carbon dots. • Amphiphilic carbon dots/morin-Al{sup 3+} was used as a selective turn-on probe for Al{sup 3+}. • The method was employed to intracellular imaging Al{sup 3+} in living cells.

On coordinates and coordinate transformation in Einstein's theory of gravitation

International Nuclear Information System (INIS)

Chou Peiyuan

1983-01-01

This investigation is a further exposition of the significance of coordinates and their transformation in Einstein's theory of gravitation. The author considers the static axisymmetric field as an example, starts with its metric in the cylindrical coordinates, transforms this metric and the field equations into the Weyl-Levi-Civita system of coordinates, and supplements them with the harmonic condition. Both of the field equations and the harmonic condition are then transformed back to the original Cartesian system. Solutions for the static fields of an infinite plane with uniform surface density and an infinite rod with uniform linear density of matter, and of a body with spherical symmetry, are obtained again to show the necessity of the harmonic condition in their solutions. The fact that under the harmonic condition the solutions of the field equations for these problems contain their corresponding Newtonian potentials as approximations, is a strong support to the argument that the harmonic condition should be a physical supplement to Einstein's theory of gravitation. (Auth.)

Unpacking Coordination Benefits in Supply Networks

DEFF Research Database (Denmark)

Petrick, Irene J.; Maitland, Carleen; Pogrebnyakov, Nicolai

2016-01-01

This paper examines how coordination among firms in supply networks generates benefits in the short and long terms for firms. It focuses on information technology (IT) and process improvement coordination. Analysis was performed on quantitative and qualitative data from a sample of SMEs in plastics...... manufacturing in Pennsylvania. Results indicate that coordination on both IT and process improvement leads to short- and long-term benefits. These relationships were mediated by the adoption of innovations (when coordinating on IT) and access to new capabilities (in process improvement coordination......). These results extend the understanding of how participation in supply networks benefits individual firms....

Information theoretic measures of network coordination in high-frequency scalp EEG reveal dynamic patterns associated with seizure termination.

Science.gov (United States)

Stamoulis, Catherine; Schomer, Donald L; Chang, Bernard S

2013-08-01

How a seizure terminates is still under-studied and, despite its clinical importance, remains an obscure phase of seizure evolution. Recent studies of seizure-related scalp EEGs at frequencies >100 Hz suggest that neural activity, in the form of oscillations and/or neuronal network interactions, may play an important role in preictal/ictal seizure evolution (Andrade-Valenca et al., 2011; Stamoulis et al., 2012). However, the role of high-frequency activity in seizure termination, is unknown, if it exists at all. Using information theoretic measures of network coordination, this study investigated ictal and immediate postictal neurodynamic interactions encoded in scalp EEGs from a relatively small sample of 8 patients with focal epilepsy and multiple seizures originating in temporal and/or frontal brain regions, at frequencies ≤ 100 Hz and >100 Hz, respectively. Despite some heterogeneity in the dynamics of these interactions, consistent patterns were also estimated. Specifically, in several seizures, linear or non-linear increase in high-frequency neuronal coordination during ictal intervals, coincided with a corresponding decrease in coordination at frequencies interval, which continues during the postictal interval. This may be one of several possible mechanisms that facilitate seizure termination. In fact, inhibition of pairwise interactions between EEGs by other signals in their spatial neighborhood, quantified by negative interaction information, was estimated at frequencies ≤ 100 Hz, at least in some seizures. Copyright © 2013 Elsevier B.V. All rights reserved.

Object-Based Coregistration of Terrestrial Photogrammetric and ALS Point Clouds in Forested Areas

Science.gov (United States)

Polewski, P.; Erickson, A.; Yao, W.; Coops, N.; Krzystek, P.; Stilla, U.

2016-06-01

Airborne Laser Scanning (ALS) and terrestrial photogrammetry are methods applicable for mapping forested environments. While ground-based techniques provide valuable information about the forest understory, the measured point clouds are normally expressed in a local coordinate system, whose transformation into a georeferenced system requires additional effort. In contrast, ALS point clouds are usually georeferenced, yet the point density near the ground may be poor under dense overstory conditions. In this work, we propose to combine the strengths of the two data sources by co-registering the respective point clouds, thus enriching the georeferenced ALS point cloud with detailed understory information in a fully automatic manner. Due to markedly different sensor characteristics, coregistration methods which expect a high geometric similarity between keypoints are not suitable in this setting. Instead, our method focuses on the object (tree stem) level. We first calculate approximate stem positions in the terrestrial and ALS point clouds and construct, for each stem, a descriptor which quantifies the 2D and vertical distances to other stem centers (at ground height). Then, the similarities between all descriptor pairs from the two point clouds are calculated, and standard graph maximum matching techniques are employed to compute corresponding stem pairs (tiepoints). Finally, the tiepoint subset yielding the optimal rigid transformation between the terrestrial and ALS coordinate systems is determined. We test our method on simulated tree positions and a plot situated in the northern interior of the Coast Range in western Oregon, USA, using ALS data (76 x 121 m2) and a photogrammetric point cloud (33 x 35 m2) derived from terrestrial photographs taken with a handheld camera. Results on both simulated and real data show that the proposed stem descriptors are discriminative enough to derive good correspondences. Specifically, for the real plot data, 24

High-pressure luminescence spectroscopy of EuAl2O4 phosphor

International Nuclear Information System (INIS)

Zorenko, Yu.; Gorbenko, V.; Grinberg, M.; Turos-Matysiak, R.; Kuklinski, B.

2007-01-01

EuAl 2 O 4 powder phosphor was prepared by solid-state reaction of EuO and Al 2 O 3 oxides in vacuum. The influence of conditions of preparation on spectral lineshape of Eu 2+ emission was analyzed. It was found that the fluorescence spectra of vacuum-prepared EuAl 2 O 4 samples at 300 K present the superposition of three bands peaked at 430, 500 and 528 nm, corresponding to the 4f 6 5d 1 →4f 7 ( 8 S 7/2 ) transition of Eu 2+ ions in the different sites of EuAl 2 O 4 lattice. The luminescence of Eu 2+ centers in EuAl 2 O 4 host was also studied using the high-pressure spectroscopy up to 67 kbar. It was found that the bright green-yellow fluorescence of EuAl 2 O 4 at 300 K in the band peaked at 520-530nm range can be presented by superposition of two Gaussian sub-bands. The different pressure shifts -23 and -27cm -1 /kbar for two sub-bands were found. Such a structure of the emission spectrum was attributed to the existence of two different Eu 2+ centers in the Eu II 2+ sites of EuAl 2 O 4 lattice with higher coordination number

The structural role and homogeneous redox equilibria of iron in peraluminous, metaluminous and peralkaline silicate melts

Science.gov (United States)

Dickenson, M. P.; Hess, P. C.

1986-02-01

The compositional dependence of the redox ratio (FeO/FeO1.5) has been experimentally determined in K2O-Al2O3-SiO2-Fe2O3-FeO (KASFF) and K2O-CaO-Al2O3-SiO2-Fe2O3-FeO (KCASFF) silicate melts. Compositions were equilibrated at 1,450° C in air, with 78 mol % SiO2. KASFF melts have from 1 to 5 mol % Fe2O3 and include both peraluminous (K2OAl2O3) compositions. KCASFF melts have 1 mol % Fe2O3 encompassing peraluminous, metaluminous (CaO+K2O>Al2O3) and peralkaline compositions. Peralkaline KASFF melts with 1 mol % Fe2O3 have low and constant values for the redox ratio, whereas in peraluminous melts the redox ratio increases with increasing (K2O/Al2O3). Increasing total iron concentration increases the redox ratio in peraluminous melts and slightly decreases the redox ratio in peralkaline melts. Substituting CaO for K2O at fixed total iron (1 mol %) increases the redox ratio in both peraluminous and metaluminous KCASFF melts; however, the redox ratio in peralkaline KCASFF melts is not affected by this exchange. These data indicate that Fe3+ is in four-fold coordination, with K+ or Ca2+ providing local charge balance. The tetrahedral ferric species is most stable in peralkaline melts and least stable in peraluminous melts, due to the competition between Al3+ and Fe3+ for charge balancing cations in the latter melt. Tetrahedral Fe3+ is also less stable when Ca2+ provides local charge balance. The data are consistent with a network modifying role for Fe2+ in the melt. The data are interpreted to reflect the effects of melt composition on the partitioning of K+ and Ca2+ and Fe3+ and Al3+ between various species in the melt. These relationships are discussed in terms of homogeneous equilibria between various iron-bearing and iron-free melt species. The results also reflect the effect of liquid composition on the exchange potentials μFe3+ Al-1 and μCa0.5K-1. The exchange potentials are relatively constant in peralkaline melts, but decrease in metaluminous and peraluminous

The curvature coordinate system

DEFF Research Database (Denmark)

Almegaard, Henrik

2007-01-01

The paper describes a concept for a curvature coordinate system on regular curved surfaces from which faceted surfaces with plane quadrangular facets can be designed. The lines of curvature are used as parametric lines for the curvature coordinate system on the surface. A new conjugate set of lin...

Preparation and luminescence of green-emitting ZnAl{sub 2}O{sub 4}:Mn{sup 2+} phosphor thin films

Energy Technology Data Exchange (ETDEWEB)

Huang, Ing-Bang [Department of Materials Science and Engineering, National Formosa University, Huwei, Yunlin 632, Taiwan (China); Chang, Yee-Shin [Department of Electronic Engineering, National Formosa University, Huwei, Yunlin 632, Taiwan (China); Chen, Hao-Long [Department of Electronic Engineering, Kao Yuan University, Lujhu, Kaohsiung 821, Taiwan (China); Hwang, Ching Chiang [Department of Biotechnology, Mingdao University, Chang-Hua 52345, Taiwan (China); Jian, Chen-Jhu; Chen, Yu-Shiang [Department of Materials Science and Engineering, National Formosa University, Huwei, Yunlin 632, Taiwan (China); Tsai, Mu-Tsun, E-mail: mttsai@ms23.hinet.net [Department of Materials Science and Engineering, National Formosa University, Huwei, Yunlin 632, Taiwan (China)

2014-11-03

Nanocrystalline Mn{sup 2+}-doped zinc spinel (ZnAl{sub 2}O{sub 4}:Mn{sup 2+}) green-emitting phosphor films were deposited on silicon substrate by sol–gel spin coating and subsequent heat treatment up to 1000 °C. The effects of dopant concentration and heat treatment on the optical and structural properties were investigated. The variations in sol viscosity with time, film thickness with number of layers were also examined. Thin films were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray microscopy, atomic force microscopy, and photoluminescence spectrum. Single-phase ZnAl{sub 2}O{sub 4} started to crystallize at around 600 °C, with a normal spinel structure. On annealing at 1000 °C, the films had smooth surfaces with a nanocrystalline structure. Under UV or visible light excitation, the phosphor films exhibited an intense green emission band peaking at around 512 nm, corresponding to the typical {sup 4}T{sub 1} → {sup 6}A{sub 1} transition of tetrahedral Mn{sup 2+} ions. The most intense green emission was obtained by exciting at 456 nm. The emission intensity of films was highly dependent upon the excitation wavelength, crystallinity, dopant content, and deposition conditions. The results show that the ZnAl{sub 2}O{sub 4}:Mn{sup 2+} films have good potential for use as a green phosphor for displays and/or white light-emitting diodes. - Highlights: • ZnAl2O4:Mn2 + thin film phosphors have been synthesized by a sol–gel process. • The most intense green emission was obtained by exciting at 456 nm. • Photoluminescence is highly dependent on the crystallinity and doping content. • Emission intensity can also be modulated by controlling the film thickness.

Coordinates in relativistic Hamiltonian mechanics

International Nuclear Information System (INIS)

Sokolov, S.N.

1984-01-01

The physical (covariant and measurable) coordinates of free particles and covariant coordinates of the center of inertia are found for three main forms of relativistic dynamics. In the point form of dynamics, the covariant coordinates of two directly interacting particles are found, and the equations of motion are brought to the explicitly covariant form. These equations are generalized to the case of interaction with an external electromagnetic field

Coordination between Fault-Ride-Through Capability and Overcurrent Protection of DFIG Generatorsfor Wind Farms

DEFF Research Database (Denmark)

Bak-Jensen, Birgitte; Kawady, Tamer A.; Abdel-Rahman, Mansour H.

2009-01-01

Due to the increasing penetration of wind farms in power systems, stability issues arise strongly for power system operation. Doubly-Fed Induction Generators (DFIG) are charac-terized with some unique features during normal/abnormal op-erating conditions as compared with singly-fed ones. Fault ri...... on protective relaying coordination in wind farms.......-Through (FRT) mainly aims to delay a disconnecting of the DFIG units during grid faults for a possible time to restore the system stability if the fault is cleared within a permissible time. This strategy may, however, affect the performance of related protective elements during fault periods. In this paper......, the Coor-dination between Fault Ride-Through Capability and Overcur-rent Protection of DFIG Wind Generators in MV Networks is in-vestigated. Simulation test cases using MATLAB-Simulink are implemented on a 345-MW wind farm in AL-Zaafarana, Egypt. The simulation results show the influence of FRT capability...

Does the Al substitution in C–S–H(I) change its mechanical property?

KAUST Repository

Oh, Jae Eun; Clark, Simon M.; Monteiro, Paulo J.M.

2011-01-01

This study examines the influence of Al substitution for Si on the bulk modulus of calcium silicate hydrate I [C-S-H(I)], a structural analogue of C-S-H, by performing high-pressure synchrotron X-ray diffraction experiments in two C-S-H(I) samples: one a hydration product of alkali-activated slag and the other a synthetic C-S-H(I). The test result shows that not only the bulk modulus but also the incompressibility of the lattice parameters a, b, and c of two C-S-H(I) samples are very similar to each other, regardless of the Al substitution. This result may be due to the four-coordinated configuration of the substituted Al, which makes the dreierketten silicate chains maintain the same arrangement after the substitution. © 2010 Elsevier Ltd.

Nuclear Energy Advanced Modeling and Simulation (NEAMS) Accident Tolerant Fuels High Impact Problem: Coordinate Multiscale FeCrAl Modeling

Energy Technology Data Exchange (ETDEWEB)

Gamble, K. A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Hales, J. D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zhang, Y. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Andersson, D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Capolungo, L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Wirth, B. D. [Univ. of Tennessee, Knoxville, TN (United States)

2017-07-26

Since the events at the Fukushima-Daiichi nuclear power plant in March 2011 significant research has unfolded at national laboratories, universities and other institutions into alternative materials that have potential enhanced ac- cident tolerance when compared to traditional UO2 fuel zircaloy clad fuel rods. One of the potential replacement claddings are iron-chromium-alunimum (FeCrAl) alloys due to their increased oxidation resistance [1–4] and higher strength [1, 2]. While the oxidation characteristics of FeCrAl are a benefit for accident tolerance, the thermal neu- tron absorption cross section of FeCrAl is about ten times that of Zircaloy. This neutronic penalty necessitates thinner cladding. This allows for slightly larger pellets to give the same cold gap width in the rod. However, the slight increase in pellet diameter is not sufficient to compensate for the neutronic penalty and enriching the fuel beyond the current 5% limit appears to be necessary [5]. Current estimates indicate that this neutronic penalty will impose an increase in fuel cost of 15-35% [1, 2]. In addition to the neutronic disadvantage, it is anticipated that tritium release to the coolant will be larger because the permeability of hydrogen in FeCrAl is about 100 times higher than in Zircaloy [6]. Also, radiation-induced hardening and embrittlement of FeCrAl need to be fully characterized experimentally [7]. Due to the aggressive development schedule for inserting some of the potential materials into lead test assemblies or rods by 2022 [8] multiscale multiphysics modeling approaches have been used to provide insight into these the use of FeCrAl as a cladding material. The purpose of this letter report is to highlight the multiscale modeling effort for iron-chromium-alunimum (FeCrAl) cladding alloys as part of the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program through its Accident Tolerant Fuel (ATF) High Impact Problem (HIP). The approach taken throughout the HIP is to

Electronic materials with a wide band gap: recent developments

Directory of Open Access Journals (Sweden)

Detlef Klimm

2014-09-01

Full Text Available The development of semiconductor electronics is reviewed briefly, beginning with the development of germanium devices (band gap Eg = 0.66 eV after World War II. A tendency towards alternative materials with wider band gaps quickly became apparent, starting with silicon (Eg = 1.12 eV. This improved the signal-to-noise ratio for classical electronic applications. Both semiconductors have a tetrahedral coordination, and by isoelectronic alternative replacement of Ge or Si with carbon or various anions and cations, other semiconductors with wider Eg were obtained. These are transparent to visible light and belong to the group of wide band gap semiconductors. Nowadays, some nitrides, especially GaN and AlN, are the most important materials for optical emission in the ultraviolet and blue regions. Oxide crystals, such as ZnO and β-Ga2O3, offer similarly good electronic properties but still suffer from significant difficulties in obtaining stable and technologically adequate p-type conductivity.

Identification of the hydrate gel phases present in phosphate-modified calcium aluminate binders

Energy Technology Data Exchange (ETDEWEB)

Chavda, Mehul A.; Bernal, Susan A. [Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom); Apperley, David C. [Solid-State NMR Group, Department of Chemistry, Durham University, Durham DH1 3LE (United Kingdom); Kinoshita, Hajime [Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom); Provis, John L., E-mail: j.provis@sheffield.ac.uk [Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom)

2015-04-15

The conversion of hexagonal calcium aluminate hydrates to cubic phases in hydrated calcium aluminate cements (CAC) can involve undesirable porosity changes and loss of strength. Modification of CAC by phosphate addition avoids conversion, by altering the nature of the reaction products, yielding a stable amorphous gel instead of the usual crystalline hydrate products. Here, details of the environments of aluminium and phosphorus in this gel were elucidated using solid-state NMR and complementary techniques. Aluminium is identified in both octahedral and tetrahedral coordination states, and phosphorus is present in hydrous environments with varying, but mostly low, degrees of crosslinking. A {sup 31}P/{sup 27}Al rotational echo adiabatic passage double resonance (REAPDOR) experiment showed the existence of aluminium–phosphorus interactions, confirming the formation of a hydrated calcium aluminophosphate gel as a key component of the binding phase. This resolves previous disagreements in the literature regarding the nature of the disordered products forming in this system.

The horizontally homogeneous model equations of incompressible atmospheric flow in general orthogonal coordinates

DEFF Research Database (Denmark)

Jørgensen, Bo Hoffmann

2003-01-01

The goal of this brief report is to express the model equations for an incompressible flow which is horizontally homogeneous. It is intended as a computationally inexpensive starting point of a more complete solution for neutral atmospheric flow overcomplex terrain. This idea was set forth...... by Ayotte and Taylor (1995) and in the work of Beljaars et al. (1987). Unlike the previous models, the present work uses general orthogonal coordinates. Strong conservation form of the model equations is employedto allow a robust and consistent numerical procedure. An invariant tensor form of the model...

Structural Characterization of MAO and Related Aluminum Complexes. 1. Solid-State 27 Al NMR with Comparison to EFG Tensors from ab Initio Molecular Orbital Calculations

Energy Technology Data Exchange (ETDEWEB)

Bryant, Pamela L.; Harwell, Chris; Mrse, Anthony A.; Emery, Earl F.; Gan, Zhedong; Caldwell, Tod; Reyes, Arneil P.; Kuhns, Philip; Hoyt, David W.; Simeral, Larry S.; Hall, Randall W.; Butler, Leslie G.

2001-11-07

Aminato and propanolato aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three 27Al NMR techniques optimized for large 27Al Quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. The 27Al quadrupole coupling constants and asymmetry parameters of molecular species, both experimental and derived from ab initio molecular orbital calculations, are correlated with structure.

Structural characterization of MAO and related aluminum complexes. 1. Solid-state (27)Al NMR with comparison to EFG tensors from ab initio molecular orbital calculations.

Science.gov (United States)

Bryant, P L; Harwell, C R; Mrse, A A; Emery, E F; Gan, Z; Caldwell, T; Reyes, A P; Kuhns, P; Hoyt, D W; Simeral, L S; Hall, R W; Butler, L G

2001-12-05

Experimental and ab initio molecular orbital techniques are developed for study of aluminum species with large quadrupole coupling constants to test structural models for methylaluminoxanes (MAO). The techniques are applied to nitrogen- and oxygen-containing complexes of aluminum and to solid MAO isolated from active commercial MAO preparations. (Aminato)- and (propanolato)aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three (27)Al NMR techniques optimized for large (27)Al quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. Four-membered (aminato)aluminum complexes with AlN(4) coordination yield slightly smaller C(q) values than similar AlN(2)C(2) sites: 12.2 vs 15.8 MHz. Planar 3-coordinate AlN(2)C sites have the largest C(q) values, 37 MHz. In all cases, molecular orbital calculations of the electric field gradient tensors yields C(q) and eta values that match with experiment, even for a large hexameric (aminato)aluminum cage. A D(3d) symmetry hexaaluminum oxane cluster, postulated as a model for MAO, yields a calculated C(q) of -23.7 MHz, eta = 0.7474, and predicts a spectrum that is too broad to match the field-swept NMR of methylaluminoxane, which shows at least three sites, all with C(q) values greater than 15 MHz but less than 21 MHz. Thus, the proposed hexaaluminum cluster, with its strained four-membered rings, is not a major component of MAO. However, calculations for dimers of the cage complex, either edge-bridged or face-bridged, show a much closer match to experiment. Also, MAO preparations differ, with a gel form of MAO having significantly larger (27)Al C(q) values than a nongel form, a conclusion reached on the basis of (27)Al NMR line widths in field-swept NMR spectra acquired from 13 to 24 T.

45 CFR 1310.23 - Coordinated transportation.

Science.gov (United States)

2010-10-01

... 45 Public Welfare 4 2010-10-01 2010-10-01 false Coordinated transportation. 1310.23 Section 1310... START PROGRAM HEAD START TRANSPORTATION Special Requirements § 1310.23 Coordinated transportation. (a) Each agency providing transportation services must make reasonable efforts to coordinate transportation...

ANTIMONY HALIDES AND HgX2 (X = Cl, Br AMINE ADDUCTS: SYNTHESIS AND INFRARED STUDY

Directory of Open Access Journals (Sweden)

NDONGO GUEYE

2013-12-01

Full Text Available Eight new SbF3, SbCl5 and HgX2 (X = Cl, Br amine adducts have been synthesized and their infrared study carried out. Discrete structures have been suggested on the basis of elemental analysis and infrared data, the coordination number of antimony varying from five to nine, while the environment around Hg is tetrahedral.

Dielectric and optical properties of glasses of CdO-B2O3 system

International Nuclear Information System (INIS)

Semin, V.N.; Mal'tsev, V.T.; Panich, A.E.

1986-01-01

Dielectric and optical properties of glasses of CdO-B 2 O 3 system are investigated. It is shown, that on changing the composition, cadmic-borate glasses undergo structural changes, similar to those, taking place in lead-borate glasses, and the maximum part of the boron atoms in the oxygen tetrahedral coordination is at CdO:B 2 O 3 =3:2

Palygorskite Hybridized Carbon Nanocomposite as a High ...

African Journals Online (AJOL)

NICO

Pd nanoparticles were deposited on the hybrid support as an electrocatalyst for formic acid oxida- tion. .... synthetic procedure using conventional borohydride reduction .... as Al2O3, CaO and MgO, which may exist in both the tetrahedral.

Optimization of strong and weak coordinates

NARCIS (Netherlands)

Swart, M.; Bickelhaupt, F.M.

2006-01-01

We present a new scheme for the geometry optimization of equilibrium and transition state structures that can be used for both strong and weak coordinates. We use a screening function that depends on atom-pair distances to differentiate strong coordinates from weak coordinates. This differentiation

Formulation and catalytic performance of MOF-derived Fe@C/Al composites for high temperature Fischer–Tropsch synthesis

KAUST Repository

Oar-Arteta, Lide; Valero-Romero, Marí a José ; Wezendonk, Tim; Kapteijn, Freek; Gascon, Jorge

2017-01-01

High productivity towards C-2-C-4 olefins together with high catalyst stability are key for optimum operation in high temperature Fischer-Tropsch synthesis (HT-FTS). Here, we report the fabrication of Fe@C/Al composites that combine both the outstanding catalytic properties of the Fe-BTC MOF-derived Fe catalyst and the excellent mechanical resistance and textural properties provided by the inorganic AlOOH binder. The addition of AlOOH to Fe-BTC followed by pyrolysis in N-2 atmosphere at 500 degrees C results in composites with a large mesoporosity, a high Fe/Fe3O4 ratio, 10-35 nm average Fe crystallite size and coordinatively unsaturated Al3+ sites. In catalytic terms, the addition of AlOOH binder gives rise to enhanced C-2-C-4 selectivity and catalyst mechanical stability in HT-FTS, but at high Al contents the activity decreases. Altogether, the productivity of these Fe@C/Al composites is well above most known Fe catalysts for this process.

Formulation and catalytic performance of MOF-derived Fe@C/Al composites for high temperature Fischer–Tropsch synthesis

KAUST Repository

Oar-Arteta, Lide

2017-11-15

High productivity towards C-2-C-4 olefins together with high catalyst stability are key for optimum operation in high temperature Fischer-Tropsch synthesis (HT-FTS). Here, we report the fabrication of Fe@C/Al composites that combine both the outstanding catalytic properties of the Fe-BTC MOF-derived Fe catalyst and the excellent mechanical resistance and textural properties provided by the inorganic AlOOH binder. The addition of AlOOH to Fe-BTC followed by pyrolysis in N-2 atmosphere at 500 degrees C results in composites with a large mesoporosity, a high Fe/Fe3O4 ratio, 10-35 nm average Fe crystallite size and coordinatively unsaturated Al3+ sites. In catalytic terms, the addition of AlOOH binder gives rise to enhanced C-2-C-4 selectivity and catalyst mechanical stability in HT-FTS, but at high Al contents the activity decreases. Altogether, the productivity of these Fe@C/Al composites is well above most known Fe catalysts for this process.

Service Coordination Policies and Models: National Status.

Science.gov (United States)

Harbin, Gloria L.; Bruder, M.; Mazzarella, C.; Gabbard, G.; Reynolds, C.

This report discusses the findings of a study that investigated state coordination of early intervention services for infants, toddlers, and young children with disabilities. State Part C coordinators participated in a survey that sought their perceptions of values under girding service coordination, approach to service coordination, policies,…

Short-range order in amorphous thin films of indium selenides

International Nuclear Information System (INIS)

Zakharov, V.P.; Poltavtsev, Yu.G.; Sheremet, G.P.

1982-01-01

A structure of the short-range order and a character of interatomic interactions in indium selenides Insub(1-x)Sesub(x) with 0.333 <= x <= 0.75, obtained in the form of amorphous films 0.05-0.80 μm thick are studied using electron diffraction method. It is found out that mostly tetrahedrical coordination of nearest neighbours in the vicinity of indium atoms is characteristic for studied amorphous films, and coordination of selenium atoms is different. Amorphous film with x=0.75 posesses a considereably microheterogeneous structure of the short-range order, which is characterized by the presence of microunclusions of amorphous selenium and atoms of indium, octohedrically coordinated by selenium atoms

Micro practices of coordination based on complex adaptive systems: user needs and strategies for coordinating public health in Denmark.

Science.gov (United States)

Terkildsen, Morten Deleuran; Wittrup, Inge; Burau, Viola

2015-01-01

Many highly formalised approaches to coordination poorly fit public health and recent studies call for coordination based on complex adaptive systems. Our contribution is two-fold. Empirically, we focus on public health, and theoretically we build on the patient perspective and treat coordination as a process of contingent, two-level negotiations of user needs. The paper draws on the concept of user needs-based coordination and sees coordination as a process, whereby needs emerging from the life world of the user are made amenable to the health system through negotiations. The analysis is based on an explorative case study of a health promotion initiative in Denmark. It adopts an anthropological qualitative approach and uses a range of qualitative data. The analysis identifies four strategies of coordination: the coordinator focusing on the individual user or on relations with other professionals; and the manager coaching the coordinator or providing structural support. Crucially, the coordination strategies by management remain weak as they do not directly relate to specific user needs. In process of bottom-up negotiations user needs become blurred and this is especially a challenge for management. The study therefore calls for an increased focus on the level nature of negotiations to bridge the gap that currently weakens coordination strategies by management.

Effect of strontium on liquid structure of Al-Si hypoeutectic alloys using high-energy X-ray diffraction

International Nuclear Information System (INIS)

Srirangam, P.; Kramer, M.J.; Shankar, S.

2011-01-01