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Sample records for 3d transition metals

  1. Interface magnetism of 3d transition metals

    Niklasson, A. M. N.; Johansson, B.; Skriver, Hans Lomholt

    1999-01-01

    The layered resolved magnetic spin moments of the magnetic 3d bilayer interfaces Fe/V bcc, Fe/Co bcc, Fe/Cu bcc, Co/V bcc, Co/Ni fee, Co/Cu fee, Ni/V fee, Ni/Cr fcc, Ni/Cu fee and the magnetic surfaces Fe bcc, Co bcc, Co fee, and Ni fee are calculated for the (001), (011), and (111) orientations by...

  2. Correlated electron pseudopotentials for 3d-transition metals

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc − Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature

  3. Correlated electron pseudopotentials for 3d-transition metals

    Trail, J. R.; Needs, R. J.

    2015-02-01

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc - Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature.

  4. Correlated electron pseudopotentials for 3d-transition metals

    Trail, J. R., E-mail: jrt32@cam.ac.uk; Needs, R. J. [Theory of Condensed Matter Group, Cavendish Laboratory, J J Thomson Avenue, Cambridge CB3 0HE (United Kingdom)

    2015-02-14

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc − Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature.

  5. Semiconductor-metal transition in semiconductor melts with 3d metal admixtures

    Electrical conductivity and thermoelectric power measurements were performed for liquid semiconductor alloys Se0.5Te0.5 doped with 3d metals in a wide temperature range (up to 1600 K) under ambient pressures of argon gas (up to 30 MPa). Structure changes were studied by means of X-ray diffraction method. The 3d metal admixtures affect electrophysical properties and a temperature of the semiconductor-metal transition (SMT)

  6. Metal - Insulator Transition in 3D Quantum Percolation

    Travenec, Igor

    2007-01-01

    We present the metal - insulator transition study of a quantum site percolation model on simple cubic lattice. Transfer matrix method is used to calculate transport properties - Landauer conductance - for the binary distribution of energies. We calculate the mobility edge in disorder (ratio of insulating sites) - energy plane in detail and we find the extremal critical disorder somewhat closer to the classical percolation threshold, than formerly reported. We calculate the critical exponent $...

  7. Magnetic properties of 3d transition metal chains on vicinal Cu(111) surface

    Density functional theory (DFT) is applied in our study to describe magnetic properties of 3d transition metal (TM) nanowires on a stepped Cu(111) surface. The basic template to study such metallic chains on the Cu(111) surface is an embedded Fe chain at one-atom distance away from the upper edge of the monoatomic surface step. Chains of 3d transition metal atoms from Sc to Ni are added on top of the Fe chain. At the beginning of the 3d row, the chains show antiferromagnetic order. A small energy difference between ferromagnetic and antiferromagnetic order is obtained for the Mn-Fe system. Cr forms an antiferromagnetic chain, whereas Fe, Co, and Ni chains are ferromagnetically coupled to the embedded Fe chain.

  8. First-principles calculations on implanted TiO2 by 3d transition metal ions

    2009-01-01

    3d transition metal (V, Cr and Fe) ions are implanted into TiO2 by the method of metal ion implantation. The electronic band structures of TiO2 films doped 3d transition metal ions have been analyzed by ab initio band calculations based on a self-consistent full-potential linearized augmented plane-wave method within the first-principle formalism. Influence of implantation on TiO2 films is examined by the method of UV-visible spectrometry. The results of experiment and calculation show that the optical band gap of TiO2 films is narrowed by ion implantation. The calculation shows that the 3d state of V, Cr and Fe ions plays a significant role in red shift of UV-Vis absorbance spectrum.

  9. Magnetism of 3d transition metal atoms on W(001): submonolayer films

    Ondráček, Martin; Kudrnovský, Josef; Turek, Ilja; Máca, František

    2007-01-01

    Roč. 61, - (2007), s. 894-898. ISSN 1742-6588 R&D Projects: GA MŠk OC 150; GA ČR GA202/04/0583 Institutional research plan: CEZ:AV0Z10100521; CEZ:AV0Z20410507 Keywords : magnetism * tungsten surface * 3d - transition metals Subject RIV: BM - Solid Matter Physics ; Magnetism

  10. A magnetic resonance study of 3d transition metals and thermal donors in silicon

    This thesis describes a study of 3d-transition metal impurities in silicon (titanium and iron in particular) and a study of oxygen-related heat-treatment centers in silicon, both carried out mainly by magnetic resonances techniques like EPR and ENDOR. 119 refs.; 31 figs.; 14 tabs

  11. Magnetism of 3d transition-metal monolayers on Rh(100)

    A. Al-Zubi; Bihlmayer, G.; Blügel, S.

    2011-01-01

    We employ the full-potential linearized augmented plane-wave method to report a systematic density-functional theory study of the magnetic properties of the 3d transition-metal (V, Cr, Mn, Fe, Co, and Ni) monolayers deposited on the Rh(100) substrate. We find that all monolayer films are magnetic. The size of the local magnetic moments across the transition-metal series follows Hund's rule with a maximum magnetic moment of 3.77 mu(B) for Mn. The largest induced magnetic moment of about 0.46 m...

  12. 3d Transition Metal Adsorption Induced Vally-polarized Anomalous Hall Effect in Germanene

    Zhou, P; Sun, L. Z.

    2015-01-01

    Based on DFT+U and Berry curvature calculations, we study the electronic structures and topological properties of 3d transition metal (TM) atom (from Ti to Co) adsorbed germanene (TM-germanene). We find that valley-polarized anomalous hall effect (VAHE) can be realized in germanene by adsorbing Cr, Mn, or Co atom on its surface. A finite valley hall voltage can be easily detected in its nanoribbon, which is important for valleytronics devices. Moreover, different valley-polarized current and ...

  13. Magnetic moments and hyperfine fields at Fe in 3d-transition metals

    The magnetic moments and hyperfine fields at Fe sites in 3d-transition metals are calculated using the first principle discrete variational method in local density approximation. Although a large positive moment is retained at each Fe site, the hyperfine fields varied from large negative to large positive values. It is concluded that the absence of Moessbauer magnetic splitting does not necessarily imply the absence of local magnetic moments. (orig.)

  14. Local electronic structure and magnetic properties of 3d transition metal doped GaAs

    LIN He; DUAN HaiMing

    2008-01-01

    The local electronic structure and magnetic properties of GaAs doped with 3d transition metal (Sc, Ti, V, Cr, Mn, Fe, Co, Ni) were studied by using discrete varia-tional method (DVM) based on density functional theory. The calculated result in-dicated that the magnetic moment of transition metal increases first and then de-creases, and reaches the maximum value when Mn is doped into GaAs. In the case of Mn concentration of 1.4%, the magnetic moment of Mn is in good agreement with the experimental result. The coupling between impure atoms in the system with two impure atoms was found to have obvious variation. For different transition metal, the coupling between the impure atom and the nearest neighbor As also has dif-ferent variation.

  15. First principles study of 3d transition metal doped Cu3N

    Interstitially doped Cu3N represents a model system to study “enclosed atoms” in a cuboctahedral environment. Based on density functional theory calculations using the generalized gradient approximation, we report a systematic study of 3d-transition metals (TM), as well as Li-, H-, and Pd-doped Cu3N, whose stabilities and magnetic properties are investigated. The interposition of 3d-TM atoms leads to mechanically stable yet brittle structures, with Sc, Mn, Ni, Cu, Zn possessing relatively small positive (endothermic) formation energies (0.12∼0.54eV/TM), suggesting it may be easier to realize them experimentally than other 3d-TM elements. Li-, H-, Pd-doping in Cu3N are exothermic, while Ti, V, Cr, Fe, and Co have higher formation energy (0.93∼1.39 eV/TM) at a doping concentration 3.7 %. The fully 3d-TM doped Cu3N systems exhibit a wide spectrum of magnetic properties, ranging from weak antiferromagnetic (Sc-), antiferromagnetic (Ti-, V-, Cr-) to ferromagnetic (Mn-, Fe-, Co-) and non-magnetic (Ni-, Cu-, Zn-) behaviour. In particular, Ti:Cu3N exhibits weak itinerant magnetic properties with a large positive magnetovolume effect. All the 3d-TM atom intercalations into cubic Cu3N lead to a semiconductor-to-metal transition for both 100% and 3.7% doping, with the exception of Ni:Cu3N exhibiting a weak metallic or narrow semiconducting behaviour depending on the doping concentration.

  16. First principles study of 3d transition metal doped Cu{sub 3}N

    Cui, X.Y., E-mail: carl.cui@sydney.edu.au [School of Physics, University of Sydney, Sydney, New South Wales 2006 (Australia); Australian Centre for Microscopy and Microanalysis, University of Sydney, Sydney, New South Wales 2006 (Australia); Soon, A. [School of Physics, University of Sydney, Sydney, New South Wales 2006 (Australia); Department of Materials Science and Engineering, Yonsei University, Seoul (Korea, Republic of); Phillips, A.E. [School of Physics, University of Sydney, Sydney, New South Wales 2006 (Australia); Zheng, R.K.; Liu, Z.W. [Australian Centre for Microscopy and Microanalysis, University of Sydney, Sydney, New South Wales 2006 (Australia); Delley, B. [Paul Scherrer Institut, WHGA/123 CH-5232 Villigen PSI (Switzerland); Ringer, S.P. [Australian Centre for Microscopy and Microanalysis, University of Sydney, Sydney, New South Wales 2006 (Australia); Stampfl, C. [School of Physics, University of Sydney, Sydney, New South Wales 2006 (Australia)

    2012-09-15

    Interstitially doped Cu{sub 3}N represents a model system to study 'enclosed atoms' in a cuboctahedral environment. Based on density functional theory calculations using the generalized gradient approximation, we report a systematic study of 3d-transition metals (TM), as well as Li-, H-, and Pd-doped Cu{sub 3}N, whose stabilities and magnetic properties are investigated. The interposition of 3d-TM atoms leads to mechanically stable yet brittle structures, with Sc, Mn, Ni, Cu, Zn possessing relatively small positive (endothermic) formation energies (0.12{approx}0.54eV/TM), suggesting it may be easier to realize them experimentally than other 3d-TM elements. Li-, H-, Pd-doping in Cu{sub 3}N are exothermic, while Ti, V, Cr, Fe, and Co have higher formation energy (0.93{approx}1.39 eV/TM) at a doping concentration 3.7 %. The fully 3d-TM doped Cu{sub 3}N systems exhibit a wide spectrum of magnetic properties, ranging from weak antiferromagnetic (Sc-), antiferromagnetic (Ti-, V-, Cr-) to ferromagnetic (Mn-, Fe-, Co-) and non-magnetic (Ni-, Cu-, Zn-) behaviour. In particular, Ti:Cu{sub 3}N exhibits weak itinerant magnetic properties with a large positive magnetovolume effect. All the 3d-TM atom intercalations into cubic Cu{sub 3}N lead to a semiconductor-to-metal transition for both 100% and 3.7% doping, with the exception of Ni:Cu{sub 3}N exhibiting a weak metallic or narrow semiconducting behaviour depending on the doping concentration.

  17. X-ray Emission Spectroscopy in Magnetic 3d-Transition Metals

    Iota, V; Park, J; Baer, B; Yoo, C; Shen, G

    2003-11-18

    The application of high pressure affects the band structure and magnetic interactions in solids by modifying nearest-neighbor distances and interatomic potentials. While all materials experience electronic changes with increasing pressure, spin polarized, strongly electron correlated materials are expected to undergo the most dramatic transformations. In such materials, (d and f-electron metals and compounds), applied pressure reduces the strength of on-site correlations, leading to increased electron delocalization and, eventually, to loss of its magnetism. In this ongoing project, we study the electronic and magnetic properties of Group VIII, 3d (Fe, Co and Ni) magnetic transition metals and their compounds at high pressures. The high-pressure properties of magnetic 3d-transition metals and compounds have been studied extensively over the years, because of iron being a major constituent of the Earth's core and its relevance to the planetary modeling to understand the chemical composition, internal structure, and geomagnetism. However, the fundamental scientific interest in the high-pressure properties of magnetic 3d-electron systems extends well beyond the geophysical applications to include the electron correlation-driven physics. The role of magnetic interactions in the stabilization of the ''non-standard'' ambient pressure structures of Fe, Co and Ni is still incompletely understood. Theoretical studies have predicted (and high pressure experiments are beginning to show) strong correlations between the electronic structure and phase stability in these materials. The phase diagrams of magnetic 3d systems reflect a delicate balance between spin interactions and structural configuration. At ambient conditions, the crystal structures of {alpha}-Fe(bcc) and {var_epsilon}-Co(hcp) phases depart from the standard sequence (hcp {yields} bcc{yields} hcp {yields} fcc), as observed in all other non-magnetic transition metals with increasing the d

  18. Adsorption of Ge nanowire with 3d transition metals: A density-functional theory study

    Using density-functional theory calculations, we investigate the energetic, electronic and magnetic properties of 3d transition metals adsorption on hydrogen-passivated germanium nanowire along [0 0 1] direction. It is found that most of the adatoms prefer to bind on the HH site, while the Sc adatom prefers to the Top site. The atoms of good conducting metals, such as Cu and Zn form weak bonding with the wire, however, those such as Ti, V, Fe, Co, and Ni have relative larger binding energies. In addition, various types of wires can be obtained depending on the adatom species, including nonmagnetic metals (Sc or Cu adsorption) and semiconductors (Ni or Zn adsorption), weak-ferromagnetic metals (Ti or V adsorption), ferromagnetic semiconductor (Cr adsorption), and more interesting the ferromagnetic half-metals (Mn, Fe or Co adsorption) with 100% spin-polarization at the Fermi level. These ferromagnetic wires should have potential applications in the fields of quasi-one-dimensional spintronics devices. Detail analysis of the density of states indicates that the ferromagnetism originates mainly from spin-split of the TM-3d states. Furthermore, the effect of on-site Coulomb interaction on the stability of the three ferromagnetic half-metallic wires is also examined, and it is found that the half-metallic ground state of Mn- or Co-adsorbed wire is more robust than that of Fe-adsorbed wire.

  19. Optical properties of 3d transition metal ion-doped sodium borosilicate glass

    Graphical abstract: Photographs of undoped (SiO2)50 (Na2O)25 (B2O3)25 (SiNaB) glass and transition metal ion-doped (TM)0.5 (SiO2)49.5 (Na2O)25 (B2O3)25 glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO2-Na2O-B2O3 glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO2-Na2O-B2O3 glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states

  20. Optical properties of 3d transition metal ion-doped sodium borosilicate glass

    Wen, Hongli [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China); Tanner, Peter A., E-mail: peter.a.tanner@gmail.com [Department of Science and Environmental Studies, The Hong Kong Institute of Education, 10 Lo Ping Road, Tai Po, N.T., Hong Kong Special Administrative Region (Hong Kong)

    2015-03-15

    Graphical abstract: Photographs of undoped (SiO{sub 2}){sub 50} (Na{sub 2}O){sub 25} (B{sub 2}O{sub 3}){sub 25} (SiNaB) glass and transition metal ion-doped (TM){sub 0.5} (SiO{sub 2}){sub 49.5} (Na{sub 2}O){sub 25} (B{sub 2}O{sub 3}){sub 25} glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO{sub 2}-Na{sub 2}O-B{sub 2}O{sub 3} glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO{sub 2}-Na{sub 2}O-B{sub 2}O{sub 3} glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states.

  1. 3d Transition Metal Adsorption Induced the valley-polarized Anomalous Hall Effect in Germanene

    Zhou, P.; Sun, L. Z.

    2016-06-01

    Based on DFT + U and Berry curvature calculations, we study the electronic structures and topological properties of 3d transition metal (TM) atom (from Ti to Co) adsorbed germanene (TM-germanene). We find that valley-polarized anomalous Hall effect (VAHE) can be realized in germanene by adsorbing Cr, Mn, or Co atoms on its surface. A finite valley Hall voltage can be easily detected in their nanoribbon, which is important for valleytronics devices. Moreover, different valley-polarized current and even reversible valley Hall voltage can be archived by shifting the Fermi energy of the systems. Such versatile features of the systems show potential in next generation electronics devices.

  2. Hydrogen adsorption of nitrogen-doped carbon nanotubes functionalized with 3d-block transition metals

    Michael R Mananghaya

    2015-04-01

    A systematic study of the most stable configurations, calculation of the corresponding binding and free energies of functionalized 3d transition metals (TMs) on (10,0) Single Walled Carbon Nanotube (SWCNT) doped with porphyrin-like nitrogen defects (4ND-CNxNT) using spin-polarized density functional theory (DFT) formalism with flavours of LDA and GGA exchange-correlation (XC) functionals has been made. A thorough analysis showed that the electronic and magnetic properties of SWCNT are dependent on the TMs absorbed wherein, the composite material TM/4ND-CNxNT can act as a medium for storing hydrogen at room temperature manifested through favourable adsorption energy.

  3. First-principles study on structural stability of 3d transition metal alloying magnesium hydride

    2006-01-01

    A first-principles plane-wave pseudopotential method based on the density functional theory was used to investigate the energy and electronic structure of magnesium hydride (MgH2) alloyed by 3d transition metal elements. Through calculations of the negative heat formation of magnesium hydride alloyed by X (X denotes 3d transition metal) element, it is found that when a little X (not including Sc) dissolves into magnesium hydride, the structural stability of alloying systems decreases, which indicates that the dehydrogenation properties of MgH2 can be improved. After comparing the densities of states(DOS) and the charge distribution of MgH2 with or without X alloying, it is found that the improvement for the dehydrogenation properties of MgH2 alloyed by X attributes to the fact that the weakened bonding between magnesium and hydrogen is caused by the stronger interactions between X (not including Cu) and hydrogen. The calculation results of the improvement for the dehydrogenation properties of MgH2-X (X=Ti, V, Mn, Fe, Co,Ni, Cu) systems are in agreement with the experimental results. Hence, the dehydrogenation properties of MgH2 are expected to be improved by addition of Cr, Zn alloying elements.

  4. Structural and thermodynamic properties of 3-d transition metals: Pseudopotential theory revisited

    Structural and thermodynamic properties of 3d-transition metals are calculated in terms of the pseudopotential theory. The s-p and d-electrons are treated in a pseudoadiabatic approximation in such a way so that the s-p and d-electron are treated separately under the same footing. The s-p electrons are treated in terms of the conventional second-order pseudopotential theory, while the tightly bound d-electrons are treated in terms of the Wills-Harrison prescription that makes use of the Fridel rectangular electron-density of states (DOS) model. The predictions of the structural phase stability and other relevant thermodynamic properties are found to be consistent with experiments for almost all of the metals. (author). 16 refs, 5 tabs

  5. Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals

    Kitchin, J. R.; Nørskov, Jens Kehlet; Barteau, M. A.;

    2004-01-01

    The modification of the electronic and chemical properties of Pt(111) surfaces by subsurface 3d transition metals was studied using density-functional theory. In each case investigated, the Pt surface d-band was broadened and lowered in energy by interactions with the subsurface 3d metals......, resulting in weaker dissociative adsorption energies of hydrogen and oxygen on these surfaces. The magnitude of the decrease in adsorption energy was largest for the early 3d transition metals and smallest for the late 3d transition metals. In some cases, dissociative adsorption was calculated to be...... endothermic. The surfaces investigated in this study had no lateral strain in them, demonstrating that strain is not a necessary factor in the modification of bimetallic surface properties. The implications of these findings are discussed in the context of catalyst design, particularly for fuel cell...

  6. Potentiometric and spectroscopic study of the interaction of 3d transition metal ions with inositol hexakisphosphate

    Veiga, Nicolás; Macho, Israel; Gómez, Kerman; González, Gabriel; Kremer, Carlos; Torres, Julia

    2015-10-01

    Among myo-inositol phosphates, the most abundant in nature is the myo-inositol hexakisphosphate, InsP6. Although it is known to be vital to cell functioning, the biochemical research into its metabolism needs chemical and structural analysis of all the protonation, complexation and precipitation processes that it undergoes in the biological media. In view of its high negative charge at physiological level, our group has been leading a thorough research into the InsP6 chemical and structural behavior in the presence of the alkali and alkaline earth metal ions essential for life. The aim of this article is to extend these studies, dealing with the chemical and structural features of the InsP6 interaction with biologically relevant 3d transition metal ions (Fe(II), Fe(III), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)), in a non-interacting medium and under simulated physiological conditions. The metal-complex stability constants were determined by potentiometry, showing under ligand-excess conditions the formation of mononuclear species in different protonation states. Under metal ion excess, polymetallic species were detected for Fe(II), Fe(III), Zn(II) and Cu(II). Additionally, the 31P NMR and UV-vis spectroscopic studies provided interesting structural aspects of the strong metal ion-InsP6 interaction.

  7. 3d Transition Metal Adsorption Induced the valley-polarized Anomalous Hall Effect in Germanene.

    Zhou, P; Sun, L Z

    2016-01-01

    Based on DFT + U and Berry curvature calculations, we study the electronic structures and topological properties of 3d transition metal (TM) atom (from Ti to Co) adsorbed germanene (TM-germanene). We find that valley-polarized anomalous Hall effect (VAHE) can be realized in germanene by adsorbing Cr, Mn, or Co atoms on its surface. A finite valley Hall voltage can be easily detected in their nanoribbon, which is important for valleytronics devices. Moreover, different valley-polarized current and even reversible valley Hall voltage can be archived by shifting the Fermi energy of the systems. Such versatile features of the systems show potential in next generation electronics devices. PMID:27312176

  8. Calculated Specific Volumes and Magnetic Moments of the 3d Transition Metal Monoxides

    Skriver, Hans Lomholt; Andersen, O. K.; Johansson, B.

    We have performed self-consistent, spin-polarized band structure calculations as a function of the lattice spacing for the 3d metal monoxides in order to obtain the equilibrium lattice constants. The calculated binding from the 3d electrons and the occurrence of antiferromagnetism account...

  9. Recipe for High Moment Materials with Rare-earth and 3d Transition Metal Composites

    Autieri, Carmine; Kumar, P. Anil; Walecki, Dirk; Webers, Samira; Gubbins, Mark A.; Wende, Heiko; Sanyal, Biplab

    2016-01-01

    Materials with high volume magnetization are perpetually needed for the generation of sufficiently large magnetic fields by writer pole of magnetic hard disks, especially for achieving increased areal density in storage media. In search of suitable materials combinations for this purpose, we have employed density functional theory to predict the magnetic coupling between iron and gadolinium layers separated by one to several monolayers of 3d transition metals (Sc-Zn). We demonstrate that it is possible to find ferromagnetic coupling for many of them and in particular for the early transition metals giving rise to high moment. Cr and Mn are the only elements able to produce a significant ferromagnetic coupling for thicker spacer layers. We also present experimental results on two trilayer systems Fe/Sc/Gd and Fe/Mn/Gd. From the experiments, we confirm a ferromagnetic coupling between Fe and Gd across a 3 monolayers Sc spacer or a Mn spacer thicker than 1 monolayer. In addition, we observe a peculiar dependence of Fe/Gd magnetic coupling on the Mn spacer thickness. PMID:27381456

  10. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  11. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-01

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

  12. Electronic and Magnetic Properties of 3d Transition-Metal-Doped Ⅲ-Ⅴ Magnetic Semi conductor

    ZENG Yong-Zhi; HUANG Mei-Chun

    2004-01-01

    @@ A systematic study based on an ab initio calculation within a local spin density approximation is applied to material design of GaAs- and GaP-base doped by 3d transition metals. It is found that the ferromagnetic (FM) state is ready to achieve by V-, Cr- and Mn-doped GaP and GaAs.

  13. Local electronic structure and magnetic properties of 3d transition metal doped GaAs

    2008-01-01

    The local electronic structure and magnetic properties of GaAs doped with 3 transition metal(Sc,Ti,V,Cr,Mn,Fe,Co,Ni) were studied by using discrete varia tional method(DVM) based on density functional theory.The calculated result in dicated that the magnetic moment of transition metal increases first and then de creases,and reaches the maximum value when Mn is doped into GaAs.In the cas of Mn concentration of 1.4%,the magnetic moment of Mn is in good agreement wit the experimental result.The coupling between impure atoms in the system with tw impure atoms was found to have obvious variation.For different transition meta the coupling between the impure atom and the nearest neighbor As also has dif ferent variation.

  14. Defect energetics and magnetic properties of 3d-transition-metal-doped topological crystalline insulator SnTe

    Na, Wang; Jianfeng, Wang; Chen, Si; Bing-Lin, Gu; Wenhui, Duan

    2016-01-01

    The introduction of magnetism in SnTe-class topological crystalline insulators is a challenging subject with great importance in the quantum device applications. Based on the first-principles calculations, we have studied the defect energetics and magnetic properties of 3d transition-metal (TM)-doped SnTe. We find that the doped TM atoms prefer to stay in the neutral states and have comparatively high formation energies, suggesting that the uniform TM doping in SnTe with a higher concentratio...

  15. Magnetic properties of zigzag (0,9) GaAs nanotube doped with 3d transition metals

    R Fathi; T Movlarooy

    2016-01-01

    of 3d transition metals (Sc, Ti, Cr, Mn , Fe, Co, Ni) in both far and close situations were studied based on spin polarised density functional theory using the generalized gradient approximation (LDA) with SIESTA code. The electronic structures show that zigzag (0,9) GaAs nanotubes are non-magnetic semiconductors with direct band gap. It was revealed that doping of 11.11 % Fe and Mn concentrations substituted in Ga sites in ferromagnetic phase in far situation and Cr sites in ferromagnetic ph...

  16. Synthesis, characterization and antifungal activities of 3d-transition metal complexes of 1-acetylpiperazinyldithioc arbamate, M(acpdtc) 2

    Mohammad, Ali; Varshney, Charu; Nami, Shahab A. A.

    2009-07-01

    A series of mononuclear 3d-transition metal complexes of the type M(acpdtc) 2 have been synthesized (where acpdtc = 1-acetylpiperazinyldithiocarbamate, M = Mn(II), Fe(II), Co(II), Ni(II) and Cu(II)). The ligand and its complexes have been characterized by micro analysis (CHNS), TG/DSC, FT-IR, UV-vis, 1H NMR, magnetic susceptibility and conductance measurements. On the basis IR spectroscopy a symmetrical bidentate coordination has been observed for the 1-acetylpiperazinyldithiocarbamate moiety in all the complexes. On the basis of UV-vis spectra and magnetic susceptibility measurement a square-planar geometry has been proposed for the Ni(II) and Cu(II) complexes while the other complexes have been found to acquire a distorted-tetrahedral structure. The thermogravimetric and differential scanning calorimetric profile of the ligand indicates a two-step decomposition pattern while the complexes exhibit a three-stage thermogram forming metal sulfide as the eventual end product. The molar conductivity data of 1 mM solution in DMSO of the complexes is in close accord to their non-electrolytic behaviour. The ligand and its 3d-transition metal complexes have also been tested for their antifungicidal activity by agar well diffusion method using Fusarium sp. and Sclerotina sp. The maximum activity has been observed in case of Mn(II) and Fe(II) complexes.

  17. Structural, electronic and magnetic properties of 3d transition metal atom adsorbed germanene: A first-principles study

    Pang, Qing, E-mail: pangqingjkd@163.com [College of Science, Xi' an University of Architecture and Technology, Xi' an 710055, Shaanxi (China); Li, Long; Zhang, Chun-Ling [College of Science, Xi' an University of Architecture and Technology, Xi' an 710055, Shaanxi (China); Wei, Xiu-Mei [College of Physics and Information Technology, Shaanxi Normal University, Xi' an 710062, Shaanxi (China); Song, Yu-Ling [College of Physics and Electronic Engineering, Nanyang Normal University, Nanyang 473061, Henan (China)

    2015-06-15

    The structural, electronic and magnetic properties of germanene adsorbed with 10 different 3d transition metal (TM) atoms have been investigated by using the spin-polarized DFT calculations. The 3d TM adatoms we considered prefer to bind to the hexagon hollow site of germanene, except Zn which favors to bind to the valley site. A strong covalent bonding character between TM adatom and germanene layer is found in most of TM/germanene adsorption systems. By means of adsorption, the germanene can exhibit various electronic and magnetic properties depending on the adatom species, such as nonmagnetic metal (Cu adsorption), nonmagnetic semiconductor (Ni or Zn adsorption), ferromagnetic metal (Cr or Mn adsorption), ferromagnetic semiconductor (V adsorption), and more particular, ferromagnetic half-metal (Sc, Ti, Fe or Co adsorption) with 100% spin-polarization at the Fermi level. In addition, Cr adatom introduces the largest magnetic moment in germanene, while Sc, Ti, V, Mn, Fe and Co adatoms all generate nearly integer magnetic moments. The effects of the on-site Coulomb interaction as well as the magnetic interaction between TM adatoms on the stability of the half-metallic TM/germanene systems are also considered, and the results show that the half-metallic states for the Sc/germanene and Ti/germanene are all robust. These ferromagnetic TM/germanene systems should have potential applications in the fields of two-dimensional spintronics devices. The analysis of the PDOS indicates the ferromagnetic property of the obtained TM/germanene systems mainly resulted from the spin-split of the TM 3d states. - Highlights: • Most of the 3d TM adatoms considered prefer to bind to the hexagon hollow site of germanene. • Strong covalent bonding between adatom and germanene is found in most of TM/germanene systems. • Germanene exhibits various electronic and magnetic properties depending on the adatom species. • The ferromagnetic property of TM/germanene systems mainly

  18. Structural studies on transition metal oxides with only one or two electrons in the 3d shell

    Transition metal oxides with only one or two electrons in the 3d-shell are particularily interesting, as diffraction may more easily isolate the impact of the active electrons. The vanadate AV2O5 shows a variety of low-dimensional phenomena. We confirm the persistence of charge ordering of LiV2O5 down to 2 K by single crystal neutron diffraction and present an electron density study. We were able to solve the complex, distorted tetragonal hollandite (K2V8O16) structure below the MI-transition at 175 K revealing a dimerization of the vanadium ions in one of two vanadium chains and a zig-zag-chain formation in the neighbouring chain. CaCrO3 is a d2 system with the unusual Cr oxidation state 4+. It appears to be a bad metal, as found in optical spectroscopy, but in contrast to most metallic transition metal oxides CaCrO3 orders antiferromagnetically with a pronounced structural anomaly occuring just at the Neel temperature. Cubic spinels AM2O4 with magnetic M ions have attracted strong attention due to intrinsic frustration. We determined the electron density of ZnV2O4

  19. Intra-chain superexchange couplings in quasi-1D 3d transition-metal magnetic compounds

    Xiang, Hongping; Tang, Yingying; Zhang, Suyun; He, Zhangzhen

    2016-07-01

    The electronic structure and magnetic properties of the quasi-1D transition-metal borates PbMBO4 (M  =  Ti, V, Cr, Mn, Fe, Co) have been investigated by density functional theory, including electronic correlation. The results evidence PbCrBO4 and PbFeBO4 as antiferromagnetic (AFM) semiconductors (intra-chain AFM and inter-chain FM) and PbMnBO4 as a ferromagnetic (FM) semiconductor (both intra- and inter-chain FM) in accordance with experimental observations. For non-synthesized PbTiBO4, PbVBO4, and PbCoBO4, the ground-state magnetic structures are paramagnetic, FM, and paramagnetic, respectively. In this series of compounds, there are two kinds of superexchange couplings dominating their magnetic properties, i.e. the direction M–M delocalization superexchange and indirect M–O–M correlation superexchange. For PbMBO4 with M 3+ d  n , n  ⩽  3 (M  =  V and Cr), the main intra-chain spin coupling is the M–M t 2g–t 2g direct delocalization superexchange, while for PbMBO4 with M 3+ d  n , n  >  3 (M  =  Mn and Fe), the main intra-chain spin coupling is the near 90° M–O–M e g–p–e g indirect correlation superexchange.

  20. Intra-chain superexchange couplings in quasi-1D 3d transition-metal magnetic compounds.

    Xiang, Hongping; Tang, Yingying; Zhang, Suyun; He, Zhangzhen

    2016-07-13

    The electronic structure and magnetic properties of the quasi-1D transition-metal borates PbMBO4 (M  =  Ti, V, Cr, Mn, Fe, Co) have been investigated by density functional theory, including electronic correlation. The results evidence PbCrBO4 and PbFeBO4 as antiferromagnetic (AFM) semiconductors (intra-chain AFM and inter-chain FM) and PbMnBO4 as a ferromagnetic (FM) semiconductor (both intra- and inter-chain FM) in accordance with experimental observations. For non-synthesized PbTiBO4, PbVBO4, and PbCoBO4, the ground-state magnetic structures are paramagnetic, FM, and paramagnetic, respectively. In this series of compounds, there are two kinds of superexchange couplings dominating their magnetic properties, i.e. the direction M-M delocalization superexchange and indirect M-O-M correlation superexchange. For PbMBO4 with M (3+) d  (n) , n  ⩽  3 (M  =  V and Cr), the main intra-chain spin coupling is the M-M t 2g-t 2g direct delocalization superexchange, while for PbMBO4 with M (3+) d  (n) , n  >  3 (M  =  Mn and Fe), the main intra-chain spin coupling is the near 90° M-O-M e g-p-e g indirect correlation superexchange. PMID:27213502

  1. Neutron detection with LiCaAlF6 scintillator doped with 3d-transition metal ions

    Capability of thermal neutron detection was examined for LiCaAlF6 (LiCAF) scintillators doped with 3d-transition metal ions. Their radioluminescence spectra were measured with an 241-Am source to simulate 6Li(n, α)3H reaction. The sufficiently intense radioluminescence was observed for the Mn, Co and Cu dopants, while only a weak one was observed for Ti, V, Fe and Ni. A Mn doped LiCAF crystal, which showed the highest radioluminescence intensity, was coupled with a Si avalanche photodiode for the examination of its neutron response. It was confirmed that the average current of the photodiode clearly increased under excitation with 13.5 meV neutron flux. -- Highlights: •Neutron detection with 3d-transition metal ions doped LiCaAlF6 is investigated. •Single crystals of Ti, V, Mn, Fe, Co, Ni and Cu doped LiCaAlF6 are grown. •In α-ray induced emission spectra, Mn doped LiCaAlF6 showed highest intensity. •Mn doped LiCaAlF6 coupled with Si-APD exhibited a clear neutron signal

  2. Electronic structure and optical property of 3d transition metal doped (5,5) boron nitride nanotube

    The electronic structure and magnetic and optical properties of a 3d transition metal M (M = V, Cr, Mn, Fe) doped (5,5) boron nitride (B19MN20) nanotube are investigated by using the first-principles projector augmented wave potential within density functional theory under the generalized gradient approximation. It is found that B19VN20 and B19MnN20 systems are ideal candidates for spintronic applications, and the B19CrN20 system seems to be a promising diluted magnetic semiconductor. The analyses of optical dielectric functions show that B19CrN20 exhibits a new main peak at about 0.3 eV, and thus may be utilized in fields that are associated with infrared technology, such as infrared detectors, infrared masers, and so on. (orig.)

  3. Abrupt symmetry decrease in the ThT2Al20 alloys (T = 3d transition metal)

    Th-T-Al system, where T-3d transition metals, was studied at ThT2Al20 stoichiometry to establish the influence of T on the structural stability of ternary aluminide formed. Different alloys were prepared, varying T in the row from Ti to Fe. Using electron microscopy and X-ray diffraction methods it was found that ThT2Al20 phase adopts CeCr2Al20 structure type when T = Ti, V, and Cr. Starting from Mn, the symmetry of the stable Al-rich phase, which forms in the alloys with the same composition, decreases from cubic to orthorhombic. The results of Density Functional Theory (DFT) calculations coincide with experiments. Concepts of the Theory of Coordination Compounds and Jahn–Teller effect were used to explain the observed abrupt change of the symmetry. These considerations were supported by DFT calculations. - Highlights: • Type of transition metal influences symmetry change in the ThT2Al20 alloys. • It was found that cubic ThT2Al20 phase is stable for T = Ti, V and Cr. • When T = Mn, Fe–Al + orthorhombic ThT2Al10 are formed, lowering the symmetry. • Experimental results and DFT calculations were in full agreement. • TCC and of Jahn–Teller effect were used for explanation of the results

  4. Abrupt symmetry decrease in the ThT{sub 2}Al{sub 20} alloys (T = 3d transition metal)

    Uziel, A.; Bram, A.I. [Department of Materials Engineering, Ben-Gurion University of the Negev, Beer-Sheva, 8410501 (Israel); Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva, 8410501 (Israel); Venkert, A. [Nuclear Research Center-Negev, POB 9001, Beer-Sheva (Israel); Kiv, A.E.; Fuks, D. [Department of Materials Engineering, Ben-Gurion University of the Negev, Beer-Sheva, 8410501 (Israel); Meshi, L., E-mail: louisa@bgu.ac.il [Department of Materials Engineering, Ben-Gurion University of the Negev, Beer-Sheva, 8410501 (Israel); Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva, 8410501 (Israel)

    2015-11-05

    Th-T-Al system, where T-3d transition metals, was studied at ThT{sub 2}Al{sub 20} stoichiometry to establish the influence of T on the structural stability of ternary aluminide formed. Different alloys were prepared, varying T in the row from Ti to Fe. Using electron microscopy and X-ray diffraction methods it was found that ThT{sub 2}Al{sub 20} phase adopts CeCr{sub 2}Al{sub 20} structure type when T = Ti, V, and Cr. Starting from Mn, the symmetry of the stable Al-rich phase, which forms in the alloys with the same composition, decreases from cubic to orthorhombic. The results of Density Functional Theory (DFT) calculations coincide with experiments. Concepts of the Theory of Coordination Compounds and Jahn–Teller effect were used to explain the observed abrupt change of the symmetry. These considerations were supported by DFT calculations. - Highlights: • Type of transition metal influences symmetry change in the ThT{sub 2}Al{sub 20} alloys. • It was found that cubic ThT{sub 2}Al{sub 20} phase is stable for T = Ti, V and Cr. • When T = Mn, Fe–Al + orthorhombic ThT{sub 2}Al{sub 10} are formed, lowering the symmetry. • Experimental results and DFT calculations were in full agreement. • TCC and of Jahn–Teller effect were used for explanation of the results.

  5. Defect energetics and magnetic properties of 3 d-transition-metal-doped topological crystalline insulator SnTe

    Wang, Na; Wang, JianFeng; Si, Chen; Gu, Bing-Lin; Duan, WenHui

    2016-08-01

    The introduction of magnetism in SnTe-class topological crystalline insulators is a challenging subject with great importance in the quantum device applications. Based on the first-principles calculations, we have studied the defect energetics and magnetic properties of 3 d transition-metal (TM)-doped SnTe. We find that the doped TM atoms prefer to stay in the neutral states and have comparatively high formation energies, suggesting that the uniform TMdoping in SnTe with a higher concentration will be difficult unless clustering. In the dilute doping regime, all the magnetic TMatoms are in the high-spin states, indicating that the spin splitting energy of 3 d TM is stronger than the crystal splitting energy of the SnTe ligand. Importantly, Mn-doped SnTe has relatively low defect formation energy, largest local magnetic moment, and no defect levels in the bulk gap, suggesting that Mn is a promising magnetic dopant to realize the magnetic order for the theoretically-proposed large-Chern-number quantum anomalous Hall effect (QAHE) in SnTe.

  6. Positron decay in benzene solutions of 3d transition metal acetylacetonates and dipivaloylmethanates

    The lifetime spectra of positrons and positronium were measured in benzene solutions containing metal acetylacetonates and dipivaloylmethanates. The lifetime of orthopositronium (o-Ps) observed in pure benzene, 3.20 ns, was not significantly affected by the diamagnetic aluminum, nickel(II), and zinc complexes dissolved in benzene, whereas the lifetime was reduced by the paramagnetic manganese(III), iron(III), chromium(III), cobalt(II), and diamagnetic cobalt(III) complexes with the increase in their concentration, e.g., down to 1.60 ns in the case of 0.20 M Mn(acac)3. The intensity (I2) of o-Ps decreased rapidly with an increase in the solute concentration and became saturated at about 0.05 M. The rate constants of the o-Ps annihilation were correlated with polarographic apparent half-wave potentials of the complexes. The large reaction rate constants for Mn(acac)3 and Fe(acac)3 were attributed to the oxidation of o-Ps by the complexes, which show the potentials less negative than -0.5 V vs. mercury pool in benzene--methanol

  7. First-principles study of nitric oxide oxidation on Pt(111) versus Pt overlayer on 3d transition metals

    Catalytic oxidation of NO to NO2 is a significant research interest for improving the quality of air through exhaust gas purification systems. In this paper, the authors studied this reaction on pure Pt and Pt overlayer on 3d transition metals using kinetic Monte Carlo simulations coupled with density functional theory based first principles calculations. The authors found that on the Pt(111) surface, NO oxidation proceeds via the Eley–Rideal mechanism, with O2 dissociative adsorption as the rate-determining step. The oxidation path via the Langmuir–Hinshelwood mechanism is very slow and does not significantly contribute to the overall reaction. However, in the Pt overlayer systems, the oxidation of NO on the surface is more thermodynamically and kinetically favorable compared to pure Pt. These findings are attributed to the weaker binding of O and NO on the Pt overlayer systems and the binding configuration of NO2 that promotes easier N-O bond formation. These results present insights for designing affordable and efficient catalysts for NO oxidation

  8. Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms: Coupled cluster and multireference methods

    Balabanov, Nikolai B.; Peterson, Kirk A.

    2006-08-01

    Recently developed correlation consistent basis sets for the first row transition metal elements Sc-Zn have been utilized to determine complete basis set (CBS) scalar relativistic electron affinities, ionization potentials, and 4s23dn -2-4s1dn -1 electronic excitation energies with single reference coupled cluster methods [CCSD(T), CCSDT, and CCSDTQ] and multireference configuration interaction with three reference spaces: 3d4s, 3d4s4p, and 3d4s4p3d'. The theoretical values calculated with the highest order coupled cluster techniques at the CBS limit, including extrapolations to full configuration interaction, are well within 1kcal/mol of the corresponding experimental data. For the early transition metal elements (Sc-Mn) the internally contracted multireference averaged coupled pair functional method yielded excellent agreement with experiment; however, the atomic properties for the late transition metals (Mn-Zn) proved to be much more difficult to describe with this level of theory, even with the largest reference function of the present work.

  9. Vacuum Referred Binding Energy of the Single 3d, 4d, or 5d Electron in Transition Metal and Lanthanide Impurities in Compounds

    Rogers, E.G.; Dorenbos, P.

    2014-01-01

    The vacuum referred binding energy (VRBE) of the single electron in the lowest energy 3d level of Sc2 +, V4 +, Cr5 +, the lowest 4d level of Y2 +, Zr3 +, Nb4 +, Mo5 + and the lowest 5d level of Ta4 +, and W5 + in various compounds are determined by means of the chemical shift model. They will be compared with the VRBE in the already established lowest 3d level of Ti3 + and the lowest 5d level of Eu2 + and Ce3 +. Clear trends with changing charge of the transition metal (TM) cation and with ch...

  10. Structural, electronic and magnetic properties of 3d transition metals embedded graphene-like carbon nitride sheet: A DFT + U study

    Zhang, Shuai; Chi, Runze; Li, Chong; Jia, Yu

    2016-03-01

    Using first-principles calculations, we have investigated the structural, electronic and magnetic properties of 3d transition-metals (TMs) embedded two dimensional graphene-like carbon nitride sheet (TMs@g-CN). Our results show that TMs embed in the cavity of g-CN sheet regularly and keep intact of the planar structure, though there is Jahn-Teller distortion inevitably. Additionally, the nonmagnetic and semiconducting sheet can be significantly modulated to be magnetic and metallic behaviors induced by the resonant impurity states between TMs 3d and g-CN 2p orbitals. Moreover, we also explore the magnetic coupling of TMs@g-CN and find that it varies dramatically with the change of the distance between TMs, i.e., from ferromagnetic (FM) to antiferromagnetic (AFM) transition. Finally, the underlying physical mechanism of the above findings is discussed.

  11. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS2

    Single adsorption of different atoms on pristine two-dimensional monolayer MoS2 have been systematically investigated by using density functional calculations with van der Waals correction. The adatoms cover alkali metals, alkaline earth metals, main group metal, 3d-transition metals, coinage metal and nonmetal atoms. Depending on the adatom type, metallic, semimetallic or semiconducting behavior can be found in direct bandgap monolayer MoS2. Additionally, local or long-range magnetic moments of two-dimensional MoS2 sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS2 monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application

  12. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS2

    X. D. Li

    2015-05-01

    Full Text Available Single adsorption of different atoms on pristine two-dimensional monolayer MoS2 have been systematically investigated by using density functional calculations with van der Waals correction. The adatoms cover alkali metals, alkaline earth metals, main group metal, 3d-transition metals, coinage metal and nonmetal atoms. Depending on the adatom type, metallic, semimetallic or semiconducting behavior can be found in direct bandgap monolayer MoS2. Additionally, local or long-range magnetic moments of two-dimensional MoS2 sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS2 monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application.

  13. Dilute Magnetic Semiconductor and Half-Metal Behaviors in 3 d Transition-Metal Doped Black and Blue Phosphorenes: A First-Principles Study

    Yu, Weiyang; Zhu, Zhili; Niu, Chun-Yao; Li, Chong; Cho, Jun-Hyung; Jia, Yu

    2016-02-01

    We present first-principles density-functional calculations for the structural, electronic, and magnetic properties of substitutional 3 d transition metal (TM) impurities in two-dimensional black and blue phosphorenes. We find that the magnetic properties of such substitutional impurities can be understood in terms of a simple model based on the Hund's rule. The TM-doped black phosphorenes with Ti, V, Cr, Mn, Fe, and Ni impurities show dilute magnetic semiconductor (DMS) properties while those with Sc and Co impurities show nonmagnetic properties. On the other hand, the TM-doped blue phosphorenes with V, Cr, Mn, and Fe impurities show DMS properties, with Ni impurity showing half-metal properties, whereas Sc- and Co-doped systems show nonmagnetic properties. We identify two different regimes depending on the occupation of the hybridized electronic states of TM and phosphorous atoms: (i) bonding states are completely empty or filled for Sc- and Co-doped black and blue phosphorenes, leading to nonmagnetic; (ii) non-bonding d states are partially occupied for Ti-, V-, Cr-, Mn-, Fe- and Ni-doped black and blue phosphorenes, giving rise to large and localized spin moments. These results provide a new route for the potential applications of dilute magnetic semiconductor and half-metal in spintronic devices by employing black and blue phosphorenes. PACS numbers: 73.22.-f, 75.50.Pp, 75.75. + a

  14. Dilute Magnetic Semiconductor and Half-Metal Behaviors in 3d Transition-Metal Doped Black and Blue Phosphorenes: A First-Principles Study.

    Yu, Weiyang; Zhu, Zhili; Niu, Chun-Yao; Li, Chong; Cho, Jun-Hyung; Jia, Yu

    2016-12-01

    We present first-principles density-functional calculations for the structural, electronic, and magnetic properties of substitutional 3d transition metal (TM) impurities in two-dimensional black and blue phosphorenes. We find that the magnetic properties of such substitutional impurities can be understood in terms of a simple model based on the Hund's rule. The TM-doped black phosphorenes with Ti, V, Cr, Mn, Fe, and Ni impurities show dilute magnetic semiconductor (DMS) properties while those with Sc and Co impurities show nonmagnetic properties. On the other hand, the TM-doped blue phosphorenes with V, Cr, Mn, and Fe impurities show DMS properties, with Ni impurity showing half-metal properties, whereas Sc- and Co-doped systems show nonmagnetic properties. We identify two different regimes depending on the occupation of the hybridized electronic states of TM and phosphorous atoms: (i) bonding states are completely empty or filled for Sc- and Co-doped black and blue phosphorenes, leading to nonmagnetic; (ii) non-bonding d states are partially occupied for Ti-, V-, Cr-, Mn-, Fe- and Ni-doped black and blue phosphorenes, giving rise to large and localized spin moments. These results provide a new route for the potential applications of dilute magnetic semiconductor and half-metal in spintronic devices by employing black and blue phosphorenes. PACS numbers: 73.22.-f, 75.50.Pp, 75.75. + a. PMID:26858159

  15. First-Principles Study of Magnetic Properties of 3dTransition Metals Doped in ZnO Nanowires

    Duan Yifeng

    2009-01-01

    Full Text Available Abstract The defect formation energies of transition metals (Cr, Fe, and Ni doped in the pseudo-H passivated ZnO nanowires and bulk are systematically investigated using first-principles methods. The general chemical trends of the nanowires are similar to those of the bulk. We also show that the formation energy increases as the diameter of the nanowire decreases, indicating that the doping of magnetic ions in the ZnO nanowire becomes more difficult with decreasing diameter. We also systematically calculate the ferromagnetic properties of transition metals doped in the ZnO nanowire and bulk, and find that Cr ions of the nanowire favor ferromagnetic state, which is consistent with the experimental results. We also find that the ferromagnetic coupling state of Cr is more stable in the nanowire than in the bulk, which may lead to a higherT cuseful for the nano-materials design of spintronics.

  16. Nitrogen oxidative activation in the radiolysis process of dioxide hydrocarbon composition, oxygen-nitrogen over 3-D transition metals

    Full text: The radiochemical process of nitrogen fixation in carbon dioxide, oxygen-nitrogen composition in 3-d metal (iron, nickel) was studied. Bifunctional character of surface's role in the generation of radiolysis products was postulated: a) Chemisorption's of molecular ions (N2+, CO2+, O2+ ) on the surface of metal and their dissociative neutralization. b) Coordination of nitrogen and carbon oxide being generated in nitrosyl and carbonyl-nitrosyl complex of iron and nickel. Total yield of the products is over the rang 6,4†7,5, to explain radiolysis' what contribution of only neutral products is impossible. Evidently in the generation of final products, defined contribution brings in molecular ions N2+ (N+) and CO2+ . Interaction character of these ions with nickel proposes the formation of the relation between unpaired electrons N2+ and CO2+ with unfilled d-sub level of this metals with the nickel nitride generation [Ni-N=N+] and binding energy in ion diazotate decreases to twice. The yield of nitrogen dioxide on radiolysis of the air gave GNO2 =0,8±0,2 molecule/100eV which is proper to the date in the literature. Kinetic curve appears rapidly in the saturation. Air radiolysis over iron gave the following results: GNO2 = 2,75 ± 0,25, GN2O= 9,0 ± 1,0 molecule/100eV. Thus total yield of radiolysis products is Σ G = 10,5 ± 12,0 molecule/100eV

  17. Nitrogen oxidative activation in the radiolysis process of dioxide hydrocarbon composition, oxygen-nitrogen over 3-d transition metals

    The radiochemical process of nitrogen fixation in carbon dioxide, oxygen-nitrogen composition in 3-d metal (iron, nickel) was studied. Bifunctional character of surface's role in the generation of radiolysis products was postulated: a) Chemisorption's of molecular ions (N2+, CO2+, O2+ ) on the surface of metal and their dissociative neutralization. b) Coordination of nitrogen and carbon oxide being generated in nitrosyl and carbonyl-nitrosyl complex of iron and nickel. Total yield of the products is over the rang 6,4†7,5, to explain radiolysis' what contribution of only neutral products is impossible. Evidently in the generation of final products, defined contribution brings in molecular ions N2+ (N+) and CO2+ . Interaction character of these ions with nickel proposes the formation of the relation between unpaired electrons N2+ and CO2+ with unfilled d-sub level of this metals with the nickel nitride generation [Ni-N=N+] and binding energy in ion diazotate decreases to twice. The yield of nitrogen dioxide on radiolysis of the air gave GNO2 =0,8±0,2 molecule/100eV which is proper to the date in the literature. Kinetic curve appears rapidly in the saturation. Air radiolysis over iron gave the following results: GNO2 = 2,75 ± 0,25, GN2O= 9,0 ± 1,0 molecule/100eV. Thus total yield of radiolysis products is Σ G = 10,5 ± 12,0 molecule/100eV. (author)

  18. Drawing the geometry of 3d transition metal-boron pairs in silicon from electron emission channeling experiments

    Silva, D. J.; Wahl, U.; Correia, J. G.; Augustyns, V.; Lima, T. A. L.; Costa, A.; Bosne, E.; da Silva, M. R.; Araújo, J. P.; Pereira, L. M. C.

    2016-03-01

    Although the formation of transition metal-boron pairs is currently well established in silicon processing, the geometry of these complexes is still not completely understood. We investigated the lattice location of the transition metals manganese, iron, cobalt and nickel in n- and p+ -type silicon by means of electron emission channeling. For manganese, iron and cobalt, we observed an increase of sites near the ideal tetrahedral interstitial position by changing the doping from n- to p+ -type Si. Such increase was not observed for Ni. We ascribe this increase to the formation of pairs with boron, driven by Coulomb interactions, since the majority of iron, manganese and cobalt is positively charged in p+ -type silicon while Ni is neutral. We propose that breathing mode relaxation around the boron ion within the pair causes the observed displacement from the ideal tetrahedral interstitial site. We discuss the application of the emission channeling technique in this system and, in particular, how it provides insight on the geometry of such pairs.

  19. 4f-3d interaction and magnetic anisotropy in ThMn12-type rare-earth transition-metal compounds

    Rare-earth (R) transition-metal (T) compounds of the R(T,M)12-type with R=Y or one of the heavy-rare-earth elements, T=Fe or Co and M=Ti, V, Mo or Si, have been studied at 4.2 K in the Amsterdam High-Field Installation in magnetic fields up to 38 T and at temperatures between 4.2 and 1000 K in other magnetometers. The 4f-3d interaction is derived from magnetization measurements on single-crystalline particles that are free to rotate in the applied fields. The stabilizing element M is shown to have a pronounced influence on the 4f-3d interaction strength in these compounds. The large variation in Curie temperatures of the Y compounds and the different types of magnetic anisotropy found in the Y compounds demonstrate that the element M plays an important role in establishing these properties as well. (orig.)

  20. X-Ray Emission Spectra and Electronic Structures of Red Phosphorus, 3d Transition-Metal Phosphides and III V Compounds

    Sugiura, Chikara

    1995-07-01

    The P Kβ emission spectra in fluorescence from red amorphous phosphorus, 3d transition-metal phosphides TiP, CrP, FeP, Fe2P, Fe3P, CoP, Co2P, Ni5P4, Ni2P, Ni3P, Cu3P, ZnP2 (black) and Zn3P2, and the semiconducting phosphides of the III-V type, BP, AlP, GaP and InP are measured with a high-resolution two-crystal vacuum spectrometer equipped with Ge(111) crystals. The influence of the metal atoms appears distinctly on the P Kβ fluorescence emission spectra. The measured spectra are compared with available X-ray emission and XPS valence-band spectra and theoretical energy-band calculations on a common energy scale. It is shown that considerable p-d, s mixing occurs in the valence bands of the 3d transition-metal phosphides and the P 3p states mix fairly with the P 3s states in the valence bands of red phosphorus, Gap and InP

  1. Controlling the carrier lifetime of nearly threading-dislocation-free ZnO homoepitaxial films by 3d transition-metal doping

    Chichibu, S. F.; Kojima, K.; Yamazaki, Y.; Furusawa, K.; Uedono, A.

    2016-01-01

    Carrier lifetime in nearly threading-dislocation-free ZnO homoepitaxial films was controlled by doping 3d transition-metals (TMs), Ni and Mn. The photoluminescence lifetime of the near-band-edge emission (τPL) was decreased linearly by increasing TM concentration, indicating that such TMs are predominant nonradiative recombination centers (NRCs). From this relationship, exciton capture-cross-section ( σex ) of 2.4 × 10-15 cm2 is obtained. Because σex of native-NRCs (Zn-vacancy complexes) is likely larger than this value, the linear dependence of the internal quantum efficiency on τPL observed in our TM-doped ZnO and unintentionally doped ZnO in literatures indicates that the concentrations of native-NRCs in the latter are "lower than" 1016-1017 cm-3.

  2. Laser printing of 3D metallic interconnects

    Beniam, Iyoel; Mathews, Scott A.; Charipar, Nicholas A.; Auyeung, Raymond C. Y.; Piqué, Alberto

    2016-04-01

    The use of laser-induced forward transfer (LIFT) techniques for the printing of functional materials has been demonstrated for numerous applications. The printing gives rise to patterns, which can be used to fabricate planar interconnects. More recently, various groups have demonstrated electrical interconnects from laser-printed 3D structures. The laser printing of these interconnects takes place through aggregation of voxels of either molten metal or of pastes containing dispersed metallic particles. However, the generated 3D structures do not posses the same metallic conductivity as a bulk metal interconnect of the same cross-section and length as those formed by wire bonding or tab welding. An alternative is to laser transfer entire 3D structures using a technique known as lase-and-place. Lase-and-place is a LIFT process whereby whole components and parts can be transferred from a donor substrate onto a desired location with one single laser pulse. This paper will describe the use of LIFT to laser print freestanding, solid metal foils or beams precisely over the contact pads of discrete devices to interconnect them into fully functional circuits. Furthermore, this paper will also show how the same laser can be used to bend or fold the bulk metal foils prior to transfer, thus forming compliant 3D structures able to provide strain relief for the circuits under flexing or during motion from thermal mismatch. These interconnect "ridges" can span wide gaps (on the order of a millimeter) and accommodate height differences of tens of microns between adjacent devices. Examples of these laser printed 3D metallic bridges and their role in the development of next generation electronics by additive manufacturing will be presented.

  3. Accurate electronic and chemical properties of 3d transition metal oxides using a calculated linear response U and a DFT + U(V) method

    Xu, Zhongnan; Kitchin, John R., E-mail: jkitchin@andrew.cmu.edu [Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Ave., Pittsburgh, Pennsylvania 15213 (United States); Joshi, Yogesh V.; Raman, Sumathy [Exxon-Mobil Research and Engineering, 1545 Route 22 E St. 1, Annandale, New Jersey 08801 (United States)

    2015-04-14

    We validate the usage of the calculated, linear response Hubbard U for evaluating accurate electronic and chemical properties of bulk 3d transition metal oxides. We find calculated values of U lead to improved band gaps. For the evaluation of accurate reaction energies, we first identify and eliminate contributions to the reaction energies of bulk systems due only to changes in U and construct a thermodynamic cycle that references the total energies of unique U systems to a common point using a DFT + U(V ) method, which we recast from a recently introduced DFT + U(R) method for molecular systems. We then introduce a semi-empirical method based on weighted DFT/DFT + U cohesive energies to calculate bulk oxidation energies of transition metal oxides using density functional theory and linear response calculated U values. We validate this method by calculating 14 reactions energies involving V, Cr, Mn, Fe, and Co oxides. We find up to an 85% reduction of the mean average error (MAE) compared to energies calculated with the Perdew-Burke-Ernzerhof functional. When our method is compared with DFT + U with empirically derived U values and the HSE06 hybrid functional, we find up to 65% and 39% reductions in the MAE, respectively.

  4. Accurate electronic and chemical properties of 3d transition metal oxides using a calculated linear response U and a DFT + U(V) method

    We validate the usage of the calculated, linear response Hubbard U for evaluating accurate electronic and chemical properties of bulk 3d transition metal oxides. We find calculated values of U lead to improved band gaps. For the evaluation of accurate reaction energies, we first identify and eliminate contributions to the reaction energies of bulk systems due only to changes in U and construct a thermodynamic cycle that references the total energies of unique U systems to a common point using a DFT + U(V ) method, which we recast from a recently introduced DFT + U(R) method for molecular systems. We then introduce a semi-empirical method based on weighted DFT/DFT + U cohesive energies to calculate bulk oxidation energies of transition metal oxides using density functional theory and linear response calculated U values. We validate this method by calculating 14 reactions energies involving V, Cr, Mn, Fe, and Co oxides. We find up to an 85% reduction of the mean average error (MAE) compared to energies calculated with the Perdew-Burke-Ernzerhof functional. When our method is compared with DFT + U with empirically derived U values and the HSE06 hybrid functional, we find up to 65% and 39% reductions in the MAE, respectively

  5. Five novel transition metal coordination polymers with 2D/3D framework structure based on flexible H2tzda and ancillary ligand bpe

    Five new transition metal coordination polymers based on H2tzda and co-ligand bpe, {[M(tzda)(bpe)].H2O}n [M=Zn(1), Cd(2), Mn(3), Co(4)] and [Ni2(tzda)2(bpe)2(H2O)]n (5) [H2tzda=(1,3,4-thiadiazole-2,5-diyldithio)diacetic acid, bpe=1,2-bis(4-pyridyl)ethane], have been hydrothermally synthesized and structurally characterized. Compounds 1-4 feature a 2D-layered architecture generated from [M(tzda)]n moiety with double-chain structure cross-linking bpe spacers. However, the conformations bpe adopts in 3 and 4 are different from those in 1 and 2 due to the rotation of C-C single bond in bpe. Polymer 5 exhibits an interesting 3D porous framework with 2-fold interpenetration, in which intriguing 1D double helix chains are observed. The photoluminescence properties of 1 and 2 in the solid-state at room temperature are investigated. In addition, variable-temperature magnetic data show weak antiferromagnetic behavior in 3-5. - Graphical abstract: Five new transition metal coordination polymers based on flexible H2tzda and bpe have been hydrothermally synthesized and characterized by X-ray diffraction, luminescent emission spectra and low-temperature magnetic measurements, respectively.

  6. First-principles modeling of 3d-transition-metal-atom adsorption on silicene: a linear-response DFT  +  U approach

    By employing DFT  +  U calculations with the linear response method, we investigate the interactions between various 3d transition-metal atoms (Cr, Mn, Fe, Co) and silicene. In the cases of two-dimensional (2D) FeSi2 and CoSi2, the metal atoms tend to penetrate into the silicene layer. While CoSi2 is non-magnetic, FeSi2 exhibits a total magnetic moment of 2.21 μ B/cell. Upon the examination of 2D MSi6, a trend in anti-ferromagnetic (AFM) favorability in the z-direction is observed according to our DFT  +  U calculations. In the ferromagnetic (FM) states (less stable), each primary unit cell of CrSi6, MnSi6, and FeSi6 possesses different levels of total magnetization (4.01, 5.18, and 2.00 μ B/cell, respectively). The absolute magnetization given by AFM MSi6 structures varies in the range of 5.33–5.84 μ B/cell. A direct band gap in AFM MnSi6 (0.2 eV) is predicted, while the metastable FM FeSi6 structure has a wider band gap (0.85 eV). Interestingly, there are superexchange interactions between metal atoms in the MSi6 systems, which result in the AFM alignments. (paper)

  7. DFT+U study of electrical levels and migration barriers of early 3 d and 4 d transition metals in silicon

    Marinopoulos, A. G.; Santos, P.; Coutinho, J.

    2015-08-01

    Owing to their strong interaction with carriers, early 3 d -row (Ti, V, and Cr) and 4 d -row (Zr, Nb, and Mo) transition metals (TMs) are undesired contaminants in solar- and electronic-grade Si. The increasing stringent control of contamination levels is urging an accurate picture of their electronic structure. In the present work, the electrical levels and migration energies of these TMs are determined by means of standard density-functional theory (DFT) and a rotationally invariant formulation of DFT+U . The latter approach improves on the treatment of electronic correlations at the TM sites and relies on on-site Hubbard Coulomb and Hund's exchange parameters U and J , respectively. These are calculated self-consistently from linear-response theory without fitting to experimental data. The effect of correlation was found more pronounced for Ti and V, with a strong impact on the location of their electrical levels. In most cases, the agreement with the experimental data is satisfactory allowing the identification of the type and character of the levels. For Cr and Mo in particular, the results resolve longstanding controversies concerning the type and position of the levels. The obtained migration barriers display moderate charge-state and correlation dependency. High barriers were found for all metals studied, with the exception of Cr, confirming them as slow diffusers in silicon among the whole TM family.

  8. Structure and magnetic properties of the 3d transition-metal mono-borides TM–B (TM=Mn, Fe, Co) under pressures

    In this paper, spin-polarization and pressure effects on the structural and electronic properties of the 3d transition-metal mono-borides TM–B (TM=Mn, Fe, Co) have been studied by using both local spin-density approximation (LSDA) and generalized gradient approximation (GGA) within the framework of density-functional theory (DFT). At equilibrium, spin-polarization calculations show that MnB and FeB compounds carry magnetic moment. The non-spin-polarization results show that the non-magnetic state is unstable for MnB and FeB compounds, but a stable non-magnetic phase for CoB compound, which is discussed in the framework of the well-known Stoner criterion. The calculated lattice parameters, bulk moduli, their first-pressure derivatives and magnetic moments agree well with experimental and other theoretical results. Significant differences in volume and in bulk modulus were found between the magnetic and non-magnetic case reached 4%, 22%, respectively. The effect of pressure on the crystal structure reflects in a compression of the unit cell volume with a decreasing in the magnetic moment. The density of states of MnB and FeB ferromagnetic compounds are significantly modified under high pressures. The exchange energy decreases with increasing pressure, at approximately V/V0=0.6, the exchange energy becomes absent in ferromagnetic compounds causes mirror in upper and lowers half panels. Finally, we notice that spin-polarization and pressure play a crucially important role in determining the electronic and structural properties of 3d transition-metal mono-borides. - Highlights: • Spin polarization and pressure effects on TM–B (TM=Mn, Fe, Co) have been investigated. • The non-spin-polarization results show that the non-magnetic state is stable for CoB. • The magnetic states of MnB and FeB are found more stable than their nonmagnetic states. • We report significant differences between the magnetic and non-magnetic cases. • The density of states of MnB and Fe

  9. First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge

    Cabaret, Delphine; Bordage, Amélie; Juhin, Amélie; Arfaoui, M.; Gaudry, Emilie

    2010-01-01

    We first present an extended introduction of the various methods used to extract electronic and structural information from the K pre-edge X-ray absorption spectra of 3d transition metal ions. The K pre-edge structure is then modelled for a selection of 3d transition metal compounds and analyzed using first-principles calculations based on the density functional theory (DFT) in the local density approximation (LDA). The selected compounds under study are presented in an ascending order of ele...

  10. First-principles study of site occupancy of dilute 3d, 4d and 5d transition metal solutes in L10 TiAl

    Using a statistical-mechanical Wagner-Schottky model parametrized by first-principles density-functional (DFT-GGA) calculations on 32-atom supercells, we predict the lattice site occupancy of 3d (Ti-Cu), 4d (Zr-Ag) and 5d (Hf-Au) transition-metal elements in L10 TiAl intermetallic compound as a function of both alloy composition and temperature. The effects of local atomic relaxations, anisotropic lattice distortions, as well as magnetism on point defect energetics are fully taken into account. Our calculations show that, at all alloy compositions and temperatures, Zr and Hf consistently show a preference for the Ti sublattice, while Co, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt and Au consistently show a preference for the Al sublattice. In contrast, the site preference of V, Cr, Mn, Fe, Ni, Cu, Nb, Mo, Tc, Ta and W strongly depend on both alloy stoichiometry and temperature. Our calculated results compare favorably with the existing theoretical and experimental studies in the literature

  11. 3D modeling of metallic grain growth

    George, D.; Carlson, N.; Gammel, J.T.; Kuprat, A.

    1999-06-01

    This paper will describe simulating metallic grain growth using the Gradient Weighted Moving Finite Elements code, GRAIN3D. The authors also describe the set of mesh topology change operations developed to respond to changes in the physical topology such as the collapse of grains and to maintain uniform calculational mesh quality. Validation of the method is demonstrated by comparison to analytic calculations. The authors present results of multigrain simulations where grain boundaries evolve by mean curvature motion and include results which incorporate grain boundary orientation dependence.

  12. Structural, mechanical and electronic properties of 3d transition metal nitrides in cubic zincblende, rocksalt and cesium chloride structures: a first-principles investigation

    We report systematic results from ab initio calculations with density functional theory on three cubic structures, zincblende (zb), rocksalt (rs) and cesium chloride (cc), of the ten 3d transition metal nitrides. We computed lattice constants, elastic constants, their derived moduli and ratios that characterize mechanical properties. Experimental measurements exist in the literature of lattice constants for rs-ScN, rs-TiN and rs-VN and of elastic constants for rs-TiN and rs-VN, all of which are in good agreement with our computational results. Similarly, computed Vickers hardness (HV) values for rs-TiN and rs-VN are consistent with earlier experimental results. Several trends were observed in our rich data set of 30 compounds. All nitrides, except for zb-CrN, rs-MnN, rs-FeN, cc-ScN, cc-CrN, cc-NiN and cc-ZnN, were found to be mechanically stable. A clear correlation in the atomic density with the bulk modulus (B) was observed with maximum values of B around FeN, MnN and CrN. The shear modulus, Young’s modulus, HV and indicators of brittleness showed similar trends and all showed maxima for cc-VN. The calculated value of HV for cc-VN was about 30 GPa, while the next highest values were for rs-ScN and rs-TiN, about 24 GPa. A relation (HV∝θD2) between HV and Debye temperature (θD) was investigated and verified for each structure type. A tendency for anti-correlation of the elastic constant C44, which strongly influences stability and hardness, with the number of electronic states around the Fermi energy was observed. (paper)

  13. Identification of the transition arrays 3d74s-3d74p in Br X and 3d64s-3d64p in Br XI

    We report a beam-foil study of multiply ionized bromine in the region 400-1300A, performed with 6 and 8 MeV Br ions from a tandem accelerator. At these energies transitions belonging to Fe-like Br X and Mn-like Br XI are expected to be prominent. We have identified 31 lines as 3d74s-3d74p transitions in Br X, from which 16 levels of the previously unknown 3d74s configuration could be established. We have also added 6 new 3d74p levels to the 99 previously known. For Br XI we have classified 9 lines as 3d64s-3d64p combinations. The line identifications have been corroborated by isoelectronic comparisons and theoretical calculations using the superposition-of-configurations technique. (orig.)

  14. Experimental investigation of off-stoichiometry and 3d transition metal (Mn, Ni, Cu-substitution in single-crystalline FePt thin films

    Takuya Ono

    2016-05-01

    Full Text Available In L10 (fct-FePt thin films, both tuning Fe and Pt concentrations and substitution with third-metal were studied for magnetic characteristic optimization. We investigated single-crystalline FePt-X (X = Mn, Ni, Cu thin films grown epitaxially on MgO(001 substrates at a substrate temperature of 350  °C by changing Fe, Pt, and X contents, and explored the effects of off-stoichiometry and 3d-metal-substitution. The magnetic moment per atom (m of FePt-X films as a function of the effective number of valence electrons (neff in 3d metal sites follows the Slater-Pauling-type trend, by which m decreases by the neff deviation from neff = 8, independently of the X metal and the Pt concentration. The magnetic anisotropy (Ku exhibits neff dependence similar to m. This trend was almost independent of the Pt concentration after compensation using the theoretical prediction on the relation between Ku and Fe/Pt concentrations. Such a trend has been proved for stoichiometric FePt-X films, but it was clarified as robust against off-stoichiometry. The compensated Ku ( K u comp of FePt-Mn and FePt-Cu followed a similar trend to that predicted by the rigid-band model, although the K u comp of the FePt-Mn thin films dropped more rapidly than the rigid band calculation. However, it followed the recent first-principles calculation.

  15. Electric dipole transitions for 3d64s-3d64p in Mn I

    Kabakçı, Selda; Özdemir, Leyla; Usta, Betül Karaçoban

    2015-10-01

    We have calculated the logarithmic weighted oscillator strengths and transition probabilities (or rates) for 3d64s-3d64p electric dipole transitions in neutral manganese (Mn I, Z=25) by using two configuration interaction methods (the multiconfiguration Hartree-Fock (MCHF) method within the framework of Breit-Pauli relativistic corrections developed by Fischer and Cowan's relativistic Hartree-Fock (HFR) method). Results obtained have been compared with other calculations and experiments.

  16. Superconductivity, magnetism and metal-insulator transitions in some ternary and pseudoternary 3d-, 4d- and 5d-metal oxides

    Electron conduction effects have been found to be particularly important in the metallic compounds LiV2O4 and possibly Sr2Ir1-xRuxO4 (x > 0.7), but not in metallic Sr1-xLaxVO3 (x 2IrO4 and ZnV2O4 to be (Mott-Hubbard) insulators. The LiV2O4 spinel compound is especially interesting, because the V ions exhibit rather clear local moment (S = 1/2) behavior even though the compound is a metal

  17. CASPT2 study of inverse sandwich-type dinuclear 3d transition metal complexes of ethylene and dinitrogen molecules: similarities and differences in geometry, electronic structure, and spin multiplicity.

    Nakagaki, Masayuki; Sakaki, Shigeyoshi

    2015-07-01

    The spin multiplicities and coordination structures of inverse sandwich-type complexes (ISTCs) of ethylene and dinitrogen molecules with 3d transition metal elements (Sc to Ni), (μ-C2H4)[M(AIP)]2 and (μ-N2)[M(AIP)]2 (AIPH = (Z)-1-amino-3-iminoprop-1-ene; M = Sc to Ni) were investigated by the CASPT2 method. In both ethylene and dinitrogen ISTCs of the early 3d transition metals (Sc to Cr), sandwiched ethylene and dinitrogen ligands coordinate with two metal atoms in an η(2)-side-on form and their ground states have an open-shell singlet spin multiplicity. The η(1)-end-on coordination structure of dinitrogen ISTCs is considerably less stable than the η(2)-side-on form in these metals. For the late 3d transition metals (Mn to Ni), ethylene and dinitrogen ISTCs exhibit interesting similarities and differences in spin multiplicity and structure as follows: in ethylene ISTCs of Mn to Ni, the ground state has an open-shell singlet spin multiplicity like those of the ISTCs of early transition metals. However, the ethylene ligand is considerably distorted, in which the ethylene carbon atoms have a tetrahedral-like structure similar to sp(3) carbon and each of them coordinates with one metal in a μ-η(1):η(1) structure. These geometrical features are completely different from those of ISTCs of the early transition metals. In dinitrogen ISTCs of Mn to Ni, on the other hand, the ground state has a high spin multiplicity from nonet (Mn) to triplet (Ni). The η(2)-side-on coordination structure of the dinitrogen ligand is as stable as the η(1)-end-on form in the Mn complex but the η(1)-end-on structure is more stable than the η(2)-side-on form in the Fe to Ni complexes. All these interesting similarities and differences between ethylene and dinitrogen ISTCs and between the early and late transition metal elements arise from the occupation of several important molecular orbitals. PMID:26041561

  18. Study of morphology effects on magnetic interactions and band gap variations for 3d late transition metal bi-doped ZnO nanostructures by hybrid DFT calculations

    Datta, Soumendu, E-mail: soumendu@bose.res.in; Baral, Sayan; Mookerjee, Abhijit [Department of Condensed Matter Physics and Material Sciences, S.N. Bose National Centre for Basic Sciences, JD Block, Sector-III, Salt Lake City, Kolkata 700 098 (India); Kaphle, Gopi Chandra [Central Department of Physics, Tribhuvan University, Kathmandu (Nepal)

    2015-08-28

    Using density functional theory (DFT) based electronic structure calculations, the effects of morphology of semiconducting nanostructures on the magnetic interaction between two magnetic dopant atoms as well as a possibility of tuning band gaps have been studied in the case of the bi-doped (ZnO){sub 24} nanostructures with the impurity dopant atoms of the 3d late transition metals—Mn, Fe, Co, Ni, and Cu. To explore the morphology effect, three different structures of the host (ZnO){sub 24} nano-system, having different degrees of spatial confinement, have been considered: a two dimensional nanosheet, a one dimensional nanotube, and a finite cage-shaped nanocluster. The present study employs hybrid density functional theory to accurately describe the electronic structure of all the systems. It is shown here that the magnetic coupling between the two dopant atoms remains mostly anti-ferromagnetic in the course of changing the morphology from the sheet geometry to the cage-shaped geometry of the host systems, except for the case of energetically most stable bi-Mn doping, which shows a transition from ferromagnetic to anti-ferromagnetic coupling with decreasing aspect ratio of the host system. The effect of the shape change, however, has a significant effect on the overall band gap variations of both the pristine as well as all the bi-doped systems, irrespective of the nature of the dopant atoms and provides a means for easy tunability of their optoelectronic properties.

  19. Study of morphology effects on magnetic interactions and band gap variations for 3d late transition metal bi-doped ZnO nanostructures by hybrid DFT calculations

    Using density functional theory (DFT) based electronic structure calculations, the effects of morphology of semiconducting nanostructures on the magnetic interaction between two magnetic dopant atoms as well as a possibility of tuning band gaps have been studied in the case of the bi-doped (ZnO)24 nanostructures with the impurity dopant atoms of the 3d late transition metals—Mn, Fe, Co, Ni, and Cu. To explore the morphology effect, three different structures of the host (ZnO)24 nano-system, having different degrees of spatial confinement, have been considered: a two dimensional nanosheet, a one dimensional nanotube, and a finite cage-shaped nanocluster. The present study employs hybrid density functional theory to accurately describe the electronic structure of all the systems. It is shown here that the magnetic coupling between the two dopant atoms remains mostly anti-ferromagnetic in the course of changing the morphology from the sheet geometry to the cage-shaped geometry of the host systems, except for the case of energetically most stable bi-Mn doping, which shows a transition from ferromagnetic to anti-ferromagnetic coupling with decreasing aspect ratio of the host system. The effect of the shape change, however, has a significant effect on the overall band gap variations of both the pristine as well as all the bi-doped systems, irrespective of the nature of the dopant atoms and provides a means for easy tunability of their optoelectronic properties

  20. Understanding ferromagnetism and optical absorption in 3d transition metal-doped cubic ZrO2 with the modified Becke-Johnson exchange-correlation functional

    The electronic structure, magnetic, and optical properties in cubic crystalline phase of Zr1−xTMxO2 (TM = V, Mn, Fe, and Co) at x = 6.25% are studied using density functional theory with the Generalized Gradient Approximation and the modified Becke-Johnson of the exchange-correlation energy and potential. In our calculations, the zirconia is a p-type semiconductor and has a large band gap. We evaluated the possibility of long-range magnetic order for transition metal ions substituting Zr. Our results show that ferromagnetism is the ground state in V, Mn, and Fe-doped ZrO2 and have a high value of energy in Mn-doped ZrO2. However, in Co-doped ZrO2, antiferromagnetic ordering is more stable than the ferromagnetic one. The exchange interaction mechanism has been discussed to explain the responsible of this stability. Moreover, it has been found that the V, Mn, and Fe transition metals provide half-metallic properties considered to be the leading cause, responsible for ferromagnetism. Furthermore, the optical absorption spectra in the TM -doped cubic ZrO2 are investigated

  1. First-principles study on the magnetism and electronic structure in 3d transition metal (X=Sc, V, Cr, Mn, Fe, Ni, Cu) doped CoO

    Liu, R. X.; Wang, X. C.; Chen, G. F.; Yang, B. H.

    2016-03-01

    We have studied the electronic structure and magnetism of the single transitional metal element X=Sc, V, Cr, Mn, Fe, Ni, Cu-doped CoO systems by first-principles calculations. At X=Sc, Cr, Cu, the binding energy of the doped systems is lower than pure CoO, suggesting that these systems are energetically stable. In the Sc, V, Cr, Mn, Fe, Ni, Cu-doped 2×2×2 CoO supercells, the total magnetic moments are 3.03, 5.64, 6.80, 7.70, 6.93, 2.30 and 1.96 μB, respectively. At X=Cr and Fe, the doped CoO systems are half-metallic with a high spin polarization. The large magnetic moment and high spin polarization in the Cr and Fe-doped CoO are important for the design of the spintronic devices.

  2. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen.

    Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Pickup, David M; Liu, Yi-Sheng; Edström, Kristina; Guo, Jinghua; Chadwick, Alan V; Duda, Laurent C; Bruce, Peter G

    2016-07-01

    During the charging and discharging of lithium-ion-battery cathodes through the de- and reintercalation of lithium ions, electroneutrality is maintained by transition-metal redox chemistry, which limits the charge that can be stored. However, for some transition-metal oxides this limit can be broken and oxygen loss and/or oxygen redox reactions have been proposed to explain the phenomenon. We present operando mass spectrometry of (18)O-labelled Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2, which demonstrates that oxygen is extracted from the lattice on charging a Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2 cathode, although we detected no O2 evolution. Combined soft X-ray absorption spectroscopy, resonant inelastic X-ray scattering spectroscopy, X-ray absorption near edge structure spectroscopy and Raman spectroscopy demonstrates that, in addition to oxygen loss, Li(+) removal is charge compensated by the formation of localized electron holes on O atoms coordinated by Mn(4+) and Li(+) ions, which serve to promote the localization, and not the formation, of true O2(2-) (peroxide, O-O ~1.45 Å) species. The quantity of charge compensated by oxygen removal and by the formation of electron holes on the O atoms is estimated, and for the case described here the latter dominates. PMID:27325095

  3. Magnetic Circular Dichroism in Resonant Raman Scattering in the Perpendicular Geometry at the L edge of 3d Transition Metal Systems

    We measured circular dichroism in resonant x-ray scattering 3dn→2p53dn+1→3s13dn+1 with incidence perpendicular to the magnetization where the absorption dichroism vanishes. The advantages of photon scattering over other techniques make it possible to study a wide range of materials. The Ni L3 dichroism in NiFe2O 4 is (28±5)% in agreement with a localized model. In the metal Co the dichroism is reduced to (10.4±1)% (L3) and (6.8±1.5)% (7.5 eV above L3 ), indicating a large sensitivity to the nature of the valence states despite the fact that this spectroscopy is based on inner shell transitions. copyright 1999 The American Physical Society

  4. 3D printing of liquid metals as fugitive inks for fabrication of 3D microfluidic channels.

    Parekh, Dishit P; Ladd, Collin; Panich, Lazar; Moussa, Khalil; Dickey, Michael D

    2016-05-21

    This paper demonstrates a simple method to fabricate 3D microchannels and microvasculature at room temperature by direct-writing liquid metal as a sacrificial template. The formation of a surface oxide skin on the low-viscosity liquid metal stabilizes the shape of the printed metal for planar and out-of-plane structures. The printed structures can be embedded in a variety of soft (e.g. elastomeric) and rigid (e.g. thermoset) polymers. Both acid and electrochemical reduction are capable of removing the oxide skin that forms on the metal, which destabilizes the ink so that it withdraws from the encapsulating material due to capillary forces, resulting in nearly full recovery of the fugitive ink at room temperature. Whereas conventional fabrication procedures typically confine microchannels to 2D planes, the geometry of the printed microchannels can be varied from a simple 2D network to complex 3D architectures without using lithography. The method produces robust monolithic structures without the need for any bonding or assembling techniques that often limit the materials of construction of conventional microchannels. Removing select portions of the metal leaves behind 3D metal features that can be used as antennas, interconnects, or electrodes for interfacing with lab-on-a-chip devices. This paper describes the capabilities and limitations of this simple process. PMID:27025537

  5. Inkjet printing of 3D metallic silver complex microstructures

    Wits, Wessel W.; Sridhar, Ashok

    2010-01-01

    To broaden the scope of inkjet printing, this paper focuses on printing of an organic silver complex ink on glass substrates towards the fabrication of metallic 3D microstructures. The droplet formation sequence of the inkjet printer is optimised to print continuous layers of metal. A brief discussion on orientation trials, aimed at optimising the print parameters, is followed by two different methodologies of printing 3D microstructures: wet-in-wet and wet-in-dry. The surface topography of t...

  6. Inkjet printing of 3D metallic silver complex microstructures

    Wits, Wessel W.; Sridhar, Ashok

    2010-01-01

    To broaden the scope of inkjet printing, this paper focuses on printing of an organic silver complex ink on glass substrates towards the fabrication of metallic 3D microstructures. The droplet formation sequence of the inkjet printer is optimised to print continuous layers of metal. A brief discussi

  7. Direct numerical simulation of 3D transitional fluid flows

    Full text: For the numerical simulation of the 2D-3D transitional homogeneous and stratified incompressible viscous fluid flows, characterizing by the full Navier-Stokes equations, the splitting on physical factors method is used. The explicit hybrid finite difference scheme of the method has the following behaviors: the second order of accuracy in space, minimum scheme viscosity and dispersion, workable in wide range of Reynolds and Froude numbers and monotonicity. The efficiency of the developed numerical method and the advanced performance of the supercomputers allowed simulating 2D-3D transitional uncompressible viscous fluid flows around the bluff bodies in particular around a cylinder. By the numerical simulation of the fluid flows around 3D circular cylinder it was found that the transition to 3D regime arrives at Re>200. At 200< Re<300 the mode A with wavelength 3.5 d<λ<4.0 d (where d is the diameter of the cylinder) for 3D structures along the axis of a cylinder was observed. At 300< Re<400 the mode B with wavelength 0.8 d<λ<0.9 d was observed. At Re=300 the both modes A and B were observed simultaneously. The regime with large dislocations previously discovered experimentally was first obtained numerically at 210< Re<260. This regime is characterized by flow phase dislocation along the axis of the cylinder and as the effect by the amplitude fall of the lift force coefficient and the variations in the drag coefficient. There was simulated numerically the initiation of the attached internal waves behind the circular cylinder and upstream disturbance area at low Froude and moderate Reynolds numbers. (author)

  8. Structure and magnetism of 3d and 4d transition-metal alloys TT' (T = Mn, Fe and T' = Rh, Pd) with CuAu-I type ordered structure

    Yamada, H. [Faculty of Science, Shinshu University, Asahi 3-1-1, Matsumoto 390-8621 (Japan)]. E-mail: hyamada@gipac.shinshu-u.ac.jp; Shimizu, H. [Faculty of Science, Shinshu University, Asahi 3-1-1, Matsumoto 390-8621 (Japan); Yamamoto, K. [Faculty of Science, Shinshu University, Asahi 3-1-1, Matsumoto 390-8621 (Japan); Uebayashi, K. [Faculty of Science, Shinshu University, Asahi 3-1-1, Matsumoto 390-8621 (Japan)

    2006-05-18

    First-principle band calculations of 3d and 4d transition-metal alloys FeRh, FePd, MnRh and MnPd with CuAu-I type ordered structure are carried out by a linear muffin-tin orbital method within an atomic sphere approximation, where a generalized gradient correction for exchange-correlation potential is taken into account. Total energies for paramagnetic, ferromagnetic and three kinds of antiferromagnetic states are estimated as a function of lattice constants a and c. Observed lattice constants and spin structures of these alloys are well described by the present calculations. It is shown that the paramagnetic (non-magnetic) state without local magnetic moments is not stable in CsCl-type structure for these alloys.

  9. Calculated surface-energy anomaly in the 3d metals

    Aldén, M.; Skriver, Hans Lomholt; Mirbt, S.;

    1992-01-01

    Local-spin-density theory and a Green’s-function technique based on the linear muffin-tin orbitals method have been used to calculate the surface energy of the 3d metals. The theory explains the variation of the values derived from measurements of the surface tension of liquid metals including th...... pronounced anomaly occurring between vanadium and nickel in terms of a decrease in the d contribution caused by spin polarization....

  10. Toward Rational Design of 3d Transition Metal Catalysts for CO2 Hydrogenation Based on Insights into Hydricity-Controlled Rate-Determining Steps.

    Mondal, Bhaskar; Neese, Frank; Ye, Shengfa

    2016-06-01

    Carbon dioxide functionalization attracts much interest due to the current environmental and energy challenges. Our earlier work (Mondal, B.; Neese, F.; Ye, S. Inorg. Chem. 2015, 54, 7192-7198) demonstrated that CO2 hydrogenation mediated by base metal catalysts [M(H)(η(2)-H2)(PP3(Ph))](n+) (M = Co(III) and Fe(II), n = 1, 2; PP3(Ph) = tris(2-(diphenylphosphino)phenyl)phosphine) features discrete rate-determining steps (RDSs). Specifically, the reaction with [Co(III)(H)(η(2)-H2)(PP3(Ph))](2+) passes through a hydride-transfer RDS, whereas the conversion with [Fe(II)(H)(η(2)-H2)(PP3(Ph))](+) traverses a H2-splitting RDS. More importantly, we found that the nature and barrier of the RDS likely correlate with the hydride affinity or hydricity of the dihydride intermediate [M(H)2(PP3(Ph))]((n-1)+) generated by H2-splitting. In the present contribution, following this notion we design a series of potential Fe(II) and Co(III) catalysts, for which the respective dihydride species possess differential hydricities, and computationally investigated their reactivity toward CO2 hydrogenation. Our results reveal that lowering the hydrictiy of [Co(III)(H)2(PP3(Ph))](+) by introducing anionic anchors in PP3(Ph) dramatically decreases the hydride-transfer RDS barrier, as shown for the enhanced reactivity of [Co(H)(η(2)-H2)(CP3(Ph))](+) and [Co(H)(η(2)-H2)(SiP3(Ph))](+) (CP3(Ph) = tris(2-(diphenylphosphino)phenyl)methyl, SiP3(Ph) = tris(2-(diphenylphosphino)phenyl)silyl), while the same ligand modification increases the H2-splitting RDS barriers for [Fe(H)(η(2)-H2)(CP3(Ph))] and [Fe(H)(η(2)-H2)(SiP3(Ph))] relative to that for [Fe(H)(η(2)-H2)(PP3(Ph))](+). Conversely, upon increasing the hydricity of [Fe(II)(H)2(PP3(Ph))] by adding an electron-withdrawing group to PP3(Ph), the transformation with [Fe(H)(η(2)-H2)(PP3(PhNO2))](+) (PP3(PhNO2) = tris(2-(diphenylphosphino)-4-nitrophenyl)phosphine) is predicted to encounter a lower barrier for H2-splitting and a higher barrier for

  11. Mechanochemical Synthesis of 3d Transition-Metal-1,2,4-Triazole Complexes as Precursors for Microwave-Assisted and Thermal Conversion to Coordination Polymers with a High Influence on the Dielectric Properties.

    Brede, Franziska A; Heine, Johanna; Sextl, Gerhard; Müller-Buschbaum, Klaus

    2016-02-01

    The complexes [MCl2 (TzH)4 ] (M=Mn (1), Fe (2); TzH=1,2,4-1H-triazole) and [ZnCl2 (TzH)2 ] (3) have been obtained by mechanochemical reactions of the corresponding divalent metal chloride and 1,2,4-1H-triazole. They were successfully used as precursors for the formation of coordination polymers either by a microwave-assisted reaction or by thermal conversion. For manganese, the conversion directly yielded 1∞ [MnCl2 TzH] (4), whereas for the iron-containing precursor, 1∞ [FeCl2 TzH] (6), was formed via the intermediate coordination polymer 1∞ [FeCl(TzH)2 ]Cl (5). For cobalt, the isotypic polymer 1∞ [CoCl(TzH)2 ]Cl (7) was obtained, but exclusively by a microwave-induced reaction directly from CoCl2 . The crystal structures were resolved from single crystals and powders. The dielectric properties were determined and revealed large differences in permittivity between the precursor complexes and the rigid chain-like coordination polymers. Whereas the monomeric complexes exhibit very different dielectric behaviour, depending on the transition metal, from "low-k" to "high-k" with the permittivity ranging from 4.3 to >100 for frequencies of up to 1000 Hz, the coordination polymers and complexes with strong intermolecular interactions are all close to "low-k" materials with very low dielectric constants up to 50 °C. Therefore, the conversion procedures can be used to deliberately influence the dielectric properties from complex to polymer and for different 3d transition-metal ions. PMID:26797710

  12. Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit

  13. Electronic structure of the 3d metals. An investigation by L-shell-photoionisation

    Richter, T.S.

    2007-12-03

    The 3d transition metal elements from Sc to Cu have been investigated by both photo electron emission and photo absorption. Experimental spectra in the 2p energy range are discussed based on atomic multiplet models and Hartree- Fock calculations. The samples have been evaporated from an electron bombardment crucible and excited/ionized by monochromatized synchrotron radiation. Fundamental effects and the main interactions which govern the electronic structure of the 3d metal atoms are covered. Common spectral features and trends in the series are discussed as well as the importance of many body electron correlation effects. (orig.)

  14. Semiconducting transition metal oxides

    Open shell transition metal oxides are usually described as Mott or charge transfer insulators, which are often viewed as being disparate from semiconductors. Based on the premise that the presence of a correlated gap and semiconductivity are not mutually exclusive, this work reviews electronic structure calculations on the binary 3d oxides, so to distill trends and design principles for semiconducting transition metal oxides. This class of materials possesses the potential for discovery, design, and development of novel functional semiconducting compounds, e.g. for energy applications. In order to place the 3d orbitals and the sp bands into an integrated picture, band structure calculations should treat both contributions on the same footing and, at the same time, account fully for electron correlation in the 3d shell. Fundamentally, this is a rather daunting task for electronic structure calculations, but quasi-particle energy calculations in GW approximation offer a viable approach for band structure predictions in these materials. Compared to conventional semiconductors, the inherent multivalent nature of transition metal cations is more likely to cause undesirable localization of electron or hole carriers. Therefore, a quantitative prediction of the carrier self-trapping energy is essential for the assessing the semiconducting properties and to determine whether the transport mechanism is a band-like large-polaron conduction or a small-polaron hopping conduction. An overview is given for the binary 3d oxides on how the hybridization between the 3d crystal field symmetries with the O-p orbitals of the ligands affects the effective masses and the likelihood of electron and hole self-trapping, identifying those situations where small masses and band-like conduction are more likely to be expected. The review concludes with an illustration of the implications of the increased electronic complexity of transition metal cations on the defect physics and doping, using

  15. Melting of Transition Metals

    Ross, M; Japel, S; Boehler, R

    2005-04-11

    We review the transition melting studies carried out at Mainz, and describe a recently developed model used to explain that the relatively low melting slopes are due to the partially filled d-bands, and the persistence of the pressure induced s-d transition. The basic tenets of the model have now been reconfirmed by new measurements for Cu and Ni. The measurements show that Cu which has a filled 3d-band, has a melt slope that is about 2.5 greater than its neighbor Ni. In the case of Mo, the apparent discrepancy of DAC melting measurements with shock melting can be explained by accounting for the change in melt slope due to the bcc-cp transition observed in the shock studies. The Fe melt curve is revisited. The possible relevance of the Jahn-Teller effect and recently observed transition metal melts with Icosahedral Short-Range Order (ISRO) is discussed.

  16. Electric-dipole allowed and intercombination transitions among the 3d5, 3d44s and 3d44p levels of Fe IV

    Oscillator strengths and transition rates for the electric-dipole (E1) allowed and intercombination transitions among 3d5, 3d44s and 3d44p levels of Fe IV are calculated using the CIV3 code of Hibbert and coworkers. Using the Hartree-Fock functions up to 3d orbitals we have also optimized 4s, 4p, 4d, 4f, 5s, 5p and 5d orbitals of which 4s and 4p are taken to be spectroscopic and the remaining orbitals represent corrections to the spectroscopic orbitals or the correlation effects. The J-dependent levels of 108 LS states are included in the calculation and the relativistic effects are accounted for via the Breit-Pauli operator. Configurations are chosen in two steps: (a) two promotions were allowed from the 3p, 3d, 4s and 4p subshells, using all the orbitals; and (b) selective promotions from the 3s subshell are included, but only to the 3s and 4s orbitals. The ab initio fine-structure levels are then fine tuned to reproduce observed energy levels as closely as possible, and the resulting wavefunctions are used to calculate oscillator strengths and transition rates for all possible E1 transitions. For many of these transitions, the present results show good agreement between the length and velocity forms while for some transitions, some large disagreements are found with other available results. The complete list of weighted oscillator strengths, transition rates, and line strengths for transitions among the fine structure levels of the three lowest configurations are presented in ascending order of wavelength.

  17. E1 transitions among the levels of the 3d5, 3d44s and 3d44p configurations in Fe IV

    Two recently published sets of data for oscillator strengths of transitions between fine-structure levels belonging to the 3d5, 3d44s and 3d44p configurations in Fe IV (Nahar and Pradhan 2005 Astron. Astrophys. 437 345; Nahar 2006 Astron. Astrophys. 448 779) show some considerable disagreements for a number of transitions. The former calculation was undertaken using the R-matrix code, in LS coupling followed by a frame transformation to obtain data for individual lines; the latter calculation used the SUPERSTRUCTURE code which provides data for individual lines directly. We discuss these differences in the light of extensive calculations of our own, using the CIV3 code. It becomes apparent that the problem lies in the 2006 calculation, and we offer some quantitative explanation of how this discrepancy has occurred. In some cases at least, it can be attributed to mis-identification of energy level labels. (fast track communication)

  18. Metal nanoparticle direct inkjet printing for low-temperature 3D micro metal structure fabrication

    Ko, Seung Hwan; Chung, Jaewon; Hotz, Nico; Nam, Koo Hyun; Grigoropoulos, Costas P.

    2010-12-01

    Inkjet printing of functional materials is a key technology toward ultra-low-cost, large-area electronics. We demonstrate low-temperature 3D micro metal structure fabrication by direct inkjet printing of metal nanoparticles (NPs) as a versatile, direct 3D metal structuring approach representing an alternative to conventional vacuum deposition and photolithographic methods. Metal NP ink was inkjet-printed to exploit the large melting temperature drop of the nanomaterial and the ease of the NP ink formulation. Parametric studies on the basic conditions for stable 3D inkjet printing of NP ink were carried out. Furthermore, diverse 3D metal microstructures, including micro metal pillar arrays, helices, zigzag and micro bridges were demonstrated and electrical characterization was performed. Since the process requires low temperature, it carries substantial potential for fabrication of electronics on a plastic substrate.

  19. Metal nanoparticle direct inkjet printing for low-temperature 3D micro metal structure fabrication

    Inkjet printing of functional materials is a key technology toward ultra-low-cost, large-area electronics. We demonstrate low-temperature 3D micro metal structure fabrication by direct inkjet printing of metal nanoparticles (NPs) as a versatile, direct 3D metal structuring approach representing an alternative to conventional vacuum deposition and photolithographic methods. Metal NP ink was inkjet-printed to exploit the large melting temperature drop of the nanomaterial and the ease of the NP ink formulation. Parametric studies on the basic conditions for stable 3D inkjet printing of NP ink were carried out. Furthermore, diverse 3D metal microstructures, including micro metal pillar arrays, helices, zigzag and micro bridges were demonstrated and electrical characterization was performed. Since the process requires low temperature, it carries substantial potential for fabrication of electronics on a plastic substrate

  20. The 3d84s-3d84p transitions in Br IX

    The spectrum of bromine was studied in the region 450-1100 A, using the beam-foil method with 6 MeV ions from a tandem accelerator. On the basis of isoelectronic extrapolations and theoretical calculations, 32 lines were classified as transitions between the 3p63d84s and 3p63d84p configurations of Co-like BrIX. Fo the 16 possible 4s levels 13 have been located, and 11 new 4p levels have been added to the previously known ones. Only 4 of all the 4p levels (45 in total) remain to be found. (orig.)

  1. 3D highly oriented nanoparticulate and microparticulate array of metal oxide materials

    Advanced nano and micro particulate thin films of 3d transition and post-transition metal oxides consisting of nanorods and microrods with parallel and perpendicular orientation with respect to the substrate normal, have been successfully grown onto various substrates by heteronucleation, without template and/or surfactant, from the aqueous condensation of solution of metal salts or metal complexes (aqueous chemical growth). Three-dimensional arrays of iron oxide nanorods and zinc oxide nanorods with parallel and perpendicular orientation are presented as well as the oxygen K-edge polarization dependent x-ray absorption spectroscopy (XAS) study of anisotropic perpendicularly oriented microrod array of ZnO performed at synchrotron radiation source facility

  2. Observation of the $^1$S$_0$ to $^3$D$_1$ clock transition in $^{175}$Lu$^+$

    Arnold, Kyle J; Roy, A; Paez, E; Wang, S; Barrett, M D

    2016-01-01

    We report the first laser spectroscopy of the $^1$S$_0$ to $^3$D$_1$ clock transition in $^{175}$Lu$^+$. Clock operation is demonstrated on three pairs of Zeeman transitions, one pair from each hyperfine manifold of the $^3$D$_1$ term. We measure the hyperfine intervals of the $^3$D$_1$ to 10 ppb uncertainty and infer the optical frequency averaged over the three hyperfine transitions to be 353.639 915 952 2 (6) THz. The lifetime of the $^3$D$_1$ state is inferred to be $174^{+23}_{-32}$ hours from the M1 coupling strength.

  3. Laser Transfer of Metals and Metal Alloys for Digital Microfabrication of 3D Objects.

    Zenou, Michael; Sa'ar, Amir; Kotler, Zvi

    2015-09-01

    3D copper logos printed on epoxy glass laminates are demonstrated. The structures are printed using laser transfer of molten metal microdroplets. The example in the image shows letters of 50 µm width, with each letter being taller than the last, from a height of 40 µm ('s') to 190 µm ('l'). The scanning microscopy image is taken at a tilt, and the topographic image was taken using interferometric 3D microscopy, to show the effective control of this technique. PMID:25966320

  4. TRANSITION FROM 2D TO 3D WITH GEOGEBRA

    MARIA MIHAILOVA

    2014-12-01

    Full Text Available This article presents the definition of projection plane, its importance for the geometry constructions used in civil engineering and comparative analysis of three opportunities for creating a three dimensional basis, used in drawing such a plane. First method consists of transforming affine and orthonormal coordinates and its application in GeoGebra is presented. Second method, using combination of spherical and polar coordinates in space, is introduced. The third suggested method is an application of descriptive geometry for transforming 2D to 3D and a new method of forming a plane of projection, which will be used later in the reviewed example below. The example shows how GeoGebra software can be used in technical drawing used in civil engineering.

  5. Resonant excitation channels in the 3d10-3d94s and 3d10-3d94p transitions of nickel-like Mo14+ and Zr12+

    Fournier, K. B.; Goldstein, W. H.; May, M.; Finkenthal, M.; Terry, J. L.

    1996-05-01

    At energies below the threshold for direct electron impact excitation, resonant excitations can make a significant contribution to the total excitation rate of a given energy level. In this paper, the rates of resonant excitation into the levels of the 3d94s and 3d94p configurations of Mo14+ have been calculated using a fully relativistic, multiconfiguration atomic structure code and detailed accounting of energy levels. By including the effects of resonant excitations in collisional-radiative models for the spectrum of Ni I-like Mo14+ and (by isoelectronic scaling) Zr12+, the ratio of the emissivity of the 3d10-4d94s E2 transitions to the emissivity of the 3d10-3d94p E1 transitions is greatly enhanced, and sensitivity to electron temperature in the ratio is introduced. This ratio is density sensitive for ne>=1013 cm-3, and therefore, given knowledge of either local temperature or density conditions, the E2-E1 ratio can serve as a diagnostic for local conditions in magnetically confined fusion plasmas. The current work demonstrates the need to include resonant excitations in collisional-radiative models of the soft x-ray emission of nickel-like ions. Good agreement is found between measurements of E1 and E2 line brightness ratios made in a tokamak plasma, and the predictions of collisional-radiative models in the present work.

  6. Resonant excitation channels in the 3d10-3d94s and 3d10-3d94p transitions of nickel-like Mo14+ and Zr12+

    At energies below the threshold for direct electron impact excitation, resonant excitations can make a significant contribution to the total excitation rate of a given energy level. In this paper, the rates of resonant excitation into the levels of the 3d94s and 3d94p configurations of Mo14+ have been calculated using a fully relativistic, multiconfiguration atomic structure code and detailed accounting of energy levels. By including the effects of resonant excitations in collisional-radiative models for the spectrum of NiI endash like Mo14+ and (by isoelectronic scaling) Zr12+, the ratio of the emissivity of the 3d10-4d94s E2 transitions to the emissivity of the 3d10-3d94p E1 transitions is greatly enhanced, and sensitivity to electron temperature in the ratio is introduced. This ratio is density sensitive for ne≥1013 cm-3, and therefore, given knowledge of either local temperature or density conditions, the E2-E1 ratio can serve as a diagnostic for local conditions in magnetically confined fusion plasmas. The current work demonstrates the need to include resonant excitations in collisional-radiative models of the soft x-ray emission of nickel-like ions. Good agreement is found between measurements of E1 and E2 line brightness ratios made in a tokamak plasma, and the predictions of collisional-radiative models in the present work. copyright 1996 The American Physical Society

  7. Regularity of transition semigroups associated to a 3D stochastic Navier-Stokes equation

    Flandoli, F.; Romito, M.

    2006-01-01

    A 3D stochastic Navier-Stokes equation with a suitable non degenerate additive noise is considered. The regularity in the initial conditions of every Markov transition kernel associated to the equation is studied by a simple direct approach. A by-product of the technique is the equivalence of all transition probabilities associated to every Markov transition kernel.

  8. Time Evolution in 3D Metal Microstructures-Recrystallization

    Juul Jensen, Dorte; Schmidt, Søren

    2009-01-01

    The three dimensional x-ray diffraction (3DXRD) concept is shortly described and new experimental updates are highlighted. The potentials and limitation of the 3DXRD method are compared to those of other 3D methods. 3DXRD has been used for in-situ studies of recrystallization and new migration rate...... results are presented. Migration mechanism for boundary segments surrounding a recrystallizing grain are described and discussed....

  9. The Transition from 2-D Brachytherapy to 3-D High Dose Rate Brachytherapy

    Brachytherapy is a major treatment modality in the treatment of common cancers including cervical cancer. This publication addresses the recent technological change in brachytherapy treatment planning with better access to 3-D volumetric patient imaging modalities including computed tomography (CT) and magnetic resonance (MR) as opposed to traditional 2-D planar images. In the context of 2-D and 3-D brachytherapy, the publication provides definitions, clinical indications, transitioning milestones, commissioning steps, quality assurance measures, and a related questionnaire. Staff training and resourcing are also addressed. The publication will serve as a guide to radiotherapy departments in Member States who wish to make the transition from 2-D to 3-D brachytherapy

  10. 3D Microstructure Modeling of Porous Metal Filters

    Hejtmánek, Vladimír; Čapek, M.

    2012-01-01

    Roč. 2, č. 3 (2012), s. 344-352. ISSN 2075-4701. [International Conference on Porous Metals and Metallic Foams /7./. Busan, 18.09.2011-21.09.2011] R&D Projects: GA ČR(CZ) GAP204/11/1206; GA ČR GA203/09/1353 Institutional support: RVO:67985858 Keywords : porous metal filter * stochastic reconstruction * microstructural descriptors Subject RIV: CF - Physical ; Theoretical Chemistry

  11. XUV spectra of 2nd transition row elements: identification of 3d-4p and 3d-4f transition arrays

    Lokasani, Ragava; Long, Elaine; Maguire, Oisin; Sheridan, Paul; Hayden, Patrick; O'Reilly, Fergal; Dunne, Padraig; Sokell, Emma; Endo, Akira; Limpouch, Jiri; O'Sullivan, Gerry

    2015-12-01

    The use of laser produced plasmas (LPPs) in extreme ultraviolet/soft x-ray lithography and metrology at 13.5 nm has been widely reported and recent research efforts have focused on developing next generation sources for lithography, surface morphology, patterning and microscopy at shorter wavelengths. In this paper, the spectra emitted from LPPs of the 2nd transition row elements from yttrium (Z = 39) to palladium (Z = 46), with the exception of zirconium (Z = 40) and technetium (Z = 43), produced by two Nd:YAG lasers which delivered up to 600 mJ in 7 ns and 230 mJ in 170 ps, respectively, are reported. Intense emission was observed in the 2-8 nm spectral region resulting from unresolved transition arrays (UTAs) due to 3d-4p, 3d-4f and 3p-3d transitions. These transitions in a number of ion stages of yttrium, niobium, ruthenium and rhodium were identified by comparison with results from Cowan code calculations and previous studies. The theoretical data were parameterized using the UTA formalism and the mean wavelength and widths were calculated and compared with experimental results.

  12. Liquid Phase 3D Printing for Quickly Manufacturing Metal Objects with Low Melting Point Alloy Ink

    Wang, Lei; Jing LIU

    2014-01-01

    Conventional 3D printings are generally time-consuming and printable metal inks are rather limited. From an alternative way, we proposed a liquid phase 3D printing for quickly making metal objects. Through introducing metal alloys whose melting point is slightly above room temperature as printing inks, several representative structures spanning from one, two and three dimension to more complex patterns were demonstrated to be quickly fabricated. Compared with the air cooling in a conventional...

  13. Liquid Phase 3D Printing for Quickly Manufacturing Metal Objects with Low Melting Point Alloy Ink

    Wang, Lei

    2014-01-01

    Conventional 3D printings are generally time-consuming and printable metal inks are rather limited. From an alternative way, we proposed a liquid phase 3D printing for quickly making metal objects. Through introducing metal alloys whose melting point is slightly above room temperature as printing inks, several representative structures spanning from one, two and three dimension to more complex patterns were demonstrated to be quickly fabricated. Compared with the air cooling in a conventional 3D printing, the liquid-phase-manufacturing offers a much higher cooling rate and thus significantly improves the speed in fabricating metal objects. This unique strategy also efficiently prevents the liquid metal inks from air oxidation which is hard to avoid otherwise in an ordinary 3D printing. Several key physical factors (like properties of the cooling fluid, injection speed and needle diameter, types and properties of the printing ink, etc.) were disclosed which would evidently affect the printing quality. In addit...

  14. A systematic study of neutral and charged 3d-metal trioxides and tetraoxides

    Pradhan, Kalpataru; Gutsev, Gennady L.; Weatherford, Charles A.; Jena, Purusottam

    2011-04-01

    Using density functional theory with generalized gradient approximation, we have performed a systematic study of the structure and properties of neutral and charged trioxides (MO3) and tetraoxides (MO4) of the 3d-metal atoms. The results of our calculations revealed a number of interesting features when moving along the 3d-metal series. (1) Geometrical configurations of the lowest total energy states of neutral and charged trioxides and tetraoxides are composed of oxo and/or peroxo groups, except for CuO3- and ZnO3- which possess a superoxo group, CuO4+ and ZnO4+ which possess two superoxo groups, and CuO3+, ZnO3+, and ZnO4- which possess an ozonide group. While peroxo groups are found in the early and late transition metals, all oxygen atoms bind chemically to the metal atom in the middle of the series. (2) Attachment or detachment of an electron to/from an oxide often leads to a change in the geometry. In some cases, two dissociatively attached oxygen atoms combine and form a peroxo group or a peroxo group transforms into a superoxo group and vice versa. (3) The adiabatic electron affinity of as many as two trioxides (VO3 and CoO3) and four tetraoxides (TiO4, CrO4, MnO4, and FeO4) are larger than the electron affinity of halogen atoms. All these oxides are hence superhalogens although only VO3 and MnO4 satisfy the general superhalogen formula.

  15. 2D to 3D transition of polymeric carbon nitride nanosheets

    The transition from a prevalent turbostratic arrangement with low planar interactions (2D) to an array of polymeric carbon nitride nanosheets with stronger interplanar interactions (3D), occurring for samples treated above 650 °C, was detected by terahertz-time domain spectroscopy (THz-TDS). The simulated 3D material made of stacks of shifted quasi planar sheets composed of zigzagged polymer ribbons, delivered a XRD simulated pattern in relatively good agreement with the experimental one. The 2D to 3D transition was also supported by the simulation of THz-TDS spectra obtained from quantum chemistry calculations, in which the same broad bands around 2 THz and 1.5 THz were found for 2D and 3D arrays, respectively. This transition was also in accordance with the tightening of the interplanar distance probably due to an interplanar π bond contribution, as evidenced also by a broad absorption around 2.6 eV in the UV–vis spectrum, which appeared in the sample treated at 650 °C, and increased in the sample treated at 700 °C. The band gap was calculated for 1D and 2D cases. The value of 3.374 eV for the 2D case is, within the model accuracy and precision, in a relative good agreement with the value of 3.055 eV obtained from the experimental results. - Graphical abstract: 2D lattice mode vibrations and structural changes correlated with the so called “2D to 3D transition”. - Highlights: • A 2D to 3D transition has been detected for polymeric carbon nitride. • THz-TDS allowed us to discover and detect the 2D to 3D transition of polymeric carbon nitride. • We propose a structure for polymeric carbon nitride confirming it with THz-TDS

  16. 2D to 3D transition of polymeric carbon nitride nanosheets

    Chamorro-Posada, Pedro [Dpto. de Teoría de la Señal y Comunicaciones e IT, Universidad de Valladolid, ETSI Telecomunicación, Paseo Belén 15, 47011 Valladolid (Spain); Vázquez-Cabo, José [Dpto. de Teoría de la Señal y Comunicaciones, Universidad de Vigo, ETSI Telecomunicación, Lagoas Marcosende s/n, Vigo (Spain); Sánchez-Arévalo, Francisco M. [Instituto de Investigaciones en Materiales (IIM), Universidad Nacional Autónoma de México, Apdo. Postal 70–360, Cd. Universitaria, México D.F. 04510 (Mexico); Martín-Ramos, Pablo [Dpto. de Teoría de la Señal y Comunicaciones e IT, Universidad de Valladolid, ETSI Telecomunicación, Paseo Belén 15, 47011 Valladolid (Spain); Laboratorio de Materiales Avanzados (Advanced Materials Laboratory) ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martín-Gil, Jesús; Navas-Gracia, Luis M. [Laboratorio de Materiales Avanzados (Advanced Materials Laboratory) ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Dante, Roberto C., E-mail: rcdante@yahoo.com [Laboratorio de Materiales Avanzados (Advanced Materials Laboratory) ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain)

    2014-11-15

    The transition from a prevalent turbostratic arrangement with low planar interactions (2D) to an array of polymeric carbon nitride nanosheets with stronger interplanar interactions (3D), occurring for samples treated above 650 °C, was detected by terahertz-time domain spectroscopy (THz-TDS). The simulated 3D material made of stacks of shifted quasi planar sheets composed of zigzagged polymer ribbons, delivered a XRD simulated pattern in relatively good agreement with the experimental one. The 2D to 3D transition was also supported by the simulation of THz-TDS spectra obtained from quantum chemistry calculations, in which the same broad bands around 2 THz and 1.5 THz were found for 2D and 3D arrays, respectively. This transition was also in accordance with the tightening of the interplanar distance probably due to an interplanar π bond contribution, as evidenced also by a broad absorption around 2.6 eV in the UV–vis spectrum, which appeared in the sample treated at 650 °C, and increased in the sample treated at 700 °C. The band gap was calculated for 1D and 2D cases. The value of 3.374 eV for the 2D case is, within the model accuracy and precision, in a relative good agreement with the value of 3.055 eV obtained from the experimental results. - Graphical abstract: 2D lattice mode vibrations and structural changes correlated with the so called “2D to 3D transition”. - Highlights: • A 2D to 3D transition has been detected for polymeric carbon nitride. • THz-TDS allowed us to discover and detect the 2D to 3D transition of polymeric carbon nitride. • We propose a structure for polymeric carbon nitride confirming it with THz-TDS.

  17. Analysis of the spectrum six times ionized zinc (Zn VII): the 3d6-3d54p transition array

    The spectrum of zinc was photographed in the 100-300 A region on a 10.7 m grazing incidence spectrograph using a triggered spark light source. 335 lines were classified in the Zn VII 3d6-3d54p transition array, resulting in the establishment of 30 of the 34 levels of the 3d6 configuration and 103 of the 214 levels of the 3d54p. The ground configuration 3d6 was described by a generalized least-squares fit (GLSF) involving orthogonal operators to a set of 3dN configurations. This yielded a mean error of 3 cm-1 for its level values. The excited configruation was described by the conventional Slater Condon parameter set, giving a mean error of 105 cm-1. (orig.)

  18. Oligocyclopentadienyl transition metal complexes

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  19. Quantitative determination of spin-dependent quasiparticle renormalization in ferromagnetic 3d metals

    Sanchez-Barriga, Jaime; Varykhalov, Andrei; Fink, Joerg; Rader, Oliver; Duerr, Hermann; Eberhardt, Wolfgang [Bessy GmbH, Berlin (Germany)

    2008-07-01

    Spin dependent low-energy electronic excitations in 3d ferromagnets are of special interest due to the need of a microscopic understanding of the electronic structure of solids. Low-energy electrons (or holes) become dressed by a cloud of excitations resulting in quasiparticles of a finite lifetime and a different effective mass. These type of excitations have been studied by many theoretical methods, and it has been found that because of many body effects no sharp quasiparticle peaks exist for binding energies larger than 2 eV. Interestingly, it has been shown that strong correlation effects could particularly affect majority spin electrons, leading to a pronounced damping of quasiparticles at binding energies around 2 eV and above. In order to give an experimental corroboration to these findings, we have performed a systematic study of the spin-dependent quasiparticle lifetime and band structure of ferromagnetic 3d transition metal surfaces by means of spin and angle-resolved photoemission spectroscopy. On hcp Co(0001), fcc Ni(111) and bcc Fe(110), we have found a more pronounced renormalization of the majority spin quasiparticle spectral weight going from Ni to Co which are both strong ferromagnets. For Fe, a weak ferromagnet, such a process becomes more prominent in the minority channel.

  20. Fused filament 3D printing of ionic polymer-metal composites (IPMCs)

    Carrico, James D.; Traeden, Nicklaus W.; Aureli, Matteo; Leang, Kam K.

    2015-12-01

    This paper describes a new three-dimensional (3D) fused filament additive manufacturing (AM) technique in which electroactive polymer filament material is used to build soft active 3D structures, layer by layer. Specifically, the unique actuation and sensing properties of ionic polymer-metal composites (IPMCs) are exploited in 3D printing to create electroactive polymer structures for application in soft robotics and bio-inspired systems. The process begins with extruding a precursor material (non-acid Nafion precursor resin) into a thermoplastic filament for 3D printing. The filament is then used by a custom-designed 3D printer to manufacture the desired soft polymer structures, layer by layer. Since at this stage the 3D-printed samples are not yet electroactive, a chemical functionalization process follows, consisting in hydrolyzing the precursor samples in an aqueous solution of potassium hydroxide and dimethyl sulfoxide. Upon functionalization, metal electrodes are applied on the samples through an electroless plating process, which enables the 3D-printed IPMC structures to be controlled by voltage signals for actuation (or to act as sensors). This innovative AM process is described in detail and the performance of 3D printed IPMC actuators is compared to an IPMC actuator fabricated from commercially available Nafion sheet material. The experimental results show comparable performance between the two types of actuators, demonstrating the potential and feasibility of creating functional 3D-printed IPMCs.

  1. Fabrication of 3D metal/polymer microstructures by site-selective metal coating

    Takeyasu, N. [RIKEN (The Institute of Physical and Chemical Research), Nanophotonics Laboratory, Saitama (Japan); Tanaka, T. [RIKEN (The Institute of Physical and Chemical Research), Nanophotonics Laboratory, Saitama (Japan); PRESTO, JST, Saitama (Japan); Kawata, S. [RIKEN (The Institute of Physical and Chemical Research), Nanophotonics Laboratory, Saitama (Japan); Osaka University, Department of Applied Physics, Osaka (Japan); CREST, JST, Saitama (Japan)

    2008-02-15

    Three-dimensional silver/polymer conjugated microstructures were fabricated by site-selective metal deposition on photopolymer structures in the sub-micrometer scale. Photopolymerizable resins with and without an amide group were independently prepared, and a three-dimensional polymer structure was fabricated with those resins by means of the two-photon-induced photopolymerization technique to confine the photopolymerization to a sub-micrometer volume. Silver was selectively deposited on the surface of the amide-containing polymer parts by electroless plating. This method can provide 3D arbitrary silver/polymer composite microstructures with sub-micrometer resolution. (orig.)

  2. Fabrication of 3D metal/polymer microstructures by site-selective metal coating

    Takeyasu, N.; Tanaka, T.; Kawata, S.

    2008-02-01

    Three-dimensional silver/polymer conjugated microstructures were fabricated by site-selective metal deposition on photopolymer structures in the sub-micrometer scale. Photopolymerizable resins with and without an amide group were independently prepared, and a three-dimensional polymer structure was fabricated with those resins by means of the two-photon-induced photopolymerization technique to confine the photopolymerization to a sub-micrometer volume. Silver was selectively deposited on the surface of the amide-containing polymer parts by electroless plating. This method can provide 3D arbitrary silver/polymer composite microstructures with sub-micrometer resolution.

  3. EXAMPLES OF 3D-TECHNOLOGIES IN FOUNDRY PROCESSES. DECREASE IN METAL CONSUMPTION IN CASTINGS

    V. S. Doroshenko

    2016-01-01

    Full Text Available The review describes the design of metal castings produced by use of 3D-technologies. Some new ways of 3D-processing of materials connected with additive processes are described, which represents the next step in environmental resource-saving production. Examples of patterns and casting of complex design with an optimal combination of materials, durability and attractive appearance are shown. Described 3D high-tech processes are expanding the existing range of metal products and the ways of its production.

  4. Analysis of 3D-printed metal for rapid-prototyped reflective terahertz optics

    Headland, Daniel; Withayachumnankul, Withawat; Webb, Michael; Ebendorff-Heidepriem, Heike; Luiten, Andre; Abbott, Derek

    2016-07-01

    We explore the potential of 3D metal printing to realize complex conductive terahertz devices. Factors impacting performance such as printing resolution, surface roughness, oxidation, and material loss are investigated via analytical, numerical, and experimental approaches. The high degree of control offered by a 3D-printed topology is exploited to realize a zone plate operating at 530 GHz. Reflection efficiency at this frequency is found to be over 90%. The high-performance of this preliminary device suggest that 3D metal printing can play a strong role in guided-wave and general beam control devices in the terahertz range.

  5. Analysis of 3D-printed metal for rapid-prototyped reflective terahertz optics

    Headland, Daniel; Webb, Michael; Ebendorff-Heidepriem, Heike; Luiten, Andre; Abbott, Derek

    2016-01-01

    We explore the potential of 3D metal printing to realize complex conductive terahertz devices. Factors impacting performance such as printing resolution, surface roughness, oxidation, and material loss are investigated via analytical, numerical, and experimental approaches. The high degree of control offered by a 3D-printed topology is exploited to realize a zone plate operating at 530 GHz. Reflection efficiency at this frequency is found to be over 90%. The high-performance of this preliminary device suggest that 3D metal printing can play a strong role in guided-wave and general beam control devices in the terahertz range.

  6. Analysis of 3D-printed metal for rapid-prototyped reflective terahertz optics.

    Headland, Daniel; Withayachumnankul, Withawat; Webb, Michael; Ebendorff-Heidepriem, Heike; Luiten, Andre; Abbott, Derek

    2016-07-25

    We explore the potential of 3D metal printing to realize complex conductive terahertz devices. Factors impacting performance such as printing resolution, surface roughness, oxidation, and material loss are investigated via analytical, numerical, and experimental approaches. The high degree of control offered by a 3D-printed topology is exploited to realize a zone plate operating at 530 GHz. Reflection efficiency at this frequency is found to be over 90%. The high-performance of this preliminary device suggest that 3D metal printing can play a strong role in guided-wave and general beam control devices in the terahertz range. PMID:27464185

  7. Printing of metallic 3D micro-objects by laser induced forward transfer.

    Zenou, Michael; Kotler, Zvi

    2016-01-25

    Digital printing of 3D metal micro-structures by laser induced forward transfer under ambient conditions is reviewed. Recent progress has allowed drop on demand transfer of molten, femto-liter, metal droplets with a high jetting directionality. Such small volume droplets solidify instantly, on a nanosecond time scale, as they touch the substrate. This fast solidification limits their lateral spreading and allows the fabrication of high aspect ratio and complex 3D metal structures. Several examples of micron-scale resolution metal objects printed using this method are presented and discussed. PMID:26832524

  8. Initiator-integrated 3D printing enables the formation of complex metallic architectures.

    Wang, Xiaolong; Guo, Qiuquan; Cai, Xiaobing; Zhou, Shaolin; Kobe, Brad; Yang, Jun

    2014-02-26

    Three-dimensional printing was used to fabricate various metallic structures by directly integrating a Br-containing vinyl-terminated initiator into the 3D resin followed by surface-initiated atomic-transfer radical polymerization (ATRP) and subsequent electroless plating. Cu- and Ni-coated complex structures, such as microlattices, hollow balls, and even Eiffel towers, were prepared. Moreover, the method is also capable of fabricating ultralight cellular metals with desired structures by simply etching the polymer template away. By combining the merits of 3D printing in structure design with those of ATRP in surface modification and polymer-assisted ELP of metals, this universal, robust, and cost-effective approach has largely extended the capability of 3D printing and will make 3D printing technology more practical in areas of electronics, acoustic absorption, thermal insulation, catalyst supports, and others. PMID:24328276

  9. Laser-assisted direct ink writing of planar and 3D metal architectures

    Skylar-Scott, Mark A.; Gunasekaran, Suman; Lewis, Jennifer A.

    2016-05-01

    The ability to pattern planar and freestanding 3D metallic architectures at the microscale would enable myriad applications, including flexible electronics, displays, sensors, and electrically small antennas. A 3D printing method is introduced that combines direct ink writing with a focused laser that locally anneals printed metallic features “on-the-fly.” To optimize the nozzle-to-laser separation distance, the heat transfer along the printed silver wire is modeled as a function of printing speed, laser intensity, and pulse duration. Laser-assisted direct ink writing is used to pattern highly conductive, ductile metallic interconnects, springs, and freestanding spiral architectures on flexible and rigid substrates.

  10. Laser-assisted direct ink writing of planar and 3D metal architectures.

    Skylar-Scott, Mark A; Gunasekaran, Suman; Lewis, Jennifer A

    2016-05-31

    The ability to pattern planar and freestanding 3D metallic architectures at the microscale would enable myriad applications, including flexible electronics, displays, sensors, and electrically small antennas. A 3D printing method is introduced that combines direct ink writing with a focused laser that locally anneals printed metallic features "on-the-fly." To optimize the nozzle-to-laser separation distance, the heat transfer along the printed silver wire is modeled as a function of printing speed, laser intensity, and pulse duration. Laser-assisted direct ink writing is used to pattern highly conductive, ductile metallic interconnects, springs, and freestanding spiral architectures on flexible and rigid substrates. PMID:27185932

  11. 3-D printing of liquid metals for stretchable and flexible conductors

    Trlica, Chris; Parekh, Dishit Paresh; Panich, Lazar; Ladd, Collin; Dickey, Michael D.

    2014-06-01

    3-D printing is an emerging technology that has been used primarily on small scales for rapid prototyping, but which could also herald a wider movement towards decentralized, highly customizable manufacturing. Polymers are the most common materials to be 3-D printed today, but there is great demand for a way to easily print metals. Existing techniques for 3-D printing metals tend to be expensive and energy-intensive, and usually require high temperatures or pressures, making them incompatible with polymers, organics, soft materials, and biological materials. Here, we describe room temperature liquid metals as complements to polymers for 3-D printing applications. These metals enable the fabrication of soft, flexible, and stretchable devices. We survey potential room temperature liquid metal candidates and describe the benefits of gallium and its alloys for these purposes. We demonstrate the direct printing of a liquid gallium alloy in both 2-D and 3-D and highlight the structures and shapes that can be fabricated using these processes.

  12. Facile 3D Metal Electrode Fabrication for Energy Applications via Inkjet Printing and Shape Memory Polymer

    Roberts, R. C.; Wu, J.; Hau, N. Y.; Chang, Y. H.; Feng, S. P.; Li, D. C.

    2014-11-01

    This paper reports on a simple 3D metal electrode fabrication technique via inkjet printing onto a thermally contracting shape memory polymer (SMP) substrate. Inkjet printing allows for the direct patterning of structures from metal nanoparticle bearing liquid inks. After deposition, these inks require thermal curing steps to render a stable conductive film. By printing onto a SMP substrate, the metal nanoparticle ink can be cured and substrate shrunk simultaneously to create 3D metal microstructures, forming a large surface area topology well suited for energy applications. Polystyrene SMP shrinkage was characterized in a laboratory oven from 150-240°C, resulting in a size reduction of 1.97-2.58. Silver nanoparticle ink was patterned into electrodes, shrunk, and the topology characterized using scanning electron microscopy. Zinc-Silver Oxide microbatteries were fabricated to demonstrate the 3D electrodes compared to planar references. Characterization was performed using 10M potassium hydroxide electrolyte solution doped with zinc oxide (57g/L). After a 300s oxidation at 3Vdc, the 3D electrode battery demonstrated a 125% increased capacity over the reference cell. Reference cells degraded with longer oxidations, but the 3D electrodes were fully oxidized for 4 hours, and exhibited a capacity of 5.5mA-hr/cm2 with stable metal performance.

  13. Facile 3D Metal Electrode Fabrication for Energy Applications via Inkjet Printing and Shape Memory Polymer

    This paper reports on a simple 3D metal electrode fabrication technique via inkjet printing onto a thermally contracting shape memory polymer (SMP) substrate. Inkjet printing allows for the direct patterning of structures from metal nanoparticle bearing liquid inks. After deposition, these inks require thermal curing steps to render a stable conductive film. By printing onto a SMP substrate, the metal nanoparticle ink can be cured and substrate shrunk simultaneously to create 3D metal microstructures, forming a large surface area topology well suited for energy applications. Polystyrene SMP shrinkage was characterized in a laboratory oven from 150-240°C, resulting in a size reduction of 1.97-2.58. Silver nanoparticle ink was patterned into electrodes, shrunk, and the topology characterized using scanning electron microscopy. Zinc-Silver Oxide microbatteries were fabricated to demonstrate the 3D electrodes compared to planar references. Characterization was performed using 10M potassium hydroxide electrolyte solution doped with zinc oxide (57g/L). After a 300s oxidation at 3Vdc, the 3D electrode battery demonstrated a 125% increased capacity over the reference cell. Reference cells degraded with longer oxidations, but the 3D electrodes were fully oxidized for 4 hours, and exhibited a capacity of 5.5mA-hr/cm2 with stable metal performance

  14. Spectroscopic investigation of the 3d 2D → nf 2F transitions in lithium

    Shahzada, S.; Shah, M.; Haq, S. U.; Nawaz, M.; Ahmed, M.; Nadeem, Ali

    2016-05-01

    We report term energies and effective quantum numbers of the odd parity 3d 2D → nf 2F series of lithium using multi-step and multi-photon laser excitation schemes. The experiments were performed using three dye lasers simultaneously pumped by the second harmonic (532 nm) of a Q-switched Nd:YAG laser in conjunction with an atomic beam apparatus and thermionic diode ion detector. The first ionization potential of lithium has been determined as 43,487.13 ± 0.02 cm- 1 from the much extended 3d 2D → nf 2F (17 ≤ n ≤ 70) series. In addition, the oscillator strengths of the 3d 2D → nf 2F (15 ≤ n ≤ 48) transitions have been determined, showing a decreasing trend with the increase in principal quantum number n.

  15. Laboratory rotational ground state transitions of NH$_3$D$^+$ and CF$^+$

    Stoffels, Alexander; Schlemmer, Stephan; Brünken, Sandra

    2016-01-01

    Aims. This paper reports accurate laboratory frequencies of the rotational ground state transitions of two astronomically relevant molecular ions, NH3D+ and CF+. Methods. Spectra in the millimeter-wave band were recorded by the method of rotational state-selective attachment of He-atoms to the molecular ions stored and cooled in a cryogenic ion trap held at 4 K. The lowest rotational transition in the A state (ortho state) of NH$_3$D$^+$ ($J_K = 1_0 - 0_0$), and the two hyperfine components of the ground state transition of CF$^+$($J = 1 - 0$) were measured with a relative precision better than $10^{-7}$. Results. For both target ions the experimental transition frequencies agree with recent observations of the same lines in different astronomical environments. In the case of NH$_3$D$^+$ the high-accuracy laboratory measurements lend support to its tentative identification in the interstellar medium. For CF$^+$ the experimentally determined hyperfine splitting confirms previous quantum-chemical calculations a...

  16. Regional Gastrointestinal Transit Times in Patients With Carcinoid Diarrhea: Assessment With the Novel 3D-Transit System

    Gregersen, Tine; Haase, Anne-Mette; Schlageter, Vincent;

    2015-01-01

    not yet been evaluated in any group of patients. We aimed to test the performance of 3D-Transit in patients with carcinoid diarrhea and to compare the patients' regional gastrointestinal transit times (GITT) and colonic motility patterns with those of healthy subjects. METHODS: Fifteen healthy volunteers......BACKGROUND/AIMS: The paucity of knowledge regarding gastrointestinal motility in patients with neuroendocrine tumors and carcinoid diarrhea re-stricts targeted treatment. 3D-Transit is a novel, minimally invasive, ambulatory method for description of gastrointestinal motility. The system has.......5 (range: 8.5-47.2) hours in patients versus 25.1 (range: 13.1-142.3) hours in healthy (P = 0.007). There was no difference in gastric emptying (P = 0.778). Median small intestinal transit time was 3.8 (range: 1.4-5.5) hours in patients versus 4.4 (range: 1.8-7.2) hours in healthy subjects (P = 0...

  17. Laser jetting of femto-liter metal droplets for high resolution 3D printed structures.

    Zenou, M; Sa'ar, A; Kotler, Z

    2015-01-01

    Laser induced forward transfer (LIFT) is employed in a special, high accuracy jetting regime, by adequately matching the sub-nanosecond pulse duration to the metal donor layer thickness. Under such conditions, an effective solid nozzle is formed, providing stability and directionality to the femto-liter droplets which are printed from a large gap in excess of 400 μm. We illustrate the wide applicability of this method by printing several 3D metal objects. First, very high aspect ratio (A/R > 20), micron scale, copper pillars in various configuration, upright and arbitrarily bent, then a micron scale 3D object composed of gold and copper. Such a digital printing method could serve the generation of complex, multi-material, micron-scale, 3D materials and novel structures. PMID:26602432

  18. 3D broadband isotropic NRI metamaterial based on metallic cross-pairs

    In this paper, a new type of 3D metamaterial composed of double periodic array of metallic cross-pairs printed on the six sides of a cubic dielectric substrate was proposed to obtain the characteristics of broadband NRI and isotropy for the applications of super lenses. The behaviors of NRI, isotropy and polarization were analyzed using the CST Microwave Studio. The results show that the proposed metamaterial exhibits not only a broadband NRI whose relative bandwidth can be up to 56.7%, but also polarization-independence and isotropy. Thus, the proposed metamaterial is a good candidate material for 3D broadband isotropic NRI metamaterial. - Highlights: → 3D metamaterial is composed of double periodic array of metallic cross-pairs printed on the six sides of a cubic dielectric substrate. → Broadband negative refraction index (NRI) with relative bandwidth of 56.7%. → Polarization-independence and isotropy.

  19. Transition from 2-D radiotherapy to 3-D conformal and intensity modulated radiotherapy

    Cancer is one of the leading causes of death globally and radiotherapy is currently an essential component in the management of cancer patients, either alone or in combination with surgery or chemotherapy, both for cure or palliation. It is now recognized that safe and effective radiotherapy service needs not only substantial capital investment in radiotherapy equipment and specially designed facilities but also continuous investment in maintenance and upgrading of the equipment to comply with the technical progress, but also in training the staff. The recent IAEA-TECDOC publication 'Setting up a Radiotherapy Programme: Clinical, Medical Physics, Radiation Protection and Safety Aspects' provides general guidelines for designing and implementing radiotherapy services in Member States. Advances in computer technology have enabled the possibility of transitioning from basic 2- dimensional treatment planning and delivery (2-D radiotherapy) to a more sophisticated approach with 3-dimensional conformal radiotherapy (3-D CRT). Whereas 2-D radiotherapy can be applied with simple equipment, infrastructure and training, transfer to 3-D conformal treatments requires more resources in technology, equipment, staff and training. A novel radiation treatment approach using Intensity Modulated Radiation Therapy (IMRT) that optimizes the delivery of radiation to irregularly shaped tumour volumes demands even more sophisticated equipment and seamless teamwork, and consequentially more resources, advanced training and more time for treatment planning and verification of dose delivery than 3-D CRT. Whereas 3-D CRT can be considered as a standard, IMRT is still evolving. Due to the increased interest of Member States to the modern application of radiotherapy the IAEA has received a number of requests for guidance coming from radiotherapy departments that wish to upgrade their facilities to 3-D CRT and IMRT through Technical Cooperation programme. These requests are expected to increase

  20. Multilayer based interferential-plasmonic structure: metal cluster 3D grating combined with dielectric mirror

    Janicki, V.; Sancho-Parramon, J.; Zorc, H. [Ruder Boskovic Institute, Zagreb (Croatia)

    2011-06-15

    A three-dimensional (3D) photonic microstructure consisting of metal clusters embedded in dielectric matrix is coated with a dielectric mirror. The produced photonic structure shows optical behaviour that combines the interferential effects of the multilayer stack and the surface plasmon resonance of metal clusters. Due to its feasibility and the possibility to widely modify the optical properties of the resulting interferential-plasmonic structure, this approach represents a promising method for the production of novel optical components. (orig.)

  1. 3D molecular line formation in dwarf carbon-enhanced metal-poor stars

    Behara, N T; Bonifacio, P; Sbordone, L; Hernandez, J I Gonzalez; Caffau, E

    2009-01-01

    We present a detailed analysis of the carbon and nitrogen abundances of two dwarf carbon-enhanced metal-poor (CEMP) stars: SDSS J1349-0229 and SDSS J0912+0216. We also report the oxygen abundance of SDSS J1349-0229. These stars are metal-poor, with [Fe/H] < -2.5, and were selected from our ongoing survey of extremely metal-poor dwarf candidates from the Sloan Digital SkySurvey (SDSS). The carbon, nitrogen and oxygen abundances rely on molecular lines which form in the outer layers of the stellar atmosphere. It is known that convection in metal-poor stars induces very low temperatures which are not predicted by `classical' 1D stellar atmospheres. To obtain the correct temperature structure, one needs full 3D hydrodynamical models. Using CO5BOLD 3D hydrodynamical model atmospheres and the Linfor3D line formation code, molecular lines of CH, NH, OH and C2 were computed, and 3D carbon, nitrogen and oxygen abundances were determined. The resulting carbon abundances were compared to abundances derived using atom...

  2. The local structure of transition metal doped semiconducting boron carbides

    Liu Jing; Dowben, P A [Department of Physics and Astronomy and the Nebraska Center for Materials and Nanoscience, Behlen Laboratory of Physics, University of Nebraska-Lincoln, PO Box 880111, Lincoln, NE 68588-0111 (United States); Luo Guangfu; Mei Waining [Department of Physics, University of Nebraska at Omaha, Omaha, NE 68182-0266 (United States); Kizilkaya, Orhan [J. Bennett Johnston Sr. Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Hwy., Baton Rouge LA 70806 (United States); Shepherd, Eric D; Brand, J I [College of Engineering, and the Nebraska Center for Materials and Nanoscience, N209 Walter Scott Engineering Center, 17th and Vine Streets, University of Nebraska-Lincoln, Lincoln, NE 68588-0511 (United States)

    2010-03-03

    Transition metal doped boron carbides produced by plasma enhanced chemical vapour deposition of orthocarborane (closo-1,2-C{sub 2}B{sub 10}H{sub 12}) and 3d metal metallocenes were investigated by performing K-edge extended x-ray absorption fine structure and x-ray absorption near edge structure measurements. The 3d transition metal atom occupies one of the icosahedral boron or carbon atomic sites within the icosahedral cage. Good agreement was obtained between experiment and models for Mn, Fe and Co doping, based on the model structures of two adjoined vertex sharing carborane cages, each containing a transition metal. The local spin configurations of all the 3d transition metal doped boron carbides, Ti through Cu, are compared using cluster and/or icosahedral chain calculations, where the latter have periodic boundary conditions.

  3. Signatures of topological phase transition in 3 d topological insulators from dynamical axion response

    Makhfudz, Imam

    2016-04-01

    Axion electrodynamics, first proposed in the context of particle physics, manifests itself in condensed matter physics in the topological field theory description of 3 d topological insulators and gives rise to magnetoelectric effect, where applying magnetic (electric) field B (E ) induces polarization (magnetization) p (m ) . We use linear response theory to study the associated topological current using the Fu-Kane-Mele model of 3 d topological insulators in the presence of time-dependent uniform weak magnetic field. By computing the dynamical current susceptibility χij jpjp(ω ) , we discover from its static limit an `order parameter' of the topological phase transition between weak topological (or ordinary) insulator and strong topological insulator, found to be continuous. The χij jpjp(ω ) shows a sign-changing singularity at a critical frequency with suppressed strength in the topological insulating state. Our results can be verified in current noise experiment on 3 d TI candidate materials for the detection of such topological phase transition.

  4. Small metal soft tissue foreign body extraction by using 3D CT guidance: A reliable method

    Tao, Kai, E-mail: davidtaothree@yahoo.com.cn [Department of Plastic Surgery, General Hospital of Shenyang Military Command, PLA, Shenyang 110016 (China); Xu, Sen, E-mail: hubeixusen@163.com [Department of Radiology, General Hospital of Shenyang Military Command, 83 Wenhua Steet, Shenhe District, Shenyang 110016, Liaoning Province (China); Liu, Xiao-yan, E-mail: kk-lxy@sohu.com [Department of Plastic Surgery, General Hospital of Shenyang Military Command, PLA, Shenyang 110016 (China); Liang, Jiu-long, E-mail: liangjiulong@sohu.com [Department of Plastic Surgery, General Hospital of Shenyang Military Command, PLA, Shenyang 110016 (China); Qiu, Tao, E-mail: anthonyqueen@vip.sina.com [Department of Plastic Surgery, General Hospital of Shenyang Military Command, PLA, Shenyang 110016 (China); Tan, Jia-nan, E-mail: tanjianan@sina.com [Department of Plastic Surgery, General Hospital of Shenyang Military Command, PLA, Shenyang 110016 (China); Che, Jian-hua, E-mail: chejianhua@163.com [Department of Plastic Surgery, General Hospital of Shenyang Military Command, PLA, Shenyang 110016 (China); Wang, Zi-hua, E-mail: rockstar520@163.com [Department of Plastic Surgery, General Hospital of Shenyang Military Command, PLA, Shenyang 110016 (China)

    2012-11-15

    Objective: To introduce a useful and accurate technique for the locating and removal of small metal foreign bodies in the soft tissues. Methods: Eight patients presented with suspected small metal foreign bodies retained in the soft tissues of various body districts. Under local anesthesia, 3-6 pieces of 5 ml syringe needles or 1 ml syringe needles were induced through three different planes around the entry point of the foreign bodies. Using these finders, the small metal FBs were confirmed under 3D CT guidance. Based on the CT findings, the soft tissues were dissected along the path of the closest needle and the FBs were easily found and removed according to the relation with the closest needle finder. Results: Eight metal foreign bodies (3 slices, 3 nails, 1 fish hook, 1 needlepoint) were successfully removed under 3D CT guidance in all patients. The procedures took between 35 min and 50 min and the operation times took between 15 min and 25 min. No complications arose after the treatment. Conclusion: 3D CT-guided technique is a good alternative for the removal of small metal foreign body retained in the soft tissues as it is relatively accurate, reliable, quick, carries a low risk of complications and can be a first-choice procedure for the extraction of small metal foreign body.

  5. Small metal soft tissue foreign body extraction by using 3D CT guidance: A reliable method

    Objective: To introduce a useful and accurate technique for the locating and removal of small metal foreign bodies in the soft tissues. Methods: Eight patients presented with suspected small metal foreign bodies retained in the soft tissues of various body districts. Under local anesthesia, 3–6 pieces of 5 ml syringe needles or 1 ml syringe needles were induced through three different planes around the entry point of the foreign bodies. Using these finders, the small metal FBs were confirmed under 3D CT guidance. Based on the CT findings, the soft tissues were dissected along the path of the closest needle and the FBs were easily found and removed according to the relation with the closest needle finder. Results: Eight metal foreign bodies (3 slices, 3 nails, 1 fish hook, 1 needlepoint) were successfully removed under 3D CT guidance in all patients. The procedures took between 35 min and 50 min and the operation times took between 15 min and 25 min. No complications arose after the treatment. Conclusion: 3D CT-guided technique is a good alternative for the removal of small metal foreign body retained in the soft tissues as it is relatively accurate, reliable, quick, carries a low risk of complications and can be a first-choice procedure for the extraction of small metal foreign body.

  6. 3D microband boundary alignments and transitions in a cold rolled commercial purity aluminum alloy

    In the study of microband formation during plastic deformation of face centered cubic metals and alloys, two theories have been proposed regarding the orientations of their boundaries: (i) they are aligned parallel to crystallographic planes associated with dislocation glide (i.e. (111) planes in FCC metals), or (ii) they are aligned in accordance with the macroscopic stress state generated during deformation. In this study, high resolution 3D electron backscatter diffraction (3D EBSD) was used to investigate the morphology and crystallographic nature of microband boundaries within a 19 × 9 × 8.6 μm volume of a deformed grain in commercial purity aluminum cold rolled to 22% reduction. It was found that microband boundaries correspond to both theories of orientation. Additionally, a single surface may contain both crystallographic and non-crystallographic alignments. Misorientations across boundaries in the regions of microband triple junctions have been identified for both boundary alignments. - Highlights: ► Reconstruction of a 3D volume of crystallographic orientations from EBSD data ► Subgrain features accurately reconstructed using specially designed strategies. ► Microband boundaries contain crystallographic and non-crystallographic alignments. ► Boundaries form by crystallographic process but rotate to non-crystallographic

  7. Formation of 3D graphene foams on soft templated metal monoliths

    Tynan, Michael K.; Johnson, David W.; Dobson, Ben P.; Coleman, Karl S.

    2016-07-01

    Graphene foams are leading contenders as frameworks for polymer thermosets, filtration/pollution control and for use as an electrode material in energy storage devices, taking advantage of graphene's high electrical conductivity and the porous structure of the foam. Here we demonstrate a simple synthesis of a macroporous 3D graphene material templated from a dextran/metal salt gel, where the metal was cobalt, nickel, copper, and iron. The gel was annealed to form a metal oxide foam prior to a methane chemical vapour deposition (CVD). Cobalt metal gels were shown to afford the highest quality material as determined by electron microscopy (SEM and TEM) and Raman spectroscopy.Graphene foams are leading contenders as frameworks for polymer thermosets, filtration/pollution control and for use as an electrode material in energy storage devices, taking advantage of graphene's high electrical conductivity and the porous structure of the foam. Here we demonstrate a simple synthesis of a macroporous 3D graphene material templated from a dextran/metal salt gel, where the metal was cobalt, nickel, copper, and iron. The gel was annealed to form a metal oxide foam prior to a methane chemical vapour deposition (CVD). Cobalt metal gels were shown to afford the highest quality material as determined by electron microscopy (SEM and TEM) and Raman spectroscopy. Electronic supplementary information (ESI) available: Raman, EDX, PXRD, TGA, electrical conductivity data and SEM. See DOI: 10.1039/c6nr02455f

  8. Formation of 3D graphene foams on soft templated metal monoliths.

    Tynan, M. K.; Johnson, D. W.; Dobson, B. P.; Coleman, K. S.

    2016-01-01

    Graphene foams are leading contenders as frameworks for polymer thermosets, filtration/pollution control and for use as an electrode material in energy storage devices, taking advantage of graphene’s high electrical conductivity and the porous structure of the foam. Here we demonstrate a simple synthesis of a macroporous 3D graphene material templated from a dextran/metal salt gel, where the metal was cobalt, nickel, copper, and iron. The gel was annealed to form a metal oxide foam prior to a...

  9. 3D CFD computations of transitional flows using DES and a correlation based transition model

    Sørensen, Niels N.

    process can be important for the aerodynamic performance. Today, the most widespread approach is to use fully turbulent computations, where the transitional process is ignored and the entire boundary layer on the wings or airfoils is handled by the turbulence model. The correlation based transition model...... has lately shown promising results, and the present paper describes the application of the model to predict the drag and shedding frequency for flow around a cylinder from sub to super-critical Reynolds numbers. Additionally, the model is applied to the flow around the DU-96 airfoil, at high angles of...

  10. EXCHANGE-SPLITTING OF ADSORBATE-INDUCED BANDS IN CHEMISORPTION ON FERROMAGNETIC 3d-METALS

    Schönhense, G.; Getzlaff, M.; Westphal, C; Heidemann, B.; Bansmann, J.

    1988-01-01

    The influence of the ferromagnetism of 3d-metal substrates upon the electronic states of "nonmagnetic" adsorbate overlayers like oxygen and sulphur has been investigated by means of photoelectron spinpolarization spectroscopy. The spectra reveal a substantial exchange splitting of the O 2p- and S 3p-derived bands in chemisorption on Fe and FeCo. This demonstrates the strong magnetic coupling of these species with the substrate.

  11. 3D Analysis of Crack Growth in Metal Using Tension Tests and XFEM

    To prevent the occurrence of fractures in metal structures, it is very important to evaluate the 3D crack growth process in those structures and any related parts. In this study, tension tests and two simulations, namely, Simulation-I and Simulation-II, were performed using XFEM to evaluate crack growth in three dimensions. In the tension test, Mode I crack growth was observed for a notched metal specimen. In Simulation-I, a 3D reconstructed model of the specimen was created using CT images of the specimen. Using this model, an FE model was constructed, and crack growth was simulated using XFEM. In Simulation-II, an ideal notch FE model of the same geometric size as the actual specimen was created and then used for simulation. Obtained crack growth simulation results were then compared. Crack growth in the metal specimen was evaluated in three dimensions. It was shown that modeling the real shape of a structure with a crack may be essential for accurately evaluating 3D crack growth

  12. Transition metals in carbohydrate chemistry

    Madsen, Robert

    1997-01-01

    This review describes the application of transition metal mediated reactions in carbohydrate synthesis. The different metal mediated transformations are divided into reaction types and illustrated by various examples on monosaccharide derivatives. Carbon-carbon bond forming reactions are further ...

  13. Dynamics of Phase Transitions: The 3D 3-state Potts model

    Berg, B A; Velytsky, A; Berg, Bernd A.; Meyer-Ortmanns, Hildegard; Velytsky, Alexander

    2004-01-01

    In studies of the QCD deconfining phase transition or cross-over by means of heavy ion experiments, one ought to be concerned about non-equilibrium effects due to heating and cooling of the system. In this paper we extend our previous study of Glauber dynamics of 2D Potts models to the 3D 3-state Potts model, which serves as an effective model for some QCD properties. We investigate the linear theory of spinodal decomposition in some detail. It describes the early time evolution of the 3D model under a quench from the disordered into the ordered phase well, but fails in 2D. Further, the quench leads to competing vacuum domains, which are difficult to equilibrate, even in the presence of a small external magnetic field. From our hysteresis study we find, as before, a dynamics dominated by spinodal decomposition. There is evidence that some effects survive in the case of a cross-over. But the infinite volume extrapolation is difficult to control, even with lattices as large as 120^3.

  14. Low-Cost Impact Detection and Location for Automated Inspections of 3D Metallic Based Structures

    Carlos Morón

    2015-05-01

    Full Text Available This paper describes a new low-cost means to detect and locate mechanical impacts (collisions on a 3D metal-based structure. We employ the simple and reasonably hypothesis that the use of a homogeneous material will allow certain details of the impact to be automatically determined by measuring the time delays of acoustic wave propagation throughout the 3D structure. The location of strategic piezoelectric sensors on the structure and an electronic-computerized system has allowed us to determine the instant and position at which the impact is produced. The proposed automatic system allows us to fully integrate impact point detection and the task of inspecting the point or zone at which this impact occurs. What is more, the proposed method can be easily integrated into a robot-based inspection system capable of moving over 3D metallic structures, thus avoiding (or minimizing the need for direct human intervention. Experimental results are provided to show the effectiveness of the proposed approach.

  15. Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

    The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M13. First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first-principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M13 structures. Several new lower energy configurations were identified, e.g., Pd13, W13, Pt13, etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au13, we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained

  16. Template-Free 3D Microprinting of Metals Using a Force-Controlled Nanopipette for Layer-by-Layer Electrodeposition.

    Hirt, Luca; Ihle, Stephan; Pan, Zhijian; Dorwling-Carter, Livie; Reiser, Alain; Wheeler, Jeffrey M; Spolenak, Ralph; Vörös, János; Zambelli, Tomaso

    2016-03-23

    A novel 3D printing method for voxel-by-voxel metal printing is presented. Hollow atomic force microscopy (AFM) cantilevers are used to locally supply metal ions in an electrochemical cell, enabling a localized electroplating reaction. By exploiting the deflection feedback of these probes, electrochemical 3D metal printing is, for the first time, demonstrated in a layer-by-layer fashion, enabling the fabrication of arbitrary-shaped geometries. PMID:26783090

  17. Simulation of the impact of 3-D porosity distribution in metallic U-10Zr fuels

    Yun, Di; Yacout, Abdellatif M.; Stan, Marius; Bauer, Theodore H.; Wright, Arthur E.

    2014-05-01

    Evolution of porosity generated in metallic U-Zr fuel irradiated in fast spectrum reactors leads to changes in fuel properties and impacts important phenomena such as heat transport and constituent redistribution. The porosity is generated as a result of the accumulation of fission gases and is affected by the possible bond sodium infiltration into the fuel. Typically, the impact of porosity development on properties, such as thermal conductivity, is accounted for through empirical correlations that are dependent on porosity and infiltrated sodium fractions. Currently available simulation tools make it possible to take into account fuel 3-D porosity distributions, potentially eliminating the need for such correlations. This development allows for a more realistic representation of the porosity evolution in metallic fuel and creates a framework for truly mechanistic fuel development models. In this work, COMSOL multi-physics simulation platform is used to model 3-D porosity distributions and simulate heat transport in metallic U-10Zr fuel. Available experimental data regarding microstructural evolution of fuel that was irradiated in EBR-II and associated phase stability information are used to guide the simulation. The impact of changes in porosity characteristics on material properties is estimated and the results are compared with calculated temperature distributions. The simulations demonstrate the developed capability and importance of accounting for detailed porosity distribution features for accurate fuel performance evaluation.

  18. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    Shi, Fa-Nian, E-mail: fshi@ua.pt [School of Science, Shenyang University of Technology, 110870 Shenyang (China); Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Rosa Silva, Ana [Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Bian, Liang [Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, Xinjiang (China)

    2015-05-15

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi{sub 2}O(1,3,5-BTC){sub 2}]{sub n} (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi{sub 4}O{sub 2}(COO){sub 12} clusters which are further connected to Mn(COO){sub 6} fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4{sup 13}.6{sup 2})(4{sup 13}.6{sup 8})(4{sup 16}.6{sup 5})(4{sup 18}.6{sup 10})(4{sup 22}.6{sup 14})(4{sup 3}) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles.

  19. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi2O(1,3,5-BTC)2]n (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi4O2(COO)12 clusters which are further connected to Mn(COO)6 fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (413.62)(413.68)(416.65)(418.610)(422.614)(43) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles

  20. Polarization matrices in simple and transition metals

    Full text: The polarization of an inhomogeneous electron gas within a metal due to electron-electron correlations is fundamental for the prediction of inelastic electron scattering experiments such as energy-lose measurements and Compton profile studies. Moreover, the polarization matrix serves as starting point for many advanced theoretical topics as quasiparticle band structures, self energies and realistic electron momentum densities. For this contribution, we calculated polarization matrices for alkali metals, as well as for the complete serves from potassium (atomic number 19) to zinc (30) including all 3d transition metals. The main topic of our work is to study how the polarization is influenced by the fast that the correlating particles are 'Bloch electrons'. These influences become visible in the polarization matrices by (i) deviations of their diagonal elements with respect to the 'homogeneous case', and by (ii) the appearance of non-diagonal elements. We obtained an excellent agreement for the simple metals Na, K and Rb with 'jellium results', and found remarkable deviations for Li and Cs. Moreover, our results show that the non-uniform character of the 3d transition elements depends sensitively on the number of d-electrons and the energetic position of the d-bands with respect to the Fermi energy. (author)

  1. Electrical Conductivity in Transition Metals

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

    The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

  2. Metal rings and discs Matlab/Simulink 3D model for ultrasonic sandwich transducer design

    Jovanović I.

    2012-01-01

    Full Text Available Metal-endings are integral part of different ultrasonic sandwich transducers. In this paper a new Matlab/Simulink 3D model of the finite metal rings and discs of various dimensions is realized. With this model, which describes both the thickness and the radial resonant modes, and the coupling between them, mechanical impedance of the sample can be easily computed. Resonance frequency-length curves for rings and disks with various materials and for different selected dimensions are given. Also, comparisons of the different approaches in determining of their resonant frequencies are shown. The proposed Matlab/Simulink model requires simpler implementation than other analytical models. That enabled modifying of 1D theory and simplified modelling and projecting of the ultrasonic sandwich transducers with short-endings. Finally, the computed and experimental results are compared. [Projekat Ministarstva nauke Republike Srbije, br. TR33035, br. III43014 i br. OI172057

  3. Breit-Pauli energy levels, transition probabilities, and lifetimes for 3d^5 levels in Fe IV of astrophysical interest

    Fischer, Charlotte Froese; Rubin, Robert H

    2004-01-01

    Energy levels, lifetimes, and transition probabilities for transitions between computed levels of 3d^5 of Fe IV are reported. The E2 and M1 transition probabilities are compared with earlier theoretical results, often only the values published by Garstang in 1958. From the available astronomical observations of optical emission lines arising from the same level, a few direct tests are now possible and they show consistency with the theoretical calculations.

  4. Transitioning from 2-D Radiation Therapy to 3-D Conformal Radiation Therapy and Intensity Modulated Radiation Therapy: Training Material

    The technology of radiation oncology has advanced very rapidly in recent years. However, the sophistication of technology available in individual radiation therapy centres varies dramatically throughout the world. Treatment capabilities with planar imaging and limited cross-sectional imaging support have been labelled as two dimensional radiation therapy (2-D RT). With increased use of more advanced cross-sectional imaging, the introduction of more complex dose calculation capabilities for treatment planning and more sophisticated treatment delivery procedures, three dimensional conformal radiation therapy (3-D CRT) can be provided. Further sophistication in treatment planning and treatment delivery capabilities enables intensity modulated radiation therapy (IMRT). Recognizing that huge disparities exist across the world, and in an attempt to aid in advancing institutional capabilities, the IAEA published ‘Transition from 2-D Radiotherapy to 3-D Conformal and Intensity Modulated Radiotherapy’ (IAEA-TECDOC-1588) in May 2008. Divided into two parts — on CRT and on IMRT — the publication provides guidelines on the transition from 2-D RT through 3-D CRT to IMRT. It is recognized that 3-D CRT is the standard of care in most radiation treatment processes and that IMRT technologies are still evolving. The publication provides clear guidelines and highlights the milestones to be achieved when transitioning from 2-D RT to 3-D CRT and IMRT. While IAEA-TECDOC-1588 provides comprehensive guidelines and milestones, the present publication provides training materials to aid professionals in the continuing education required for the implementation of more advanced treatment capabilities, especially 3-D CRT. These materials are based on the results of two consultants meetings organized by the IAEA in 2009 and 2010, primarily focused on providing guidance on what training materials were available or needed to be developed, with a special emphasis on transitioning from 2-D

  5. Development of metal-assisted chemical etching of silicon as a 3D nanofabrication platform

    Hildreth, Owen James

    The considerable interest in nanomaterials and nanotechnology over the last decade is attributed to Industry's desire for lower cost, more sophisticated devices and the opportunity that nanotechnology presents for scientists to explore the fundamental properties of nature at near atomic levels. In pursuit of these goals, researchers around the world have worked to both perfect existing technologies and also develop new nano-fabrication methods; however, no technique exists that is capable of producing complex, 2D and 3D nano-sized features of arbitrary shape, with smooth walls, and at low cost. This in part is due to two important limitations of current nanofabrication methods. First, 3D geometry is difficult if not impossible to fabricate, often requiring multiple lithography steps that are both expensive and do not scale well to industrial level fabrication requirements. Second, as feature sizes shrink into the nano-domain, it becomes increasingly difficult to accurately maintain those features over large depths and heights. The ability to produce these structures affordably and with high precision is critically important to a number of existing and emerging technologies such as metamaterials, nano-fluidics, nano-imprint lithography, and more. To overcome these limitations, this study developed a novel and efficient method to etch complex 2D and 3D geometry in silicon with controllable sub-micron to nano-sized features with aspect ratios in excess of 500:1. This study utilized Metal-assisted Chemical Etching (MaCE) of silicon in conjunction with shape-controlled catalysts to fabricate structures such as 3D cycloids, spirals, sloping channels, and out-of-plane rotational structures. This study focused on taking MaCE from a method to fabricate small pores and silicon nanowires using metal catalyst nanoparticles and discontinuous thin films, to a powerful etching technology that utilizes shaped catalysts to fabricate complex, 3D geometry using a single lithography

  6. Multiconfiguration Dirac-Hartree-Fock energy levels and transition probabilities for 3d^5 in Fe IV

    Fischer, C. Froese; Rubin, R. H.; M. Rodríguez

    2008-01-01

    Multiconfiguration Dirac-Hartree-Fock electric quadrupole (E2) and magnetic dipole (M1) transition probabilities are reported for transitions between levels of 3d^5 in [Fe IV]. The accuracy of the ab initio energy levels and the agreement in the length and velocity forms of the line strength for the E2 transitions are used as indicators of accuracy. The present E2 and M1 transition probabilities are compared with earlier Breit-Pauli results and other theories. An extensive set of transition p...

  7. Pillared layered transition metal oxides

    2003-01-01

    This paper reviews the recent progress in the synthesis and application of pillared transition metal oxides during the last decade, mainly concerning the synthetic methods, structures, physical properties and catalytic applications of the layered transition metal oxides pillared by inorganic oxides. The factors and their affecting regularity in the process of preparation, and some important results obtained in the catalytic application studies are summarized. Finally, a prospect on the potential new directions in this research area is also presented.

  8. Permeability measurements and modeling of topology-optimized metallic 3-D woven lattices

    Topology optimization was combined with a 3-D weaving technique to design and fabricate structures with optimized combinations of fluid permeability and mechanical stiffness. Two different microarchitected structures are considered: one is a “standard” weave in which all wires were included, while the other is termed an “optimized” weave as specific wires were removed to maximize the permeability of the resulting porous materials with only a limited reduction in stiffness. Permeability was measured and predicted for both structures that were 3-D woven with either Cu or Ni–20Cr wires. The as-woven wires in the Cu lattices were bonded at contact points using solder or braze while the Ni–20Cr wires were bonded at contact points using pack aluminization. Permeability was measured under laminar flow conditions in all three normal directions for unbonded and bonded samples and in the optimized structure it was found to increase between 200% and 600%, depending on direction, over the standard structures. Permeability was also predicted using finite-element modeling with as-fabricated wires positions that were identified with optical microscopy or X-ray tomography; the measurements and predictions show good agreement. Lastly, the normalized permeability values significantly exceed those found for stochastic, metallic foams and other periodic structures with a material volume fraction of over 30%

  9. 2D and 3D alkaline earth metal carboxyphosphonate hybrids: Anti-corrosion coatings for metal surfaces

    Reactions of Mg2+ (1), Ca2+ (2), Sr2+ (3), or Ba2+ (4) salts with hydroxyphosphonoacetic acid (HPAA) at a 1:1 ratio yield M-HPAA layered coordination polymers. The crystal structures of 3 (two phases) and 4 have been determined by single crystal X-ray crystallography. Both stereoisomers (R and S) of HPAA are incorporated in the metal-HPAA materials. Synergistic combinations of Sr2+ or Ba2+ and HPAA at pH 7.3 are effective corrosion inhibitors for carbon steel, but are ineffective at pH 2.0. - Graphical abstract: Syntheses, characterization and crystal structures of metal-hydroxyphosphonoacetate hybrids are reported (Metal=Sr, Ba). 2D and 3D materials were prepared. Their anti-corrosion effects were studied at pH 2.0 and 7.3. It was found that anti-corrosion efficiency was demonstrated only at pH 7.3

  10. Computed Tomography 3-D Imaging of the Metal Deformation Flow Path in Friction Stir Welding

    Schneider, Judy; Beshears, Ronald; Nunes, Arthur C., Jr.

    2005-01-01

    In friction stir welding (FSW), a rotating threaded pin tool is inserted into a weld seam and literally stirs the edges of the seam together. To determine optimal processing parameters for producing a defect free weld, a better understanding of the resulting metal deformation flow path is required. Marker studies are the principal method of studying the metal deformation flow path around the FSW pin tool. In our study, we have used computed tomography (CT) scans to reveal the flow pattern of a lead wire embedded in a FSW weld seam. At the welding temperature of aluminum, the lead becomes molten and is carried with the macro-flow of the weld metal. By using CT images, a 3-dimensional (3D) image of the lead flow pattern can be reconstructed. CT imaging was found to be a convenient and comprehensive way of collecting and displaying tracer data. It marks an advance over previous more tedious and ambiguous radiographic/metallographic data collection methods.

  11. 3s2S-3d2D electric quadrupole transitions for highly stripped Na-like ions

    A fully relativistic multiconfiguration Dirac-Fock method with Breit and QED corrections is used to calculated the 3s2S-3d2D (Z = 14-103) transition energy level separations, transition probabilities and oscillator strengths for the Na-like ions. In calculation, the author considered significant Breit and QED corrections, the results are in good agreement with recent experimental data and other theoretical values. The results show that the electric quadruple transition probabilities are in correspondence with those of E1 transitions and can not be ignored in high temperature laser plasma in ICF and MCF Fusion

  12. Island Shape-Induced Transition from 2D to 3D Growth for Pt/Pt(111)

    Jacobsen, Joachim; Jacobsen, Karsten Wedel; Stoltze, Per;

    1995-01-01

    We present a kinetic Monte Carlo simulation of the growth of Pt on Pt(111) capable of describing the experimentally observed temperature dependence of the island shapes and the growth mode. We show that the transition from a 2D growth mode at low temperatures to a 3D mode at higher temperatures is...

  13. Aerosol based direct-write micro-additive fabrication method for sub-mm 3D metal-dielectric structures

    The fabrication of 3D metal-dielectric structures at sub-mm length scale is highly important in order to realize low-loss passives and GHz wavelength antennas with applications in wearable and Internet-of-Things (IoT) devices. The inherent 2D nature of lithographic processes severely limits the available manufacturing routes to fabricate 3D structures. Further, the lithographic processes are subtractive and require the use of environmentally harmful chemicals. In this letter, we demonstrate an additive manufacturing method to fabricate 3D metal-dielectric structures at sub-mm length scale. A UV curable dielectric is dispensed from an Aerosol Jet system at 10–100 µm length scale and instantaneously cured to build complex 3D shapes at a length scale  <1 mm. A metal nanoparticle ink is then dispensed over the 3D dielectric using a combination of jetting action and tilted dispense head, also using the Aerosol Jet technique and at a length scale 10–100 µm, followed by the nanoparticle sintering. Simulation studies are carried out to demonstrate the feasibility of using such structures as mm-wave antennas. The manufacturing method described in this letter opens up the possibility of fabricating an entirely new class of custom-shaped 3D structures at a sub-mm length scale with potential applications in 3D antennas and passives. (technical note)

  14. Aerosol based direct-write micro-additive fabrication method for sub-mm 3D metal-dielectric structures

    Rahman, Taibur; Renaud, Luke; Heo, Deuk; Renn, Michael; Panat, Rahul

    2015-10-01

    The fabrication of 3D metal-dielectric structures at sub-mm length scale is highly important in order to realize low-loss passives and GHz wavelength antennas with applications in wearable and Internet-of-Things (IoT) devices. The inherent 2D nature of lithographic processes severely limits the available manufacturing routes to fabricate 3D structures. Further, the lithographic processes are subtractive and require the use of environmentally harmful chemicals. In this letter, we demonstrate an additive manufacturing method to fabricate 3D metal-dielectric structures at sub-mm length scale. A UV curable dielectric is dispensed from an Aerosol Jet system at 10-100 µm length scale and instantaneously cured to build complex 3D shapes at a length scale  <1 mm. A metal nanoparticle ink is then dispensed over the 3D dielectric using a combination of jetting action and tilted dispense head, also using the Aerosol Jet technique and at a length scale 10-100 µm, followed by the nanoparticle sintering. Simulation studies are carried out to demonstrate the feasibility of using such structures as mm-wave antennas. The manufacturing method described in this letter opens up the possibility of fabricating an entirely new class of custom-shaped 3D structures at a sub-mm length scale with potential applications in 3D antennas and passives.

  15. Role of 4p-3d orbital hybridization on band gap engineering of heavy metal glass for optoelectronic applications

    El-Diasty, Fouad, E-mail: fdiasty@yahoo.com [Physics Department, Faculty of Science, Ain Shams University, Abbasia, 11566 Cairo (Egypt); Moustafa, F.A. [Glass Department, National Research Centre, Dokki, 12311 Giza (Egypt); Abdel-Wahab, F.A. [Physics Department, Faculty of Science, Ain Shams University, Abbasia, 11566 Cairo (Egypt); Abdel-Baki, M.; Fayad, A.M. [Glass Department, National Research Centre, Dokki, 12311 Giza (Egypt)

    2014-08-25

    Highlights: • We have demonstrated that incorporation of highly electronegative p-block ions into heavy metal glasses can effectively depress their electronic band gap. • The 4p-3d orbital hybridization of SeO{sub 2} and Cr{sub 2}O{sub 3} in heavy metal glass gets success to reduce dramatically the glass Urbach tail and Fermi level while increasing the two-photon absorption coefficient one order of magnitude rather than conventional semiconductor glasses. • Applying Elliott’s model on linear absorption of the glass indicates that the glass has a direct band gap structure. - Abstract: Optoelectronic properties of glasses can be engineered by understanding the electronic structure and the symmetry of electronic states across the band gap where the chemical bonding is the origin of such electronic structure. Thus, series of heavy metal lead borate glasses of the composition 0.25B{sub 2}O{sub 3}–0.75PbO is prepared by melt quenching technique for Vis–IR photonics applications. Hybridization of p- and d-block elements, through co-substitution of Cr{sub 2}O{sub 3} and SeO{sub 2}, by B{sub 2}O{sub 3}, is used to tune effectively the glass electronic structure characteristics such as; band gap energy, Fermi level, and Urbach exciton–phonon coupling. Two-photon absorption coefficient is determined to elucidate the glass nonlinear sub-interband transitions. Chemical bond approach is applied to analyze and explain the obtained glass properties. The excitons excitation is discussed by applying Elliott’s model which indicates direct interband transition nature of the glass that is assisted by the existence of stable Frenkel excitons.

  16. Role of 4p-3d orbital hybridization on band gap engineering of heavy metal glass for optoelectronic applications

    Highlights: • We have demonstrated that incorporation of highly electronegative p-block ions into heavy metal glasses can effectively depress their electronic band gap. • The 4p-3d orbital hybridization of SeO2 and Cr2O3 in heavy metal glass gets success to reduce dramatically the glass Urbach tail and Fermi level while increasing the two-photon absorption coefficient one order of magnitude rather than conventional semiconductor glasses. • Applying Elliott’s model on linear absorption of the glass indicates that the glass has a direct band gap structure. - Abstract: Optoelectronic properties of glasses can be engineered by understanding the electronic structure and the symmetry of electronic states across the band gap where the chemical bonding is the origin of such electronic structure. Thus, series of heavy metal lead borate glasses of the composition 0.25B2O3–0.75PbO is prepared by melt quenching technique for Vis–IR photonics applications. Hybridization of p- and d-block elements, through co-substitution of Cr2O3 and SeO2, by B2O3, is used to tune effectively the glass electronic structure characteristics such as; band gap energy, Fermi level, and Urbach exciton–phonon coupling. Two-photon absorption coefficient is determined to elucidate the glass nonlinear sub-interband transitions. Chemical bond approach is applied to analyze and explain the obtained glass properties. The excitons excitation is discussed by applying Elliott’s model which indicates direct interband transition nature of the glass that is assisted by the existence of stable Frenkel excitons

  17. Merging transition-metal activation and aminocatalysis

    Rios, Ramon; Meazza, Marta

    2015-01-01

    In this review the principal enantioselective methodologies merging transition-metal catalysis and aminocatalysis are disclosed. 1 Introduction 2 Transition-Metal and Enamine Catalysis 3 Transition-Metal and Iminium Catalysis 4 Transition-Metal Catalysis and Organocascade (Iminium/Enamine) Activation 5 Conclusions and Perspectives

  18. Doping effects of 3D metal on single-phase YBa2Cu3O/sub 7-//sub δ/

    The measurements of x-ray diffraction, the temperature dependence of the dc resistance and the ac susceptibility have been performed for the single-phase 3D-metal doping systems YBa2 Cu/sub 3-//sub x/ M/sub x/ O/sub y/ (M = Fe, Co, and Ni; x = 0.025, 0.05, 0.075, 0.10, 0.25, and 0.50 for Ni and Co and 0.05, 0.075, 0.10, 0.15, and 0.20 for Fe). With an increase of impurity content, two structural transitions were observed for the Co and Fe dopants but only one for the Ni dopant. The resistivity in the normal state changes from metallic to semiconductinglike behavior and the depression of T/sub c/ is linear with the impurity concentration (x) when x<0.10. A weak Curie--Weiss type paramagnetism, which is enhanced with impurity content, exists in the samples studied. Incorporating other work on oxygen defects, we suggest that a change of oxygen content induced by doping was the dominant effect on superconductivity in these samples

  19. A 3-D coupled hydromechanical granular model for simulating the constitutive behavior of metallic alloys during solidification

    Sistaninia, M.; Phillion, A. B.; Drezet, J. -M.; Rappaz, M.

    2012-01-01

    A three-dimensional (3-D) coupled hydromechanical granular model has been developed and validated to directly predict, for the first time, hot tear formation and stress strain behavior in metallic alloys during solidification. This granular model consists of four separate 3-D modules: (i) the solidification module is used to generate the solid liquid geometry at a given solid fraction; (ii) the fluid flow module (FFM) is used to calculate the solidification shrinkage and deformation-induced p...

  20. 3d-Metal Doped into LiMn2O4 Thin Films

    Bates, J.B.; Ueda, A.; Zuhr, R.A.

    1998-11-01

    3d-metal (Me) doped LiMn{sub 2}O{sub 4} thin films were deposited by rf magnetron sputtering of Li[Mn{sub 1.9}Me{sub 0.1}]O{sub 4} targets in Ar + N{sub 2} and Ar + O{sub 2} gas mixtures and annealed at 750{degrees}C in O{sub 2} for 1 h. From XRD measurements, the structure of the Me-doped thin film was dependent upon the element and the deposition conditions. The doping level of Me/Mn of cubic phase was less than 0.1 by EDX measurements. The Ti-LiMn{sub 2}O{sub 4} films exhibited a capacity close to theoretical for stoichiometric LiMn{sub 2}O{sub 4}. This improvement at 4 V comes at the expense of the capacity at 5 V. Cells with Ti-doped films exhibited the same low capacity fade as those with undoped LiMn{sub 2}O{sub 4} cathodes. Similar electrochemical changes were observed with the Cr- and Zn-LiMn{sub 2}O{sub 4} films. The discharge capacities above 4.5 V for the Ni-doped films were about equal to those below 4.5 V, and the thin-film cells could be cycled reversibility between 3.5 and 5.3 V.

  1. SYNTHESIS, STRUCTURE AND BIOLOGICAL ACTIVITY OF N(4-ALLYL-3-THIOSEMICARBAZONES AND THEIR COORDINATION COMPOUNDS WITH SOME 3D METALS

    Vasilii GRAUR

    2016-02-01

    Full Text Available The paper presents a review of different N(4-allyl-3-thiosemicarbazones and their coordination compounds described in literature. N(4-allyl-3-thiosemicarbazide can form corresponding thiosemicarbazones with aliphatic, aromatic and heteroaromatic carbonyl compounds. In the presence of transitional metal ions they can form coordination compounds of different structures. Both coordination compounds and proligands manifest antitumor, antibacterial, antiviral, and antimalarial activities. Copper(II coordination compounds with these ligands manifest better antitumor activity than corresponding proligands. SINTEZA, STRUCTURA ŞI ACTIVITATEA BIOLOGICĂ A N(4-ALIL-3-TIOSEMICARBAZONELOR ŞI A COMPUŞILOR COORDINATIVI AI UNOR METALE 3D CU ACEŞTI LIGANZILucrarea prezintă o revistă a N(4-alil-3-tiosemicarbazonelor şi a compuşilor coordinativi cu aceşti liganzi descrise în literatura de specialitate. N(4-alil-3-tiosemicarbazida formează tiosemicarbazone cu aldehide şi cetone alifatice, aro­matice şi heteroaromatice. În prezenţa ionilor de metale de tranziţie acestea pot forma compuşi coordinativi cu diferite structuri. N(4-alil-3-tiosemicarbazonele şi compuşii coordinativi manifestă activitate antitumorală, antibacterială, antivirală şi antimalarică. Compuşii coordinativi ai cuprului cu aceşti liganzi manifestă activitate antitumorală sporită în comparaţie cu N(4-alil-3-tiosemicarbazonele corespunzătoare. 

  2. Epithelial-to-mesenchymal transition in pancreatic ductal adenocarcinoma: Characterization in a 3D-cell culture model

    Gagliano, Nicoletta; Celesti, Giuseppe; Tacchini, Lorenza; Pluchino, Stefano; Sforza, Chiarella; Rasile, Marco; Valerio, Vincenza; Laghi, Luigi; Conte, Vincenzo; Procacci, Patrizia

    2016-01-01

    AIM: To analyze the effect of three-dimensional (3D)-arrangement on the expression of epithelial-to-mesenchymal transition markers in pancreatic adenocarcinoma (PDAC) cells. METHODS: HPAF-II, HPAC, and PL45 PDAC cells were cultured in either 2D-monolayers or 3D-spheroids. Ultrastructure was analyzed by transmission electron microscopy. The expression of E-cadherin, β-catenin, N-cadherin, collagen type I (COL-I), vimentin, α-smooth muscle actin (αSMA), and podoplanin was assayed by confocal microscopy in cells cultured on 12-mm diameter round coverslips and in 3D-spheroids. Gene expression for E-cadherin, Snail, Slug, Twist, Zeb1, and Zeb2 was quantified by real-time PCR. E-cadherin protein level and its electrophoretic pattern were studied by Western blot in cell lysates obtained from cells grown in 2D-monolayers and 3D-spheroids. RESULTS: The E-cadherin/β-catenin complex was expressed in a similar way in plasma membrane cell boundaries in both 2D-monolayers and 3D-spheroids. E-cadherin increased in lysates obtained from 3D-spheroids, while cleavage fragments were more evident in 2D-monolayers. N-cadherin expression was observed in very few PDAC cells grown in 2D-monolayers, but was more evident in 3D-spheroids. Some cells expressing COL-I were observed in 3D-spheroids. Podoplanin, expressed in collectively migrating cells, and αSMA were similarly expressed in both experimental conditions. The concomitant maintenance of the E-cadherin/β-catenin complex at cell boundaries supports the hypothesis of a collective migration for these cells, which is consistent with podoplanin expression. CONCLUSION: We show that a 3D-cell culture model could provide deeper insight into understanding the biology of PDAC and allow for the detection of marked differences in the phenotype of PDAC cells grown in 3D-spheroids. PMID:27182158

  3. Testing of treatment planning system in aspect of transitioning from 3-D to IMRT

    measurement. The difference was less than 1% in simple geometries and up to 5% in complex geometries with heterogeneity. To apply an IMRT plan to a patient, one needs to verify it beforehand. As a patient-specific test we chose to perform absolute dose measurements in several critical points for single multisegment field and total dose measurements in water phantom in vertical and horizontal mode for all beams. Good agreement of calculation and measurements led us to transit from 2-D to 3-D conformal radiotherapy and to begin introducing IMRT in our clinical practice. To use IMRT in clinical practice more extensively, we need to work out a patient-specific QA protocol. In spite of the absence of required equipment and software for this QA we consider the use of IMRT in clinical practice possible because we made a basic set of tests. (author)

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

    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.

  5. Isotope shifts and hyperfine structure in the 3d 2DJ→4p 2PJ transitions in calcium II

    The isotope shift and hyperfine structure in the three 3d 2D3/2,5/2→4p2P1/2,3/2 - transitions in Ca II have been studied by fast ion beam collinear laser spectroscopy for all stable Ca isotopes. The metastable 3d states were populated within the surface ionization source of a mass separator with a probability of about 0.1%. After resonant excitation to the 4p levels with diode laser light around 850 nm the UV photons from the 4p →4s transitions to the ground state were used for detection. Hyperfine structure parameters A and B for the odd isotope 43Ca, as evaluated from the splittings observed, agree well with theoretical predictions from relativistic many-body perturbation theory. Field shift constants KFS and specific mass shift constants KSMS were extracted from the measured isotope shifts and are discussed in comparison with expectation values from theory. (orig.)

  6. Alkali and transition metal phospholides

    Major tendencies in modern chemistry of alkali and transition metal phospholides (phosphacyclopentadienides) are systematized, analyzed and generalized. Basic methods of synthesis of these compounds are presented. Their chemical properties are considered with a special focus on their complexing ability. Potential applications of phospholides and their derivatives are discussed. The bibliography includes 184 references

  7. Finite-size scaling analysis of localization transition for scalar waves in a 3D ensemble of resonant point scatterers

    Skipetrov, S E

    2016-01-01

    We use the random Green's matrix model to study the scaling properties of the localization transition for scalar waves in a three-dimensional (3D) ensemble of resonant point scatterers. We show that the probability density $p(g)$ of normalized decay rates of quasi-modes $g$ is very broad at the transition and in the localized regime and that it does not obey a single-parameter scaling law. The latter holds, however, for the small-$g$ part of $p(g)$ which we exploit to estimate the critical exponent $\

  8. Lattice Boltzmann Simulation of 3D Nematic Liquid Crystal near Phase Transition

    ZHANG Jun; TAO Rui-Bao

    2002-01-01

    Phase transition between nematic and isotropic liquid crystal is a very weak first order phase transition.We avoid to use the normal Landau-de Gennes's free energy that reduces a strong first order transition, and set up adata base of free energy calculated by means of Tao-Sheng Lin's extended molecular field theory that can explain theexperiments of the equilibrium properties of nematic liquid crystal very well. Then we use the free energy method oflattice Boltzmann developed by Oxford group to study the phase decomposition, pattern formation in the flow of theliquid crystal near transition temperature.

  9. First refraction enhanced 3D computed tomography. Application to metal matrix composites

    For the first time Metal Matrix Composites (MMC) have been investigated by 3D Computed Tomography combined with enhanced interface contrast due to X-ray refraction. X-ray refraction is a relatively new approach for the characterization of advanced materials. The related techniques of Refraction Topography and Refraction Computed Tomography have been developed and applied at our laboratory during the last decade to meet the actual demand for improved non-destructive characterization of high performance composites, ceramics and other low density materials and components. X-ray refraction occurs, when X-rays crosses interfaces of spherical or cylindrical shape (e.g. pores or fibres) in the same way as visible light is refracted by lenses. These X-ray optical effects can be observed at small scattering angles of few minutes of arc as the refractive index n of X-rays is nearly unity (n = 1 - 10-6). Due to the short X-ray wavelength of about 0.1 nm the technique determines the amount of inner surfaces and interfaces of nanometer dimensions. The technique is expected to solve many problems in understanding the meaning of micro and sub micro structures in materials science. With the results of the CT investigation, some questions could be clarified for a better understanding of fatigue failure mechanisms under cyclic loading conditions. The specimens for the test programme have been provided by MTU Aero Engines. They consist of a titanium matrix (Ti6242) reinforced by SiC fibres (SCS6). The investigations have been performed at the materials research station of BAM (BAMline) at the Synchrotron Facility BESSY in Berlin, Germany

  10. The evolution of metallicity and metallicity gradients from z=2.7-0.6 with KMOS3D

    Wuyts, Eva; Fossati, Matteo; Schreiber, Natascha M Förster; Genzel, Reinhard; Davies, Ric; Mendel, J Trevor; Naab, Thorsten; Röttgers, Bernhard; Wilman, David J; Wuyts, Stijn; Bandara, Kaushala; Beifiori, Alessandra; Belli, Sirio; Bender, Ralf; Brammer, Gabriel B; Burkert, Andreas; Chan, Jeffrey; Galametz, Audrey; Kulkarni, Sandesh K; Lang, Philipp; Lutz, Dieter; Momcheva, Ivelina G; Nelson, Erica J; Rosario, David; Saglia, Roberto P; Seitz, Stella; Tacconi, Linda J; Tadaki, Ken-ichi; Übler, Hannah; van Dokkum, Pieter

    2016-01-01

    We present measurements of the [NII]/Ha ratio as a probe of gas-phase oxygen abundance for a sample of 419 star-forming galaxies at z=0.6-2.7 from the KMOS3D near-IR multi-IFU survey. The mass-metallicity relation (MZR) is determined consistently with the same sample selection, metallicity tracer, and methodology over the wide redshift range probed by the survey. We find good agreement with long-slit surveys in the literature, except for the low-mass slope of the relation at z~2.3, where this sample is less biased than previous samples based on optical spectroscopic redshifts. In this regime we measure a steeper slope than some literature results. Excluding the AGN contribution from the MZR reduces sensitivity at the high mass end, but produces otherwise consistent results. There is no significant dependence of the [NII]/Ha ratio on SFR or environment at fixed redshift and stellar mass. The IFU data allow spatially resolved measurements of [NII]/Ha, from which we can infer abundance gradients for 180 galaxies...

  11. Laser-Directed CVD 3D Printing of Refractory Metal Rocket Propulsion Hardware Project

    National Aeronautics and Space Administration — In this project, Ultramet will develop a three-dimensional (3D) laser-directed chemical vapor deposition (CVD) additive manufacturing system to build free-form...

  12. Scaling law and critical exponent for {alpha}{sub 0} at the 3D Anderson transition

    Slevin, K. [Department of Physics, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043 (Japan); Rodriguez, A.; Roemer, R.A. [Department of Physics and Centre for Scientific Computing, University of Warwick, Coventry, CV4 7AL (United Kingdom); Vasquez, L.J.

    2009-12-15

    We use high-precision, large system-size wave function data to analyse the scaling properties of the multifractal spectra around the disorder-induced three-dimensional Anderson transition in order to extract the critical exponents of the transition. Using a previously suggested scaling law, we find that the critical exponent {nu} is significantly larger than suggested by previous results. We speculate that this discrepancy is due to the use of an oversimplified scaling relation. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  13. Communication: Systematic shifts of the lowest unoccupied molecular orbital peak in x-ray absorption for a series of 3d metal porphyrins

    García-Lastra, J. M.; Cook, P. L.; Himpsel, F.J.; Rubio, A.

    2010-01-01

    Porphyrins are widely used as dye molecules in solar cells. Knowing the energies of their frontier orbitals is crucial for optimizing the energy level structure of solar cells. We use near edge x-ray absorption fine structure (NEXAFS) spectroscopy to obtain the energy of the lowest unoccupied molecular orbital (LUMO) with respect to the N1s core level of the molecule. A systematic energy shift of the N1s to LUMO transition is found along a series of 3d metal octaethylporphyrins and explained ...

  14. Approximating Metal-Insulator Transitions

    Danieli, C.; Rayanov, K.; Pavlov, B.; Martin, G.; Flach, S

    2014-01-01

    We consider quantum wave propagation in one-dimensional quasiperiodic lattices. We propose an iterative construction of quasiperiodic potentials from sequences of potentials with increasing spatial period. At each finite iteration step the eigenstates reflect the properties of the limiting quasiperiodic potential properties up to a controlled maximum system size. We then observe approximate metal-insulator transitions (MIT) at the finite iteration steps. We also report evidence on mobility ed...

  15. Structural study of the low-temperature phase transition in Cs3D(SeO4)2

    The X-ray structure of tricaesium deuteriumbiselenate, Cs3D(SeO4)2, Mr = 686.7, has been studied at 25, 190 and 297 K with particular attention being paid to the low-temperature phase transition at Tc3 = 180 K. The structure of Cs3H(SeO4)2 has also been studied at 297 K. The data were refined in the monoclinic space group C2/m, Z = 2, at 297 and 190 K, and in P21/m, Z = 2, at 25 K (Mo Kα radiation, λ = 0.71073 A). Temperature effects on the structure are mainly noticeable in the Cs--O bond distances of the oxygen coordination polyhedra of Cs (0.016 A per 100 K on average). Accompanying the Tc3 transition, the space group changes from C2/m to P21/m, and the two SeO4 groups in the dimer become non-equivalent with one adopting HSeO-4 character and the other SeO2-4 character. As a result, the dimers have a net dipole moment and are arranged in an antipolar way, similar to K3D(SO4)2. An examination of the room-temperature structure of Cs3D(SeO4)2 and other M3H(XO4)2-type crystals reveals that the non-H atoms lie in approximately the same position in both cases and that the only major difference is that half of the hydrogens in other M3H(XO4)2-type crystals are involved in hydrogen-bonded dimers which are formed with two different adjacent selenate groups. The successive transitions in Cs3D(SeO4)2 are characterized as an order-disorder transition of the donor-oxygen atom at Tc1, reorganization of the hydrogen bonds at Tc2 and an order-disorder transition of the proton at Tc3. (orig./GSCH)

  16. Continuous phase transition and critical behaviors of 3D black hole with torsion

    We study the phase transition and the critical behavior of the BTZ black hole with torsion obtained in (1 + 2)-dimensional Poincaré gauge theory. According to Ehrenfest’s classification, when the parameters in the theory are arranged properly, the BTZ black hole with torsion may possess the second-order phase transition which is also a smaller mass/larger mass black hole phase transition. Nevertheless, the critical behavior is different from the one in the van der Waals liquid/gas system. We also calculated the critical exponents of the relevant thermodynamic quantities, which are the same as the ones obtained in the Hořava-Lifshitz black hole and the Born–Infeld black hole. (paper)

  17. Metal-to-nonmetal transitions

    Hensel, Friedrich; Holst, Bastian

    2010-01-01

    This book is devoted to nonmetal-to-metal transitions. The original ideas of Mott for such a transition in solids have been adapted to describe a broad variety of phenomena in condensed matter physics (solids, liquids, and fluids), in plasma and cluster physics, as well as in nuclear physics (nuclear matter and quark-gluon systems). The book gives a comprehensive overview of theoretical methods and experimental results of the current research on the Mott effect for this wide spectrum of topics. The fundamental problem is the transition from localized to delocalized states which describes the nonmetal-to-metal transition in these diverse systems. Based on the ideas of Mott, Hubbard, Anderson as well as Landau and Zeldovich, internationally respected scientists present the scientific challenges and highlight the enormous progress which has been achieved over the last years. The level of description is aimed to specialists in these fields as well as to young scientists who will get an overview for their own work...

  18. Atomic transition probabilities in refractory metals

    Accurate transition probabilities for a large number of spectral lines in the first and second spectra of 3d, 4d and 5d metals are being measured. Radiative lifetimes of hundreds of levels in TaI, WI, MoI, NbI, HfI, ReI, RhI, RuI, NbII, CoII++, and other atoms and ions are measured using time-resolved laser-induced fluorescence on an atom or ion beam. The atom or ion beam is produced by a versatile hollow cathode discharge source. Branching ratios of levels in WI, NbI, HfI, and ReI are measured from calibrated spectra recorded on the Kitt Peak one-meter Fourier Transform Spectrometer. The transition probability measurements are used in solar and stellar elemental abundance determination. Some of the elements mentioned above are commonly used as electrodes in discharge devices. Accurate transition probabilities are also useful in studying concentrations and the effects of sputtered electrode material on laboratory discharges

  19. 3D CFD computations of trasitional flows using DES and a correlation based transition model

    Sørensen, Niels N.; Bechmann, Andreas; Zahle, Frederik

    2011-01-01

    The present article describes the application of the correlation based transition model of Menter et al. in combination with the Detached Eddy Simulation (DES) methodology to two cases with large degree of flow separation typically considered difficult to compute. Firstly, the flow is computed over...

  20. Comparison of 3D Classical Trajectory and Transition-State Theory Reaction Cross Sections

    Koeppl, G. W.; Karplus, Martin

    1970-10-01

    Although there is excellent agreement for a system such as H+H{sub 2} --> H{sub 2}+H, in which both the potential and the particle masses are symmetric, significant deviations occur for more asymmetric reactions. A detailed analysis show that the calculated differences are from the violation of two assumptions of transition-state theory.

  1. Can symmetry transitions of complex fields enable 3-d control of fluid vorticity?

    Martin, James E. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Solis, Kyle Jameson [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

    2015-08-01

    Methods of inducing vigorous noncontact fluid flow are important to technologies involving heat and mass transfer and fluid mixing, since they eliminate the need for moving parts, pipes and seals, all of which compromise system reliability. Unfortunately, traditional noncontact flow methods are few, and have limitations of their own. We have discovered two classes of fields that can induce fluid vorticity without requiring either gravity or a thermal gradient. The first class we call Symmetry-Breaking Rational Fields. These are triaxial fields comprised of three orthogonal components, two ac and one dc. The second class is Rational Triad Fields, which differ in that all three components are alternating. In this report we quantify the induced vorticity for a wide variety of fields and consider symmetry transitions between these field types. These transitions give rise to orbiting vorticity vectors, a technology for non-contact, non-stationary fluid mixing.

  2. The influence of 3d-metal alloy additions on the elastic and thermodynamic properties of CuPd3

    Huang Shuo; Zhang Chuan-Hui; Sun Jing; Shen Jiang

    2013-01-01

    Embedded-atom method (EAM) potentials are used to investigate the effects of alloying (e.g.3d-metals) on the trends of elastic and thermodynamic properties for CuPd3 alloy.Our calculated lattice parameter,cohesive energy,and elastic constants of CuPd3 are consistent with the available experimental and theoretical data.The results of elastic constants indicate that all these alloys are mechanically stable.Further mechanical behavior analysis shows that the additions of Cr,Fe,Co,and Ni could improve the hardness of CuPd3 while V could well increase its ductility.Moreover,in order to evaluate the thermodynamic contribution of 3d-metals,the Debye temperature,phonon density of states,and vibrational entropy for CuMPd6 alloy are also investigated.

  3. Highly selective luminescence sensing of nitrite and benzaldehyde based on 3d-4f heterometallic metal-organic frameworks.

    Du, Pei-Yao; Gu, Wen; Liu, Xin

    2016-06-01

    Framework-isomeric three-dimensional (3D) Zn-Ln heterometallic metal-organic frameworks, {[Ln2Zn(abtc)2(H2O)4]·2H2O}∞ {Ln = Sm(1), Tb(2)}, were synthesized using a convenient solvothermal reaction. They can serve as excellent sensors for the specific identification of benzaldehyde and NO2(-) through a fluorescence quenching process. PMID:27117937

  4. Synthesis of transition metal carbonitrides

    Munir, Zuhair A. R. (Davis, CA); Eslamloo-Grami, Maryam (Davis, CA)

    1994-01-01

    Transition metal carbonitrides (in particular, titanium carbonitride, TiC.sub.0.5 N.sub.0.5) are synthesized by a self-propagating reaction between the metal (e.g., titanium) and carbon in a nitrogen atmosphere. Complete conversion to the carbonitride phase is achieved with the addition of TiN as diluent and with a nitrogen pressure .gtoreq.0.6 MPa. Thermodynamic phase-stability calculations and experimental characterizations of quenched samples provided revealed that the mechanism of formation of the carbonitride is a two-step process. The first step involves the formation of the nonstoichiometric carbide, TiC.sub.0.5, and is followed by the formation of the product by the incorporation of nitrogen in the defect-structure carbide.

  5. Approximating metal-insulator transitions

    Danieli, Carlo; Rayanov, Kristian; Pavlov, Boris; Martin, Gaven; Flach, Sergej

    2015-12-01

    We consider quantum wave propagation in one-dimensional quasiperiodic lattices. We propose an iterative construction of quasiperiodic potentials from sequences of potentials with increasing spatial period. At each finite iteration step, the eigenstates reflect the properties of the limiting quasiperiodic potential properties up to a controlled maximum system size. We then observe approximate Metal-Insulator Transitions (MIT) at the finite iteration steps. We also report evidence on mobility edges, which are at variance to the celebrated Aubry-André model. The dynamics near the MIT shows a critical slowing down of the ballistic group velocity in the metallic phase, similar to the divergence of the localization length in the insulating phase.

  6. Heterostructures of transition metal dichalcogenides

    Amin, Bin

    2015-08-24

    The structural, electronic, optical, and photocatalytic properties of out-of-plane and in-plane heterostructures of transition metal dichalcogenides are investigated by (hybrid) first principles calculations. The out-of-plane heterostructures are found to be indirect band gap semiconductors with type-II band alignment. Direct band gaps can be achieved by moderate tensile strain in specific cases. The excitonic peaks show blueshifts as compared to the parent monolayer systems, whereas redshifts occur when the chalcogen atoms are exchanged along the series S-Se-Te. Strong absorption from infrared to visible light as well as excellent photocatalytic properties can be achieved.

  7. 3D CFD computations of transitional flows using DES and a correlation based transition model; Wind turbines

    Soerensen, Niels N.

    2009-07-15

    The report describes the application of the correlation based transition model of Menter et. al. [1, 2] to the cylinder drag crisis and the stalled flow over an DU-96-W-351 airfoil using the DES methodology. When predicting the flow over airfoils and rotors, the laminar-turbulent transition process can be important for the aerodynamic performance. Today, the most widespread approach is to use fully turbulent computations, where the transitional process is ignored and the entire boundary layer on the wings or airfoils is handled by the turbulence model. The correlation based transition model has lately shown promising results, and the present paper describes the application of the model to predict the drag and shedding frequency for flow around a cylinder from sub to super-critical Reynolds numbers. Additionally, the model is applied to the flow around the DU-96 airfoil, at high angles of attack. (au)

  8. Direct NO decomposition over stepped transition-metal surfaces

    Falsig, Hanne; Bligaard, Thomas; Christensen, Claus H.;

    2007-01-01

    We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Bronsted-Evans-Polanyi (BEP) relations for the activation barriers of dissociation of...... diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd and Pt are the best direct NO decomposition catalysts among the 3d, 4d, and 5d metals. We analyze the NO decomposition reaction in terms of a Sabatier-Gibbs-type analysis, and we...... demonstrate that this type of analysis yields results that to within a surprisingly small margin of error are directly proportional to the measured direct NO decomposition over Ru, Rh, Pt, Pd, Ag, and An. We suggest that Pd, which is a better catalyst than Pt under the employed reaction conditions, is a...

  9. Low-Cost Open-Source Voltage and Current Monitor for Gas Metal Arc Weld 3D Printing

    A. Pinar

    2015-01-01

    Full Text Available Arduino open-source microcontrollers are well known in sensor applications for scientific equipment and for controlling RepRap 3D printers. Recently low-cost open-source gas metal arc weld (GMAW RepRap 3D printers have been developed. The entry-level welders used have minimal controls and therefore lack any real-time measurement of welder voltage or current. The preliminary work on process optimization of GMAW 3D printers requires a low-cost sensor and data logger system to measure welder current and voltage. This paper reports on the development of a low-cost open-source power measurement sensor system based on Arduino architecture. The sensor system was designed, built, and tested with two entry-level MIG welders. The full bill of materials and open source designs are provided. Voltage and current were measured while making stepwise adjustments to the manual voltage setting on the welder. Three conditions were tested while welding with steel and aluminum wire on steel substrates to assess the role of electrode material, shield gas, and welding velocity. The results showed that the open source sensor circuit performed as designed and could be constructed for <$100 in components representing a significant potential value through lateral scaling and replication in the 3D printing community.

  10. Stark broadening of 3s 3P0-3p 3D and 3p 3D-3d 3F0 transitions along carbon isoelectronic sequences of ions revisited

    The Stark widths of N II and O III spectral lines belonging to 3s 3P0-3p 3D and 3p 3D-3d 3F0 multiplets have been calculated and measured in a capillary discharge plasma. The calculations are extended to the same multiplets of F IV and Ne V ions. The plasma electron density in the capillary discharge is determined from the width of the He II Pβ line, while the electron temperature is measured from the relative intensities of N II lines. A comparison of the experimental and theoretical data shows good mutual agreement, which is well within the estimated experimental and theoretical uncertainties. The theory predicts the ratio of the corresponding N II to O III line widths to be larger than unity, in disagreement with our earlier experiment in a pulsed arc. In the new experiment, where all spectral lines were recorded under the same plasma conditions, the theoretical predictions and the results of the capillary experiment are in agreement. The possible sources of an error in the earlier experiment are indicated

  11. Electronic and thermodynamic properties of transition metal elements and compounds

    This thesis focuses on the use of band-structure calculations for studying thermodynamic properties of solids. We discuss 3d-, 4d- and 5d-transition metal carbides and nitrides. Through a detailed comparison between theoretical and experimental results, we draw conclusions on the character of the atomic bonds in these materials. We show how electronic structure calculations can be used to give accurate predictions for bonding energies. Part of the thesis is devoted to the application of the generalized gradient approximation in electronic structure calculations on transition metals. For structures with vibrational disorder, we present a method for calculating averaged phonon frequencies without using empirical information. For magnetic excitations, we show how a combined use of theoretical results and experimental data can yield information on magnetic fluctuations at high temperatures. The main results in the thesis are: Apart for an almost constant shift, theoretically calculated bonding energies for transition metal carbides and nitrides agree with experimental data or with values from analysis of thermochemical information. The electronic spectrum of transition metal carbides and nitrides can be separated into bonding, antibonding and nonbonding electronic states. The lowest enthalpy of formation for substoichiometric vanadium carbide VC1-X at zero temperature and pressure occurs for a structure containing vacancies (x not equal to 0). The generalized gradient approximation improves theoretical calculated cohesive energies for 3d-transition metals. Magnetic phase transitions are sensitive to the description of exchange-correlation effects in electronic structure calculations. Trends in Debye temperatures can be successfully analysed in electronic structure calculations on disordered lattices. For the elements, there is a clear dependence on the crystal structure (e.g., bcc, fcc or hcp). Chromium has fluctuating local magnetic moments at temperatures well above

  12. WAVELENGTHS OF THE 3p-3d TRANSITIONS OF THE Co- AND Fe-LIKE IONS : THE EFFECTS OF ELECTRON CORRELATION

    Chen, M.

    1988-01-01

    The experimental observations of the 3p6 3d9 2D - 3p5 3dl0 2p transitions of the Co-like ions and 3p6 3d8 3F4 - 3p5 3d9 3F3 of the Fe-like ions have recently been extended to highly charged ions of heavy elements up to uranium (Z = 92). A comparison between the observed energies and calculated values from the Dirac-Fock model indicated persistent diicrepancies of 3-4 eV for al1 ions. Systematic multiconfiguration Dirac-Fock caiculations for these transitions have been carried out with emphasi...

  13. 3D hybrid-porous carbon derived from carbonization of metal organic frameworks for high performance supercapacitors

    Bao, Weizhai; Mondal, Anjon Kumar; Xu, Jing; Wang, Chengyin; Su, Dawei; Wang, Guoxiu

    2016-09-01

    We report a rational design and synthesis of 3D hybrid-porous carbon with a hierarchical pore architecture for high performance supercapacitors. It contains micropores (carbonization of unique porous metal organic frameworks (MOFs). Owning to the synergistic effect of micropores and mesopores, the hybrid-porous carbon has exceptionally high ion-accessible surface area and low ion diffusion resistance, which is desired for supercapacitor applications. When applied as electrode materials in supercapacitors, 3D hybrid-porous carbon demonstrates a specific capacitance of 332 F g-1 at a constant charge/discharge current of 500 mA g-1. The supercapacitors can endure more than 10,000 cycles without degradation of capacitance.

  14. Multigrid mapping and box relaxation for simulation of the whole process of flow transition in 3-D boundary layers

    Liu, C.; Liu, Z. [Univ. of Colorado, Denver, CO (United States)

    1994-12-31

    A new multilevel technology was developed in this study which provides a successful numerical simulation for the whole process of flow transition in 3-D flat plate boundary layers, including linear growth, secondary instability, breakdown, and transition on a relatively coarse grid with low CPU cost. A fourth-order finite difference scheme on stretched and staggered grids, a fully implicit time-marching technique, a semi-coarsening multigrid based on the so-called approximate line-box relaxation, and a buffer domain for the outflow boundary conditions were all employed for high-order accuracy, good stability, and fast convergence. A new fine-coarse-fine grid mapping technique was developed to catch the large eddies and represent main roles of small eddies to keep the code running after the laminar flow breaks down. The computational results are in good agreement with linear stability theory, secondary instability theory, and some experiments. The computation also reproduced the K-type and C-type transition observed by laboratory experiments. The CPU cost for a typical case is around 2-9 CRAY-YMP hours.

  15. Hyperfine structure studies of transition metals

    This past year our studies of hyperfine structure (hfs) in metastable states of transition metals concentrated on the analysis of hfs in the four-valence electron system, Nb II. Earlier, we measured hfs intervals using the laser-rf double resonance and laser-induced fluorescence methods in a fast-ion beam of Nb+. The resulting experimental magnetic dipole and electric quadrupole interaction constants are compared to those calculated by a relativistic configuration interaction approach. These are the first hfs data on this refractory element. Theoretically, it is found that the most important contributions to the energy are the pair excitations, valence single excitations and core polarization from the shallow core. However, the inner core polarization is found to be crucial for hfs, albeit unimportant for energy. For the J=2 level at 12805 cm-1, 4d43F. the theoretical relativistic configuration A-value is in agreement with the experimental result to an accuracy of 4%. Other calculated A-values are expected to be of the same accuracy. A paper describing these results was accepted for publication. Experimental studies of the four-valence electron system V+ in the (4s+3d)4 manifold are complete. The theoretical difficulties for the 3d manifold, noted earlier for the three-valence electron Ti+, as compared to the 4d manifold appear to be repeated in the case of the four-valence electron systems (Nb+ and V+). Relativistic configuration interaction calculations are underway, after which a paper will be published

  16. Metal-mesh based transparent electrode on a 3-D curved surface by electrohydrodynamic jet printing

    Seong, Baekhoon; Yoo, Hyunwoong; Dat Nguyen, Vu; Jang, Yonghee; Ryu, Changkook; Byun, Doyoung

    2014-09-01

    Invisible Ag mesh transparent electrodes (TEs), with a width of 7 μm, were prepared on a curved glass surface by electrohydrodynamic (EHD) jet printing. With a 100 μm pitch, the EHD jet printed the Ag mesh on the convex glass which had a sheet resistance of 1.49 Ω/□. The printing speed was 30 cm s-1 using Ag ink, which had a 10 000 cPs viscosity and a 70 wt% Ag nanoparticle concentration. We further showed the performance of a 3-D transparent heater using the Ag mesh transparent electrode. The EHD jet printed an invisible Ag grid transparent electrode with good electrical and optical properties with promising applications on printed optoelectronic devices.

  17. Structural, magnetic and conduction properties of 3d-metal monoatomic wires

    From density functional theory calculations, we study the structure, magnetism and conduction properties of monoatomic wires made of all the 3d elements (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu). Wires with equidistant and alternating bond lengths are considered. Both magnetism and structure are found to play an important role for the conduction properties of the wires. Ferromagnetic wires are found to present a spin filtering effect which is not directly related with the magnitude of their magnetic moment. On the other hand, the main effect of bond length alternation is to partially destroy the transmission around the Fermi level, especially from the d bands. Ni wires are found to present particularly interesting spin filtering properties, meanwhile Cr wires present promising magnetoresistive effects. (papers)

  18. Fracture Resistance of Non-Metallic Molar Crowns Manufactured with CEREC 3D

    Madani, Dalia A.

    Objectives. To compare fracture strength and fatigue resistance of ceramic (ProCAD, Ivoclar-Vivadent) (C) and resin composite (Paradigm MZ100, 3M/ ESPE) (R) crowns made with CEREC-3D. Methods. A prepared ivorine molar tooth was duplicated to produce 40 identical prepared specimens made of epoxy resin (Viade). Twenty (C) crowns and 20 (R) were cemented to their dies using resin cement. Ten of each group were subjected to compressive loading to fracture. The remaining 10 of each group were subjected to mechanical cyclic loading for 500,000 cycles. The survivors were subjected to compressive loading to fracture. Results. No significant difference in mean fracture load was found between the two materials. However, only 30% of the (C) crowns vs. 100% of the (R) crowns survived the cyclic loading test. Conclusions. (R) crowns demonstrated higher fatigue Resistance than (C) crowns in-vitro and might better resist cracking in-vivo.

  19. Lattice Dynamics of Transition Metals

    The frequency versus wave-vector v(q) dispersion relations for the normal modes of vibration of several body-centred cubic transition metal, crystals have been measured recently at room temperature. The dispersion curves for niobium, measured by Nakagawa and Woods, displayed some very unusual features, and the results could only be fitted by means of a Born-von Kármán model if interactions out to very distant neighbours (beyond eighth) were included. Subsequent measurements on tantalum by Woods showed very similar results. This is not surprising since niobium and tantalum are in column V of the periodic table and many of their electronic properties are similar. Measurements of the dispersion curves of molybdenum by Woods and Chen and of tungsten by Chen and Brockhouse showed that although these metals, which are in column VI of the periodic table, had dispersion relations which were similar to each other, these dispersion relations were very different from those of the column V metals, niobium and tantalum. The gross features of the v(q) for molybdenum and tungsten were very nearly describable by a third neighbour axially-symmetric Born-von Kármán force model, although several important features were not reproduced by this model. One of these features is a striking anomaly in the [ζζζ] longitudinal (L) branch for molybdenum where the frequency changes from v = 6.3 x 1012 c/s at ζ = 0.92 to v= 5.5 x 1012 c/s at ζ = 1.0. If this and other observed features are Kohn anomalies, their positions are consistent with the dimensions of the Fermi suríace of the column V metals proposed by Lomer. Thus it is suggested that the striking differences between the dispersion relation for niobium and that for molybdenum (metals which are believed to have quite similar band structures) reflect differences in the Fermi energies and hence the Fermi surfaces for these materials. (author)

  20. Piperazine pivoted transition metal dithiocarbamates

    Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.

    2008-03-01

    A quadridentate ligand disodium bis(2,2'-dithiopiperazinato-2,2'-diamino diethylamine) Na 2L 2 and its self assembled transition metal complexes of the type, M 2(L 2) 2 {M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)} have been reported. The piperazine pivoted homodinuclear complexes have been characterized by a range of spectral, thermal, microanalytical and conductometric techniques. On the basis of IR and 1HNMR data a symmetrical bidentate coordination of the dithiocarbamato moiety has been observed in all the cases. The TGA profile of the ligand exhibits two stage thermolytic pattern although the complexes decompose in three steps, respectively. Metal sulfide is found to be the end product. The formation of homodinuclear complexes has been ascertained on the basis of FAB mass spectral data and a probable fragmentation pattern has been proposed. On the basis of UV-visible spectroscopic results and room temperature magnetic moment data a tetrahedral geometry has been proposed for all the complexes except for the Ni(II) and Cu(II) which are found to be square-planar.

  1. Dimensional phase transition from an array of 1D Luttinger liquids to a 3D Bose-Einstein condensate.

    Vogler, Andreas; Labouvie, Ralf; Barontini, Giovanni; Eggert, Sebastian; Guarrera, Vera; Ott, Herwig

    2014-11-21

    We study the thermodynamic properties of a 2D array of coupled one-dimensional Bose gases. The system is realized with ultracold bosonic atoms loaded in the potential tubes of a two-dimensional optical lattice. For negligible coupling strength, each tube is an independent weakly interacting 1D Bose gas featuring Tomonaga Luttinger liquid behavior. By decreasing the lattice depth, we increase the coupling strength between the 1D gases and allow for the phase transition into a 3D condensate. We extract the phase diagram for such a system and compare our results with theoretical predictions. Because of the high effective mass across the periodic potential and the increased 1D interaction strength, the phase transition is shifted to large positive values of the chemical potential. Our results are prototypical to a variety of low-dimensional systems, where the coupling between the subsystems is realized in a higher spatial dimension such as coupled spin chains in magnetic insulators. PMID:25479499

  2. A numerical study of the transition to oscillatory flow in 3D lid-driven cubic cavity flows

    Chiu, Shang-Huan; He, Jiwen; Guo, Aixia; Glowinski, Roland

    2016-01-01

    In this article, three dimensional (3D) lid-driven cubic cavity flows have been studied numerically for various values of Reynolds number ($Re$). The numerical solution of the Navier-Stokes equations modeling incompressible viscous fluid flow in a cubic cavity is obtained via a methodology combining a first order accurate operator-splitting, $L^2$-projection Stokes solver, a wave-like equation treatment of the advection and finite element methods. The numerical results obtained for Re$=$400, 1000, and 3200 show a good agreement with available numerical and experimental results in literature. Simulation results predict that the critical Re$_{cr}$ for the transition from steady flow to oscillatory (a Hopf bifurcation) is somewhere in [1870, 1875] for the mesh size $h=1/96$. Via studying the flow field distortion of fluid flow at Re before and after Re$_{cr}$, the occurrence of the first pair of Taylor-G\\"ortler-like vortices is connected to the flow field distortion at the transition from steady flow to oscilla...

  3. Properties of Transition Metal Doped Alumina

    Nykwest, Erik; Limmer, Krista; Brennan, Ray; Blair, Victoria; Ramprasad, Rampi

    Crystallographic texture can have profound effects on the properties of a material. One method of texturing is through the application of an external magnetic field during processing. While this method works with highly magnetic systems, doping is required to couple non-magnetic systems with the external field. Experiments have shown that low concentrations of rare earth (RE) dopants in alumina powders have enabled this kind of texturing. The magnetic properties of RE elements are directly related to their f orbital, which can have as many as 7 unpaired electrons. Since d-block elements can have as many as 5 unpaired electrons the effects of substitutional doping of 3d transition metals (TM) for Al in alpha (stable) and theta (metastable) alumina on the local structure and magnetic properties, in addition to the energetic cost, have been calculated by performing first-principles calculations based on density functional theory. This study has led to the development of general guidelines for the magnetic moment distribution at and around the dopant atom, and the dependence of this distribution on the dopant atom type and its coordination environment. It is anticipated that these findings can aid in the selection of suitable dopants help to guide parallel experimental efforts. This project was supported in part by an internship at the Army Research Laboratory, administered by the Oak Ridge Institute for Science and Education, along with a grant of computer time from the DoD High Performance Computing Modernization Program.

  4. Guided Evolution of Bulk Metallic Glass Nanostructures: A Platform for Designing 3D Electrocatalytic Surfaces.

    Doubek, Gustavo; Sekol, Ryan C; Li, Jinyang; Ryu, Won-Hee; Gittleson, Forrest S; Nejati, Siamak; Moy, Eric; Reid, Candy; Carmo, Marcelo; Linardi, Marcelo; Bordeenithikasem, Punnathat; Kinser, Emily; Liu, Yanhui; Tong, Xiao; Osuji, Chinedum O; Schroers, Jan; Mukherjee, Sundeep; Taylor, André D

    2016-03-01

    Electrochemical devices such as fuel cells, electrolyzers, lithium-air batteries, and pseudocapacitors are expected to play a major role in energy conversion/storage in the near future. Here, it is demonstrated how desirable bulk metallic glass compositions can be obtained using a combinatorial approach and it is shown that these alloys can serve as a platform technology for a wide variety of electrochemical applications through several surface modification techniques. PMID:26689722

  5. High precision 3D metallic microstructures produced using proton beam micromachining

    A crucial step in the development of mechanically strong microstructures is the conversion of structures made from resist material of low hardness and strength, to harder and more durable metallic microstructures. The implementation of a post lithographic process step such as electroplating offers the possibility of producing metallic structures. In proton beam micromachining (PBM) a focused MeV beam is scanned in a predetermined pattern over a resist (e.g. PMMA or SU-8), which is subsequently chemically developed. The proton beam in resist follows an almost straight path, enabling the production of microstructures with well-defined rectangular side walls. If the resist layer is laid down with a thickness of typically 50% of the proton range on a conductive substrate, then the end of range straggling and resultant end of range beam broadening does not occur in the resist, but in the substrate. The conducting substrate acts as a seed layer for plating. In this current work, smooth well-defined metallic microstructures with a height of 10 μm are produced using electrolytic Ni plating. One spin-off application is that the plated Ni structures, which have excellent side wall definition, exhibit properties that are far superior to the current 2000 lines per inch gold grid resolution standard used by many nuclear microscopy groups worldwide

  6. Micro-electrical discharge machining of 3D micro-molds from Pd40Cu30P20Ni10 metallic glass by using laminated 3D micro-electrodes

    Xu, Bin; Wu, Xiao-yu; Ma, Jiang; Liang, Xiong; Lei, Jian-guo; Wu, Bo; Ruan, Shuang-chen; Wang, Zhen-long

    2016-03-01

    For obtaining 3D micro-molds with better surface quality (slight ridges) and mechanical properties, in this paper 3D micro-electrodes were fabricated and applied to micro-electrical discharge machining (micro-EDM) to process Pd40Cu30P20Ni10 metallic glass. First, 100 μm-thick Cu foil was cut to obtain multilayer 2D micro-structures and these were connected to fit 3D micro-electrodes (with feature sizes of less than 1 mm). Second, under the voltage of 80 V, pulse frequency of 0.2MHZ, pulse width of 800 ns and pulse interval of 4200 ns, the 3D micro-electrodes were applied to micro-EDM for processing Pd40Cu30P20Ni10 metallic glass. The 3D micro-molds with feature within 1 mm were obtained. Third, scanning electron microscope, energy dispersive spectroscopy and x-ray diffraction analysis were carried out on the processed results. The analysis results indicate that with an increase in the depth of micro-EDM, carbon on the processed surface gradually increased from 0.5% to 5.8%, and the processed surface contained new phases (Ni12P5 and Cu3P).

  7. Investigation of molten metal droplet deposition and solidification for 3D printing techniques

    Wang, Chien-Hsun; Tsai, Ho-Lin; Wu, Yu-Che; Hwang, Weng-Sing

    2016-09-01

    This study investigated the transient transport phenomenon during the pile up of molten lead-free solder via the inkjet printing method. With regard to the droplet impact velocity, the distance from nozzle to substrate can be controlled by using the pulse voltage and distance control apparatus. A high-speed digital camera was used to record the solder impact and examine the accuracy of the pile up. These impact conditions correspond to We  =  2.1–15.1 and Oh  =  5.4  ×  10‑3–3.8  ×  10‑3. The effects of impact velocity and relative distance between two types of molten droplets on the shape of the impact mode are examined. The results show that the optimal parameters of the distance from nozzle to substrate and the spreading factor in this experiment are 0.5 mm and 1.33. The diameter, volume and velocity of the inkjet solder droplet are around 37–65 μm, 25–144 picoliters, and 2.0–3.7 m s‑1, respectively. The vertical and inclined column structures of molten lead-free solder can be fabricated using piezoelectric ink-jet printing systems. The end-shapes of the 3D micro structure have been found to be dependent upon the distance from nozzle to substrate and the impact velocity of the molten lead-free solder droplet.

  8. Electronic Transitions in f-electron Metals at High Pressures:

    This study was to investigate unusual phase transitions driven by electron correlation effects that occur in many f-band transition metals and are often accompanied by large volume changes: ∼20% at the (delta)-α transition in Pu and 5-15% for analogous transitions in Ce, Pr, and Gd. The exact nature of these transitions has not been well understood, including the short-range correlation effects themselves, their relation to long-range crystalline order, the possible existence of remnants of the transitions in the liquid, the role of magnetic moments and order, the critical behavior, and dynamics of the transitions, among other issues. Many of these questions represent forefront physics challenges central to Stockpile materials and are also important in understanding the high-pressure behavior of other f- and d-band transition metal compounds including 3d-magnetic transition monoxide (TMO, TM=Mn, Fe, Co, Ni). The overarching goal of this study was, therefore, to understand the relationships between crystal structure and electronic structure of transition metals at high pressures, by using the nation's brightest third-generation synchrotron x-ray at the Advanced Photon Source (APS). Significant progresses have been made, including new discoveries of the Mott transition in MnO at 105 GPa and Kondo-like 4f-electron dehybridization and new developments of high-pressure resonance inelastic x-ray spectroscopy and x-ray emission spectroscopy. These scientific discoveries and technology developments provide new insights and enabling tools to understand scientific challenges in stockpile materials. The project has broader impacts in training two SEGRF graduate students and developing an university collaboration (funded through SSAAP)

  9. Fabrication and metallization of 3D electrospun nanofiberous architecture with gold and silver coating for applications related to electrochemical supercapacitors

    Park, Keon Young [University of Pennsylvania, 3451 Walnut Street, Philadelphia, PA 19104 (United States); Ramaraj, B. [Research and Development Department, Central Institute of Plastics Engineering and Technology (CIPET), 630, Phase IV, GIDC, Vatva, Ahmedabad 382445 (India); Choi, Won Suk [Department of Chemistry, Hannam University, 461-6 Jeon min-dong, Yuseoung-gu, Daejeon 305-811 (Korea, Republic of); Yoon, Kuk Ro, E-mail: kryoon@hannam.ac.kr [Department of Chemistry, Hannam University, 461-6 Jeon min-dong, Yuseoung-gu, Daejeon 305-811 (Korea, Republic of)

    2013-11-01

    We have engineered a metallic architecture with high surface area and ultralow density for applications related to electrochemical supercapacitors. This is achieved first by design and fabrication of new annular collector template for electrospinning process, then the extrusion of polystyrene (PS) nanofiber through the fabricated annulus collector template followed by electroless plating of nanofiber assembly with gold and silver. The resultant three dimensional structures were characterized by optical microscopy (OM), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The OM images suggest that the fabrication process causes the electrospun fibers to be hinged to one another, maximizing contact junctions enhancing mechanical stability. The coated structure has a superior surface area, is robust, and is freestanding – making it an attractive architectural design for an electrode. The SEM images show interlocking of nanofibers to one another, further indicating the potential application for this system as a high surface area, low density charge collector ideal for nanostructured growths. - Graphical abstract: A new annular collector template was designed and fabricated to create a 3D electrospun nanofiber assembly. This ultralight 3D architecture with high surface was electroless plated with silver and gold to assess its suitability for applications related to electrochemical supercapacitors. This structure is highly conductive leading us to believe that this product can be utilized as an alternate electrode charge collector. - Highlights: • A metallic architecture with high surface area and ultralow density was fabricated. • A new annular collector template for electrospinning was designed and fabricated. • Electrospun PS nanofibers with 3D structure were coated with silver and gold. • The coated structure is

  10. Fabrication and metallization of 3D electrospun nanofiberous architecture with gold and silver coating for applications related to electrochemical supercapacitors

    We have engineered a metallic architecture with high surface area and ultralow density for applications related to electrochemical supercapacitors. This is achieved first by design and fabrication of new annular collector template for electrospinning process, then the extrusion of polystyrene (PS) nanofiber through the fabricated annulus collector template followed by electroless plating of nanofiber assembly with gold and silver. The resultant three dimensional structures were characterized by optical microscopy (OM), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The OM images suggest that the fabrication process causes the electrospun fibers to be hinged to one another, maximizing contact junctions enhancing mechanical stability. The coated structure has a superior surface area, is robust, and is freestanding – making it an attractive architectural design for an electrode. The SEM images show interlocking of nanofibers to one another, further indicating the potential application for this system as a high surface area, low density charge collector ideal for nanostructured growths. - Graphical abstract: A new annular collector template was designed and fabricated to create a 3D electrospun nanofiber assembly. This ultralight 3D architecture with high surface was electroless plated with silver and gold to assess its suitability for applications related to electrochemical supercapacitors. This structure is highly conductive leading us to believe that this product can be utilized as an alternate electrode charge collector. - Highlights: • A metallic architecture with high surface area and ultralow density was fabricated. • A new annular collector template for electrospinning was designed and fabricated. • Electrospun PS nanofibers with 3D structure were coated with silver and gold. • The coated structure is

  11. Development of 3D Visualization Technology for Medium-and Large-sized Radioactive Metal Wastes from Decommissioning Nuclear Facilities

    The most important point of decommissioning nuclear facilities and nuclear power plants is to spend less money and do this process safely. In order to perform a better decommissioning nuclear facilities and nuclear power plants, a data base of radioactive waste from decontamination and decommissioning of nuclear facilities should be constructed. This data base is described herein, from the radioactive nuclide to the shape of component of nuclear facilities, and representative results of the status and analysis are presented. With the increase in number of nuclear facilities at the end of their useful life, the demand of decommissioning technologies will continue to grow for years to come. This analysis of medium-and large-sized radioactive metal wastes and 3D visualization technology of the radioactive metal wastes using the 3D-SCAN are planned to be used for constructing data bases. The data bases are expected to be used on development of the basic technologies for decommissioning nuclear facilities 4 session

  12. 6Li detection in metal-poor stars: can 3D model atmospheres solve the second lithium problem?

    Steffen, M; Caffau, E; Bonifacio, P; Ludwig, H -G; Spite, M

    2012-01-01

    The presence of 6Li in the atmospheres of metal-poor halo stars is usually inferred from the detection of a subtle extra depression in the red wing of the 7Li doublet line at 670.8 nm. However, the intrinsic line asymmetry caused by convective flows in the photospheres of cool stars is almost indistinguishable from the asymmetry produced by a weak 6Li blend on a (presumed) symmetric 7Li profile. Previous determinations of the 6Li/ 7Li isotopic ratio based on 1D model atmospheres, ignoring the convection-induced line asymmetry, must therefore be considered as upper limits. By comparing synthetic 1D LTE and 3D non-LTE line profiles of the Li 670.8 nm feature, we quantify the differential effect of the convective line asymmetry on the derived 6Li abundance as a function of effective temperature, gravity, and metallicity. As expected, we find that the asymmetry effect systematically reduces the resulting 6Li/7Li ratios. Depending on the stellar parameters, the 3D-1D offset in 6Li/7Li ranges between -0.005 and -0....

  13. Fabrication techniques for multiscale 3D-MEMS with vertical metal micro- and nanowire integration

    This paper presents different low-temperature and high-throughput LIGA-like processes for the batch fabrication of metal micro systems that use long nano- or microwires perpendicularly rising from a substrate. First, circuit paths and seed layers are fabricated applying standard UV lithography and PVD. Second, three lithography techniques are used, namely ion track lithography, enhanced UV lithography and aligned x-ray lithography, to structure 20–400 µm thick polymer films. Ion track lithography is only used to fabricate extremely high aspect ratio cylindrical pores with 0.1–1 µm diameter and 20–100 µm length. The aligned UV and x-ray lithographies are employed to structure templates for various micro system components. Third, these polymer templates are filled using low-temperature electroplating processes transferring the polymer openings into metal structures. Finally, the polymer is dry etched to release all metal structures. These structures are applicable in future accelerometers and gas flow sensors. Using five configurations to define five different functional structures, we demonstrate fabrication processes applying the three different types of lithography. The main aspects concern the combination of both standard lithography techniques and especially developed lithography techniques. Furthermore, these aspects comprise the use of structures created by lithography for high aspect ratio polymer templates and multilayer electroplating with varying aspect ratios. The growth in place of nanowire arrays and micropillars along with surrounding structures is the key feature for low-temperature large-scale micro-nano integration technology without harmful transfer technologies. (paper)

  14. 1D to 3D dimensional crossover in the superconducting transition of the quasi-one-dimensional carbide superconductor Sc3CoC4.

    He, Mingquan; Wong, Chi Ho; Shi, Dian; Tse, Pok Lam; Scheidt, Ernst-Wilhelm; Eickerling, Georg; Scherer, Wolfgang; Sheng, Ping; Lortz, Rolf

    2015-02-25

    The transition metal carbide superconductor Sc(3)CoC(4) may represent a new benchmark system of quasi-one-dimensional (quasi-1D) superconducting behavior. We investigate the superconducting transition of a high-quality single crystalline sample by electrical transport experiments. Our data show that the superconductor goes through a complex dimensional crossover below the onset T(c) of 4.5 K. First, a quasi-1D fluctuating superconducting state with finite resistance forms in the [CoC(4)](∞) ribbons which are embedded in a Sc matrix in this material. At lower temperature, the transversal Josephson or proximity coupling of neighboring ribbons establishes a 3D bulk superconducting state. This dimensional crossover is very similar to Tl(2)Mo(6)Se(6), which for a long time has been regarded as the most appropriate model system of a quasi-1D superconductor. Sc(3)CoC(4) appears to be even more in the 1D limit than Tl(2)Mo(6)Se(6). PMID:25643644

  15. Three-dimensional distribution of the ISM in the Milky Way Galaxy. IV. 3D molecular fraction and Galactic-scale H I-to-H2 transition

    Sofue, Yoshiaki; Nakanishi, Hiroyuki

    2016-08-01

    Three-dimensional (3D) distribution of the volume-density molecular fraction, defined by f_mol^ρ =ρ _H_2/(ρ _{H I}+ρ _H_2), is studied in the Milky Way Galaxy. The molecular front appears at galacto-centric distance of R ˜ 8 kpc, where the galactic-scale phase transition from atomic to molecular hydrogen occurs with f_mol^ρ dropping from ˜0.8 to 0.2 within a radial interval as narrow as ˜0.5 kpc. The f_mol^ρ front is much sharper than that of the surface density molecular fraction. The f_mol^ρ front also appears in the direction vertical to the galactic plane with a full width of the high-f_mol^ρ disk to be ˜100 pc. The radial and vertical f_mol^ρ profiles, particularly the front behavior, are fitted by theoretical curves calculated using the observed density profile and assumed radiation field and metallicity with exponential gradients. The molecular fraction was found to be enhanced along spiral arms at radii R ˜ 6 to 10 kpc, such as the Perseus arm. This implies that the molecular clouds are produced from H I in the arms and are dissociated in the interarm regions in the transition region around the molecular front. We also show that there is a threshold value of mean H I density, over which H I is transformed into molecular gas.

  16. 3D dislocation dynamics: stress-strain behavior and hardening mechanisms in fcc and bcc metals

    A dislocation dynamics (DD) model for plastic deformation, connecting the macroscopic mechanical properties to basic physical laws governing dislocation mobility and related interaction mechanisms, has been developed. In this model there is a set of critical reactions that determine the overall results of the simulations, such as the stress-strain curve. These reactions are annihilation, formation of jogs, junctions, and dipoles and cross-slip. In this paper, we discuss these reactions and the manner in which they influence the simulated stress-strain behavior of fcc and bcc metals. In particular, we examine the formation (zipping) and strength of dipoles and junctions, and effect of jogs, using the dislocation dynamics model. We show that the strengths (unzipping) of these reactions for various configurations can be determined by direct evaluation of the elastic interactions. Next, we investigate the phenomenon of hardening in metals subjected to cascade damage. The investigated microstructure consists of small dislocation loops decorating the mobile dislocations. Preliminary results reveal that these loops act as hardening agents, trapping the dislocations and resulting in increased yield stress

  17. Superconducting Metallic Glass Transition-Edge-Sensors

    Hays, Charles C. (Inventor)

    2013-01-01

    A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

  18. 3D-HST GRISM SPECTROSCOPY OF A GRAVITATIONALLY LENSED, LOW-METALLICITY STARBURST GALAXY AT z = 1.847

    We present Hubble Space Telescope (HST) imaging and spectroscopy of the gravitational lens SL2SJ02176-0513, a cusp arc at z = 1.847. The UV continuum of the lensed galaxy is very blue, which is seemingly at odds with its redder optical colors. The 3D-HST WFC3/G141 near-infrared spectrum of the lens reveals the source of this discrepancy to be extremely strong [O III] λ5007 and Hβ emission lines with rest-frame equivalent widths of 2000 ± 100 and 520 ± 40 Å, respectively. The source has a stellar mass ∼108 M☉, sSFR ∼ 100 Gyr–1, and detection of [O III] λ4363 yields a metallicity of 12 + log (O/H) = 7.5 ± 0.2. We identify local blue compact dwarf analogs to SL2SJ02176-0513, which are among the most metal-poor galaxies in the Sloan Digital Sky Survey. The local analogs resemble the lensed galaxy in many ways, including UV/optical spectral energy distribution, spatial morphology, and emission line equivalent widths and ratios. Common to SL2SJ02176-0513 and its local counterparts is an upturn at mid-IR wavelengths likely arising from hot dust heated by starbursts. The emission lines of SL2SJ02176-0513 are spatially resolved owing to the combination of the lens and the high spatial resolution of HST. The lensed galaxy is composed of two clumps with combined size re ∼300 pc, and we resolve significant differences in UV color and emission line equivalent width between them. Though it has characteristics occasionally attributed to active galactic nuclei, we conclude that SL2SJ02176-0513 is a low-metallicity star-bursting dwarf galaxy. Such galaxies will be found in significant numbers in the full 3D-HST grism survey.

  19. 3D-HST GRISM SPECTROSCOPY OF A GRAVITATIONALLY LENSED, LOW-METALLICITY STARBURST GALAXY AT z = 1.847

    Brammer, Gabriel B.; Sanchez-Janssen, Ruben [European Southern Observatory, Alonso de Cordova 3107, Casilla 19001, Vitacura, Santiago (Chile); Labbe, Ivo; Franx, Marijn; Fumagalli, Mattia; Patel, Shannon [Leiden Observatory, Leiden University, 2300-RA Leiden (Netherlands); Da Cunha, Elisabete; Rix, Hans-Walter; Schmidt, Kasper B.; Van der Wel, Arjen [Max Planck Institute for Astronomy (MPIA), Koenigstuhl 17, D-69117 Heidelberg (Germany); Erb, Dawn K. [Department of Physics, University of Wisconsin-Milwaukee, P.O. Box 413, Milwaukee, WI 53201 (United States); Lundgren, Britt; Momcheva, Ivelina; Nelson, Erica; Skelton, Rosalind E.; Van Dokkum, Pieter G.; Wake, David A.; Whitaker, Katherine E. [Department of Astronomy, Yale University, New Haven, CT 06520 (United States); Marchesini, Danilo [Physics and Astronomy Department, Tufts University, Robinson Hall, Room 257, Medford, MA 02155 (United States); Quadri, Ryan, E-mail: gbrammer@eso.org [Carnegie Observatories, 813 Santa Barbara Street, Pasadena, CA 91101 (United States)

    2012-10-10

    We present Hubble Space Telescope (HST) imaging and spectroscopy of the gravitational lens SL2SJ02176-0513, a cusp arc at z = 1.847. The UV continuum of the lensed galaxy is very blue, which is seemingly at odds with its redder optical colors. The 3D-HST WFC3/G141 near-infrared spectrum of the lens reveals the source of this discrepancy to be extremely strong [O III] {lambda}5007 and H{beta} emission lines with rest-frame equivalent widths of 2000 {+-} 100 and 520 {+-} 40 A, respectively. The source has a stellar mass {approx}10{sup 8} M{sub Sun }, sSFR {approx} 100 Gyr{sup -1}, and detection of [O III] {lambda}4363 yields a metallicity of 12 + log (O/H) = 7.5 {+-} 0.2. We identify local blue compact dwarf analogs to SL2SJ02176-0513, which are among the most metal-poor galaxies in the Sloan Digital Sky Survey. The local analogs resemble the lensed galaxy in many ways, including UV/optical spectral energy distribution, spatial morphology, and emission line equivalent widths and ratios. Common to SL2SJ02176-0513 and its local counterparts is an upturn at mid-IR wavelengths likely arising from hot dust heated by starbursts. The emission lines of SL2SJ02176-0513 are spatially resolved owing to the combination of the lens and the high spatial resolution of HST. The lensed galaxy is composed of two clumps with combined size r{sub e} {approx}300 pc, and we resolve significant differences in UV color and emission line equivalent width between them. Though it has characteristics occasionally attributed to active galactic nuclei, we conclude that SL2SJ02176-0513 is a low-metallicity star-bursting dwarf galaxy. Such galaxies will be found in significant numbers in the full 3D-HST grism survey.

  20. The role of 3D microenvironmental organization in MCF-7 epithelial–mesenchymal transition after 7 culture days

    Foroni, Laura [Pathology Unit, Department of Haematology, Oncology and Clinical Pathology, S. Orsola-Malpighi Hospital, Bologna University (Italy); Vasuri, Francesco, E-mail: vasurifrancesco@libero.it [Pathology Unit, Department of Haematology, Oncology and Clinical Pathology, S. Orsola-Malpighi Hospital, Bologna University (Italy); Chair of Vascular Surgery, Department of Specialistic Surgery and Anaesthesiological Sciences, S. Orsola-Malpighi Hospital, Bologna University (Italy); Valente, Sabrina [Pathology Unit, Department of Haematology, Oncology and Clinical Pathology, S. Orsola-Malpighi Hospital, Bologna University (Italy); Gualandi, Chiara [Department of Chemistry “G. Ciamician” and National Consortium of Materials Science and Technology (INSTM, RU Bologna), Bologna University (Italy); Focarete, Maria Letizia [Department of Chemistry “G. Ciamician” and National Consortium of Materials Science and Technology (INSTM, RU Bologna), Bologna University (Italy); Health Science and Technologies–Interdepartmental Center for Industrial Research (HST-ICIR), Bologna University (Italy); Caprara, Giacomo [Pathology Unit, Department of Haematology, Oncology and Clinical Pathology, S. Orsola-Malpighi Hospital, Bologna University (Italy); Scandola, Mariastella [Department of Chemistry “G. Ciamician” and National Consortium of Materials Science and Technology (INSTM, RU Bologna), Bologna University (Italy); D' Errico-Grigioni, Antonia; Pasquinelli, Gianandrea [Pathology Unit, Department of Haematology, Oncology and Clinical Pathology, S. Orsola-Malpighi Hospital, Bologna University (Italy)

    2013-06-10

    We present a multi-technique study on in vitro epithelial–mesenchymal transition (EMT) in human MCF-7 cells cultured on electrospun scaffolds of poly(L-lactic acid) (PLA), with random and aligned fiber orientations. Our aim is to investigate the morphological and genetic characteristics induced by extracellular matrix in tumor cells cultured in different 3D environments, and at different time points. Cell vitality was assessed with AlamarBlue at days 1, 3, 5 and 7. Scanning electron microscopy was performed at culture days 3 and 7. Immunohistochemistry (for E-cadherin, β-catenin, cytokeratins, nucleophosmin, tubulin, Ki-67 and vimentin), immunofluorescence (for F-actin) western blot (for E-cadherin, β-catenin and vimentin) and transmission electron microscopy were carried out at day 7. An EMT gene array followed by PCR analysis confirmed the regulation of selected genes. At day 7, scanning electron microscopy on aligned-PLA revealed spindle-shaped cells gathered in buds and ribbon-like structures, with a higher nucleolar/nuclear ratio and a loss in E-cadherin and β-catenin at immunohistochemistry and western blot. An up-regulation of SMAD2, TGF-β2, TFPI2 and SOX10 was found in aligned-PLA compared to random-PLA cultured cells. The topography of the extracellular matrix has a role in tumor EMT, and a more aggressive phenotype characterizes MCF-7 cells cultured on aligned-PLA scaffold. -- Highlights: • After 7 culture days an aligned-PLA scaffold induces a spindle shape to MCF-7 cells. • Despite these changes, the aligned MCF-7 cells keep an epithelial phenotype. • The extracellular environment alone influences the E-cadherin/β-catenin axis. • The extracellular environment can promote the epithelial–mesenchymal transition.

  1. The role of 3D microenvironmental organization in MCF-7 epithelial–mesenchymal transition after 7 culture days

    We present a multi-technique study on in vitro epithelial–mesenchymal transition (EMT) in human MCF-7 cells cultured on electrospun scaffolds of poly(L-lactic acid) (PLA), with random and aligned fiber orientations. Our aim is to investigate the morphological and genetic characteristics induced by extracellular matrix in tumor cells cultured in different 3D environments, and at different time points. Cell vitality was assessed with AlamarBlue at days 1, 3, 5 and 7. Scanning electron microscopy was performed at culture days 3 and 7. Immunohistochemistry (for E-cadherin, β-catenin, cytokeratins, nucleophosmin, tubulin, Ki-67 and vimentin), immunofluorescence (for F-actin) western blot (for E-cadherin, β-catenin and vimentin) and transmission electron microscopy were carried out at day 7. An EMT gene array followed by PCR analysis confirmed the regulation of selected genes. At day 7, scanning electron microscopy on aligned-PLA revealed spindle-shaped cells gathered in buds and ribbon-like structures, with a higher nucleolar/nuclear ratio and a loss in E-cadherin and β-catenin at immunohistochemistry and western blot. An up-regulation of SMAD2, TGF-β2, TFPI2 and SOX10 was found in aligned-PLA compared to random-PLA cultured cells. The topography of the extracellular matrix has a role in tumor EMT, and a more aggressive phenotype characterizes MCF-7 cells cultured on aligned-PLA scaffold. -- Highlights: • After 7 culture days an aligned-PLA scaffold induces a spindle shape to MCF-7 cells. • Despite these changes, the aligned MCF-7 cells keep an epithelial phenotype. • The extracellular environment alone influences the E-cadherin/β-catenin axis. • The extracellular environment can promote the epithelial–mesenchymal transition

  2. Phonons in Ultrathin Oxide Films: 2D to 3D Transition in FeO on Pt(111).

    Spiridis, N; Zając, M; Piekarz, P; Chumakov, A I; Freindl, K; Goniakowski, J; Kozioł-Rachwał, A; Parliński, K; Ślęzak, M; Ślęzak, T; Wdowik, U D; Wilgocka-Ślęzak, D; Korecki, J

    2015-10-30

    The structural and magnetic properties of ultrathin FeO(111) films on Pt(111) with thicknesses from 1 to 16 monolayers (MLs) were studied using the nuclear inelastic scattering of synchrotron radiation. A distinct evolution of vibrational characteristics with thickness, revealed in the phonon density of states (PDOS), shows a textbook transition from 2D to 3D lattice dynamics. For the thinnest films of 1 and 2 ML, the low-energy part of the PDOS followed a linear ∝E dependence in energy that is characteristic for two-dimensional systems. This dependence gradually transforms with thickness to the bulk ∝E^{2} relationship. Density-functional theory phonon calculations perfectly reproduced the measured 1-ML PDOS within a simple model of a pseudomorphic FeO/Pt(111) interface. The calculations show that the 2D PDOS character is due to a weak coupling of the FeO film to the Pt(111) substrate. The evolution of the vibrational properties with an increasing thickness is closely related to a transient long-range magnetic order and stabilization of an unusual structural phase. PMID:26565477

  3. Feasibility Study on 3-D Printing of Metallic Structural Materials with Robotized Laser-Based Metal Additive Manufacturing

    Ding, Yaoyu; Kovacevic, Radovan

    2016-05-01

    Metallic structural materials continue to open new avenues in achieving exotic mechanical properties that are naturally unavailable. They hold great potential in developing novel products in diverse industries such as the automotive, aerospace, biomedical, oil and gas, and defense. Currently, the use of metallic structural materials in industry is still limited because of difficulties in their manufacturing. This article studied the feasibility of printing metallic structural materials with robotized laser-based metal additive manufacturing (RLMAM). In this study, two metallic structural materials characterized by an enlarged positive Poisson's ratio and a negative Poisson's ratio were designed and simulated, respectively. An RLMAM system developed at the Research Center for Advanced Manufacturing of Southern Methodist University was used to print them. The results of the tensile tests indicated that the printed samples successfully achieved the corresponding mechanical properties.

  4. Feasibility Study on 3-D Printing of Metallic Structural Materials with Robotized Laser-Based Metal Additive Manufacturing

    Ding, Yaoyu; Kovacevic, Radovan

    2016-07-01

    Metallic structural materials continue to open new avenues in achieving exotic mechanical properties that are naturally unavailable. They hold great potential in developing novel products in diverse industries such as the automotive, aerospace, biomedical, oil and gas, and defense. Currently, the use of metallic structural materials in industry is still limited because of difficulties in their manufacturing. This article studied the feasibility of printing metallic structural materials with robotized laser-based metal additive manufacturing (RLMAM). In this study, two metallic structural materials characterized by an enlarged positive Poisson's ratio and a negative Poisson's ratio were designed and simulated, respectively. An RLMAM system developed at the Research Center for Advanced Manufacturing of Southern Methodist University was used to print them. The results of the tensile tests indicated that the printed samples successfully achieved the corresponding mechanical properties.

  5. Conventional Design Calculation &3D Modeling of Metal Forming Heavy duty Hydraulic Press.

    Abhijeet S Khandekar

    2015-06-01

    Full Text Available The design optimization & structure frame analysis of a heavy duty metal forming hydraulic press has been proposed. In this paper the structural analysis & design optimization of hydraulic press has been done and a comparative study of results of finite element analysis of a press with 300 ton capacity has been conducted. It is not possible for the real experimental studies to take into consideration the influence of the connections between the main beams and the rest parts of the construction, the influence of the long it udinal and transverse ribbings as well as the influence of the supports on the overall stressed state of the construction. Moreover, the research esthatuseforthemajorityofthetestcasesdifferentstrainmeasurementsturnouttobequitehardandexpensive.Allthesepr oblemscouldbesolvedsuccessfullybytheuseofcomputermodelingprocedures.Itispossibletoperform2Dor 3Dcomputerstudies.The2Dcomputerstudiesgiveideaoftheplanarbehavioroftheconstructionandlacktheopportunity ofshowingtheinfluenceofsupportsortheconnectionsoftheconstruction.Itisonlythe3Dmodelsthatcouldsatisfyallther equirementsfor examiningthegeneralstressedstateofthecarryingmetalconstruction.Withregardtothis,thecreationof3- Dmodelsforresearchingandanalyzingthebehaviorofametal forming hydraulic press,becomesthemaingoalofthepresentwork.Intheinitialphaseof thestudy,conventionaldesigncalculationsproposedbyIndianStandardRuleswereperformed.Thepressdesignwasmo deledwithsolids,Loadsandboundaryconditionswereappliedtosolidmodel.Assignmaterialtothesolidmodel.FiniteEl ementmeshesweregeneratedfromthesolidmodel.Afteracomparisonofthefiniteelementanalyses,andtheconventiona lcalculations,theanalysiswasfoundtogivethemostrealisticresults.Asaresultofthis study,adesign optimizationfor a heavy duty meal forming hydraulic presshasbeendone.

  6. Magnetic excitations in transition metals

    A brief review is given of the spin dynamics of the 3d elements Fe, Co, Ni and Cr. These materials have proved difficult to investigate thoroughly because the excitations extend to very high energies, but should be well suited to study with spallation neutron sources as demonstrated by recent measurements on pure iron at IPNS

  7. Mono, bi- and trinuclear metal complexes derived from new benzene-1,4-bis(3-pyridin-2-ylurea) ligand. Spectral, magnetic, thermal and 3D molecular modeling studies

    El-ghamry, Mosad A.; Saleh, Akila A.; Khalil, Saied M. E.; Mohammed, Amira A.

    2013-06-01

    New bis (pyridylurea) ligand, H2L, was synthesized by the reaction of ethylpyridine-2-carbamate (EPC) and p-phenylenediamine. The ligand was characterized by elemental analysis, IR, 1H NMR, electronic and mass spectra. Reaction of the prepared ligand with Co2+, Ni2+, Cu2+, Fe3+, VO2+ and UO22+ ions afforded mono, bi- and trinuclear metal complexes. Also, new mixed ligand complexes of the ligand H2L and 8-hydroxyquinoline (8-HQ) with Co2+, Ni2+, Cu2+ and Fe3+ ions were synthesized. The ligand behaves as bi- and tetradentate toward the transition metal ions, coordination via the pyridine sbnd N, the carbonyl sbnd O and/or the amidic sbnd N atoms in a non, mono- and bis-deprotonated form. The complexes were characterized by elemental and thermal analyses, IR, electronic and mass spectra as well as conductance and magnetic susceptibility measurements. The results showed that the metal complexes exhibited different geometrical arrangements such as square planar, tetrahedral, octahedral and square pyramidal arrangements. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. 3D molecular modeling of the ligand, H2L and a representative complex were studied.

  8. 3D Online Submicron Scale Observation of Mixed Metal Powder's Microstructure Evolution in High Temperature and Microwave Compound Fields

    Dan Kang

    2014-01-01

    Full Text Available In order to study the influence on the mechanical properties caused by microstructure evolution of metal powder in extreme environment, 3D real-time observation of the microstructure evolution of Al-Ti mixed powder in high temperature and microwave compound fields was realized by using synchrotron radiation computerized topography (SR-CT technique; the spatial resolution was enhanced to 0.37 μm/pixel through the designed equipment and the introduction of excellent reconstruction method for the first time. The process of microstructure evolution during sintering was clearly distinguished from 2D and 3D reconstructed images. Typical sintering parameters such as sintering neck size, porosity, and particle size of the sample were presented for quantitative analysis of the influence on the mechanical properties and the sintering kinetics during microwave sintering. The neck size-time curve was obtained and the neck growth exponent was 7.3, which indicated that surface diffusion was the main diffusion mechanism; the reason was the eddy current loss induced by the external microwave fields providing an additional driving force for mass diffusion on the particle surface. From the reconstructed images and the curve of porosity and average particle size versus temperature, it was believed that the presence of liquid phase aluminum accelerated the densification and particle growth.

  9. A nanoporous 3D zinc(II) metal-organic framework for selective absorption of benzaldehyde and formaldehyde

    Moradpour, Tahereh; Abbasi, Alireza; Van Hecke, Kristof

    2015-08-01

    A new 3D nanoporous metal-organic framework (MOF), [[Zn4O(C24H15N6O6)2(H2O)2]·6H2O·DMF]n (1) based on 4,4‧,4″-s-triazine-1,3,5-triyltri-p-aminobenzoate (TATAB) ligand was solvothermally synthesized and characterized by single-crystal X-ray diffraction, Powder X-ray diffraction (PXRD), infrared spectroscopy (IR) and Brunauer-Emmett-Teller (BET) analyses. X-ray single crystal diffraction analysis reveals that 1 exhibits a 3D network with new kvh1 topology. Semi-empirical (AM1) calculations were carried out to obtain stable conformers for TATAB ligand. In addition, the absorption of two typical aldehydes (benzaldehyde and formaldehyde) in the presence of 1 was investigated and the effect of the aldehyde concentration, exposure time and temperature was studied. It was found that compound 1 has a potential for the absorption of aldehydes under mild conditions.

  10. Antiferromagnetic spin chain behavior and a transition to 3D magnetic order in Cu(D,L-alanine)2: Roles of H-bonds

    Calvo, Rafael; Sartoris, Rosana P.; Calvo, Hernán L.; Chagas, Edson F.; Rapp, Raul E.

    2016-05-01

    We study the spin chain behavior, a transition to 3D magnetic order and the magnitudes of the exchange interactions for the metal-amino acid complex Cu(D,L-alanine)2•H2O, a model compound to investigate exchange couplings supported by chemical paths characteristic of biomolecules. Thermal and magnetic data were obtained as a function of temperature (T) and magnetic field (B0). The magnetic contribution to the specific heat, measured between 0.48 and 30 K, displays above 1.8 K a 1D spin-chain behavior that can be fitted with an intrachain antiferromagnetic (AFM) exchange coupling constant 2J0=(-2.12±0.08) cm-1 (defined as ℋex(i,i+1) = -2J0SiṡSi+1), between neighbor coppers at 4.49 Å along chains connected by non-covalent and H-bonds. We also observe a narrow specific heat peak at 0.89 K indicating a phase transition to a 3D magnetically ordered phase. Magnetization curves at fixed T = 2, 4 and 7 K with B0 between 0 and 9 T, and at T between 2 and 300 K with several fixed values of B0 were globally fitted by an intrachain AFM exchange coupling constant 2J0=(-2.27±0.02) cm-1 and g = 2.091±0.005. Interchain interactions J1 between coppers in neighbor chains connected through long chemical paths with total length of 9.51 Å cannot be estimated from magnetization curves. However, observation of the phase transition in the specific heat data allows estimating the range 0.1≤|2J1|≤0.4 cm-1, covering the predictions of various approximations. We analyze the magnitudes of 2J0 and 2J1 in terms of the structure of the corresponding chemical paths. The main contribution in supporting the intrachain interaction is assigned to H-bonds while the interchain interactions are supported by paths containing H-bonds and carboxylate bridges, with the role of the H-bonds being predominant. We compare the obtained intrachain coupling with studies of compounds showing similar behavior and discuss the validity of the approximations allowing to calculate the interchain

  11. Self-arrangement of nanoparticles toward crystalline metal oxides with high surface areas and tunable 3D mesopores

    Lee, Hyung Ik; Lee, Yoon Yun; Kang, Dong-Uk; Lee, Kirim; Kwon, Young-Uk; Kim, Ji Man

    2016-02-01

    We demonstrate a new design concept where the interaction between silica nanoparticles (about 1.5 nm in diameter) with titania nanoparticles (anatase, about 4 nm or 6 nm in diameter) guides a successful formation of mesoporous titania with crystalline walls and controllable porosity. At an appropriate solution pH (~1.5, depending on the deprotonation tendencies of two types of nanoparticles), the smaller silica nanoparticles, which attach to the surface of the larger titania nanoparticles and provide a portion of inactive surface and reactive surface of titania nanoparticles, dictate the direction and the degree of condensation of the titania nanoparticles, resulting in a porous 3D framework. Further crystallization by a hydrothermal treatment and subsequent removal of silica nanoparticles result in a mesoporous titania with highly crystalline walls and tunable mesopore sizes. A simple control of the Si/Ti ratio verified the versatility of the present method through the successful control of mean pore diameter in the range of 2-35 nm and specific surface area in the ranges of 180-250 m2 g-1. The present synthesis method is successfully extended to other metal oxides, their mixed oxides and analogues with different particle sizes, regarding as a general method for mesoporous metal (or mixed metal) oxides.

  12. Electronic doping of transition metal oxide perovskites

    Cammarata, Antonio; Rondinelli, James M.

    2016-05-01

    CaFeO3 is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO3. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

  13. Structural, electronic, and magnetic properties of 3D metal trioxide and tetraoxide superhalogen cluster-doped monolayer BN

    Meng, Jingjing; Li, Dan; Niu, Yuan; Zhao, Hongmin; Liang, Chunjun; He, Zhiqun

    2016-07-01

    The structural, electronic, and magnetic properties of monolayer BN doped with 3D metal trioxide and tetraoxide superhalogen clusters are investigated using first-principle calculations. TMO3(4)-doped monolayer BN exhibits a low negative formation energy, whereas TM atoms embedded in monolayer BN show a high positive formation energy. TMO3(4) clusters are embedded more easily in monolayer BN than TM atoms. Compared with TMO3-doped structures, TMO4-doped structures have a higher structural stability because of their higher binding energies. Given their low negative formation energies, TMO4-doped structures are more favored for specific applications than TMO3-doped structures and TM atom-doped structures. Large magnetic moments per supercell and significant ferromagnetic couplings between a TM atom and neighboring B and N atoms on the BN layer were observed in all TMO4-doped structures, except for TiO4-doped structures.

  14. Self-assembly synthesis of precious-metal-free 3D ZnO nano/micro spheres with excellent photocatalytic hydrogen production from solar water splitting

    Guo, Si-yao; Zhao, Tie-jun; Jin, Zu-quan; Wan, Xiao-mei; Wang, Peng-gang; Shang, Jun; Han, Song

    2015-10-01

    A simple and straightforward solution growth routine is developed to prepare microporous 3D nano/micro ZnO microsphere with a large BET surface area of 288 m2 g-1 at room temperature. The formation mechanism of the hierarchical 3D nano/micro ZnO microsphere and its corresponding hydrogen evolution performance has been deeply discussed. In particular, this novel hierarchical 3D ZnO microspheres performs undiminished hydrogen evolution for at least 24 h under simulated solar light illumination, even under the condition of no precious metal as cocatalyst. Since the complex production process of photocatalysts and high cost of precious metal cocatalyst remains a major constraint that hinders the application of solar water splitting, this 3D nano/micro ZnO microspheres could be expected to be applicable in the precious-metal-free solar water splitting system due to its merits of low cost, simple procedure and high catalytic activity.

  15. 分子轨道近似在八面体共价晶体中3d过渡金属离子轨道角动量和旋-轨耦合中的应用%Application of Approximate Molecular-orbital Approach to the Angular Momentum and Spin-orbit Coupling of 3d Transition-metal Ions in Octahetral Covalent Crystals

    周一阳

    2001-01-01

    用分子轨道近似推导了3d过渡金属离子在八面体晶体中轨道角动量和旋-轨耦合矩阵,同时得到了这些矩阵元与3d离子在纯晶体场近似下的矩阵之间的关系.通过以上矩阵元和关系可以很容易地计算3d离子在八面体晶体中的旋-轨、自旋-自旋和塞曼作用矩阵.%The matrices of angular momentum and spin-orbit coupling for 3dtransition-metal ions in octahetral symmetry are derived by an approximate molecular-orbital approach. The relationships of these matrices with those for 3d ions within pure crystal-field approximation are also obtained. From above matrices and relationships one can calculate easily the spin-orbit, spin-spin and Zeeman interaction matrices for 3d ions in octahetral symmetry.

  16. Co-culture of 3D tumor spheroids with fibroblasts as a model for epithelial–mesenchymal transition in vitro

    Epithelial–mesenchymal transition (EMT) acts as a facilitator of metastatic dissemination in the invasive margin of malignant tumors where active tumor–stromal crosstalks take place. Co-cultures of cancer cells with cancer-associated fibroblasts (CAFs) are often used as in vitro models of EMT. We established a tumor–fibroblast proximity co-culture using HT-29 tumor spheroids (TSs) with CCD-18co fibroblasts. When co-cultured with TSs, CCD-18co appeared activated, and proliferative activity as well as cell migration increased. Expression of fibronectin increased whereas laminin and type I collagen decreased in TSs co-cultured with fibroblasts compared to TSs alone, closely resembling the margin of in vivo xenograft tissue. Active TGFβ1 in culture media significantly increased in TS co-cultures but not in 2D co-cultures of cancer cells–fibroblasts, indicating that 3D context-associated factors from TSs may be crucial to crosstalks between cancer cells and fibroblasts. We also observed in TSs co-cultured with fibroblasts increased expression of α-SMA, EGFR and CTGF; reduced expression of membranous β-catenin and E-cadherin, together suggesting an EMT-like changes similar to a marginal region of xenograft tissue in vivo. Overall, our in vitro TS–fibroblast proximity co-culture mimics the EMT-state of the invasive margin of in vivo tumors in early metastasis. - Highlights: • An adjacent co-culture of tumor spheroids and fibroblasts is presented as EMT model. • Activation of fibroblasts and increased cell migration were shown in co-culture. • Expression of EMT-related factors in co-culture was similar to that in tumor tissue. • Crosstalk between spheroids and fibroblasts was demonstrated by secretome analysis

  17. Co-culture of 3D tumor spheroids with fibroblasts as a model for epithelial–mesenchymal transition in vitro

    Kim, Sun-Ah, E-mail: j.sarah.k@gmail.com [Department of Biomedicine & Health Sciences, College of Medicine, The Catholic University of Korea, Seoul 137-701 (Korea, Republic of); Lee, Eun Kyung, E-mail: leeek@catholic.ac.kr [Department of Biochemistry, College of Medicine, The Catholic University of Korea, Seoul 137-701 (Korea, Republic of); Cancer Evolution Research Center, College of Medicine, The Catholic University of Korea, Seoul 137-701 (Korea, Republic of); Kuh, Hyo-Jeong, E-mail: hkuh@catholic.ac.kr [Department of Biomedicine & Health Sciences, College of Medicine, The Catholic University of Korea, Seoul 137-701 (Korea, Republic of); Cancer Evolution Research Center, College of Medicine, The Catholic University of Korea, Seoul 137-701 (Korea, Republic of)

    2015-07-15

    Epithelial–mesenchymal transition (EMT) acts as a facilitator of metastatic dissemination in the invasive margin of malignant tumors where active tumor–stromal crosstalks take place. Co-cultures of cancer cells with cancer-associated fibroblasts (CAFs) are often used as in vitro models of EMT. We established a tumor–fibroblast proximity co-culture using HT-29 tumor spheroids (TSs) with CCD-18co fibroblasts. When co-cultured with TSs, CCD-18co appeared activated, and proliferative activity as well as cell migration increased. Expression of fibronectin increased whereas laminin and type I collagen decreased in TSs co-cultured with fibroblasts compared to TSs alone, closely resembling the margin of in vivo xenograft tissue. Active TGFβ1 in culture media significantly increased in TS co-cultures but not in 2D co-cultures of cancer cells–fibroblasts, indicating that 3D context-associated factors from TSs may be crucial to crosstalks between cancer cells and fibroblasts. We also observed in TSs co-cultured with fibroblasts increased expression of α-SMA, EGFR and CTGF; reduced expression of membranous β-catenin and E-cadherin, together suggesting an EMT-like changes similar to a marginal region of xenograft tissue in vivo. Overall, our in vitro TS–fibroblast proximity co-culture mimics the EMT-state of the invasive margin of in vivo tumors in early metastasis. - Highlights: • An adjacent co-culture of tumor spheroids and fibroblasts is presented as EMT model. • Activation of fibroblasts and increased cell migration were shown in co-culture. • Expression of EMT-related factors in co-culture was similar to that in tumor tissue. • Crosstalk between spheroids and fibroblasts was demonstrated by secretome analysis.

  18. Electronic spectroscopy of transition metal dimer

    Qian, Yue; 钱玥

    2013-01-01

    This thesis reports laser spectroscopic studies of gas-phase transition metal dimers using laser ablation/reaction with free jet expansion and laser-induced fluorescence (LIF) spectroscopy technique. Themolecules studied in this work are palladium dimer (Pd2) and vanadium dimer (V2). Many compounds formed from these transition metals are important and functional catalysts in chemical reactions. Therefore, it is of great significance to start from the fundamental level to understand the prope...

  19. Magnetic properties of thin films obtained by ion implantation of 3d metals in polyethylene-terephthalate

    Polymer films containing small metal particles have been attracting particular interest because of their unique properties. Implantation of metal ions in polymers is one of the methods to synthesize metal-polymer nano-composite materials. Ion implantation makes possible the magnetic nano-structures with controlled parameters. Previously, we showed that 3d-metal implantation into numerous polymers (polymethylmethacrylate, phosphorus containing polymethylmethacrylate) resulted in the formation of a composite film consisting of metal nanoparticles buried in an implanted layer. The particles are usually found to be distributed randomly in the surface layer. It has been established that structural peculiarities, phase composition, and magnetic properties of synthesized metal-polymer systems depend on the type of the initial polymer matrix, ion types, as well as conditions of ion implantation. In the present study we have been prepared thin metal-polymer composite films by ion-beam implantation of Fe+ and Co+ ions in polyethylene terephthalate. The implantation of 40 keV ions at room temperature with doses from 2·1016 to 3·1017 cm-2 have been performed, with the ion current density not exceeding 10 μA/cm2. The magnetic properties have been investigated both by ferromagnetic resonance (FMR) and vibrating sample magnetometry (VSM). FMR spectra were recorded using magnetic radio spectrometer Varian E-12 with frequency of 9.5 GHz at room temperature. The dependencies of FMR spectra on orientation have been measured for all samples. Measurements were carried out for two orientations of the sample, normal direction of the films being either parallel or perpendicular to dc magnetic field. The values of the effective magnetization were calculated from orientation dependencies. Thin ferromagnetic films (TFF) have been shown to form for samples with both implanted ions. For samples implanted with Co+ ions, the appearance of FMR lines occurs at doses markedly greater than those

  20. 3D-FEM analysis of SPP excitation through nanoholes in asymmetric metal-insulator-metal structure at tip of circular truncated conical fiber

    Oshikane, Y.; Murai, K.; Nakano, M.

    2014-09-01

    3D-electromagnetic (EM) analysis of surface plasmon polaritons (SPPs) excited by a single-mode (SM) propagation of visible lightwave in an optical fiber has been studied with a 3D-FEM package based on a finite element method. End of the fiber is formed to be a circular cone by wet etching process, and is FIBed to make a circular truncated conical shape with a flat circular surface a few micrometers in diameter. The flat end is covered with three layers of asymmetric metalinsulator- metal structure, thin metallic layer (M1), thick insulator layer (I), and thick metallic layer (M2), respectively. The outermost M2 layer has FIBed nanoholes to convert light waves at the extremity of the fiber into SPPs efficiently, and a bright tiny point light source will be generated on the surface of the M2 layer. In this study, the 3D-FEM models consists of both the MIM structure and the shrinking optical fiber tip coated with a metallic thin film has been designed and analyzed numerically. By applying perfect electric conductor and perfect magnetic conductor to planes containing the axis of rotation, the FEM model has a quarter of the circular truncated conical shape. The FEM analysis is formed in two steps. At the first step, a FEM mode analysis is performed to obtain a solution corresponding to the SM propagation in the fiber. The second level of action is the FEM analysis of EM field in the whole of model to find a stationary solution with the solution of mode analysis. Characteristic of wavelength-dependent excitation, propagation, and focusing of the SPPs will be presented with several experimental results of trial products of the fiber tip.

  1. Three-Dimensional Distribution of the ISM in the Milky Way Galaxy: IV. 3D Molecular Fraction and Galactic-Scale HI-to-H$_2$ Transition

    Sofue, Yoshiaki

    2016-01-01

    Three dimensional (3D) distribution of the volume-density molecular fraction, defined by fmol_rho=rho_H2/(rho_HI + rho_H2), is studied in the Milky Way Galaxy. The molecular front appears at galacto-centric distance of R \\sim 8 kpc, where the phase transition from atomic to molecular hydrogen occurs suddenly with fmol_rho dropping from \\sim 0.8 to 0.2 within a radial interval as narrow as \\sim 0.5 kpc. The front in fmol_rho is much sharper than that for surface density molecular fraction. The front also appears in the vertical direction with a full width of the high-fmol_rho disk to be \\sim 100 pc. The radial and vertical fmol_rho profiles, particularly the front behaviors, are fitted by theoretical curves calculated using the observed density profile and assumed radiation field and metallicity with exponential gradients. The molecular fraction was found to be enhanced along the Perseus and some other spiral arms. The fmol_rho arms imply that the molecular clouds are produced from HI gas in the spiral arms an...

  2. 3D high resolution mineral phase distribution and seismic velocity structure of the transition zone: predicted by a full spherical-shell compressible mantle convection model

    Geenen, T.; Heister, T.; Van Den Berg, A. P.; Jacobs, M.; Bangerth, W.

    2011-12-01

    We present high resolution 3D results of the complex mineral phase distribution in the transition zone obtained by numerical modelling of mantle convection. We extend the work by [Jacobs and van den Berg, 2011] to 3D and illustrate the efficiency of adaptive mesh refinement for capturing the complex spatial distribution and sharp phase transitions as predicted by their model. The underlying thermodynamical model is based on lattice dynamics which allows to predict thermophysical properties and seismic wave speeds for the applied magnesium-endmember olivine-pyroxene mineralogical model. The use of 3D geometry allows more realistic prediction of phase distribution and seismic wave speeds resulting from 3D flow processes involving the Earth's transition zone and more significant comparisons with interpretations from seismic tomography and seismic reflectivity studies aimed at the transition zone. Model results are generated with a recently developed geodynamics modeling application based on dealII (www.dealii.org). We extended this model to incorporate both a general thermodynamic model, represented by P,T space tabulated thermophysical properties, and a solution strategy that allows for compressible flow. When modeling compressible flow in the so called truncated anelastic approximation framework we have to adapt the solver strategy that has been proven by several authors to be highly efficient for incompressible flow to incorporate an extra term in the continuity equation. We present several possible solution strategies and discuss their implication in terms of robustness and computational efficiency.

  3. Metal Enrichment of The Primordial Interstellar Medium through 3-D Hydrodynamical Evolution of The First Supernova Remnant

    Nakasato, N; Nakasato, Naohito; Shigeyama, Toshikazu

    2000-01-01

    The long-term evolution of supernova remnants (SNRs) in the primordial interstellar medium (ISM) with an inhomogeneous structure is calculated to investigate metal enrichment of the primordial gas. For this purpose, we have constructed a parallel 3-D hydrodynamics code incorporating the radiative cooling and self-gravity. The self-gravity and radiative cooling develop the inhomogeneous structure of the ISM from a small perturbation with a power-law spectrum. The resultant density ranges from 0.5 cm$^{-3}$ to 10$^6$ cm $^{-3}$. Calculations for a supernova (SN) with the progenitor mass of 20 solar mass are performed as the first step of a series of our study. It is found from the results that a single SN distributes some of newly synthesized heavy elements into a dense filament of the ISM with densities ranging from 100 to 10$^4$ cm$^{-3}$ depending on where the SN explodes. Thus, the metallicity [Mg/H] of the dense filaments polluted by the SN ejecta becomes $-2.7\\pm0.5$. From these filaments, the first Popul...

  4. Pore-controlled formation of 0D metal complexes in anionic 3D metal-organic frameworks

    Zhang, MW; Bosch, M; Zhou, HC

    2015-01-01

    The host-guest chemistry between a series of anionic MOFs and their trapped counterions was investigated by single crystal XRD. The PCN-514 series contains crystallographically identifiable metal complexes trapped in the pores, where their formation is controlled by the size and shape of the MOF pores. A change in the structure and pore size of PCN-518 indicates that the existence of guest molecules may reciprocally affect the formation of host MOFs.

  5. Nitrogen-rich transition metal nitrides

    Salamat, Ashkan; Hector, Andrew L.; Kroll, Peter; McMillan, Paul F.

    2013-01-01

    The solid state chemistry leading to the synthesis and characterization of metal nitrides with N:M ratios >1 is summarized. Studies of these compounds represent an emerging area of research. Most transition metal nitrides have much lower nitrogen contents, and they often form with non- or sub-stoichiometric compositions. These materials are typically metallic with often superconducting properties, and they provide highly refractory, high hardness materials with many technological applications...

  6. Patterning process exploration of metal 1 layer in 7nm node with 3D patterning flow simulations

    Gao, Weimin; Ciofi, Ivan; Saad, Yves; Matagne, Philippe; Bachmann, Michael; Oulmane, Mohamed; Gillijns, Werner; Lucas, Kevin; Demmerle, Wolfgang; Schmoeller, Thomas

    2015-03-01

    In 7mn node (N7), the logic design requires the critical poly pitch (CPP) of 42-45nm and metal 1 (M1) pitch of 28- 32nm. Such high pattern density pushes the 193 immersion lithography solution toward its limit and also brings extremely complex patterning scenarios. The N7 M1 layer may require a self-aligned quadruple patterning (SAQP) with triple litho-etch (LE3) block process. Therefore, the whole patterning process flow requires multiple exposure+etch+deposition processes and each step introduces a particular impact on the pattern profiles and the topography. In this study, we have successfully integrated a simulation tool that enables emulation of the whole patterning flow with realistic process-dependent 3D profile and topology. We use this tool to study the patterning process variations of N7 M1 layer including the overlay control, the critical dimension uniformity (CDU) budget and the lithographic process window (PW). The resulting 3D pattern structure can be used to optimize the process flow, verify design rules, extract parasitics, and most importantly, simulate the electric field and identify hot spots for dielectric reliability. As an example application, we will report extractions of maximum electric field at M1 tipto- tip which is one of the most critical patterning locations and we will demonstrate the potential of this approach for investigating the impact of process variations on dielectric reliability. We will also present simulations of an alternative M1 patterning flow, with a single exposure block using extreme ultraviolet lithography (EUVL) and analyze its advantages compared to the LE3 block approach.

  7. Electronic structure of hcp transition metals

    Jepsen, O.; Andersen, O. Krogh; Mackintosh, A. R.

    1975-01-01

    Using the linear muffin-tin-orbital method described in the previous paper, we have calculated the electronic structures of the hcp transition metals, Zr, Hf, Ru, and Os. We show how the band structures of these metals may be synthesized from the sp and d bands, and illustrate the effects of...... bands. This gives rise to a Fermi surface which is topologically equivalent to that recently found in Ti, and which does not support open orbits when the magnetic field is sufficiently great that breakdown is complete. It is suggested that the Fermi surface of Hf is probably similar, although very...... majority of the transition metals....

  8. Metal complexes as antibacterial agents: Synthesis, characterization and antibacterial activity of some 3d metal complexes of sulphadimidine

    Adedibu Clement Tella

    2010-06-01

    Full Text Available Metal complexes of Sulphadimidine(SAD were synthesized.The complexes were formulated as [Co(SAD2Cl2], [Cu(SAD2 (H2O2], [Ni (SAD2 Cl2 H2O], [Cd (SAD2 Br2], [Fe (SAD3](H­2O­3 and [Mn (SAD2Cl2] characterized by elemental Analysis, conductivity, IR , UV-Vis, Magnet moment and 1H-NMR and Mass spectroscopies. Co(II, Mn (II,  and Ni(II sulphadimidine complexes consist of metal ion which coordinates through amino nitrogen of the terminal NH2 group and oxygen of sulfonamidic group of the two molecules of sulphadimidine ligand and two halide ions to form octahedral structure while Cd(II coordinates with sulphadimidine through amino nitrogen of the terminal NH2 group with two bromine ions to complete tetrahedral structure. In Cu(II sulphadimidine complex, copper ion coordinates through both pyrimidinic nitrogen (heterocyclic nitrogen and sulfonamidic nitrogen of the two molecules of sulphadimidine. Fe(III coordinates to three molecules of sulphadimidine through heterocyclic nitrogen (pyrimidinic nitrogen and sulfonamidic nitrogen,with three molecules of water outside the coordination sphere. Both Fe(III and Cu(II complexes exhibit octahedral geometry. The antibacterial activity of the complexes and the ligands was investigated against Esherichia coli,  Staphylococcus aureus and Klebsiella pneumonia .  The data obtained revealed that the complexes showed greater activity against the three micro-organisms when compared to parent compound. Stability constant of the complexes were evaluated for the metal salts, the order of stability constant b was found to be Cu (II > Fe (III >Ni(II> Co (II > Cd (II.The values of stability constant (b was found to be log 6.31, 5.93, 5.29, 4.63 and 3.92, respectively. The stability constant data revealed that this ligand may be used as antidote or chelating agent for medical treatment of metals overload or poisoning.

  9. Transition metal contacts to graphene

    Politou, Maria, E-mail: Maria.Politou@imec.be; De Gendt, Stefan; Heyns, Marc [KU Leuven, 3001 Leuven (Belgium); imec, Kapeldreef 75, 3001 Leuven (Belgium); Asselberghs, Inge; Radu, Iuliana; Conard, Thierry; Richard, Olivier; Martens, Koen; Huyghebaert, Cedric; Tokei, Zsolt [imec, Kapeldreef 75, 3001 Leuven (Belgium); Lee, Chang Seung [SAIT, Samsung Electronics Co., Suwon 443-803 (Korea, Republic of); Sayan, Safak [imec, Kapeldreef 75, 3001 Leuven (Belgium); Intel Corporation, 2200 Mission College Blvd, Santa Clara, California 95054 (United States)

    2015-10-12

    Achieving low resistance contacts to graphene is a common concern for graphene device performance and hybrid graphene/metal interconnects. In this work, we have used the circular Transfer Length Method (cTLM) to electrically characterize Ag, Au, Ni, Ti, and Pd as contact metals to graphene. The consistency of the obtained results was verified with the characterization of up to 72 cTLM structures per metal. Within our study, the noble metals Au, Ag and Pd, which form a weaker bond with graphene, are shown to result in lower contact resistance (Rc) values compared to the more reactive Ni and Ti. X-ray Photo Electron Spectroscopy and Transmission Electron Microscopy characterization for the latter have shown the formation of Ti and Ni carbides. Graphene/Pd contacts show a distinct intermediate behavior. The weak carbide formation signature and the low Rc values measured agree with theoretical predictions of an intermediate state of weak chemisorption of Pd on graphene.

  10. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    Andersen, Kirsten; Thygesen, Kristian S.

    2013-01-01

    We study the collective electronic excitations in metallic single-layer and bilayer transition metal dichalcogenides (TMDCs) using time dependent density functional theory in the random phase approximation. For very small momentum transfers (below q≈0.02 Å−1), the plasmon dispersion follows the √q...

  11. Transition Metal Catalyzed Synthesis of Aryl Sulfides

    Chad C. Eichman

    2011-01-01

    Full Text Available The presence of aryl sulfides in biologically active compounds has resulted in the development of new methods to form carbon-sulfur bonds. The synthesis of aryl sulfides via metal catalysis has significantly increased in recent years. Historically, thiolates and sulfides have been thought to plague catalyst activity in the presence of transition metals. Indeed, strong coordination of thiolates and thioethers to transition metals can often hinder catalytic activity; however, various catalysts are able to withstand catalyst deactivation and form aryl carbon-sulfur bonds in high-yielding transformations. This review discusses the metal-catalyzed arylation of thiols and the use of disulfides as metal-thiolate precursors for the formation of C-S bonds.

  12. Guidelines for radiation oncology centres in AFRA Member States intending to make a transition from 2-D to 3-D treatment planning and delivery

    The IAEA Regional Technical Cooperation Project RAF/6/031 on Medical Physics in Support of Cancer Management aims to strengthen national and regional medical physics capabilities to sustain radiotherapy treatments in the AFRA1 Member States. In particular, it aims at increasing the number of qualified medical physicists in the region as well as improving the level of medical physics by establishing regional training and continuous development programmes. Eighteen National Project Coordinators (NPCs) nominated by participating AFRA Member States are engaged in the project. RAF/6/031 was approved by the IAEA in 2005 for an initial five year duration. A coordination meeting is held every two years where the NPCs and IAEA Technical and Project Management Officers establish the project's training and development programmes. During the first coordination meeting at Cape Town in November 2005, it was decided to convene a Task Force Meeting to review the status of treatment planning in radiotherapy in AFRA Member States and prepare a guidance document on the transition from 2-D to 3-D treatment planning. This Task Force Meeting took place at the IAEA's Headquarters in Vienna on 23-26 April 2007. The resulting guidance document highlights the milestones that have to be achieved by radiotherapy centres routinely implementing 2-D computerized treatment planning before making a transition to 3-D treatment planning and delivery. The implementation of 3-D planning by radiotherapy centres that have not yet met these milestones could lead to serious mistakes in treatments. A self-assessment questionnaire was also prepared during the Task Force Meeting. Member States that are planning to make a transition to 3-D planning are advised to assess their existing capabilities through this questionnaire. The same questionnaire could also be useful for the IAEA staff and external experts when assessing the readiness of a radiotherapy centre to make a safe and effective transition to 3-D

  13. Efficient photocarrier injection in a transition metal oxide heterostructure

    Muraoka, Y; Ueda, Y; Hiroi, Z

    2002-01-01

    An efficient method for doping a transition metal oxide (TMO) with hole carriers is presented: photocarrier injection (PCI) in an oxide heterostructure. It is shown that an insulating vanadium dioxide (VO sub 2) film is rendered metallic under light irradiation by PCI from an n-type titanium dioxide (TiO sub 2) substrate doped with Nb. Consequently, a large photoconductivity, which is exceptional for TMOs, is found in the VO sub 2 /TiO sub 2 :Nb heterostructure. We propose an electronic band structure where photoinduced holes created in TiO sub 2 :Nb can be transferred into the filled V 3d band via the low-lying O 2p band of VO sub 2. (letter to the editor)

  14. Synthesis and Exploratory Catalysis of 3d Metals: Group-Transfer Reactions, and the Activation and Functionalization of Small Molecules Including Greenhouse Gases

    Mindiola, Daniel J.

    2014-05-07

    Our work over the past three years has resulted in the development of electron rich and low-coordinate vanadium fragments, molecular nitrides of vanadium and parent imide systems of titanium, and the synthesis of phosphorus containing molecules of the 3d transition metal series. Likewise, with financial support from BES Division in DOE (DE-FG02-07ER15893), we now completed the full characterization of the first single molecular magnet (SMM) of Fe(III). We demonstrated that this monomeric form of Fe(III) has an unusual slow relaxation of the magnetization under zero applied field. To make matters more interesting, this system also undergoes a rare example of an intermediate to high-spin transition (an S = 3/2 to S = 5/2 transition). In 2010 we reported the synthesis of the first neutral and low-coordinate vanadium complexes having the terminal nitride functionality. We have now completed a full study to understand formation of the nitride ligand from the metastable azide precursor, and have also explored the reactivity of the nitride ligand in the context of incomplete and complete N-atom transfer. During the 2010-2013 period we also discovered a facile approach to assemble low-coordinate and low-valent vanadium(II) complexes and exploit their multielectron chemistry ranging from 1-3 electrons. Consequently, we can now access 3d ligand frameworks such as cyclo-P3 (and its corresponding radical anion), nitride radical anions and cations, low-coordinate vanadium oxo’s, and the first example of a vanadium thionitrosyl complex. A cis-divacant iron(IV) imido having some ligand centered radical has been also discovered, and we are in the process of elucidating its electronic structure (in particular the sign of zero field splitting and the origin of its magnitude), bonding and reactivity. We have also revisited some paramagnetic and classic metallocene compounds with S >1/2 ground states in order to understand their reactivity patterns and electronic structure. Lastly

  15. 3D Plasmonic Ensembles of Graphene Oxide and Nobel Metal Nanoparticles with Ultrahigh SERS Activity and Sensitivity

    Jing Lin

    2016-01-01

    Full Text Available We describe a comparison study on 3D ensembles of graphene oxide (GO and metal nanoparticles (silver nanoparticles (AgNPs, gold nanoparticles (GNPs, and gold nanorods (GNRs for surface-enhanced Raman scattering (SERS application. For the first time, GNRs were successfully assembled on the surfaces of GO by means of electrostatic interactions without adding any surfactant. The SERS properties of GO/AgNPs, GO/GNPs, and GO/GNRs were compared using 2-mercaptopyridine (2-Mpy as probing molecule. We found that GO/AgNPs and GO/GNPs substrates are not suitable for detecting 2-Mpy due to the very strong π-π stacking interaction between the 2-Mpy molecules and sp2 carbon structure of GO. Conversely, the GO/GNRs substrates show ultrahigh SERS activity and sensitivity of 2-Mpy with the detection limit as low as ~10-15 M, which is ~2-3 orders of magnitude higher than that of the corresponding GNRs.

  16. Positional isomerism-driven two 3D pillar-layered metal-organic frameworks: Syntheses, topological structures and photoluminescence properties

    Sun, Yayong; Zhao, Siwei; Ma, Haoran; Han, Yi; Liu, Kang; Wang, Lei

    2016-06-01

    Two novel three-dimensional (3D) pillar-layered metal-organic frameworks (MOFs), namely [Zn2(μ2-OH)(boaba)(1,4-bmimb)]n (1) and {[Zn5K2(μ2-H2O)2(boaba)4(1,2-bmimb)2(H2O)2]·H2O}n (2), were prepared by hydrothermal reactions (H3boaba=3,5-bis-oxyacetate-benzoic acid; 1,4-bmimb=1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene; 1,2-bmimb =1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene). Notably, 1 exhibits a (3,5)-connected binodal (63)(69·8)-gra net with binuclear [Zn2(μ2-OH)(COO)]2+ clusters, while 2 shows a novel (4,4,5,9)-connected 4-nodal net constructed from the unique Zn(II)-K(I) heterometal rod-like substructures. The results indicate that the disposition of the 2-methylimidazolyl groups of bis(imidazole) ligands have a significant effect on structural diversity. Moreover, the photoluminescence properties of 1 and 2 have been investigated.

  17. Fiber-to-Waveguide and 3D Chip-to-Chip Light Coupling Based on Bent Metal-Clad Waveguides

    Lu, Zhaolin; Shi, Kaifeng

    2016-01-01

    Efficient fiber-to-waveguide light coupling has been a key issue in integrated photonics for many years. The main challenge lies in the huge mode mismatch between an optical fiber and a single mode waveguide. Herein, we present a novel fiber-to-waveguide coupler, named "L-coupler", through which the light fed from the top of a chip can bend 90{\\deg} with low reflection and is then efficiently coupled into an on-chip Si waveguide within a short propagation distance (<20{\\mu}m). The key element is a bent metal-clad waveguide with a big matched input port. According to our finite-difference time-domain (FDTD) simulation, the coupling efficiency is over 80% within a broad range of working wavelengths in the near-infrared regime for a transverse electric input Gaussian wave. The coupler is polarization-dependent, with very low coupling efficiency (6%-9%) for transverse magnetic waves. The coupler can also be used for three-dimensional (3D) chip-to-chip optical interconnection by efficiently coupling light into ...

  18. Chemical vapour deposition: Transition metal carbides go 2D

    Gogotsi, Yury

    2015-11-01

    The unique properties of 2D materials, such as graphene or transition metal dichalcogenides, have been attracting much attention in the past decade. Now, metallically conductive and even superconducting transition metal carbides are entering the game.

  19. Application of Approximate Molecular-orbital Approach to the Angular Momentum and Spin-orbit Coupling of 3d Transition-metal Ions in Tetrahetral Covalent Crystals%分子轨道近似在四面体共价晶体中3d过渡金属离子 轨道角动量和旋-轨耦合中的应用

    周一阳

    2001-01-01

    The matrices of angular momentum and spin-orbit coupling for 3dtransition-metal ions in tetrahetral symmetry are derived by an approximate molecular-orbital approach. The relationships of these matrices with those for 3d ions within pure crystal-field approximation are also obtained. From these matrices and relationships one can calculate easily the spin-orbit, spin-spin and Zeeman interaction matrices for 3d ions in tetrahetral symmetry. The matrices of the spin-orbit, spin-spin and Zeeman interactions are useful for dealing with the properties, such as fine-structure spectra, Zeeman and exchange splittings, electron paramagnetic resonance parameters, magnetization, magnetic heat, magnetic susceptibility and so on for 3d ions in tetrahetral covalent crystals, especially, in semiconductors. In addition, the ligand orbitals for octahetral and tetrahetral symmetry and the overlap integrals between 3d ions and ligands are discussed.%用分子轨道近似推导了3d过渡金属离子在四面体晶体中轨道角动量和旋-轨耦合矩阵,同时得到了这些矩阵元与3d离子在纯晶体场近似下的矩阵之间的关系.通过以上矩阵元和关系可以很容易地计算3d离子在四面体晶体中的旋-轨、自旋-自旋和塞曼作用矩阵.这些旋-轨、自旋-自旋和塞曼作用矩阵对研究3d离子在四面体共价晶体中(尤其是半导体中)的超精细光谱、塞曼和交换分裂、电子顺磁共振参数、磁化强度、磁比热、磁化率等都是有用的.另外,还讨论了八面体和四面体对称下的配体轨道,以及3d离子和配体间的重迭积分.

  20. Nuclear Scattering from Transition Metals

    Hira, Ajit; McKeough, James; Valerio, Mario; Cathey, Tommy

    2016-03-01

    In view of the continued interest in the scattering of light projectiles by metallic nuclei, we present a computational study of the interactions between different nuclear species of atoms such as H through F (Z neutron scattering can be used to record holographic images of materials. We have developed a FORTRAN computer program to compute stopping cross sections and scattering angles in Ag and other metals for the small nuclear projectiles, using Monte Carlo calculation. This code allows for different angles of incidence. Next, simulations were done in the energy interval from 50 to 210 keV. The computational results thus obtained are compared with relevant experimental data. The data are further analyzed to identify periodic trends in terms of the atomic number of the projectile. Such studies also have potential applications in nuclear physics and in nuclear medicine. Funding from National Science Foundation.

  1. An in-depth spectroscopic examination of molecular bands from 3D hydrodynamical model atmospheres I. Formation of the G-band in metal-poor dwarf stars

    Gallagher, A J; Bonifacio, P; Ludwig, H -G; Steffen, M; Spite, M

    2016-01-01

    Recent developments in the three-dimensional (3D) spectral synthesis code Linfor3D have meant that, for the first time, large spectral wavelength regions, such as molecular bands, can be synthesised with it in a short amount of time. A detailed spectral analysis of the synthetic G-band for several dwarf turn-off-type 3D atmospheres (5850 <= T_eff [K] <= 6550, 4.0 <= log g <= 4.5, -3.0 <= [Fe/H] <= -1.0) was conducted, under the assumption of local thermodynamic equilibrium. We also examine carbon and oxygen molecule formation at various metallicity regimes and discuss the impact it has on the G-band. Using a qualitative approach, we describe the different behaviours between the 3D atmospheres and the traditional one-dimensional (1D) atmospheres and how the different physics involved inevitably leads to abundance corrections, which differ over varying metallicities. Spectra computed in 1D were fit to every 3D spectrum to determine the 3D abundance correction. Early analysis revealed that the ...

  2. Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses.

    Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K; Mukherjee, Sundeep

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent 'Stoner type' magnetization for the amorphous alloys in contrast to 'Heisenberg type' in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study. PMID:27143686

  3. Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

    Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe–Co metallic glass system of composition [(Co1‑x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

  4. Transition metal based layered double hydroxides tailored for energy conversion and storage

    Xia Long; Zilong Wang; Shuang Xiao; Yiming An; Shihe Yang

    2016-01-01

    Layered double hydroxides (LDHs) are a class of clays with brucite like layers and intercalated anions. The first (3d) series transition metals based LDHs (TM-LDHs) are attracting increasing interest in the field of energy conversion and storage processes due to their unique physicochemical properties. In this article, we review recent developments in the synthesis and applications of TM-LDH in these areas including water splitting, CO2 conversion, metal-air batteries and supercapacitors and ...

  5. Magnetic Behavior of Some Rare-Earth Transition-Metal Perovskite Oxide Systems

    Kenji Yoshii; Akio Nakamura; Masaichiro Mizumaki; Naoshi Ikeda; Jun'ichiro Mizuki

    2004-01-01

    Magnetic properties were investigated for the rare-earth 3d-transition metal oxides with the perovskite structure. Intriguing magnetic phenomena were reviewed for a few systems:magnetization peak effect in the titanates, magnetization reversal in the chromites and metallic ferromagnetism in the cobaltites. The results suggest an important role of the rare-earth ions for the magnetic properties of such complex oxides.

  6. 3D printing of soft and wet systems benefit from hard-to-soft transition of transparent shape memory gels (presentation video)

    Furukawa, Hidemitsu; Gong, Jin; Makino, Masato; Kabir, Md. Hasnat

    2014-04-01

    Recently we successfully developed novel transparent shape memory gels. The SMG memorize their original shapes during the gelation process. In the room temperature, the SMG are elastic and show plasticity (yielding) under deformation. However when heated above about 50˚C, the SMG induce hard-to-soft transition and go back to their original shapes automatically. We focus on new soft and wet systems made of the SMG by 3-D printing technology.

  7. Three-dimensional (3-D) metal-organic frameworks with 3-pyridin-4-yl-benzoate defining new (3,6)-connected net topologies

    Reactions of different metal salts with 3-pyridin-4-yl-benzoic acid (3,4-Hpybz) under ambient condition afford a series of 3-D metal-organic frameworks with two new types of (3,6)-connected net topologies. In the isomorphic complexes [M2(μ-H2O)(3,4-pybz)4]n (MII=MnII for 1, ZnII for 2, or CdII for 3), the octahedral metal nodes are extended by the 3-connected pybz tectons to constitute 3-D arrays with the Schlaefli symbol of (3.4.5)(32.44.55.62.72), whereas [Pb(3,4-pybz)2]n (4) shows a completely different 3-D (42.6)2(44.62.89) framework, which represents a subnet of the (4,8)-connected fluorite lattice. - Graphical abstract: This work presents a series of 3-D metal-organic frameworks with 3-pyridin-4-yl-benzoate, which display new (3,6)-connected net topologies of (3.4.5)(32.44.55.62.72) for MnII/ZnII/CdII and (42.6)2(44.62.89) for PbII species.

  8. Magnetic behavior of inorganic-organic hybrid phosphite compounds with 3-d transition metals

    The (C2H10N2)[M(HPO3)F3](MIII=V, Cr, Fe) [I], (C2H10N2)[M3(HPO3)4] (MII=Mn, Co) [II] and (C2H10N2)0.5[Fe(HPO3)2](MIII=V, Fe) [III] compounds have been synthesized by using mild hydrothermal conditions. The crystal structure of the compounds shows different dimensionality. The compounds exhibit antiferromagnetic behavior, with hysteresis loops for the bimetallic (C2H10N2)[Mn2.09Co0.91(HPO3)4] and (C2H10N2)0.5[V0.48Fe0.52(HPO3)2] phases, indicating the existence of a ferrimagnetic behavior probably due to a spin descompensation

  9. Mesoporous Transition Metal Oxides for Supercapacitors

    Yan Wang

    2015-10-01

    Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  10. Fluid metals the liquid-vapor transition of metals

    Hensel, Friedrich

    2014-01-01

    This is a long-needed general introduction to the physics and chemistry of the liquid-vapor phase transition of metals. Physicists and physical chemists have made great strides understanding the basic principles involved, and engineers have discovered a wide variety of new uses for fluid metals. Yet there has been no book that brings together the latest ideas and findings in the field or that bridges the conceptual gap between the condensed-matter physics relevant to a dense metallic liquid and the molecular chemistry relevant to a dilute atomic vapor. Friedrich Hensel and William Warren seek

  11. Magnetism in a number of Metal Organic Frameworks (MOFs) with 1D and 3D characteristics: An experimental and analytical study

    Hamida, Youcef

    Metal Organic Frameworks (MOFs) exhibit many excellent physical properties including magnetic properties for potential applications in devices. More importantly for the subject of this thesis, MOFs are ideal for the realization of low dimensional magnetism because of the large selection of ligands connecting magnetic centers in making the framework. The materials studied in this thesis include ten magnetic MOFs of the form M(L1)(L2) [M = Cu, Ni, Co, Fe, Mn; L1 = NDC, bpdc, BDC, BODC, N3; L2 = DMF, H2O, TED, bpy]. Polycrystalline powder samples as well as single crystal samples were synthesized. Their crystal structures were determined, and their magnetic and thermodynamic properties were measured and analyzed. Eight of these materials were characterized as 1D magnets and two as 3D magnets. In the 1D case it is found that above Tm [the temperature at which the magnetic susceptibility chi(T) has a peak] the magnetic behavior of MOFs (S ≥ 1) can be well described with the Classical Fisher Model (CFM). Near and below TC the spins take a more definite orientation than allowed for in the CFM and hence the Ising Model (IM) was used for fitting. Both CFM and IM yield fairly consistent intrachain couplings ( J) when applied in their appropriate temperature region. To estimate the interchain exchange (J'), the susceptibility for a magnetic chain in the mean field of neighboring chains is used. In all cases, as expected, the ratio of J to J' was less than 10%. The special case of Cu(N3)2bpy ( S = ½) was analyzed with the spin ½ IM. Although the specific heat data (Ctotal) for most of the 1D MOFs showed no clear phase transition, a low temperature fit to the electron-phonon specific heats yielded apparent heavy fermion-like gamma values on the order of several hundred mJ/mol K2. The lattice specific heat (Clattice) was estimated using a Debye-Einstein hybrid model. Subtracting Clattice from Ctotal, magnetic specific heat ( CM) with a broad peak characteristic of low

  12. 3D hybrid-porous carbon derived from carbonization of metal organic frameworks for high performance supercapacitors

    Bao, Weizhai; Mondal, Anjon Kumar; Xu, Jing; Wang, Chengyin; Su, Dawei; Wang, Guoxiu

    2016-09-01

    We report a rational design and synthesis of 3D hybrid-porous carbon with a hierarchical pore architecture for high performance supercapacitors. It contains micropores (3D hybrid-porous carbon demonstrates a specific capacitance of 332 F g-1 at a constant charge/discharge current of 500 mA g-1. The supercapacitors can endure more than 10,000 cycles without degradation of capacitance.

  13. Transition-metal dichalcogenides for spintronic applications

    Zibouche, Nourdine; Kuc, Agnieszka; Heine, Thomas [School of Engineering and Science, Jacobs University Bremen (Germany); Musfeldt, Janice [Department of Chemistry, University of Tennessee, Knoxville, TN (United States)

    2014-10-15

    Spin-orbit splitting in transition-metal dichalcogenide monolayers is investigated on the basis of density-functional theory within explicit two-dimensional periodic boundary conditions. The spin-orbit splitting reaches few hundred meV and increases with the size of the metal and chalcogen atoms, resulting in nearly 500 meV for WTe{sub 2}. Furthermore, we find that similar to the band gap, spin-orbit splitting changes drastically under tensile strain. In centrosymmetric transition metal dichalcogenide bilayers, spin-orbit splitting is suppressed by the inversion symmetry. However, it could be induced if the inversion symmetry is explicitly broken, e.g. by a potential gradient normal to the plane, as it is present in heterobilayers (Rashba-splitting). In such systems, the spin-orbit splitting could be as large as for the heavier monolayer that forms heterobilayer. These properties of transition metal dichalcogenide materials suggest them for potential applications in opto-, spin- and straintronics. (copyright 2014 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Transition-metal dichalcogenides for spintronic applications

    Spin-orbit splitting in transition-metal dichalcogenide monolayers is investigated on the basis of density-functional theory within explicit two-dimensional periodic boundary conditions. The spin-orbit splitting reaches few hundred meV and increases with the size of the metal and chalcogen atoms, resulting in nearly 500 meV for WTe2. Furthermore, we find that similar to the band gap, spin-orbit splitting changes drastically under tensile strain. In centrosymmetric transition metal dichalcogenide bilayers, spin-orbit splitting is suppressed by the inversion symmetry. However, it could be induced if the inversion symmetry is explicitly broken, e.g. by a potential gradient normal to the plane, as it is present in heterobilayers (Rashba-splitting). In such systems, the spin-orbit splitting could be as large as for the heavier monolayer that forms heterobilayer. These properties of transition metal dichalcogenide materials suggest them for potential applications in opto-, spin- and straintronics. (copyright 2014 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. (Electronic structure and reactivities of transition metal clusters)

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  16. Lattice Location of Transition Metals in Semiconductors

    2002-01-01

    %IS366 %title\\\\ \\\\Transition metals (TMs) in semiconductors have been the subject of considerable research for nearly 40 years. This is due both to their role as important model impurities for deep centers in semiconductors, and to their technological impact as widespread contaminants in Si processing, where the miniaturization of devices requires to keep their sheet concentration below 10$^{10}$ cm$^{-2}$. As a consequence of the low TM solubility, conventional ion beam methods for direct lattice location have failed completely in identifying the lattice sites of isolated transition metals. Although electron paramagnetic resonance (EPR) has yielded valuable information on a variety of TM centers, it has been unable to detect certain defects considered by theory, e.g., isolated interstitial or substitutional Cu in Si. The proposed identity of other EPR centers such as substitutional Fe in Si, still needs confirmation by additional experimental methods. As a consequence, the knowledge on the structural propert...

  17. The phosphorus and the transition metals chemistry

    The 1988 progress report, concerning the Polytechnic School unit (France), which studies the phosphorus and the transition metals chemistry, is presented. The laboratory activities are related to the following topics: the phosporus heterocyclic chemistry, the phosphorus-carbon double bonds chemistry, the new transition metals phosphorus compounds, the phosphonates and their uses. Some practical applications of homogeneous catalysis and new materials synthesis are investigated. The main results obtained are: the discovery of the tetra-phosphafulvalenes, the utilization of a new synthesis method of the phosphorus-carbon double bonds and the stabilization of the α-phosphonyled carbanions by the lithium diisopropylamidourea. The papers, the congress communications and the thesis are also shown

  18. Magnetic properties of 4d transition-metal clusters

    We analyze the stability of magnetic states obtained within the tight-binding model solved by molecular dynamics for cubo-octahedral (fcc) and icosahedral clusters of 3d (Ni and Co) and 4d (Pd, Rh, and Ru) transition metals. The magnetic states are stabilized by the Hund close-quote s rule exchange interaction between the d orbitals. Taking realistic parameters deduced from band structure calculations and spectroscopic data, we obtained saturated ferromagnetism for Ni13, Co13, and Pd13 clusters, while Rh13 fcc and Ru13 clusters are partially magnetic, with an antiferromagnetic orientation of the moments on the central atoms in Ru clusters. Our results for 4d transition-metal clusters agree qualitatively with the recent experimental data and with other calculations. Metastable magnetic clusters were identified in several situations. We found a dependence of the equilibrium lattice constant on the magnetization in the considered clusters which may be explained by the character of wave functions in the cluster electronic structure. copyright 1996 The American Physical Society

  19. Transformation paths in transition-metal disilicides

    Káňa, Tomáš; Šob, Mojmír; Vitek, V.

    2011-01-01

    Roč. 465, - (2011), s. 61-64. ISSN 1662-9795. [MSMF /6./ Materials Structure and Micromechanics of Fracture. Brno, 28.06.2010-30.06.2010] R&D Projects: GA AV ČR IAA100100920; GA MŠk(CZ) OC10008 Institutional research plan: CEZ:AV0Z20410507 Keywords : transition-metal disilicides * transformation path * structural stability * electronic structure Subject RIV: BM - Solid Matter Physics ; Magnetism

  20. Non-LTE line formation of Fe in late-type stars - III. 3D non-LTE analysis of metal-poor stars

    Amarsi, A M; Asplund, M; Barklem, P S; Collet, R

    2016-01-01

    As one of the most important elements in astronomy, iron abundance determinations need to be as accurate as possible. We investigate the accuracy of spectroscopic iron abundance analyses using archetypal metal-poor stars. We perform detailed 3D non-LTE radiative transfer calculations based on 3D hydrodynamic Stagger model atmospheres, and employ a new model atom that includes new quantum-mechanical neutral hydrogen collisional rate coefficients. With the exception of the red giant HD122563, we find that the 3D non-LTE models achieve Fe i/Fe ii excitation and ionization balance as well as not having any trends with equivalent width to within modelling uncertainties of 0.05 dex, all without having to invoke any microturbulent broadening; for HD122563 we predict that the current best parallax-based surface gravity is over-estimated by 0.5 dex. Using a 3D non-LTE analysis, we infer iron abundances from the 3D model atmospheres that are roughly 0.1 dex higher than corresponding abundances from 1D MARCS model atmos...

  1. Ferroelectric control of metal-insulator transition

    He, Xu; Jin, Kui-juan; Ge, Chen; Ma, Zhong-shui; Yang, Guo-zhen

    2016-03-01

    We propose a method of controlling the metal-insulator transition of one perovskite material at its interface with another ferroelectric material based on first principle calculations. The operating principle is that the rotation of oxygen octahedra tuned by the ferroelectric polarization can modulate the superexchange interaction in this perovskite. We designed a tri-color superlattice of (BiFeO3)N/LaNiO3/LaTiO3, in which the BiFeO3 layers are ferroelectric, the LaNiO3 layer is the layer of which the electronic structure is to be tuned, and LaTiO3 layer is inserted to enhance the inversion asymmetry. By reversing the ferroelectric polarization in this structure, there is a metal-insulator transition of the LaNiO3 layer because of the changes of crystal field splitting of the Ni eg orbitals and the bandwidth of the Ni in-plane eg orbital. It is highly expected that a metal-transition can be realized by designing the structures at the interfaces for more materials.

  2. Aging of Transition Metal Dichalcogenide Monolayers.

    Gao, Jian; Li, Baichang; Tan, Jiawei; Chow, Phil; Lu, Toh-Ming; Koratkar, Nikhil

    2016-02-23

    Two-dimensional sheets of transition metal dichalcogenides are an emerging class of atomically thin semiconductors that are considered to be "air-stable", similar to graphene. Here we report that, contrary to current understanding, chemical vapor deposited transition metal dichalcogenide monolayers exhibit poor long-term stability in air. After room-temperature exposure to the environment for several months, monolayers of molybdenum disulfide and tungsten disulfide undergo dramatic aging effects including extensive cracking, changes in morphology, and severe quenching of the direct gap photoluminescence. X-ray photoelectron and Auger electron spectroscopy reveal that this effect is related to gradual oxidation along the grain boundaries and the adsorption of organic contaminants. These results highlight important challenges associated with the utilization of transition metal dichalcogenide monolayers in electronic and optoelectronic devices. We also demonstrate a potential solution to this problem, featuring encapsulation of the monolayer sheet by a 10-20 nm thick optically transparent polymer (parylene C). This strategy is shown to successfully prevent the degradation of the monolayer material under accelerated aging (i.e., high-temperature, oxygen-rich) conditions. PMID:26808328

  3. Strongly correlated transition metal compounds investigated by soft X-ray spectroscopies and multiplet calculations

    Jiménez-Mier, J., E-mail: jimenez@nucleares.unam.mx [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); Olalde-Velasco, P. [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); The Advanced Light Source, Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States); Herrera-Pérez, G.; Carabalí -Sandoval, G. [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); Chavira, E. [Instituto de Investigaciones en Materiales, UNAM, 04510 México, DF (Mexico); Yang, W.-L.; Denlinger, J. [The Advanced Light Source, Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States)

    2014-10-15

    Direct probe of Mott–Hubbard (MH) to charge-transfer (CT) insulator transition in the MF{sub 2} (M = Cr–Zn) family of compounds was observed by combining F K and M L X-ray emission spectra (XES). This transition is evident as a crossover of the F-2p and M-3d occupied states. By combining F K XES data with F K edge X-ray absorption (XAS) data we directly obtained values for the M-3d Hubbard energy (U{sub dd}) and the F-2p to M-3d charge-transfer energy (Δ{sub CT}). Our results are in good agreement with the Zaanen–Sawatzky–Allen theory. We also present three examples where X-ray absorption at the transition metal L{sub 2,3} edges is used to study the oxidation state of various strongly correlated transition metal compounds. The metal oxidation state is obtained by direct comparison with crystal field multiplet calculations. The compounds are CrF{sub 2}, members of the La{sub 1−x}Sr{sub x}CoO{sub 3} family, and the MVO{sub 3} (M = La and Y) perovskites.

  4. Hydrodenitrogenation of pyridine over transition metal nitrides

    Milad, I.K.; Smith, K.J. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical Engineering

    1997-11-01

    The use of transition metal nitrides (TMN) as catalysts for hydrodenitrogenation (HDN) was discussed. A study was conducted in which a series of unsupported and supported Mo, Fe, W, Co, Nb, Cr, V and Ti nitrides were examined as catalysts for the HDN of pyridine at atmospheric pressure and 350 degrees C. The catalysts were prepared by temperature programmed nitridation of the metal oxide with NH{sub 3}. It was shown that a single nitride phase was present in each of the catalysts. The Mo nitride showed the greatest activity per gram of catalyst. Co and Fe nitrides showed the highest activities per surface area of the unsupported catalyst. Metal nitrides with lower heats of formation showed higher HDN activity. 1 tab.

  5. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    Pandey, Mohnish; Rasmussen, Filip Anselm; Kuhar, Korina;

    2016-01-01

    -principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy, while the TMDs based on group IV metals form only...... shallow defect levels and are thus predicted to be defect-tolerant. Interestingly, all the defect sensitive TMDs have valence and conduction bands with a very similar orbital composition. This indicates a bonding/antibonding nature of the gap, which in turn suggests that dangling bonds will fall inside...... the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to nonpolar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within...

  6. Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System

    Lavrynenko, O. M.; Pavlenko, O. Yu; Shchukin, Yu S.

    2016-02-01

    The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

  7. Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System.

    Lavrynenko, O M; Pavlenko, O Yu; Shchukin, Yu S

    2016-12-01

    The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations. PMID:26847693

  8. Polymorphism of iron at high pressure: A 3D phase-field model for displacive transitions with finite elastoplastic deformations

    Vattré, A.; Denoual, C.

    2016-07-01

    A thermodynamically consistent framework for combining nonlinear elastoplasticity and multivariant phase-field theory is formulated at large strains. In accordance with the Clausius-Duhem inequality, the Helmholtz free energy and time-dependent constitutive relations give rise to displacive driving forces for pressure-induced martensitic phase transitions in materials. Inelastic forces are obtained by using a representation of the energy landscape that involves the concept of reaction pathways with respect to the point group symmetry operations of crystal lattices. On the other hand, additional elastic forces are derived for the most general case of large strains and rotations, as well as nonlinear, anisotropic, and different elastic pressure-dependent properties of phases. The phase-field formalism coupled with finite elastoplastic deformations is implemented into a three-dimensional Lagrangian finite element approach and is applied to analyze the iron body-centered cubic (α-Fe) into hexagonal close-packed (ɛ-Fe) phase transitions under high hydrostatic compression. The simulations exhibit the major role played by the plastic deformation in the morphological and microstructure evolution processes. Due to the strong long-range elastic interactions between variants without plasticity, a forward α → ɛ transition is energetically unfavorable and remains incomplete. However, plastic dissipation releases considerably the stored strain energy, leading to the α ↔ ɛ ↔α‧ (forward and reverse) polymorphic phase transformations with an unexpected selection of variants.

  9. Resonant inverse photoemission study of late transition metals at 3p absorption edge

    Full text: Resonant inverse photoemission spectra (RIPES) of late transition metals (TM) were observed near TM 3p absorption edge. The RIPES spectra of polycrystalline Co, Ni and Cu, as well as single crystal Ni, were observed. Figure 1 shows resonant IPES spectra of polycrystalline Co, Ni and Cu, which were prepared by evaporation. These spectra ware excited by energy above 3p absorption edge (off-resonance). Since a core hole is created by these energies, TM 3d → 3p fluorescence peak is observed in each spectrum at high energy, which is indicated by vertical bars. The main peak just above EF is TM 3d structure, while TM 4sp is observed at 10 ∼ 15 eV. In resonant spectra, the 3d structure changes its intensity, while the 4sp structure does not. In case of Ni metal, satellite structures are also observed at about 2 and 4 eV. From a calculation by Tanaka and Jo, which is based on the Anderson impurity model, the observation of satellite structures suggests the 10 ∼ 20 % 3d8 in ground state The RIPES spectra in this study give us a direct evidence of 3d8 component in Ni metal

  10. Integrated Voltage—Current Monitoring and Control of Gas Metal Arc Weld Magnetic Ball-Jointed Open Source 3-D Printer

    Yuenyong Nilsiam

    2015-11-01

    Full Text Available To provide process optimization of metal fabricating self-replicating rapid prototyper (RepRap 3-D printers requires a low-cost sensor and data logger system to measure current (I and voltage (V of the gas metal arc welders (GMAW. This paper builds on previous open-source hardware development to provide a real-time measurement of welder I-V where the measuring circuit is connected to two analog inputs of the Arduino that is used to control the 3-D printer itself. Franklin firmware accessed through a web interface that is used to control the printer allows storing the measured values and downloading those stored readings to the user’s computer. To test this custom current and voltage monitoring device this study reports on its use on an upgraded all metal RepRap during the printing of aluminum alloy (ER1100, ER4043, ER4943, ER4047, and ER5356. The voltage and current data were analyzed on a per alloy basis and also layer-by-layer in order to evaluate the device’s efficacy as a monitoring device for 3-D printing and the results of the integrated design are discussed.

  11. 3D numerical modeling of the lateral transition between viscous overthrusting and folding with application to the Helvetic nappe system

    Spitz, Richard; Schmalholz, Stefan; Kaus, Boris

    2016-04-01

    The Helvetic nappe system of the European Alps is generally described as a complex of fold and thrust belts. While the overall geology of the system has been studied in detail, the understanding of the tectonic development and mechanical interconnection between overthrusting and folding is still incomplete. One clue comes from the mechanical stratigraphy and the corresponding lateral transition from overthrusting to folding, which is characteristic for the Helvetic nappe system. We employ a three-dimensional numerical model with linear and non-linear viscous rheology to investigate the control of the lateral variation in the thickness of a weak detachment horizon on the transition from folding to overthrusting during continental shortening. The model configuration is based on published work based on 2D numerical simulations. The simulations are conducted with the three-dimensional staggered-grid finite difference code LaMEM (Lithosphere and Mantle Evolution Model), which allows for coupled nonlinear thermo-mechanical modeling of lithospheric deformation with visco-elasto-plastic rheology and computation on massive parallel machines. Our model configuration consists of a stiff viscous layer, with a pre-existing weak zone, resting within a weaker viscous matrix. The reference viscosity ratio μL/μM (for the same strain rate) between the layer and matrix ranges from 10 to 200. The simulations were run with several distinct initial geometries by altering the thickness of the detachment horizon below the stiff layer across the configurations. Shortening with a constant bulk rate is induced by the prescription of a horizontal velocity on one side of the model. The first results of our simulations highlight the general importance of the initial geometry on the lateral transition from overthrusting to folding. Additionally, models with a stepwise lateral variation of the detachment horizon indicate a fold development orthogonal to the main compressional axis.

  12. Infrared absorption spectra of transition metals-doped soda lime silica glasses

    Infrared (IR) absorption spectra of some prepared undoped and transition metals-doped soda-lime-silicate glasses have been studied in the region of 400-4000 cm-1. IR spectra were analyzed to determine and differentiate the various vibrational modes by applying a deconvolution method to the IR spectra. Although the first sight reveals close similarity between the different transition metal- (TM) doped samples; careful inspection indicates some minor differences depending on the type of TM ions. These observed data are correlated with similar energy of the 3d orbitals of TM atoms in the neutral state and when the atoms are ionized, the 3d orbitals becomes more stable than the 4 s orbitals.

  13. SIMULATION PROCESS OF REMOVING NON-METALLIC INCLUSIONS IN ALUMINUM ALLOYS USING THE PROGRAM FLOW-3D

    N. V. Sletova; I. N. Volnov; S. P. Zadrutsky; V. A. Chaikin

    2015-01-01

    The perspective materials for making fining preparations for the silumins are the calcium and strontium carbonates from the environmental safety point of view are shown. Principle possibility of using dispersed carbonates in the fining mixtures is confirmed by late inoculation process research using simulation FLOW-3D.The high efficiency of the fining mixture with the inoculants effect is confirmed by the industrial tests

  14. SIMULATION PROCESS OF REMOVING NON-METALLIC INCLUSIONS IN ALUMINUM ALLOYS USING THE PROGRAM FLOW-3D

    N. V. Sletova

    2015-05-01

    Full Text Available The perspective materials for making fining preparations for the silumins are the calcium and strontium carbonates from the environmental safety point of view are shown. Principle possibility of using dispersed carbonates in the fining mixtures is confirmed by late inoculation process research using simulation FLOW-3D.The high efficiency of the fining mixture with the inoculants effect is confirmed by the industrial tests

  15. Numerical 3D Investigation of Non-Metallic (Glass, Carbon) Fiber Pull-out Micromechanics (in Concrete Matrix)

    Krasņikovs, A; Khabaz, A; Teļnova, I; Machanovsky, A; Klavinsh, J

    2010-01-01

    In the paper short glass and carbon fiber micro-mechanics in concrete matrix is under consideration. In present work was performed pull-out 3D numerical modeling. Numerical results were compared with realized experiments for single and few (fibre bundle) AR glass and carbon fibers pulling out of concrete matrix. Investigated were one fiber pull-out dynamics as well micro-stresses in the material. During performed single fiber pull out experiments were established such process mains steps: a) ...

  16. Covalent bonding and bandgap formation in transition-metal aluminides: di-aluminides of group VIII transition metals

    In this paper we study the electronic structure, electron density distribution and bonding mechanism in transition-metal (TM) di-aluminides Al2TM formed by metals of group VIII (TM=Fe,Ru,Os) and crystal structures of TM di-silicides C11b (MoSi2), C40 (CrSi2) and C54 (TiSi2). A peculiar feature of the electronic structure of these TM di-aluminides is the existence of a semiconducting gap at the Fermi level. A substitution of a 3d TM by 4d or 5d metal enhances the width of the gap. From the analysis of the charge-density distribution and the crystal-orbital overlap population we conclude that the bonding between atoms has strong covalent character. This is confirmed not only from the enhanced charge density halfway between atoms, but also by a clear bonding-antibonding splitting of the electronic states. Groups of bonding and antibonding states corresponding to a particular bonding configuration of atoms are separated by a gap. As such a gap is observed in all bonding configurations among atoms in the unit cell it results in a gap in the total density of states. The bandgap exists at a certain electron per atom ratio e/A∼4.67 and also occurs in TM di-aluminides of groups VII and IX. For group VIII TM di-aluminides the Fermi level falls just in the gap. (author)

  17. X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites

    Gandhiraman, Ram P.; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E.; Chen, Bin; Meyyappan, M.

    2014-01-01

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties...

  18. Infrared evidence of a Slater metal-insulator transition in NaOsO3

    Lo Vecchio, I.; Perucchi, A.; Di Pietro, P.; Limaj, O.; Schade, U.; Sun, Y; ARAI, M.; Yamaura, K.; Lupi, S.

    2013-01-01

    The magnetically driven metal-insulator transition (MIT) was predicted by Slater in the fifties. Here a long-range antiferromagnetic (AF) order can open up a gap at the Brillouin electronic band boundary regardless of the Coulomb repulsion magnitude. However, while many low-dimensional organic conductors display evidence for an AF driven MIT, in three-dimensional (3D) systems the Slater MIT still remains elusive. We employ terahertz and infrared spectroscopy to investigate the MIT in the NaOs...

  19. Raman spectroscopy of transition metal dichalcogenides.

    Saito, R; Tatsumi, Y; Huang, S; Ling, X; Dresselhaus, M S

    2016-09-01

    Raman spectroscopy of transition metal dichalcogenides (TMDs) is reviewed based on our recent theoretical and experimental works. First, we discuss the semi-classical and quantum mechanical description for the polarization dependence of Raman spectra of TMDs in which the optical dipole transition matrix elements as a function of laser excitation energy are important for understanding the polarization dependence of the Raman intensity and Raman tensor. Overviewing the symmetry of TMDs, we discuss the dependence of the Raman spectra of TMDs on layer thickness, polarization, laser energy and the structural phase. Furthermore, we discuss the Raman spectra of twisted bilayer and heterostructures of TMDs. Finally, we give our perspectives on the Raman spectroscopy of TMDs. PMID:27388703

  20. Electrical conduction in transition-metal salts

    Grado-Caffaro, M.A.; Grado-Caffaro, M. [Scientific Consultants, Madrid (Spain)

    2016-08-01

    We predict that a given transition-metal salt as, for example, a K{sub 2}CuCl{sub 4}.2H{sub 2}O-type compound, can behave as an electrical conductor in the paramagnetic case. In fact, we determine the electrical conductance in a salt of this type. This conductance is found to be quantised in agreement with previous well-known results. Related mathematical expressions in the context of superexchange interaction are obtained. In addition, we determine the corresponding (macroscopically viewed) current density and the associated electron wave functions.

  1. Magnetic correlations in doped transition metal oxides

    The authors review recent reactor- and spallation-source-based neutron scattering experiments on the magnetic fluctuations and order in a variety of doped transition metal oxides. In particular, data are shown for the NiO chain compound, Y2-xCaxBaNiO5, the two-dimensional cuprate superconductors La2-xSrxCuO4 and YBa2Cu3 O6+x, and the classical three-dimensional ''Mott-Hubbard'' system V2-yO3

  2. Catabolism of hyaluronan: involvement of transition metals

    Šoltés, Ladislav; Kogan, Grigorij

    2009-01-01

    One of the very complex structures in the vertebrates is the joint. The main component of the joint is the synovial fluid with its high-molar-mass glycosaminoglycan hyaluronan, which turnover is approximately twelve hours. Since the synovial fluid does not contain any hyaluronidases, the fast hyaluronan catabolism is caused primarily by reductive-oxidative processes. Eight transition metals – V23, Mn25, Fe26, Co27, Ni28, Cu29, Zn30, and Mo42 – naturally occurring in living organism are essent...

  3. Electrical conduction in transition-metal salts

    We predict that a given transition-metal salt as, for example, a K2CuCl4.2H2O-type compound, can behave as an electrical conductor in the paramagnetic case. In fact, we determine the electrical conductance in a salt of this type. This conductance is found to be quantised in agreement with previous well-known results. Related mathematical expressions in the context of superexchange interaction are obtained. In addition, we determine the corresponding (macroscopically viewed) current density and the associated electron wave functions.

  4. Strain Engineering of Transition Metal Dichalcogenides

    Dadgar, Ali; Pasupathy, Abhay; Herman, Irving; Wang, Dennis; Kang, Kyungnam; Yang, Eui-Hyeok

    The application of strain to materials can cause changes to bandwidth, effective masses, degeneracies and even structural phases. In the case of the transition metal dichalcogenide (TMD) semiconductors, small strain (around 1 percent) is expected to change band gaps and mobilities, while larger strains are expected to cause phase changes from the triangular 2H phase to orthorhombic 1T' phases. We will describe experimental techniques to apply small and large (around 10 percent) strains to one or few layer samples of the TMD semiconductors, and describe the effect of the strain using optical (Raman, photoluminescence) and cryogenic transport techniques.

  5. Phenotypic transition maps of 3D breast acini obtained by imaging-guided agent-based modeling

    Tang, Jonathan; Enderling, Heiko; Becker-Weimann, Sabine; Pham, Christopher; Polyzos, Aris; Chen, Chen-Yi; Costes, Sylvain V

    2011-02-18

    We introduce an agent-based model of epithelial cell morphogenesis to explore the complex interplay between apoptosis, proliferation, and polarization. By varying the activity levels of these mechanisms we derived phenotypic transition maps of normal and aberrant morphogenesis. These maps identify homeostatic ranges and morphologic stability conditions. The agent-based model was parameterized and validated using novel high-content image analysis of mammary acini morphogenesis in vitro with focus on time-dependent cell densities, proliferation and death rates, as well as acini morphologies. Model simulations reveal apoptosis being necessary and sufficient for initiating lumen formation, but cell polarization being the pivotal mechanism for maintaining physiological epithelium morphology and acini sphericity. Furthermore, simulations highlight that acinus growth arrest in normal acini can be achieved by controlling the fraction of proliferating cells. Interestingly, our simulations reveal a synergism between polarization and apoptosis in enhancing growth arrest. After validating the model with experimental data from a normal human breast line (MCF10A), the system was challenged to predict the growth of MCF10A where AKT-1 was overexpressed, leading to reduced apoptosis. As previously reported, this led to non growth-arrested acini, with very large sizes and partially filled lumen. However, surprisingly, image analysis revealed a much lower nuclear density than observed for normal acini. The growth kinetics indicates that these acini grew faster than the cells comprising it. The in silico model could not replicate this behavior, contradicting the classic paradigm that ductal carcinoma in situ is only the result of high proliferation and low apoptosis. Our simulations suggest that overexpression of AKT-1 must also perturb cell-cell and cell-ECM communication, reminding us that extracellular context can dictate cellular behavior.

  6. Suppression of Structural Phase Transition in VO2 by Epitaxial Strain in Vicinity of Metal-insulator Transition

    Yang, Mengmeng; Yang, Yuanjun; Bin Hong; Wang, Liangxin; Hu, Kai; Dong, Yongqi; Xu, Han; Huang, Haoliang; Zhao, Jiangtao; Chen, Haiping; Song, Li; Ju, Huanxin; Zhu, Junfa; Bao, Jun; Li, Xiaoguang; Gu, Yueliang; Yang, Tieying; Gao, Xingyu; Luo, Zhenlin; Gao, Chen

    2016-03-01

    Mechanism of metal-insulator transition (MIT) in strained VO2 thin films is very complicated and incompletely understood despite three scenarios with potential explanations including electronic correlation (Mott mechanism), structural transformation (Peierls theory) and collaborative Mott-Peierls transition. Herein, we have decoupled coactions of structural and electronic phase transitions across the MIT by implementing epitaxial strain on 13-nm-thick (001)-VO2 films in comparison to thicker films. The structural evolution during MIT characterized by temperature-dependent synchrotron radiation high-resolution X-ray diffraction reciprocal space mapping and Raman spectroscopy suggested that the structural phase transition in the temperature range of vicinity of the MIT is suppressed by epitaxial strain. Furthermore, temperature-dependent Ultraviolet Photoelectron Spectroscopy (UPS) revealed the changes in electron occupancy near the Fermi energy EF of V 3d orbital, implying that the electronic transition triggers the MIT in the strained films. Thus the MIT in the bi-axially strained VO2 thin films should be only driven by electronic transition without assistance of structural phase transition. Density functional theoretical calculations further confirmed that the tetragonal phase across the MIT can be both in insulating and metallic states in the strained (001)-VO2/TiO2 thin films. This work offers a better understanding of the mechanism of MIT in the strained VO2 films.

  7. LETTER TO THE EDITOR: Variation of adatom to substrate charge transfer value along the first-row transition metal series on Mo(110)

    Magkoev, T. T.; Christmann, K.; Lecante, P.; Moutinho, A. M. C.

    2002-04-01

    Adsorption of the first-row transition 3d metals (Ti-Cu) on the atomically clean Mo(110) surface in ultra-high-vacuum conditions has been studied by Auger electron spectroscopy and work function measurements (Anderson method). In this letter it is shown that adsorption behaviour of the metals under consideration systematically changes along the 3d series. The observed correlation between the systematic change of the dipole moments and the values of the charge transfer from adatom to substrate along the period leads us to the conclusion that the metal 3d orbitals play an important role in the formation of the chemisorption bond.

  8. First principle investigation of the magnetic properties of transition metal doped (ZnS)n (n=1-16) clusters

    Kaur, Navjot; Singh, Kanchan L.; Sharma, Hitesh

    2015-08-01

    The magnetic properties of (ZnS)n clusters (n = 1 - 16) due to 3d transition metals have been investigated using spin polarized density functional theory. The transition metals are more stable at Zn site than at the S site in (ZnS)n clusters. The binding energy of (ZnS)n clusters increases significantly on doping with transition metal indicating enhanced structural stability of the doped (ZnS)n clusters. All 3d transition metals induced magnetic moment of order 5μB-1μB per atom in all (ZnS)n clusters. The magnetic moment is mainly localized on the TM dopant. The magnetic moment increases gradually with the increase in number of electrons in 3d orbital which is in accordance with Hund's rule till Mn and decreases thereafter. All 3d TMs retain their atomic magnetic moment in ZnS clusters of all sizes. Ti, V, Cr and Mn interact anti-ferromagnetically with the surrounding S and Zn, whereas Sc, Fe, Co, Ni and Cu interact with ferromagnetic interactions.

  9. Tunable magnetocaloric effect in transition metal alloys

    Belyea, Dustin D.; Lucas, M. S.; Michel, E.; Horwath, J.; Miller, Casey W.

    2015-10-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based “high entropy alloys” in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants.

  10. Methyl Complexes of the Transition Metals.

    Campos, Jesús; López-Serrano, Joaquín; Peloso, Riccardo; Carmona, Ernesto

    2016-05-01

    Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last five years. After a panoramic overview on M-CH3 compounds of Groups 3 to 11, which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity. PMID:26991740

  11. Transition Metal Nitrides: A First Principles Study

    Pathak, Ashish; Singh, A. K.

    2016-04-01

    The present work describes the structural stability and electronic and mechanical properties of transition metal nitrides (TmNs: B1 cubic structure (cF8, Fm ‾ overline 3 m)) using first principles density functional theory (DFT) within generalized gradient approximation (GGA). The lattice constant of TmNs increases with increasing the atomic radii of the transition metals. Stability of the TmNs decreases from IVB to VIB groups due to increase in formation energy/atom. The bonding characteristics of these nitrides have been explained based on electronic density of states and charge density. All the TmNs satisfy Born stability criteria in terms of elastic constants except CrN and MoN that do not exist in equilibrium binary phase diagrams. The groups IVB and V-VIB nitrides are associated with brittle and ductile behaviour based on G/B ratios, respectively. The estimated melting temperatures of these nitrides exhibit reasonably good agreement with calculated with B than those of the C11 for all nitrides.

  12. Hybrid nickel manganese oxide nanosheet-3D metallic dendrite percolation network electrodes for high-rate electrochemical energy storage

    Nguyen, Tuyen; Eugénio, Sónia; Boudard, Michel; Rapenne, Laetitia; Carmezim, M. João; Silva, Teresa M.; Montemor, M. Fátima

    2015-07-01

    This work reports the fabrication, by electrodeposition and post-thermal annealing, of hybrid electrodes for high rate electrochemical energy storage composed of nickel manganese oxide (Ni0.86Mn0.14O) nanosheets over 3D open porous dendritic NiCu foams. The hybrid electrodes are made of two different percolation networks of nanosheets and dendrites, and exhibit a specific capacitance value of 848 F g-1 at 1 A g-1. The electrochemical tests revealed that the electrodes display an excellent rate capability, characterized by capacitance retention of approximately 83% when the applied current density increases from 1 A g-1 to 20 A g-1. The electrodes also evidenced high charge-discharge cycling stability, which attained 103% after 1000 cycles.

  13. Large Scale 3-D Dislocation Dynamics and Atomistic Simulations of Flow and Strain-Hardening Behavior of Metallic Micropillars

    Rao, Satish

    2015-03-01

    Experimental studies show strong strengthening effects for micrometer-scale FCC as well as two-phase superalloy crystals, even at high initial dislocation densities. This talk shows results from large-scale 3-D discrete dislocation simulations (DDS) used to explicitly model the deformation behavior of FCC Ni (flow stress and strain-hardening) as well as superalloy microcrystals for diameters ranging from 1 - 20 microns. The work shows that two size-sensitive athermal hardening processes, beyond forest and precipitation hardening, are sufficient to develop the dimensional scaling of the flow stress, stochastic stress variation, flow intermittency and, high initial strain-hardening rates, similar to experimental observations for various materials. In addition, 3D dislocation dynamics simulations are used to investigate strain-hardening characteristics and dislocation microstructure evolution with strain in large 20 micron size Ni microcrystals (bulk-like) under three different loading axes: 111, 001 and 110. Three different multi-slip loading axes, , and , are explored for shear strains of ~0.03 and final dislocation densities of ~1013/m2. The orientation dependence of initial strain hardening rates and dislocation microstructure evolution with strain are discussed. The simulated strain hardening results are compared with experimental data under similar loading conditions from bulk single-crystal Ni. Finally, atomistic simulation results on the operation of single arm sources in Ni bipillars with a large angle grain boundary is discussed. The atomistic simulation results are compared with experimental mechanical behavior data on Cu bipillars with a similar large angle grain boundary. This work was supported by AFOSR (Dr. David Stargel), and by a grant of computer time from the DOD High Performance Computing Modernization Program, at the Aeronautical Systems Center/Major Shared Resource Center.

  14. Strain field due to transition metal impurities in Ni and Pd

    Hitesh Sharma; S Prakash

    2003-01-01

    The strain field due to body centered substitutional transition metal impurities in Ni and Pd metals are investigated. The calculations are carried out in the discrete lattice model of the metal using Kanzaki lattice static method. The effective ion–ion interaction potential due to Wills and Harrison is used to evaluate dynamical matrix and the impurity-induced forces. The results for atomic displacements due to 3d, 4d and 5d impurities (Fe, Co, Cu, Nb, Mo, Pd, Pt and Au) in Ni and (Fe, Co, Cu, Ni, Nb, Mo, Pt and Au) impurities in Pd are given up to 25 NN’s of impurity and these are compared with the available experimental data. The maximum displacements of 4.6% and 3.8% of 1NN distance are found for NiNb and PdNb alloys respectively, while the minimum displacements of 0.63% and 0.23% of 1NN distance are found for NiFe and PdFe alloys respectively. Except for Cu, the atomic displacements are found to be proportional to the core radii and d state radius. The relaxation energies for 3d impurities are found less than those for 4d and 5d impurities in Ni and Pd metals. Therefore, 3d impurities may easily be solvable in these metals.

  15. Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System

    Lavrynenko, O. M.; Pavlenko, O. Yu; Shchukin, Yu S.

    2016-01-01

    The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are f...

  16. Transition metal based layered double hydroxides tailored for energy conversion and storage

    Xia Long

    2016-05-01

    Full Text Available Layered double hydroxides (LDHs are a class of clays with brucite like layers and intercalated anions. The first (3d series transition metals based LDHs (TM-LDHs are attracting increasing interest in the field of energy conversion and storage processes due to their unique physicochemical properties. In this article, we review recent developments in the synthesis and applications of TM-LDH in these areas including water splitting, CO2 conversion, metal-air batteries and supercapacitors and the underlying mechanisms of these processes. In addition, current challenges and possible strategies are discussed from the viewpoint of material design and performance.

  17. Study of concentrated metal-ammonia solutions: magnetic properties and non metal-metal transition

    The magnetic susceptibility of alkali metal-liquid ammonia solutions has been measured in the concentration range where the solutions show a progressive passage toward the metallic state. The Knight shift of the metal nuclei and the nitrogen nucleus have been determined as a function of concentration and temperature, in Na-NH3 and Cs-NH3 solutions. A phenomenological analysis of the transport properties of metal-ammonia solutions is also presented. This analysis permits the presentation of a model for the mechanism of the transition to the metallic state. (author)

  18. New Layered Ternary Transition-Metal Tellurides

    Mar, Arthur

    Several new ternary transition-metal tellurides, a class of compounds hitherto largely unexplored, have been synthesized and characterized. These are layered materials whose structures have been determined by single -crystal X-ray diffraction methods. The successful preparation of the compound TaPtTe_5 was crucial in developing an understanding of the MM'Te_5 (M = Nb, Ta; M' = Ni, Pd, Pt) series of compounds, which adopt either of two possible closely-related layered structures. Interestingly, the compound TaPdTe _5 remains unknown. Instead, the compound Ta_4Pd_3Te _{16} has been prepared. Its structure is closely related to that of the previously prepared compound Ta_3Pd _3Te_{14}. The physical properties of these compounds have been measured and correlated with the metal substitutions and interlayer separations. A new series of compounds, MM'Te _4 (M = Nb, Ta; M' = Ru, Os, Rh, Ir), has been discovered. The structure of NbIrTe_4 serves as a prototype: it is an ordered variant of the binary telluride WTe_2. Electronic band-structure calculations have been performed in order to rationalize the trends in metal-metal and tellurium -tellurium bonding observed in WTe_2 and the MM'Te_4 phases. Extension of these studies to include main-group metals has resulted in the synthesis of the new layered ternary germanium tellurides TiGeTe_6, ZrGeTe_4 , and HfGeTe_4. Because germanium can behave ambiguously in its role as a metalloid element, it serves as an anion by capping the metal-centered trigonal prisms and also as a cation in being coordinated in turn by other tellurium atoms in a trigonal pyramidal fashion. Structural relationships among these compounds are illustrated through the use of bicapped trigonal prisms and trigonal pyramids as the basic structural building blocks. The electrical and magnetic properties of these compounds have been measured. Insight into the unusual bonding and physical properties of these germanium-containing compounds has been gained through

  19. Density functional theory studies of transition metal nanoparticles in catalysis

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua;

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...

  20. Smoothing of ultrathin silver films by transition metal seeding

    Anders, André; Byon, Eungsun; Kim, Dong-Ho; Fukuda, Kentaro; Lim, Sunnie H. N.

    2006-11-01

    The nucleation and coalescence of silver islands on coated glass was investigated by in situ measurements of the sheet resistance. Sub-monolayer amounts of niobium and other transition metals were deposited prior to the deposition of silver. It was found that in some cases, the transition metals lead to coalescence of silver at nominally thinner films with smoother topology. The smoothing or roughening effects by the presence of the transition metal can be explained by kinetically limited transition metal islands growth and oxidation, followed by defect-dominated nucleation of silver.

  1. Will 3D printers manufacture your meals?

    Bommel, K.J.C. van

    2013-01-01

    These days, 3D printers are laying down plastics, metals, resins, and other materials in whatever configurations creative people can dream up. But when the next 3D printing revolution comes, you'll be able to eat it.

  2. Radiation damage of transition metal carbides

    Dixon, G.

    1991-01-01

    In this grant period we have investigated electrical properties of transition metal carbides and radiation-induced defects produced by low-temperature electron irradiation in them. Special attention has been given to the composition VC[sub 0.88] in which the vacancies on the carbon sublattice of this fcc crystal order to produce a V[sub 8]C[sub 7] superlattice. The existence of this superlattice structure was found to make the crystal somewhat resistant to radiation damage at low doses and/or at ambient temperature. At larger doses significant changes in the resistivity are produced. Annealing effects were observed which we believe to be connected with the reconstitution of the superlattice structure.

  3. Catalytic and surface oxidation processes on transition metal surfaces

    Jaatinen, Sampsa

    2007-01-01

    Transition metals are technologically important catalytic materials. The transition metal catalysts are used for example in petroleum and fertilizer industry. In the car industry the catalytic materials are used in the catalytic converters. Because of the industrial importance the catalytic metals have been widely studied throughout the past decades. Nonetheless, the oxidation mechanisms of small molecules and the effect of alloying to catalytic properties of metals are not fully understood. ...

  4. Synthesis, crystal structure and photo luminescent property of a 3D metal-organic hybrid of Cd(II) constructed by two different bridging carboxylate

    Biswajit Bhattacharya; Rajdip Dey; Debajyoti Ghoshal

    2013-05-01

    A solvothermal reaction of cadmium (II) nitrate with succinic acid and isonicotinic acid creates a novel 3D metal-organic framework, [Cd3(isonicotinate)2(suc)2] (1). Single crystal X-ray structure determination reveals that complex 1 posses two crystallographically independent Cd(II) centres. The succinate anion acts here as a heptadented ligand and binds five Cd(II) centre simultaneously. The heptacoordinated Cd(II) centres are oxo-bridged by succinate moiety and the hexacoordinated metal centres are terminally connected through four different succinate moiety to make the overall 2D sheet arrangement. In unit cell, the ratio of hexadented Cd(II) and heptadented Cd(II) is 1:2. The new compound was also characterized by luminescence spectra and compared with the luminescence spectra of the pure isonicotinic acid.

  5. Two step formation of metal aggregates by surface X-ray radiolysis under Langmuir monolayers: 2D followed by 3D growth

    Smita Mukherjee

    2015-12-01

    Full Text Available In order to form a nanostructured metallic layer below a Langmuir monolayer, radiolysis synthesis was carried out in an adapted geometry that we call surface X-ray radiolysis. In this procedure, an X-ray beam produced by a synchrotron beamline intercepts the surface of an aqueous metal-ion solution covered by a Langmuir monolayer at an angle of incidence below the critical angle for total internal reflection. Underneath the organic layer, the X-ray beam induces the radiolytic synthesis of a nanostructured metal–organic layer whose ultrathin thickness is defined by the vertical X-ray penetration depth. We have shown that increasing the X-ray flux on the surface, which considerably enhances the kinetics of the silver layer formation, results in a second growth regime of silver nanocrystals. Here the formation of the oriented thin layer is followed by the appearance of a 3D powder of silver clusters.

  6. Ordering in binary transition metal alloys

    Rusakov, G. [Institute for Metal Physics UB RAS, 18 Kovalevskoj St., 620990 Ekaterinburg (Russian Federation); Ural State Technical University - UPI, 19 Mira St., 620002 Ekaterinburg (Russian Federation); Son, L., E-mail: ldson@yandex.ru [Ural State Pedagogical University, 26 Cosmonavtov Ave, 620017 Ekaterinburg (Russian Federation); Efimova, E. [Institute for Metal Physics UB RAS, 18 Kovalevskoj St., 620990 Ekaterinburg (Russian Federation); Ural State Technical University - UPI, 19 Mira St., 620002 Ekaterinburg (Russian Federation); Dubinin, N. [Institute for Metallurgy UB RAS, 101 Amundsen St., 620016 Ekaterinburg (Russian Federation); Ural State Technical University - UPI, 19 Mira St., 620002 Ekaterinburg (Russian Federation)

    2012-03-20

    We present the phenomenological thermodynamic modeling of binary alloys which demonstrate solubility of the components at high temperatures, and form intermediate phase near equiatomic composition at lower ones (the so-called sigma-phase). Besides, the regular solution miscibility gap takes place also. The nonequilibrium thermodynamic potential is written out as a sum of the free energy of regular solution and polynomial term of scalar order parameter {phi}, which describes the {sigma}-phase ordering. There are four parameters in the model: the energy of regular solution mixing, the energy of {sigma}-phase formation at zero temperature, and the widths of temperature and concentration intervals of {sigma}-phase existence in the alloy with frozen-in random distribution of components. Up to now, both phase transitions which take place in a number of transition metals binary alloys (the {sigma}-phase formation and miscibility in the regular solution) have been treated separately. In present work, the standard technique of phase diagram calculation allows us to analyze all possible phase diagrams which may arise in the alloy.

  7. Transition-metal substitutions in iron chalcogenides

    Bezusyy, V. L.; Gawryluk, D. J.; Malinowski, A.; Cieplak, Marta Z.

    2015-03-01

    The a b -plane resistivity and Hall effect are studied in Fe1 -yMyTe0.65Se0.35 single crystals doped with two transition-metal elements, M = Co or Ni, over a wide doping range, 0 ≤y ≤0.2 . The superconducting transition temperature, Tc, reaches zero for Co at y ≃0.14 and for Ni at y ≃0.032 , while the resistivity at the Tc onset increases weakly with Co doping, and strongly with Ni doping. The Hall coefficient RH, positive for y =0 , remains so at high temperatures for all y , while it changes sign to negative at low T for y >0.135 (Co) and y >0.06 (Ni). The analysis based on a two-band model suggests that at high T residual hole pockets survive the doping, but holes get localized upon the lowering of T , so that the effect of the electron doping on the transport becomes evident. The suppression of the Tc by Co impurity is related to electron doping, while in the case of the Ni impurity strong electron localization most likely contributes to fast decrease of the Tc.

  8. Self-assembled 3D flower-like α-Fe2O3 microstructures and their superior capability for heavy metal ion removal

    Hierarchically 3D flower-like α-Fe2O3 microstructures have been synthesized through a urea-assisted hydrothermal synthetic route. The product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The as-prepared product was consisted of hierarchically flow-like microstructures assembled from nanopetal subunits. The effects of the urea and NaOH on the morphology of the products were systematically studied, and a possible formation mechanism of the α-Fe2O3 microflowers was proposed based on the experimental results. These flower-like α-Fe2O3 microstructures were used as adsorbent for water treatment, and the results revealed excellent performance for heavy metal ion removal. With maximum capacities of 41.46 and 33.82 mg g−1 for As(V) and Cr(VI), respectively, such flower-like α-Fe2O3 microstructures are expected to be an attractive adsorbent for the removal of heavy metal ions from water. - Graphical abstract: Display Omitted - Highlights: • 3D flower-like hematite microstructures were synthesized by a hydrothermal method. • The formation mechanism of flower-like microstructures was proposed. • Effective removal of As(V) and Cr(VI) from aqueous solution

  9. Induce magnetism into silicene by embedding transition-metal atoms

    Sun, Xiaotian; Wang, Lu, E-mail: lwang22@suda.edu.cn, E-mail: yyli@suda.edu.cn; Lin, Haiping; Hou, Tingjun; Li, Youyong, E-mail: lwang22@suda.edu.cn, E-mail: yyli@suda.edu.cn [Institute of Functional Nano and Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory for Carbon-based Functional Materials and Devices, and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, Jiangsu (China)

    2015-06-01

    Embedding transition-metal (TM) atoms into nonmagnetic nanomaterials is an efficient way to induce magnetism. Using first-principles calculations, we systematically investigated the structural stability and magnetic properties of TM atoms from Sc to Zn embedded into silicene with single vacancy (SV) and double vacancies (DV). The binding energies for different TM atoms correlate with the TM d-shell electrons. Sc, Ti, and Co show the largest binding energies of as high as 6 eV, while Zn has the lowest binding energy of about 2 eV. The magnetic moment of silicene can be modulated by embedding TM atoms from V to Co, which mainly comes from the 3d orbitals of TM along with partly contributions from the neighboring Si atoms. Fe atom on SV and Mn atom on DV have the largest magnetic moment of more than 3 μB. In addition, we find that doping of N or C atoms on the vacancy site could greatly enhance the magnetism of the systems. Our results provide a promising approach to design silicene-based nanoelectronics and spintronics device.

  10. Coherent quantum dynamics of excitons in monolayer transition metal dichalcogenides

    Moody, Galan

    2016-03-14

    Transition metal dichalcogenides (TMDs) have garnered considerable interest in recent years owing to their layer thickness-dependent optoelectronic properties. In monolayer TMDs, the large carrier effective masses, strong quantum confinement, and reduced dielectric screening lead to pronounced exciton resonances with remarkably large binding energies and coupled spin and valley degrees of freedom (valley excitons). Coherent control of valley excitons for atomically thin optoelectronics and valleytronics requires understanding and quantifying sources of exciton decoherence. In this work, we reveal how exciton-exciton and exciton-phonon scattering influence the coherent quantum dynamics of valley excitons in monolayer TMDs, specifically tungsten diselenide (WSe2), using two-dimensional coherent spectroscopy. Excitation-density and temperature dependent measurements of the homogeneous linewidth (inversely proportional to the optical coherence time) reveal that exciton-exciton and exciton-phonon interactions are significantly stronger compared to quasi-2D quantum wells and 3D bulk materials. The residual homogeneous linewidth extrapolated to zero excitation density and temperature is ~1:6 meV (equivalent to a coherence time of 0.4 ps), which is limited only by the population recombination lifetime in this sample. © (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

  11. 3D video

    Lucas, Laurent; Loscos, Céline

    2013-01-01

    While 3D vision has existed for many years, the use of 3D cameras and video-based modeling by the film industry has induced an explosion of interest for 3D acquisition technology, 3D content and 3D displays. As such, 3D video has become one of the new technology trends of this century.The chapters in this book cover a large spectrum of areas connected to 3D video, which are presented both theoretically and technologically, while taking into account both physiological and perceptual aspects. Stepping away from traditional 3D vision, the authors, all currently involved in these areas, provide th

  12. 3D Animation Essentials

    Beane, Andy

    2012-01-01

    The essential fundamentals of 3D animation for aspiring 3D artists 3D is everywhere--video games, movie and television special effects, mobile devices, etc. Many aspiring artists and animators have grown up with 3D and computers, and naturally gravitate to this field as their area of interest. Bringing a blend of studio and classroom experience to offer you thorough coverage of the 3D animation industry, this must-have book shows you what it takes to create compelling and realistic 3D imagery. Serves as the first step to understanding the language of 3D and computer graphics (CG)Covers 3D anim

  13. Experiments performed with bubbly flow in vertical pipes at different flow conditions covering the transition region: simulation by coupling Eulerian, Lagrangian and 3D random walks models

    Muñoz-Cobo, José; Chiva, Sergio; El Aziz Essa, Mohamed; Mendes, Santos

    2012-08-01

    Two phase flow experiments with different superficial velocities of gas and water were performed in a vertical upward isothermal cocurrent air-water flow column with conditions ranging from bubbly flow, with very low void fraction, to transition flow with some cap and slug bubbles and void fractions around 25%. The superficial velocities of the liquid and the gas phases were varied from 0.5 to 3 m/s and from 0 to 0.6 m/s, respectively. Also to check the effect of changing the surface tension on the previous experiments small amounts of 1-butanol were added to the water. These amounts range from 9 to 75 ppm and change the surface tension. This study is interesting because in real cases the surface tension of the water diminishes with temperature, and with this kind of experiments we can study indirectly the effect of changing the temperature on the void fraction distribution. The following axial and radial distributions were measured in all these experiments: void fraction, interfacial area concentration, interfacial velocity, Sauter mean diameter and turbulence intensity. The range of values of the gas superficial velocities in these experiments covered the range from bubbly flow to the transition to cap/slug flow. Also with transition flow conditions we distinguish two groups of bubbles in the experiments, the small spherical bubbles and the cap/slug bubbles. Special interest was devoted to the transition region from bubbly to cap/slug flow; the goal was to understand the physical phenomena that take place during this transition A set of numerical simulations of some of these experiments for bubbly flow conditions has been performed by coupling a Lagrangian code, that tracks the three dimensional motion of the individual bubbles in cylindrical coordinates inside the field of the carrier liquid, to an Eulerian model that computes the magnitudes of continuous phase and to a 3D random walk model that takes on account the fluctuation in the velocity field of the

  14. Nanostructured transition metal oxides useful for water oxidation catalysis

    Frei, Heinz M; Jiao, Feng

    2013-12-24

    The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

  15. Trends in Ionization Energy of Transition-Metal Elements

    Matsumoto, Paul S.

    2005-01-01

    A rationale for the difference in the periodic trends in the ionization energy of the transition-metal elements versus the main-group elements is presented. The difference is that in the transition-metal elements, the electrons enter an inner-shell electron orbital, while in the main-group elements, the electrons enter an outer-shell electron…

  16. Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project

    Hummelshøj, Jens Strabo; Landis, David; Voss, Johannes;

    2009-01-01

    We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M1); and 1 alkali, alkaline earth or 3d/4d transition...... metal atom (M2) plus two to five (BH4)− groups, i.e., M1M2(BH4)2–5, using a number of model structures with trigonal, tetrahedral, octahedral, and free coordination of the metal borohydride complexes. Of the over 700 investigated structures, about 20 were predicted to form potentially stable alloys with...

  17. A MEMS-enabled 3D zinc–air microbattery with improved discharge characteristics based on a multilayer metallic substructure

    This paper reports the design, fabrication and testing of a three-dimensional zinc–air microbattery with improved areal energy density and areal capacity, particularly at high discharge rates. The device is based on a multilayer, micron-scale, low-resistance metallic skeleton with an improved surface area. This skeleton consists of alternating Cu and Ni layers supporting Zn as electrodeposited anode electrode, and provides a high surface area, low-resistance path for electron transfer. A proof-of-concept zinc–air microbattery based on this technology was developed, characterized and compared with its two-dimensional thin-film counterparts fabricated on the same footprint area with equal amount of the Zn anode electrode. Using this approach, we were able to improve a single-layer initial structure with a surface area of 1.3 mm2 to a scaffold structure with ten layers having a surface area of 15 mm2. Discharging through load resistances ranging from 100 to 3000 Ω, the areal energy density and areal capacity of the microbattery were measured as 2.5–3 mWh cm−2 and ∼2.5 mAh cm−2, respectively.

  18. Synthesis, structure and electrochemical behavior of a 3D crystalline copper(II) metal-organic framework

    Bai, Hong-Ye; Fan, Wei-Qiang; Liu, Chun-Bo; Shi, Wei-Dong; Yan, Yong-Sheng

    2014-05-01

    Using an flexible amide-type tripodal ligand N,N‧,N″-tris(3-pyridyl)-1,3,5-benzenetricarboxamide (L) and 1,4-benzenedicarboxylic acid (H2bdc), a three-dimensional copper(II) metal-organic framework (MOF) formulated as [Cu(bdc)(L)]n has been hydrothermally synthesized and structurally characterized by IR, elemental, X-ray single-crystal diffraction and thermal analysis. The complex crystallizes in the triclinic, space group P - 1, a = 8.891(2) Å, b = 11.760(2) Å, c = 15.348(3) Å, α = 96.73(3)°, β = 105.96(3)°, γ = 106.47(3)°, V = 1446.2(5) Å3, Mr = 666.10, Dc = 1.530 g/cm3, Z = 2, F(000) = 682, GOOF = 1.0560, μ(MoKα) = 0.817 mm-1, R = 0.0366 and wR = 0.0885. The structural analyses reveal that the title compound consists of one Cu(II) atom, two halves of bdc, and one L ligand. Each Cu(II) atom is linked by two bdc ligands and three L ligands to form a three-dimensional network. In addition, the electrochemical behavior of title compound has been studied. CCDC No. 990526.

  19. Transition metal oxofluorides comprising lone pair elements : Synthesis and Characterization

    Hu, Shichao

    2014-01-01

    Within the family of transition metal oxochlorides/bromides containing lone pair elements, the transition metal cations often adopt a low-dimensional arrangement such as 2D layers, 1D chains or 0D clusters. The reduced dimensionality is attributed to the presence of stereochemically active lone pairs which are positioned in the non-bonding orbital and will not participate in bond formation and instead act as structural spacers that help to separate coordination polyhedra around transition met...

  20. Doppler-free intermodulated fluorescence spectroscopy of $^4He$ $2^3P-3^{1,3}D$ transitions at 588 nm with a one-watt compact laser system

    Luo, Pei-Ling; Feng, Yan; Wang, Li-Bang; Shy, Jow-Tsong

    2015-01-01

    We have demonstrated Doppler-free intermodulated fluorescence spectroscopy of helium $2^3P-3^{1,3}D$ transitions in an rf discharged sealed-off cell using a compact laser system at 588 nm. An external cavity diode laser at 1176 nm was constructed to seed a Raman fiber amplifier. Laser power of more than one watt at 588 nm was produced by frequency doubling of the fiber amplifier output using a MgO:PPLN crystal. A doubling efficiency of 23 % was achieved. The power-dependent spectra of the $2^3P-3^3D$ transitions were investigated. Furthermore, the Doppler-free spectrum of the spin-forbidden $2^3P-3^1D$ transitions was observed for the first time. Our results are crucial towards precision test of QED atomic calculations, especially for improving the determination of the helium $3^1D-3^3D$ separation.

  1. Direct evidence of the symmetry change of Co-3d orbitals associated with the spin-state transition in LaCoO3 by X-ray Compton scattering

    We have investigated the electron momentum density of Co-3d electrons in LaCoO3 using X-ray Compton scattering in order to demonstrate the symmetry change of the Co(3d) electron orbital states through the spin-state transition. The electron momentum density reconstructed from the Compton profiles indicates the symmetry change in the 3d electron-orbital states between below and above 100 K, which provides the first microscopic direct evidence for the orbital symmetry change of occupied electronic state associated with the spin-state transition in LaCoO3. The reproduced electron orbital states show a covalent bond with O-2p orbitals, which is responsible for the collectiveness in the characteristics of the spin-state transition. (author)

  2. Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt-Ru nanoalloy catalysts

    Prasai, Binay; Ren, Yang; Shan, Shiyao; Zhao, Yinguang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian; Petkov, Valeri

    2015-04-01

    An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail and using the unique knowledge obtained for rationalizing their synthesis and properties targeted for optimization is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. In particular, PtxRu100-x alloy NPs, where x = 31, 49 and 75, are synthesized by wet chemistry and activated catalytically by a post-synthesis treatment involving heating under controlled N2-H2 atmosphere. So-activated NPs are evaluated as catalysts for gas-phase CO oxidation and ethanol electro-oxidation reactions taking place in fuel cells. Both as-synthesized and activated NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models both for as-synthesized and activated NPs are built by molecular dynamics simulations based on the archetypal for current theoretical modelling Sutton-Chen method. Models are refined against the experimental PDF data by reverse Monte Carlo simulations and analysed in terms of prime structural characteristics such as metal-to-metal bond lengths, bond angles and first coordination numbers for Pt and Ru atoms. Analysis indicates that, though of a similar type, the atomic structure of as-synthesized and respective activated NPs differ in several details of importance to NP catalytic properties. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the

  3. Single-Crystal to Single-Crystal Phase Transition and Segmented Thermochromic Luminescence in a Dynamic 3D Interpenetrated Ag(I) Coordination Network.

    Yan, Zhi-Hao; Li, Xiao-Yu; Liu, Li-Wei; Yu, Si-Qi; Wang, Xing-Po; Sun, Di

    2016-02-01

    A new 3D Ag(I)-based coordination network, [Ag2(pz)(bdc)·H2O]n (1; pz = pyrazine and H2bdc = benzene-1,3-dicarboxylic acid), was constructed by one-pot assembly and structurally established by single-crystal X-ray diffraction at different temperatures. Upon cooling from 298 to 93 K, 1 undergo an interesting single-crystal to single-crystal phase transition from orthorhombic Ibca (Z = 16) to Pccn (Z = 32) at around 148 K. Both phases show a rare 2-fold-interpenetrated 4-connected lvt network but incorporate different [Ag2(COO)2] dimeric secondary building units. It is worth mentioning that complex 1 shows red- and blue-shifted luminescences in the 290-170 and 140-80 K temperature ranges, respectively. The variable-temperature single-crystal X-ray crystallographic studies suggest that the argentophilic interactions and rigidity of the structure dominated the luminescence chromism trends at the respective temperature ranges. Upon being mechanically ground, 1 exhibits a slight mechanoluminescence red shift from 589 to 604 nm at 298 K. PMID:26828950

  4. Patterning Superatom Dopants on Transition Metal Dichalcogenides.

    Yu, Jaeeun; Lee, Chul-Ho; Bouilly, Delphine; Han, Minyong; Kim, Philip; Steigerwald, Michael L; Roy, Xavier; Nuckolls, Colin

    2016-05-11

    This study describes a new and simple approach to dope two-dimensional transition metal dichalcogenides (TMDCs) using the superatom Co6Se8(PEt3)6 as the electron dopant. Semiconducting TMDCs are wired into field-effect transistor devices and then immersed into a solution of these superatoms. The degree of doping is determined by the concentration of the superatoms in solution and by the length of time the films are immersed in the dopant solution. Using this chemical approach, we are able to turn mono- and few-layer MoS2 samples from moderately to heavily electron-doped states. The same approach applied on WSe2 films changes their characteristics from hole transporting to electron transporting. Moreover, we show that the superatom doping can be patterned on specific areas of TMDC films. To illustrate the power of this technique, we demonstrate the fabrication of a lateral p-n junction by selectively doping only a portion of the channel in a WSe2 device. Finally, encapsulation of the doped films with crystalline hydrocarbon layers stabilizes their properties in an ambient environment. PMID:27082448

  5. Impact Electrochemistry of Layered Transition Metal Dichalcogenides.

    Lim, Chee Shan; Tan, Shu Min; Sofer, Zdeněk; Pumera, Martin

    2015-08-25

    Layered transition metal dichalcogenides (TMDs) exhibit paramount importance in the electrocatalysis of the hydrogen evolution reaction. It is crucial to determine the size of the electrocatalytic particles as well as to establish their electrocatalytic activity, which occurs at the edges of these particles. Here, we show that individual TMD (MoS2, MoSe2, WS2, or WSe2; in general MX2) nanoparticles impacting an electrode surface provide well-defined current "spikes" in both the cathodic and anodic regions. These spikes originate from direct oxidation of the nanoparticles (from M(4+) to M(6+)) at the anodic region and from the electrocatalytic currents generated upon hydrogen evolution in the cathodic region. The positive correlation between the frequency of the impacts and the concentration of TMD nanoparticles is also demonstrated here, enabling determination of the concentration of TMD nanoparticles in colloidal form. In addition, the size of individual TMD nanoparticles can be evaluated using the charge passed during every spike. The capability of detecting both the "indirect" catalytic effect of an impacting TMD nanoparticle as well as "direct" oxidation indicates that the frequency of impacts in both the "indirect" and "direct" scenarios are comparable. This suggests that all TMD nanoparticles, which are electrochemically oxidizable (thus capable of donating electrons to electrodes), are also capable of catalyzing the hydrogen reduction reaction. PMID:26241193

  6. Transition metal-free olefin polymerization catalyst

    Sen, Ayusman (State College, PA); Wojcinski, II, Louis M. (State College, PA); Liu, Shengsheng (State College, PA)

    2001-01-01

    Ethylene and/or propylene are polymerized to form high molecular weight, linear polymers by contacting ethylene and/or propylene monomer, in the presence of an inert reaction medium, with a catalyst system which consists essentially of (1) an aluminum alkyl component, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum and diethylaluminum hydride and (2) a Lewis acid or Lewis acid derivative component, such as B (C.sub.6 F.sub.5).sub.3, [(CH.sub.3).sub.2 N (H) (C.sub.6 H.sub.5)].sup.+ [B (C.sub.6 F.sub.5)4].sup.-, [(C.sub.2 H.sub.5).sub.3 NH].sup.+ [B C.sub.6 F.sub.5).sub.4 ],.sup.-, [C(C.sub.6 F.sub.5).sub.3 ].sup.+ [B(C.sub.6 F.sub.5).sub.4 ].sup.-, (C.sub.2 H.sub.5).sub.2 Al(OCH.sub.3), (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butyl-4-methylphenoxide), (C.sub.2 H.sub.5)Al(2,6 -di-t-butylphenoxide).sub.2, (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butylphonoxide) , 2,6 -di-t-butylphenol.multidot.methylaluminoxane or an alkylaluminoxane, and which may be completely free any transition metal component(s).

  7. Potassium 4,4'-Bis(dinitromethyl)-3,3'-azofurazanate: A Highly Energetic 3D Metal-Organic Framework as a Promising Primary Explosive.

    Tang, Yongxing; He, Chunlin; Mitchell, Lauren A; Parrish, Damon A; Shreeve, Jean'ne M

    2016-04-25

    Environmentally acceptable alternatives to toxic lead-based primary explosives are becoming increasingly important for energetic materials. In this study, potassium 4,4'-bis(dinitromethyl)-3,3'-azofurazanate, comprising two dinitromethyl groups and an azofurazan moiety, was synthesized and isolated as a new energetic 3D metal-organic framework (MOF). Several attractive properties, including a density of 2.039 g cm(-3) , a decomposition temperature of 229 °C, a detonation velocity of 8138 m s(-1) , a detonation pressure of 30.1 GPa, an impact sensitivity of 2 J, and friction sensitivity of 20 N make 4 a good candidate as a green primary explosive. PMID:27008350

  8. Interpenetrating metal-organic and inorganic 3D networks: a computer-aided systematic investigation. Part II [1]. Analysis of the Inorganic Crystal Structure Database (ICSD)

    Interpenetration in metal-organic and inorganic networks has been investigated by a systematic analysis of the crystallographic structural databases. We have used a version of TOPOS (a package for multipurpose crystallochemical analysis) adapted for searching for interpenetration and based on the concept of Voronoi-Dirichlet polyhedra and on the representation of a crystal structure as a reduced finite graph. In this paper, we report comprehensive lists of interpenetrating inorganic 3D structures from the Inorganic Crystal Structure Database (ICSD), inclusive of 144 Collection Codes for equivalent interpenetrating nets, analyzed on the basis of their topologies. Distinct Classes, corresponding to the different modes in which individual identical motifs can interpenetrate, have been attributed to the entangled structures. Interpenetrating nets of different nature as well as interpenetrating H-bonded nets were also examined

  9. Site preference of early transition metal elements in C15 NbCr2

    The site preference of early 3d (Ti, V), 4d (Zr, Mo) and 5d (Hf, Ta, W) transition metal elements in C15 NbCr2 Laves phase was studied using first-principles calculations. According to the present calculations, at T 0 K, Zr, Hf and Ta consistently have a preference for the Nb sites in Nb-rich, Cr-rich and stoichiometric NbCr2, while the site preference of Ti, V, Mo and W varies strongly with alloy composition. Using a statistical-mechanical Wagner-Schottky model based on the canonical ensemble, the finite temperature site occupancy behavior of those transition metal elements in NbCr2 was further predicted. It was found that the site preference of Ti, V, Mo and W also depends strongly on temperature. The calculated results compare favorably with the experimental measurements using ALCHEMI and synchrotron X-ray diffraction techniques

  10. EUROPEANA AND 3D

    D. Pletinckx

    2012-09-01

    Full Text Available The current 3D hype creates a lot of interest in 3D. People go to 3D movies, but are we ready to use 3D in our homes, in our offices, in our communication? Are we ready to deliver real 3D to a general public and use interactive 3D in a meaningful way to enjoy, learn, communicate? The CARARE project is realising this for the moment in the domain of monuments and archaeology, so that real 3D of archaeological sites and European monuments will be available to the general public by 2012. There are several aspects to this endeavour. First of all is the technical aspect of flawlessly delivering 3D content over all platforms and operating systems, without installing software. We have currently a working solution in PDF, but HTML5 will probably be the future. Secondly, there is still little knowledge on how to create 3D learning objects, 3D tourist information or 3D scholarly communication. We are still in a prototype phase when it comes to integrate 3D objects in physical or virtual museums. Nevertheless, Europeana has a tremendous potential as a multi-facetted virtual museum. Finally, 3D has a large potential to act as a hub of information, linking to related 2D imagery, texts, video, sound. We describe how to create such rich, explorable 3D objects that can be used intuitively by the generic Europeana user and what metadata is needed to support the semantic linking.

  11. Solid works 3D

    This book explains modeling of solid works 3D and application of 3D CAD/CAM. The contents of this book are outline of modeling such as CAD and 2D and 3D, solid works composition, method of sketch, writing measurement fixing, selecting projection, choosing condition of restriction, practice of sketch, making parts, reforming parts, modeling 3D, revising 3D modeling, using pattern function, modeling necessaries, assembling, floor plan, 3D modeling method, practice floor plans for industrial engineer data aided manufacturing, processing of CAD/CAM interface.

  12. First-principles calculations of the vacancy formation energy in transition and noble metals

    Korzhavyi, P.A.; Abrikosov, Igor A.; Johansson, Börje; Ruban, Andrei; Skriver, Hans Lomholt

    1999-01-01

    Abstract: The vacancy formation energy and the vacancy formation volume of the 3d, 4d, and 5d transition and noble metals have been calculated within the local-density approximation. The calculations employ the order-N locally self-consistent Green's-function method in conjunction with a supercell...... approach and include electrostatic multipole corrections to the atomic sphere approximation. The results are in excellent agreement with available full-potential calculations and with the vacancy formation energies obtained in positron annihilation measurements. The variation of the vacancy formation...

  13. Homoleptic transition metal complexes of the 7-azaindolide ligand featuring κ(1)-N1 coordination.

    Przyojski, Jacob A; Kiewit, Monica L; Fillman, Kathlyn L; Arman, Hadi D; Tonzetich, Zachary J

    2015-10-01

    Homoleptic complexes of the anion of 7-azaindole (AzaIn) were synthesized and characterized for a series of 3d transition metals. For Mn(II), Fe(II), and Co(II), complexes of formula Na2[M(AzaIn)4]·2L (L = tetrahydrofuran (THF), 2-MeTHF, toluene, or benzene) were isolated by treatment of the corresponding metal chloride salts with 7-azaindole in the presence of sodium hexamethyldisilazide. The complexes adopt tetrahedral geometries with exclusive coordination to the transition metal ion through the pyrrolic N1 nitrogen atoms of the AzaIn ligands. Solid-state structures of the complexes demonstrate that the sodium cations remain tightly associated with the coordination entities through interaction with both the pyrrolic and pyridine nitrogen atoms of the azaindolide ligands. For Fe(II), replacement of the sodium cations by other alkali metal ions (Li or K) generates new complexes that demonstrate similar coordination geometries to the sodium salts. As a means of comparison, the Fe(II) complex of 4-azaindolide was also investigated. Na2[Fe(4-AzaIn)4]·2L adopts a similar solution structure to the 7-azaindolide complexes as judged by NMR spectroscopy and cyclic voltammetry. Density functional theory calculations were performed to investigate the bonding in the 7-azaindolide complexes. Results demonstrate that 7-azaindolide-κ(1)-N1 is a nearly pure sigma donor ligand that features a high degree of ionic character in its bonding to mid 3d transition metal ions. PMID:26378471

  14. Optical excitations of transition-metal oxides under the orbital multiplicity effects

    We investigated optical excitations of transition-metal (TM) oxides with metal oxygen octahedra taking account of the orbital multiplicity effects. We predicted excitation energies of intersite d-d transitions and p-d transitions of TM oxides. We compared the evaluated excitation energies with reported experimental data, and found that they are in good agreement with each other. Moreover, we could demonstrate possible answers for a few long-standing problems of the low-frequency spectral features in some early 3d TM oxides: (i) the broad and multi-peak structures of the d-d transitions (ii) the low values (around 2 eV) of the d-d transition energies for some t2g1 and t2g2 systems, and (iii) the lack of the d-d transition below 4.0 eV region for LaCrO3, one of the t2g3 systems. These indicate that our approach considering the orbital multiplicity effects could provide good explanations of intriguing features in the optical spectra of some early TM oxides. In addition, we showed that optical spectroscopy can be useful as a powerful tool to investigate spin and/or orbital correlations in the TM ions. Finally, we discussed the implications of the orbital multiplicity in the Zannen-Sawatzky-Allen scheme, which has been used successfully to classify correlated electron systems

  15. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    Takanabe, Kazuhiro

    2015-03-05

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  16. A 3D chiral metal-organic framework based on left-handed helices containing 3-amino-1 H-1,2,4-triazole ligand

    A chiral metal-organic framework, [Cu(atr)(OH)]·0.5H2O·0.5en (1) (Hatr=3-amino-1 H-1,2,4-triazole, en=ethylenediamine), was constructed via diffusion reaction of the achiral Hatr ligand and CuSO4 as starting materials. Compound 1 crystallizes in the chiral space group P3221 and features a porous metal-organic framework with 44.1% solvent-accessible volume fabricated by left-handed helices with a pitch height of lp=10.442 Å. Six helices gather around in a cycle forming a large honeycomb channel with a 6.58 Å inner diameter. Cu(II) center and atr‒ ligand regarded as 3-connected nodes, compound 1 can be simplified to a 3-c uninodal (4.122) (qtz-h) topological network. A gradual decreasing in the magnetic moment depending on temperature decreasing indicates an antiferromagnetic interaction in 1. The powder XRD confirms the bulk sample is a single crystal pure phase, and the thermogravimetric analysis shows the thermal stability of 1 is up to ca. 240 °C. - Highlights: • The present 3D chiral MOF is built from achiral Hatr ligand. • Six left-handed helices gather into a honeycomb channel in chiral sp P3221. • Compound 1 shows a 3-c uninodal (4.122) or qtz-h topological network. • Compound 1 indicates an antiferromagnetic interaction

  17. Laser-ignited frontal polymerization of shape-controllable poly(VI-co-AM) hydrogels based on 3D templates toward adsorption of heavy metal ions

    Fan, Suzhen; Liu, Sisi; Wang, Xiao-Qiao; Wang, Cai-Feng; Chen, Su

    2016-06-01

    Given the increasing heavy metal pollution issue, fast preparation of polymeric hydrogels with excellent adsorption property toward heavy metal ions is very attractive. In this work, a series of poly( N-vinylimidazole-co-acrylamide) (poly(VI-co-AM)) hydrogels were synthesized via laser-ignited frontal polymerization (LIFP) for the first time. The dependence of frontal velocity and temperature on two factors monomer ratios and initiator concentrations was systematically investigated. Poly(VI-co-AM) hydrogels with any self-supporting shapes can be synthesized by a one-step LIFP in seconds through the application of 3D templates. These shape-persistent hydrogels are pH-responsive and exhibit excellent adsorption/desorption characteristics toward Mn(II), Zn(II), Cd(II), Ni(II), Cu(II) and Co(II) ions, and the adsorption conformed to the pseudo-second-order kinetic model. The reusability of the hydrogels toward mental ions adsorption was further researched, which suggested that the hydrogels can be reused without serious decrease in adsorption capacity. This work might open a promising strategy to facilely prepare shape-controllable hydrogels and expand the application of LIFP.

  18. The metallicities of stars with and without transiting planets

    Buchhave, Lars A.; Latham, David W.

    2015-01-01

    Host star metallicities have been used to infer observational constraints on planet formation throughout the history of the exoplanet field. The giant planet metallicity correlation has now been widely accepted, but questions remain as to whether the metallicity correlation extends to the small...... terrestrial-sized planets. Here, we report metallicities for a sample of 518 stars in the Kepler field that have no detected transiting planets and compare their metallicity distribution to a sample of stars that hosts small planets (). Importantly, both samples have been analyzed in a homogeneous manner...... using the same set of tools (Stellar Parameters Classification tool). We find the average metallicity of the sample of stars without detected transiting planets to be and the sample of stars hosting small planets to be . The average metallicities of the two samples are indistinguishable within the...

  19. Open 3D Projects

    Felician ALECU

    2010-01-01

    Full Text Available Many professionals and 3D artists consider Blender as being the best open source solution for 3D computer graphics. The main features are related to modeling, rendering, shading, imaging, compositing, animation, physics and particles and realtime 3D/game creation.

  20. Mechanisms of transition-metal gettering in silicon

    MYERS JR.,SAMUEL M.; SEIBT,M.; SCHROTER,W.

    2000-03-23

    The atomic process, kinetics, and equilibrium thermodynamics underlying the gettering of transition-metal impurities in Si are reviewed from a mechanistic perspective. Methods for mathematical modeling of gettering are reviewed and illustrated. Needs for further research are discussed.

  1. 1D to 3D and Chiral to Noncentrosymmetric Metal-Organic Complexes Controlled by the Amount of DEF Solvent: Photoluminescent and NLO Properties.

    Wen, Yuehong; Sheng, Tianlu; Zhuo, Chao; Zhu, Xiaoquan; Hu, Shengmin; Cao, Wenhai; Li, Haoran; Zhang, Hao; Wu, Xintao

    2016-05-01

    A mixture of 2D and 1D metal-organic complexes, [ZnL(H2O)2·G1·DEF·2H2O]n (1a: G1 = naphthalene-2,7-disulfonate; DEF = N,N-diethylformamide) and [ZnL(H2O)3·G1·DEF·2H2O]n (2), has been prepared from a hydrogenated Schiff base L and Zn(II) in a DEF-contained solvent system under mild conditions. The yields of 1a and 2 are equivalent; however, they can be tuned by varying the amount of DEF solvent. Increasing the use of DEF tends to form pure 1a, while decreasing it generates 2. Without DEF, another novel 3D four-connected CdSO4 (cds) framework [ZnL(H2O)2·G1·2H2O]n (3) composed of alternated right-handed and left-handed helical chains has been constructed. The amount of DEF solvent has a significant impact on the diverse coordination architectures of 1-3, which is rare in the preparation of metal-organic complexes. The photoluminescence of complexes 1-3 along with naphthalene-2,7-disulfonate has been investigated in the solid state. The luminescent emission of G1 was enhanced greatly after being confined into metal-organic networks. In addition, complexes 1-3 display second-harmonic generation efficiencies, which are approximately 0.58, 0.42, 0.32, and 0.52 times as much as that of potassium dihydrogen phosphate. PMID:27093469

  2. 3d-3d correspondence revisited

    Chung, Hee-Joong; Dimofte, Tudor; Gukov, Sergei; Sułkowski, Piotr

    2016-04-01

    In fivebrane compactifications on 3-manifolds, we point out the importance of all flat connections in the proper definition of the effective 3d {N}=2 theory. The Lagrangians of some theories with the desired properties can be constructed with the help of homological knot invariants that categorify colored Jones polynomials. Higgsing the full 3d theories constructed this way recovers theories found previously by Dimofte-Gaiotto-Gukov. We also consider the cutting and gluing of 3-manifolds along smooth boundaries and the role played by all flat connections in this operation.

  3. Trends in catalytic NO decomposition over transition metal surfaces

    Falsig, Hanne; Bligaard, Thomas; Rass-Hansen, Jeppe;

    2007-01-01

    The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional...... theory calculations. We show specifically why the key problem in using transition metal surfaces to catalyze direct NO decomposition is their significant relative overbinding of atomic oxygen compared to atomic nitrogen....

  4. Transition metal complexing with polymetric sulfur-containing fibrous ligand

    A study was made on interaction of Cr4, V5, Cu2 transition metals with thioamidated polymeric PVS-PAN-T ligand of fibrous structure. Sorption characteristics of PVS-PAN-T, depending on pH and temperature of solutions of copper, chromium and vanadium salts were determined. Parameters of ESR spectra of PVS-PAN-T compounds with transition metals enabled to determine the structure of formed coordination centers

  5. Excited states and transition metal compounds with quantum Monte Carlo

    Bande, Annika

    2007-01-01

    To the most challenging electron structure calculations belong weak interactions, excited state calculations, transition metals and properties. In this work the performance of variational (VMC) and fixed-node diffusion quantum Monte Carlo (FN-DMC) is tested for challenging electron structure problems using the quantum Monte Carlo amolqc code by Lüchow et al. The transition metal compounds under consideration are vanadium oxides. Here excitation, ionization, oxygen atom and molecule abstractio...

  6. Infrared evidence of a Slater metal-insulator transition in NaOsO₃.

    Vecchio, I Lo; Perucchi, A; Di Pietro, P; Limaj, O; Schade, U; Sun, Y; Arai, M; Yamaura, K; Lupi, S

    2013-01-01

    The magnetically driven metal-insulator transition (MIT) was predicted by Slater in the fifties. Here a long-range antiferromagnetic (AF) order can open up a gap at the Brillouin electronic band boundary regardless of the Coulomb repulsion magnitude. However, while many low-dimensional organic conductors display evidence for an AF driven MIT, in three-dimensional (3D) systems the Slater MIT still remains elusive. We employ terahertz and infrared spectroscopy to investigate the MIT in the NaOsO₃ 3D antiferromagnet. From the optical conductivity analysis we find evidence for a continuous opening of the energy gap, whose temperature dependence can be well described in terms of a second order phase transition. The comparison between the experimental Drude spectral weight and the one calculated through Local Density Approximation (LDA) shows that electronic correlations play a limited role in the MIT. All the experimental evidence demonstrates that NaOsO₃ is the first known 3D Slater insulator. PMID:24141899

  7. Infrared evidence of a Slater metal-insulator transition in NaOsO3

    Vecchio, I. Lo; Perucchi, A.; Di Pietro, P.; Limaj, O.; Schade, U.; Sun, Y.; Arai, M.; Yamaura, K.; Lupi, S.

    2013-01-01

    The magnetically driven metal-insulator transition (MIT) was predicted by Slater in the fifties. Here a long-range antiferromagnetic (AF) order can open up a gap at the Brillouin electronic band boundary regardless of the Coulomb repulsion magnitude. However, while many low-dimensional organic conductors display evidence for an AF driven MIT, in three-dimensional (3D) systems the Slater MIT still remains elusive. We employ terahertz and infrared spectroscopy to investigate the MIT in the NaOsO3 3D antiferromagnet. From the optical conductivity analysis we find evidence for a continuous opening of the energy gap, whose temperature dependence can be well described in terms of a second order phase transition. The comparison between the experimental Drude spectral weight and the one calculated through Local Density Approximation (LDA) shows that electronic correlations play a limited role in the MIT. All the experimental evidence demonstrates that NaOsO3 is the first known 3D Slater insulator. PMID:24141899

  8. IZDELAVA TISKALNIKA 3D

    Brdnik, Lovro

    2015-01-01

    Diplomsko delo analizira trenutno stanje 3D tiskalnikov na trgu. Prikazan je razvoj in principi delovanja 3D tiskalnikov. Predstavljeni so tipi 3D tiskalnikov, njihove prednosti in slabosti. Podrobneje je predstavljena zgradba in delovanje koračnih motorjev. Opravljene so meritve koračnih motorjev. Opisana je programska oprema za rokovanje s 3D tiskalniki in komponente, ki jih potrebujemo za izdelavo. Diploma se oklepa vprašanja, ali je izdelava 3D tiskalnika bolj ekonomična kot pa naložba v ...

  9. Electronic structure of the low-dimensional transition metal oxyhalide VOCl

    In the quest for RVB-like superconductivity, layered oxyhalides of the form MOX (M=Ti,V; X=Cl,Br) have been discussed some fifteen years ago as possible candidates. This was due to their low-dimensional crystal structure involving frustrated triangular lattice planes. While no superconducting state in these Mott insulators was observed yet, other interesting phenomena, e.g. an unconventional spin-Peierls transition, have been found in TiOX. The isostructural material VOCl has a 3d2 configuration and shows antiferromagnetic ordering below 150K; magnetic susceptibility measurements show an anisotropy along the a-axis. Electronically, however, the degree of one-dimensionality observed by photoemission is reduced compared to the well-studied 3d1 TiOX systems. LDA+U calculations indicate that VOCl is a Mott insulator despite its two 3d electrons. Upon n-doping with alkali metals new states appear in the gap without having quasi-particle character, i.e. no evidence for a metallic phase is found. A comparison between VOCl and TiOX is expected to yield new insights into the importance of one-dimensionality and multi-band Mott-Hubbard physics in the oxyhalides.

  10. Grafting 4f and 3d metal complexes into mesoporous MCM-41 silica by wet impregnation and by chemical vapour infiltration

    Hybrid organic/inorganic materials have been prepared by reacting mesoporous MCM-41 silica with transition metal β-diketonates, either by wet impregnation (WI) or by chemical vapour infiltration (CVI). Compounds obtained from Eu(III) or Gd(III) β-diketonates, both by wet impregnation and by CVI, contain chemisorbed metalorganic species with strong Si-O-Ln bonding. Compounds prepared (by CVI only) from Cu(II) or Mn(III) β-diketonates show a more complex absorption process than the lanthanides, since upon heating under dynamic vacuum they release part of the absorbed metal complex. Eu(thd)3 was more specifically used to prepare luminescent materials. It was used either alone, or with phenanthroline as an additional ligand in order to promote the so called 'antenna effect'

  11. Ternary transition metal phosphides: High-temperature superconductors

    Barz, H.; Ku, H. C.; Meisner, G. P.; Fisk, Z.; Matthias, B. T.

    1980-01-01

    Two systems of ternary transition metal phosphides with the ordered Fe2P-type hexagonal structure are reported. They have the general formula MRuP and MOsP, in which M can be Ti, Zr, or Hf. An onset of the superconducting transition temperature as high as 13.0 K is reported for the ZrRuP compound.

  12. Transition metals and mitochondrial metabolism in the heart

    Rines, Amy K.; Ardehali, Hossein

    2012-01-01

    Transition metals are essential to many biological processes in almost all organisms from bacteria to humans. Their versatility, which arises from an ability to undergo reduction–oxidation chemistry, enables them to act as critical cofactors of enzymes throughout the cell. Accumulation of metals, however, can also lead to oxidative stress and cellular damage. The importance of metals to both enzymatic reactions and oxidative stress makes them key players in mitochondria. Mitochondria are the ...

  13. 3D and Education

    Meulien Ohlmann, Odile

    2013-02-01

    Today the industry offers a chain of 3D products. Learning to "read" and to "create in 3D" becomes an issue of education of primary importance. 25 years professional experience in France, the United States and Germany, Odile Meulien set up a personal method of initiation to 3D creation that entails the spatial/temporal experience of the holographic visual. She will present some different tools and techniques used for this learning, their advantages and disadvantages, programs and issues of educational policies, constraints and expectations related to the development of new techniques for 3D imaging. Although the creation of display holograms is very much reduced compared to the creation of the 90ies, the holographic concept is spreading in all scientific, social, and artistic activities of our present time. She will also raise many questions: What means 3D? Is it communication? Is it perception? How the seeing and none seeing is interferes? What else has to be taken in consideration to communicate in 3D? How to handle the non visible relations of moving objects with subjects? Does this transform our model of exchange with others? What kind of interaction this has with our everyday life? Then come more practical questions: How to learn creating 3D visualization, to learn 3D grammar, 3D language, 3D thinking? What for? At what level? In which matter? for whom?

  14. Theory of the transition temperature of superconducting amorphous transition metals

    In the present paper first the transition temperature Tsub(c) is shown to be a local quantity, which depends on the (average) short range order, and second it is demonstrated how to calculate local electronic properties in the framework of a short range order model and the transition temperature of amorphous systems based on accepted structure models of the amorphous state. In chapter I the theoretical basis of this work is presented in brief. The model used to study the role of short range order (in periodically ordered as well as in disordered system) is described in chapter II. The results of this model for the periodically ordered case are compared in chapter III with band structure calculations. In chapter IV it is shown how to establish short range order models for disordered systems and what kind of information can be obtained with respect to the electronic properties. Finally in chapter V it is discussed to what extend the interpretation of the transition temperature Tsub(c) as being determined by short range order effects can be supported by the electronic properties, which are calculated in the chapters III and IV. (orig.)

  15. Electronic and magnetic engineering of transition metal dichalcogenides

    Tang, Youjian; Crespi, Vincent; Vincent Crespi group Team

    Transition metal dichalcogenides (TMDs) have moderate bandgaps and great potential in electronic and optoelectronic applications. We show that by intercalation and compensated doping of transition metal ions, we could generate a ``half-semiconductor'', half-metal or doped magnetic semiconductor. We will also show that covalently connecting a single layer of WS2 to a small aromatic molecule with appropriate electronegativity, it is possible to align the molecular energy levels with the WS2 conduction band edge, yielding an electronic structure of potential interest for thermoelectric applications, and covalently connecting single-layer WS2 to magnetic coordination compounds could introduce magnetization into the WS2 layer.

  16. Transition probabilities for NII 2p4f-2p3d and 2s2p23d-2s2p23p obtained by a semiclassical method

    2007-01-01

    Based on NII spectra, some transition probabilities for 2p4f-2p3d and 2s2p23d-2s2p23p are obtained by a semiclassical method. The results are in good agreement with other measurements and the data reported by the National Institute of Standards and Technology. The transition probability for a line of 424.18nm is reported for the first time. Meanwhile, a feasible method of calculating transition parameters related to special excited configurations or highly excited states is provided.

  17. Textural and morphological studies of transition metal doped SBA-15 by co-condensation method

    P H K Charan; G Ranga Rao

    2015-05-01

    The 3d transition metals were incorporated into SBA-15 matrix by co-condensation synthesis method. Very low concentrations of metals were introduced into silica framework by maintaining the metal to silica ratio in the synthesis gel at 0.01. The difference in hydrolysis rates of metal and silica precursors have led to textural modifications while demonstrating the structural integrity akin to pristine SBA-15. The physicochemical properties obtained offer some insights into the P123 micelle aggregation and mechanism of formation of silica network in the presence of metal salts under similar synthesis conditions of pure SBA-15. The metal doping into SBA-15 leads to increased pore diameters. Higher lattice constants (a0) observed in these samples are attributed to the increased pore wall thickness. The significant retention of the hexagonal mesostructure seen in LXRD indicates diminutive influence of metal salts at lower concentrations.Macroscopic morphologies studied by SEM show the formation of spheres along with conventional fibre-like rods.

  18. 3d-4f Metal-Organic Framework with Dual Luminescent Centers That Efficiently Discriminates the Isomer and Homologues of Small Organic Molecules.

    Zeng, Guang; Xing, Shanghua; Wang, Xiuru; Yang, Yulin; Ma, Dingxuan; Liang, Hongwei; Gao, Lu; Hua, Jia; Li, Guanghua; Shi, Zhan; Feng, Shouhua

    2016-02-01

    A 3d-4f luminescent metal-organic framework (MOF), [Tb2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (4), and three analogues {[La2(Cu8I8)(C12H8NO2)6(C4H8O2)2(H2O)2]·3C4H8O2·2H2O (1), [Ce2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (2), and [Eu2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (3)}, were self-assembled from copper(I) halide clusters and lanthanide metal ions with an organic linker [3-(pyridin-4-yl)benzoic acid] under solvothermal conditions. Compound 4 with high quantum yield (Φ = 68%) exhibits reversible luminescence behavior, accompanying the removal and recovery of guest molecules (1,4-dioxane). Because of the unique porous structure and dual luminescent centers of compound 4, it can efficiently differentiate benzene series with different sizes and provide readouts in corresponding optical signals. Furthermore, it also can unambiguously discriminate the isomers, homologues, and other small molecules with similar structural motifs from one another. The luminescent color of the MOF sensor in different guest solvents has obvious changes that can be clearly distinguished by the naked eye. This multicolor luminescence originates from emissions of the dual luminescent centers, and the emissions have shifted, enhanced, weakened, or quenched to different degrees. PMID:26756250

  19. Effect of site preference of 3d atoms on the electronic structure and half-metallicity of Heusler alloy Mn2YAl

    The site preference of 3d atoms Y in Mn2YAl (Y = V, Fe, Co) alloys and its influence on their electronic structures and magnetism have been studied by first-principles calculations. The results prove that elements with more valence electrons than Mn tend to enter the A (0, 0, 0) and C ( 1/2 , 1/2 , 1/2 ) sites and elements with fewer electrons prefer the B ( 1/4 , 1/4 , 1/4 ) site (Wyckoff positions). Meanwhile, it is found that for Mn2VAl and Mn2FeAl, a high spin polarization can be obtained whether the Y atom enters the (A, C) or the B site. In particular, Mn2VAl is half-metallic whether it forms the Cu2MnAl type or the Hg2CuTi type of structure. And a 100% spin polarization can be retained even when a 25% Mn-V antisite disorder occurs. This is quite preferable in practical applications. It is also found that the higher-valent element such as Co at the B ( 1/4 , 1/4 , 1/4 ) site has opposite effects and tends to close the energy gap. Finally, a systemic summarization on the electronic and magnetic properties of Mn2YAl (Y = Ti, V, Cr, Mn, Fe and Co) alloys was made. All of them except for Mn2TiAl are predicted as half-metals. The calculated total spin moment is an integral value and increases from -3μB/f.u. for Mn2TiAl to +2μB/f.u. for Mn2CoAl with increasing number of valence electrons. This agrees with the Slater-Pauling curve quite well. All the Mn2YAl alloys studied here are ferrimagnets

  20. A 3D chiral metal-organic framework based on left-handed helices containing 3-amino-1 H-1,2,4-triazole ligand

    Liu, Bing, E-mail: bliu_1203@163.com [College of Chemistry and Chemical Engineering, Shaanxi University of Sciences and Technology, Xi’an, 710021 Shaanxi (China); Yang, Tian-Yi [The High School Affricated to Shaanxi Normal University, Xi’an, 710061 Shaanxi (China); Feng, Hui-Jun; Zhang, Zong-Hui [Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an, 710062 Shaanxi (China); Xu, Ling, E-mail: xuling@snnu.edu.cn [Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an, 710062 Shaanxi (China)

    2015-10-15

    A chiral metal-organic framework, [Cu(atr)(OH)]·0.5H{sub 2}O·0.5en (1) (Hatr=3-amino-1 H-1,2,4-triazole, en=ethylenediamine), was constructed via diffusion reaction of the achiral Hatr ligand and CuSO{sub 4} as starting materials. Compound 1 crystallizes in the chiral space group P3{sub 2}21 and features a porous metal-organic framework with 44.1% solvent-accessible volume fabricated by left-handed helices with a pitch height of l{sub p}=10.442 Å. Six helices gather around in a cycle forming a large honeycomb channel with a 6.58 Å inner diameter. Cu(II) center and atr{sup ‒} ligand regarded as 3-connected nodes, compound 1 can be simplified to a 3-c uninodal (4.12{sup 2}) (qtz-h) topological network. A gradual decreasing in the magnetic moment depending on temperature decreasing indicates an antiferromagnetic interaction in 1. The powder XRD confirms the bulk sample is a single crystal pure phase, and the thermogravimetric analysis shows the thermal stability of 1 is up to ca. 240 °C. - Highlights: • The present 3D chiral MOF is built from achiral Hatr ligand. • Six left-handed helices gather into a honeycomb channel in chiral sp P3{sub 2}21. • Compound 1 shows a 3-c uninodal (4.12{sup 2}) or qtz-h topological network. • Compound 1 indicates an antiferromagnetic interaction.

  1. Theory of magnetic transition metal nanoclusters on surfaces

    Lounis, S.

    2007-04-17

    This thesis is motivated by the quest for the understanding and the exploration of complex magnetism provided by atomic scale magnetic clusters deposited on surfaces or embedded in the bulk. Use is made of the density functional theory (DFT). Acting within this framework, we have developed and implemented the treatment of non-collinear magnetism into the Juelich version of the full-potential Korringa-Kohn-Rostoker Green Function (KKR-GF) method. Firstly, the method was applied to 3d transition-metal clusters on different ferromagnetic surfaces. Different types of magnetic clusters where selected. In order to investigate magnetic frustration due to competing interactions within the ad-cluster we considered a (001) oriented surface of fcc metals, a topology which usually does not lead to non-collinear magnetism. We tuned the strength of the magnetic coupling between the ad-clusters and the ferromagnetic surface by varying the substrate from the case of Ni(001) with a rather weak hybridization of the Ni d-states with the adatom d-states to the case of Fe{sub 3ML}/Cu(001) with a much stronger hybridization due to the larger extend of the Fe wavefunctions. On Ni(001), the interaction between the Cr- as well as the Mn-dimer adatoms is of antiferromagnetic nature, which is in competition with the interaction with the substrate atoms. After performing total energy calculations we find that for Cr-dimer the ground state is collinear whereas the Mn-dimer prefers the non-collinear configuration as ground state. Bigger clusters are found to be magnetically collinear. These calculations were extended to 3d multimers on Fe{sub 3ML}/Cu(001). All neighboring Cr(Mn) moments in the compact tetramer are antiferromagnetically aligned in-plane, with the directions slightly tilted towards (outwards from) the substrate to gain some exchange interaction energy. The second type of frustration was investigated employing a Ni(111) surface, a surface with a triangular lattice of atoms, were

  2. Ab initio calculation of molecular field interactions in rare-earth transition-metal intermetallics (invited)

    Brooks, M. S. S.; Gasche, T.; Auluck, S.; Nordström, L.; Severin, L.; Trygg, J.; Johansson, B.

    1991-11-01

    The interaction, KRM, between the rare-earth 4f moment and the transition-metal 3d moments in rare-earth transition-metal intermetallics is shown to depend upon the R-5d moment, which is due to 3d-5d hybridization, and local 4f-5d exchange integrals. Both the R-5d moment and KRM may be calculated ab initio from the local spin-density approximation to density functional theory in self-consistent energy-band calculations with the localized 4f-moments fixed at their Russel-Saunders values. Detailed examples are given for the RFe2 (R=Gd-Yb) series. The exchange integrals are similar to those entering into the density functional version of Stoner theory and their energy dependence must be treated carefully. The calculated local exchange integrals are shown to be related to the molecular fields derived from spin Hamiltonians, hence to the spin-wave spectra. Reasonable agreement with values of the molecular fields extracted from inelastic neutron scattering and high field susceptibility measurements is obtained.

  3. Probable metal-insulator transition in Ag4SSe

    Highlights: • New phase transition in Ag4SSe was discovered with scanning calorimetry and supported with X-ray powder diffraction. • The thermal effect relates to the anomaly in electrical and thermal conductivity of Ag4SSe. • Similar thermal and electrical effects in K3Cu8S6 are explained with the metal-insulator transition. - Abstract: New phase transition (285 K) in low-temperature monoclinic Ag4SSe was found out below the α-β transition (358 K) after the measurements with differential scanning calorimetry. The transition reveals significant hysteresis (over 30 K). X-ray powder diffraction shows that the superlattice with doubled a and b parameters of the unit cell exists below the new transition point. The signs of this new phase transition can be found in thermal and electrical conductivity of Ag4SSe published in literature. Elusive phase transition in Ag2Se shows similar properties. The new transition is likely related to the metal-insulator type transition, like K3Cu8S6

  4. Spin-crossover behavior in cyanide-bridged iron(II)-copper(I) bimetallic 1-3D metal-organic frameworks.

    Agustí, Gloria; Muñoz, M Carmen; Gaspar, Ana B; Real, José A

    2009-04-20

    The synthesis and characterization of a series of 1-3D cyanide-bridged iron(II)-copper(I) bimetallic coordination polymers formulated as {Fe(3-Xpy)(2)[Cu(3-Xpy)(z)(CN)(2)](2)}, where 3-Xpy is a 3-halogenpyridine ligand with X = F (z = 1.5, 1), Cl (z = 1, 2 and 3), Br (z = 1, 4), and I (z = 1, 5), are reported. In all derivatives, the Fe(II) ion lies in pseudoctahedral [FeN(6)] sites defined by four in situ formed [Cu(3-Xpy)(z)(CN)(2)](-) bridging ligands and two 3-Xpy terminal ligands occupying the equatorial and axial positions, respectively. 1 consists of stacks of corrugated grids whose square windows are defined by pseudotrigonal and pseudotetrahedral [Cu(3-Fpy)(CN)(2)](-) and [Cu(3-Fpy)(2)(CN)(2)](-) units, respectively. 2 is a 3D coordination polymer with the topology of the open-framework CdSO(4). The [Cu(3-Clpy)(CN)(2)](-) rods connecting the pseudooctahedral Fe(II) sites are arranged in such a way that interpenetration is avoided. 3, an architectural isomer of 2, is defined by arrays of linear chains. 4 and 5 are isostructural to 3. Polymer 1 is essentially a low-spin (LS) compound with ca. 19% of residual Fe(II) ions in the high-spin (HS) state at 293 K. It undergoes an irreversible spin transition at T(c) = 356 K. Subsequent cooling-warming cycles give a new spin-crossover behavior characterized by T(c) = 187 K. The structural analysis at 130 and 293 K and at 293 K after irreversible transformation (293 K*) reveals a large unit cell volume variation of 67 A(3) per Fe atom. In addition to the volume change associated with the spin-state conversion, remarkable bond and angle modifications around the Cu(I) sites account for the high flexible nature of the crystal. 2 displays a complete not well-resolved two-step spin conversion, T(c1) = 169 K and T(c2) = 210 K, reflecting the occurrence of two distinct crystallographically Fe(II) sites. The large unit cell volume variation per Fe atom in 2, 59 A(3), has been rationalized in terms similar to those for 1. 1D

  5. Bonding effects in dilute transition-metal alloys

    The Moessbauer isomer-shift data of transition-metal nuclei as impurities in metals were considered in previous papers where it was shown that, once volume effects were suitably accounted for, the data fell on a ''universal'' curve. In this paper, the deviations from universality are examined in more detail in an attempt to better understand the alloying behavior. It is found that atom A as an impurity in metal B does not sustain a shift of the same magnitude as atom B does when it is an impurity in metal A. The results are discussed in terms of d-band hybridization and of the asymmetry in the solubility behavior in transition-metal-alloy phase diagrams

  6. Bonding effects in dilute transition-metal alloys

    Watson, R.E.; Swartzendruber, L.J.; Bennett, L.H.

    1981-12-01

    The Moessbauer isomer-shift data of transition-metal nuclei as impurities in metals were considered in previous papers where it was shown that, once volume effects were suitably accounted for, the data fell on a ''universal'' curve. In this paper, the deviations from universality are examined in more detail in an attempt to better understand the alloying behavior. It is found that atom A as an impurity in metal B does not sustain a shift of the same magnitude as atom B does when it is an impurity in metal A. The results are discussed in terms of d-band hybridization and of the asymmetry in the solubility behavior in transition-metal-alloy phase diagrams.

  7. Flexible metallic seal for transition duct in turbine system

    Flanagan, James Scott; LeBegue, Jeffrey Scott; McMahan, Kevin Weston; Dillard, Daniel Jackson; Pentecost, Ronnie Ray

    2014-04-22

    A turbine system is disclosed. In one embodiment, the turbine system includes a transition duct. The transition duct includes an inlet, an outlet, and a passage extending between the inlet and the outlet and defining a longitudinal axis, a radial axis, and a tangential axis. The outlet of the transition duct is offset from the inlet along the longitudinal axis and the tangential axis. The transition duct further includes an interface member for interfacing with a turbine section. The turbine system further includes a flexible metallic seal contacting the interface member to provide a seal between the interface member and the turbine section.

  8. The metal-insulator transition in magnetite.

    Cullen, J. R.; Callen, E.

    1972-01-01

    We describe an electronic model for the low temperature transition in magnetite, in which the average number of electrons on a site is non-integral. The solution of the one-dimensional problem is reviewed, and the connection of the model with the Verwey ordering is discussed. Some of the implication of the three dimensional problem are discussed.

  9. Glutathione and Transition-Metal Homeostasis in Escherichia coli▿

    Helbig, Kerstin; Bleuel, Corinna; Krauss, Gerd J.; Nies, Dietrich H.

    2008-01-01

    Glutathione (GSH) and its derivative phytochelatin are important binding factors in transition-metal homeostasis in many eukaryotes. Here, we demonstrate that GSH is also involved in chromate, Zn(II), Cd(II), and Cu(II) homeostasis and resistance in Escherichia coli. While the loss of the ability to synthesize GSH influenced metal tolerance in wild-type cells only slightly, GSH was important for residual metal resistance in cells without metal efflux systems. In mutant cells without the P-typ...

  10. 3D virtuel udstilling

    Tournay, Bruno; Rüdiger, Bjarne

    2006-01-01

    3d digital model af Arkitektskolens gård med virtuel udstilling af afgangsprojekter fra afgangen sommer 2006. 10 s.......3d digital model af Arkitektskolens gård med virtuel udstilling af afgangsprojekter fra afgangen sommer 2006. 10 s....

  11. Memristor using a transition metal nitride insulator

    Stevens, James E; Marinella, Matthew; Lohn, Andrew John

    2014-10-28

    Apparatus is disclosed in which at least one resistive switching element is interposed between at least a first and a second conducting electrode element. The resistive switching element comprises a metal oxynitride. A method for making such a resistive switching element is also disclosed.

  12. Electron-energy-loss spectroscopy on group-III nitrides and transition- metal oxides

    Niessner, W

    2000-01-01

    A main topic represent electron-energy-loss spectroscopy (EELS) studies of the group-III nitrides AlN, GaN, InN, as well as their mixing systems Al sub x Ga sub 1 sub - sub x N, In sub x Ga sub 1 sub - sub x N. In EELS measurements with excitation energies above 1 keV clear collective excitations in AlN at 21 eV and in GaN at 15 eV were observed. In the mixing system Al sub x Ga sub 1 sub - sub x M a 2-mode behaviour is observed. Up to x=0.2 a GaN-like excitation remains preserved, while from x=0.44 the eigenfrequency of a AlN-like resonance shifts continuously. With vanadium dioxide a d sup 1 transition metal oxide was studied, which passes at 68 C a semiconductor-metal transition. In the EELS valence band spectra beside band transitions from the O2p subsigma and O2p subpi band an intense signal with a loss energy of 1 eV occurs. EELS studies on W- and F-doped VO sub 2 show, that it deals with a band transition from the V3d into the pd subpi band. EELS studies were for the first time also performed at lead t...

  13. Underwater 3D filming

    Roberto Rinaldi

    2014-12-01

    Full Text Available After an experimental phase of many years, 3D filming is now effective and successful. Improvements are still possible, but the film industry achieved memorable success on 3D movie’s box offices due to the overall quality of its products. Special environments such as space (“Gravity” and the underwater realm look perfect to be reproduced in 3D. “Filming in space” was possible in “Gravity” using special effects and computer graphic. The underwater realm is still difficult to be handled. Underwater filming in 3D was not that easy and effective as filming in 2D, since not long ago. After almost 3 years of research, a French, Austrian and Italian team realized a perfect tool to film underwater, in 3D, without any constrains. This allows filmmakers to bring the audience deep inside an environment where they most probably will never have the chance to be.

  14. Metallization and charge-transfer gap closure of transition-metal iodides under pressure

    Chen, A. Li-Chung

    1993-05-01

    It is shown with resistivity and near-IR absorption measurements that NiI{sub 2}, CoI{sub 2}, and FeI{sub 2} metallize under pressure by closure of the charge-transfer energy gap at pressures of 17, 10, and 23 GPa, respectively, which is close to the antiferromagnetic-diamagnetic transition in NiI{sub 2} and CoI{sub 2}. Thus, the magnetic transitions probably are caused by the metallization; in NiI{sub 2} and CoI{sub 2}, the insulator-metal transitions are first order. Moessbauer and XRD data were also collected. Figs, 46 refs.

  15. Contrasting fluvial styles across the mid-Pleistocene climate transition in the northern shelf of the South China Sea: Evidence from 3D seismic data

    Zhuo, Haiteng; Wang, Yingmin; Shi, Hesheng; He, Min; Chen, Weitao; Li, Hua; Wang, Ying; Yan, Weiyao

    2015-12-01

    Multiple successions of buried fluvial channel systems were identified in the Quaternary section of the mid-shelf region of the northern South China Sea, providing a new case study for understanding the interplay between sea level variations and climate change. Using three commercial 3D seismic surveys, accompanied by several 2D lines and a few shallow boreholes, the sequence stratigraphy, seismic geomorphology and stratal architecture of these fluvial channels were carefully investigated. Based on their origin, dimensions, planform geometries and infill architectures, six classes of channel systems, from Class 1 to Class 6, were recognized within five sequences of Quaternary section (SQ1 to SQ5). Three types of fluvial systems among them are incised in their nature, including the trunk incised valleys (Class 1), medium incised valleys (Class 2) and incised tributaries (Class 3). The other three types are unincised, which comprise the trunk channels (Class 4), lateral migrating channels (Class 5) and the stable channels (Class 6). The trunk channels and/or the major valleys that contain braided channels at their base are hypothesized to be a product of deposition from the "big rivers" that have puzzled the sedimentologists for the last decade, providing evidence for the existence of such rivers in the ancient record. Absolute age dates from a few shallow boreholes indicate that the landscapes that were associated with these fluvial systems changed significantly near the completion of the mid-Pleistocene climate transition (MPT), which approximately corresponds to horizon SB2 with an age of ˜0.6 Ma BP. Below SB2, the Early Pleistocene sequence (SQ1) is dominated by a range of different types of unincised fluvial systems. Evidence of incised valleys is absent in SQ1. In contrast, extensive fluvial incision occurred in the successions above horizon SB2 (within SQ2-SQ5). Although recent studies call for increased incision being a product of climate-controlled increase

  16. Low-dimensional phases and formation of nano-heterostructures in transitional 3D-metal-silicon system

    Classification of low-dimensional phases and their subdivision into surface phases, two-dimensional thin-film phases and nanophases have been considered. The review of experimental data is presented on identification of low-dimensional phases stabilized by substrate deposition of Cr, CrSi2, Co and CoSi2 with Si(111) and with CrSi2(0001). Phase identification is produced on composition, electronic and atomic structure, and electrophysical properties. It has been shown that low-dimensional thin-film phases and nanophases are distinguished essentially from surface phases. It is found out that their composition is determined by not only thermodynamic growth conditions but also by kinetics of formation

  17. Magnetism of 3d transition metal nanoparticles on surfaces probed with synchrotron radiation - from ensembles towards individual objects

    Bansmann, Joachim [Institut fuer Oberflaechenchemie und Katalyse, Universitaet Ulm (Germany); Kleibert, Armin [Institut fuer Physik, Universitaet Rostock (Germany); Swiss Light Source, Paul Scherrer Institut, Villigen (Switzerland); Getzlaff, Mathias [Institut fuer Angewandte Physik, Universitaet Duesseldorf (Germany); Rodriguez, Arantxa Fraile; Nolting, Frithjof [Swiss Light Source, Paul Scherrer Institut, Villigen (Switzerland); Boeglin, Christine [Institut de Physique et de Chimie de Strasbourg, Universite de Strasbourg (France); Meiwes-Broer, Karl-Heinz [Institut fuer Physik, Universitaet Rostock (Germany)

    2010-05-15

    Mass-filtered Fe, Co and FeCo nanoparticles in the size regime from 7 to 25 nm have been deposited under soft-landing conditions onto ferromagnetic films, non-magnetic surfaces as well as embedded into Al matrices. In situ X-ray magnetic circular dichroism (XMCD) measurements reveal a ferromagnetic behaviour of FeCo nanoparticles (size: 10 nm) on Si-substrates at room temperature whereas the respective Co nanoparticles are superparamagnetic. Besides measurements on ensembles of nanoparticles, we have also carried out in situ measurements on individual Fe nanoparticles using X-ray photoemission electron microscopy at the Fe L{sub 3,2} edges. Fe nanoparticles on Co films show a magnetic contrast depending on the direction of the underlying poly-crystalline Co domains. This technique also allows to record XMCD spectra on individual nanoparticles. Spectroscopy and spectro-microscopy on magnetic particles. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  18. EPR of transition metal ions in NZP ceramics

    NZP-ceramics have been produced by different methods such as sol-gel, flux melting and sintering of dry salts or phosphates. Formation of NZP and related phases was confirmed by X-ray diffraction analysis. Electron paramagnetic resonance (EPR) was applied to evaluate a structure positions of paramagnetic ions and nature of radiation-induced centers. EPR responses from transition metal ions Fe3+ and Mn2+ with electron configuration 3d5 (ground state 6S5/2) which occurred as impurities in raw materials were registered in powders of NZP-ceramics. Fine structure arising due to high spin iron complexes is well resolved. A part of Fe3+ ions substitutes for Zr4+ and another part of one substitutes for Na+ ions in six-fold coordinated positions. A great value of hyperfine structure (hfs) constant (9.3 mT) shows a high ionic character of Mn-O bonds in the first coordination sphere. A coordination number is close to 6. Fine structure of Mn2+ ions are not well resolved. A comparison of the spectra of samples containing various alkali cations shows the substitution for cations in series of Li-Na-K-Rb-Cs does not result in fundamental variation in spectra except for CZP ceramics where the response with g=4.3 due to Fe3+ in strong ligand field rather than response with g=2.0 due to Fe3+ in weak field is observed. An investigation of some samples doped by 0.1...0.5 mole % of Fe3+ or Gd3+ has been carried out and principal spin-Hamiltonian parameters have been determined. The increase of Fe and Gd ions content as compared to impurity substituting for Zr and possibly Na in their own structural positions results in noticeable site distortion. Gamma irradiation of NZP ceramics results in formation of radiation-induced paramagnetic centers connected to phosphorus-oxygen. The nature and concentration of these centers depend on production method. The lowest defect concentration is in hot-pressed ceramics

  19. Development of dissimilar metal transition joint by hot bond rolling

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) to stainless steel piping are required for nuclear fuel reprocessing plants. The authors have developed dissimilar transition joints made of stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot bond rolling process of clad bars and clad pipes, using a newly developed mill called 'rotary reduction mill'. This report presents the manufacturing process of dissimilar transition joints produced from the clad pipe with three layers by the hot bond rolling. First, the method of hot bond rolling of clad pipe is proposed. Then, the mechanical and corrosion properties of the dissimilar transition joints are evaluated in detail by carrying out various tests. Finally, the rolling properties in the clad pipe method are discussed. (author)

  20. From 3D view to 3D print

    Dima, M.; Farisato, G.; Bergomi, M.; Viotto, V.; Magrin, D.; Greggio, D.; Farinato, J.; Marafatto, L.; Ragazzoni, R.; Piazza, D.

    2014-08-01

    In the last few years 3D printing is getting more and more popular and used in many fields going from manufacturing to industrial design, architecture, medical support and aerospace. 3D printing is an evolution of bi-dimensional printing, which allows to obtain a solid object from a 3D model, realized with a 3D modelling software. The final product is obtained using an additive process, in which successive layers of material are laid down one over the other. A 3D printer allows to realize, in a simple way, very complex shapes, which would be quite difficult to be produced with dedicated conventional facilities. Thanks to the fact that the 3D printing is obtained superposing one layer to the others, it doesn't need any particular work flow and it is sufficient to simply draw the model and send it to print. Many different kinds of 3D printers exist based on the technology and material used for layer deposition. A common material used by the toner is ABS plastics, which is a light and rigid thermoplastic polymer, whose peculiar mechanical properties make it diffusely used in several fields, like pipes production and cars interiors manufacturing. I used this technology to create a 1:1 scale model of the telescope which is the hardware core of the space small mission CHEOPS (CHaracterising ExOPlanets Satellite) by ESA, which aims to characterize EXOplanets via transits observations. The telescope has a Ritchey-Chrétien configuration with a 30cm aperture and the launch is foreseen in 2017. In this paper, I present the different phases for the realization of such a model, focusing onto pros and cons of this kind of technology. For example, because of the finite printable volume (10×10×12 inches in the x, y and z directions respectively), it has been necessary to split the largest parts of the instrument in smaller components to be then reassembled and post-processed. A further issue is the resolution of the printed material, which is expressed in terms of layers

  1. Chemical compatibility between lithium oxide and transition metals

    The chemical reactions between Li2O and transition metals (Ti, V, Cr, Mn, Fe, Ni), particularly 316 steel, have been studied up to 1273 K in sealed systems under argon and also under vacuum. Pure Li2O is inherently inert towards transition metals except when such equilibria as 4Li2O + Fe = Li5FeO4 + 3Li 2Li2O + Cr = LiCrO2 + 3Li are disturbed by removal of Li by vacuum or chemical means. The results are rationalised with the known thermodynamics. LiOH impurity has a deleterious effect on the metals and accounts for some of the supposed reactivity of LI2O. It may be possible to inhibit the corrosive reaction of LiOH and LiOT towards steel, and facilitate the release of T2, by introducing metallic lithium. (orig.)

  2. The nonmetal-metal transition in solutions of metals in molten salts

    Solutions of metals in molten salts present a rich phenomenology: localization of electrons in disordered ionic media, activated electron transport increasing with metal concentration towards a nonmetal-metal (NM-M) transition, and liquid-liquid phase separation. A brief review of progress in the study of these systems is given in this article, with main focus on the NM-M transition. After recalling the known NM-M behaviour of the component elements in the case of expanded fluid alkali metals and mercury and of solid halogens under pressure, the article focuses on liquid metal - molten salt solutions and traces the different NM-M behaviours of the alkalis in their halides and of metals added to polyvalent metal halides. (author). 51 refs, 2 figs

  3. Synthesis of some novel divalent transition metal complexes as antimicrobials

    Kaushal K. Oza; Paresh N. Patel; Hasmukh S. Patel

    2011-01-01

    A novel series of transition metal complexes have been synthesized from the reaction of 5-((3-(methylthio)-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-ylamino)methyl)quinolin-8-ol with transition metal salts. The structures of these compounds have been elucidated by elemental and spectral analysis. Furthermore, compounds were screened for in vitro antimicrobial activity against the representative panel of two Gram-positive and two Gram-negative bacteria and two strains of fungus. The various compounds show potent inhibitory action against test organisms.

  4. An inverse scattering approach to the physics of transition metals

    A method is developed for the deduction of a transition metal ion potential from a knowledge of the phase-shift nl(k). The method used is based on the distorted plane-wave scattering approximation for the deduction of non-singular potentials from scattering phase-shifts in an inverse scattering approach. The resulting electron-ion potential obtained is a finite Dirichlet series sum of short range exponential functions. The Fourier transform of the potential is obtained for applications in the area of transition metal solid state physics. (author). 14 refs, 1 tab

  5. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    Fhayli, Karim

    2016-04-14

    Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

  6. Blender 3D cookbook

    Valenza, Enrico

    2015-01-01

    This book is aimed at the professionals that already have good 3D CGI experience with commercial packages and have now decided to try the open source Blender and want to experiment with something more complex than the average tutorials on the web. However, it's also aimed at the intermediate Blender users who simply want to go some steps further.It's taken for granted that you already know how to move inside the Blender interface, that you already have 3D modeling knowledge, and also that of basic 3D modeling and rendering concepts, for example, edge-loops, n-gons, or samples. In any case, it'

  7. Spin transition of 1D, 2D and 3D iron(II) complex polymers the tug-of-war between elastic interaction and a shock-absorber effect invited review

    The structures of linear chain Fe(II) spin-crossover compounds of α,β- and α,ω-bis (tetrazol-1-yl)alkane type ligands are described in relation to their magnetic properties. The first threefold interlocked 3-D catenane Fe(II) spin-transition system, [p-tris(1,4-bis(tetrazol-1-yl)butane-N1,N1') iron(II)] bis(perchlorate), will be discussed. An analysis is made among the structures and the cooperativity of the spin-crossover behavior of polynuclear Fe(II) spin-transition materials. Refs. 42 (author)

  8. Volume variation of Gruneisen parameters of fcc transition metals

    C V Pandya; P R Vyas; T C Pandya; V B Gohel

    2002-02-01

    The volume variation of the Gruneisen parameters of ten fcc transition metals, up to 40% compression, has been studied on the basis of a model approach proposed by Antonov et al. The results are reasonably good for six metals except for Rh, Ag, Au and Ni when compared with available experimental and other theoretical values. The model requires an appropriate modification for Rh, Ag, Au and Ni.

  9. Spatiotemporal Analysis of Heavy Metal Water Pollution in Transitional China

    Huixuan Li; Yingru Li; Ming-Kuo Lee; Zhongwei Liu; Changhong Miao

    2015-01-01

    China’s socioeconomic transitions have dramatically accelerated its economic growth in last three decades, but also companioned with continuous environmental degradation. This study will advance the knowledge of heavy metal water pollution in China from a spatial–temporal perspective. Specifically, this study addressed the following: (1) spatial patterns of heavy metal water pollution levels were analyzed using data of prefecture-level cities from 2004 to 2011; and (2) spatial statistical...

  10. Characteristic test results of reduced-scale lead and 3D laminated rubber bearings for seismic isolation design of liquid metal reactor

    Yoo, B.; Lee, Jae Han [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of); Kwon, H. S. [Chungnam Univ., Taejon (Korea, Republic of)

    1999-06-01

    Through the fabrications and the tests of reduced scale rubber bearing by several times since 1995, the technology related to the bearings has been improved. In this report, several lead rubber bearings (LLRB) with different lead plug diameters, high damping rubber bearing (HLRB), and 3D-LRB made of UNISON NR (natural rubber) compounds are tested to get the hysteretic characteristics of rubber bearings. Specially, the HLRB and 3D-LRB are tested for the vertical deformation characteristics. All the test data are plotted and analyzed to be compared with design target values such as equivalent horizontal stiffness and equivalent damping ration. The variations of the equivalent horizontal stiffness and damping for the lead and the 3D-LRB are evaluated from test data in the range of 25% to 150% of shear strain in horizontal direction. As increasing the lead plug diameter up to 48 mm, the values of yield load, equivalent stiffness, and equivalent damping are increased, and the maximum damping of 31 % are horizontal performance during compression and shear tests. Through the vertical performance tests of HLRB and 3D-LRB, it is reveal that the vertical stiffness of HLRB is 15.57 ton/mm, which is much lower than target value by 1/4, and the vertical stiffness of 3D-LRB show in the range of 2.17 ton/mm to 4.4 ton/mm, which are higher than the design target 1.25 ton/mm by about 2 times. The vertical equivalent damping of HLRB is 11.48%, but the ones of 3D-LRB show large variations between 8 % and 54%. There are no difference between the first and after curves of the vertical hysteresis of 3D-LRB and no dependency of test speed because the dish springs take the vertical behaviors of 3D-LRB. (author). 8 refs., 38 tabs., 47 figs.

  11. Branching fractions and oscillator strengths for FeII transitions from the 3d6(5D)4p subconfiguration

    New experimental branching fractions and transition probabilities are reported for 56 transitions in FeII. The branching fractions are measured with a Fourier transform spectrometer and also with a high-resolution grating spectrometer on an optically thin hollow cathode discharge. Highly accurate experimental radiative lifetimes from the recent literature provide the normalization required to convert our branching fractions into absolute transition probabilities. Results are compared with experimental and theoretical values in the literature. Our new transition probabilities will establish the absolute scale for relative absorption oscillator strengths of vacuum ultraviolet lines measured using a new high-sensitivity absorption experiment at the University of Wisconsin. copyright 1996 The American Astronomical Society

  12. Absolute frequency and isotope shift of the magnesium (3 s2) 1S0→(3 s 3 d ) 1D2 two-photon transition by direct frequency-comb spectroscopy

    Peters, E.; Reinhardt, S.; Hänsch, Th. W.; Udem, Th.

    2015-12-01

    We use a picosecond frequency-doubled mode-locked titanium sapphire laser to generate a frequency comb at 431 nm in order to probe the (3 s2) 1S0 →(3 s 3 d ) 1D2 transition in atomic magnesium. Using a second, self-referenced femtosecond frequency comb, the absolute transition frequency and the 24Mg and 26Mg isotope shift is determined relative to a global-positioning-system-referenced hydrogen maser. Our result for the transition frequency of the main isotope 24Mg of 1 391 128 606.14 (12 ) MHz agrees with previous measurements and reduces its uncertainty by four orders of magnitude. For the isotope shift we find δ ν26 ,24=3915.13 (39 ) MHz. Accurate values for transition frequencies in Mg are relevant in astrophysics and to test atomic structure calculations.

  13. 3D Digital Modelling

    Hundebøl, Jesper

    wave of new building information modelling tools demands further investigation, not least because of industry representatives' somewhat coarse parlance: Now the word is spreading -3D digital modelling is nothing less than a revolution, a shift of paradigm, a new alphabet... Research qeustions. Based...... on empirical probes (interviews, observations, written inscriptions) within the Danish construction industry this paper explores the organizational and managerial dynamics of 3D Digital Modelling. The paper intends to - Illustrate how the network of (non-)human actors engaged in the promotion (and arrest) of 3......D Modelling (in Denmark) stabilizes - Examine how 3D Modelling manifests itself in the early design phases of a construction project with a view to discuss the effects hereof for i.a. the management of the building process. Structure. The paper introduces a few, basic methodological concepts...

  14. Professional Papervision3D

    Lively, Michael

    2010-01-01

    Professional Papervision3D describes how Papervision3D works and how real world applications are built, with a clear look at essential topics such as building websites and games, creating virtual tours, and Adobe's Flash 10. Readers learn important techniques through hands-on applications, and build on those skills as the book progresses. The companion website contains all code examples, video step-by-step explanations, and a collada repository.

  15. Robust half-metallic properties in inverse Heusler alloys composed of 4d transition metal elements: Zr2RhZ (Z=Al, Ga, In)

    Wang, X. T.; Lin, T. T.; Rozale, H.; Dai, X. F.; Liu, G. D.

    2016-03-01

    A first-principles approach is used to study the electronic and magnetic properties of Zr2RhZ (Z=Al, Ga, In) alloys in the Hg2CuTi-type structure. The Zr2RhZ (Z=Al, Ga, In) alloys are found to be half-metallic ferrimagnets. The half-metallicity is quite robust against hydrostatic strain and tetragonal deformation in Zr2RhZ (Z=Al, Ga, In) alloys. The magnetization of Zr2RhZ (Z=Al, Ga, In) alloys mainly originates from the 4d electrons of Zr atoms and follows the rule: Mt=Zt-18. Zr2Rh-based alloys do not contain any 3d transition metal element, which implies a wider field to search for new half-metallic materials.

  16. Calculated electronic properties of ordered alloys a handbook : the element and their 3d/3d and 4d/4d alloys

    Moruzzi, VL

    1995-01-01

    This is a handbook of calculated electronic properties of elements and of 3d/3d and 4d/4d ordered alloys. The book derives the ground-state or equilibrium properties of the metallic elements in both bcc and fcc structures, and of existing and nonexisting ordered binary transition-metal alloys in CsCl, CuAu, and Cu 3 Au structures by the analysis of binding curves, or total energy vs. volume curves, calculated from first-principles augmented-spherical-wave methods. The calculated properties, energy bands along symmetry lines in the respective Brillouin zones, and the total and I-decomposed dens

  17. Heterometallic modular metal-organic 3D frameworks assembled via new tris-β-diketonate metalloligands: nanoporous materials for anion exchange and scaffolding of selected anionic guests.

    Carlucci, Lucia; Ciani, Gianfranco; Maggini, Simona; Proserpio, Davide M; Visconti, Marco

    2010-11-01

    The modular engineering of heterometallic nanoporous metal-organic frameworks (MOFs) based on novel tris-chelate metalloligands, prepared using the functionalised β-diketone 1,3-bis(4'-cyanophenyl)-1,3-propanedione (HL), is described. The complexes [M(III)L(3)] (M=Fe(3+), Co(3+)) and [M(II)L(3)](NEt(4)) (M=Mn(2+), Co(2+), Zn(2+), Cd(2+)) have been synthesised and characterised, all of which exhibit a distorted octahedral chiral structure. The presence of six exo-oriented cyano donor groups on each complex makes it a suitable building block for networking through interactions with external metal ions. We have prepared two families of MOFs by reacting the metalloligands [M(III)L(3)] and [M(II)L(3)](-) with many silver salts AgX (X=NO(3)(-), BF(4)(-), PF(6)(-), AsF(6)(-), SbF(6)(-), CF(3)SO(3)(-), tosylate), specifically the [M(III)L(3)Ag(3)]X(3)·Solv and [M(II)L(3)Ag(3)]X(2)·Solv network species. Very interestingly, all of these network species exhibit the same type of 3D structure and crystallise in the same trigonal space group with similar cell parameters, in spite of the different metal ions, ionic charges and X(-) counteranions of the silver salts. We have also succeeded in synthesising trimetallic species such as [Zn(x)Fe(y)L(3)Ag(3)](ClO(4))((2x+3y))·Solv and [Zn(x)Cd(y)L(3)Ag(3)](ClO(4))(2)·Solv (with x+y=1). All of the frameworks can be described as sixfold interpenetrated pcu nets, considering the Ag(+) ions as simple digonal spacers. Each individual net is homochiral, containing only Δ or Λ nodes; the whole array contains three nets of type Δ and three nets of type Λ. Otherwise, taking into account the presence of weak Ag-C σ bonds involving the central carbon atoms of the β-diketonate ligands of adjacent nets, the six interpenetrating pcu networks are joined into a unique non-interpenetrated six-connected frame with the rare acs topology. The networks contain large parallel channels of approximate hexagonal-shaped sections that represent 37

  18. Dimensional effects in a disordered system near metal-insulator transitions and superconductor-insulator transitions

    Low temperature transport in disordered conducting materials implies quantum interference, Coulomb repulsion, and superconducting fluctuations. Since 2-D is the lower critical dimension for the existence of metallic and superconducting states, we have studied two quantum phase transitions - the Superconductor-to-Insulator Transition (SIT) and the Metal-to-Insulator Transition (MIT) - when the thickness of a disordered system - here a-NbSi - is lowered. The underlying problem is the transition between the different states and the conditions for a 2-D metal to exist. We have studied the field and disorder-induced SIT. The principal characteristics we have observed (renormalization, role of the field orientation) are well explained by M.P.A. Fisher's theory. However, we do not find the critical exponents values and a universal resistance at the transition as predicted by this theory. Concerning the MIT, we have decreased the thickness of a metallic system to reach the dimension 2 and an insulating state. In both transitions, the passage to the insulating state clearly shows the existence of dissipative states at zero temperature that are not predicted by conventional theories. We propose an interpretation of all our results that implies the existence of a novel phase in 2-D, a Bose Metal, between the superconducting and the metallic states. This new state has been predicted by recent theories. We trace the corresponding phase diagram for the model system NbSi with respect to concentration and film thickness. In the second appendix it is shown how superconducting thin films of NbxSi1-x are used to make transition edge sensors used in the particle detection field. (author)

  19. The Metallicities of Stars With and Without Transiting Planets

    Buchhave, Lars A

    2015-01-01

    Host star metallicities have been used to infer observational constraints on planet formation throughout the history of the exoplanet field. The giant planet metallicity correlation has now been widely accepted, but questions remain as to whether the metallicity correlation extends to the small terrestrial-sized planets. Here, we report metallicities for a sample of 518 stars in the Kepler field that have no detected transiting planets and compare their metallicity distribution to a sample of stars that hosts small planets (Rp < 1.7 R_Earth). Importantly, both samples have been analyzed in a homogeneous manner using the same set of tools (Stellar Parameters Classification tool; SPC). We find the average metallicity of the sample of stars without detected transiting planets to be [m/H]_SNTP,dwarf = -0.02 +- 0.02 dex and the sample of stars hosting small planets to be [m/H]_STP = -0.02 +- 0.02 dex. The average metallicities of the two samples are indistinguishable within the uncertainties, and the two-sample...

  20. Transition metal bioconjugates with an organometallic link between the metal and the biomolecular scaffold

    Monney, Angèle; Albrecht, Martin

    2013-01-01

    This overview compiles recent advances in the synthesis and application of organometallic bioconjugates that comprise a metal–carbon linkage between the metal and the biomolecular scaffold. This specific area of bioorganometallic chemistry has been spurred by the discovery of naturally occurring bioorganometallic compounds and afforded organometallic bioconjugates from transition metals binding to amino acids, nucleic acids and other biomolecules. These artificial bioorganometallic compounds ...

  1. Chromospheric, transition layer and coronal emission of metal deficient stars

    Boehm-Vitense, E.

    1982-01-01

    It is shown that while MgII k line emission decreases for metal deficient stars, the Ly alpha emission increases. The sum of chromospheric hydrogen and metallic emission appears to be independent of metal abundances. The total chromospheric energy loss is estimated to be 0.0004 F sub bol. The chromospheric energy input does not seem to decrease for increasing age. The transition layer emission is reduced for metal deficient stars, but it is not known whether the reduction is larger than can be explained by curve of growth effects only. Coronal X-ray emission was measured for 4 metal deficient stars. Within a 12 limit it could still be consistent with the emission of solar abundance stars.

  2. Recipe for high-Tc transition-metal chalcogenide superconductors

    The conditions for the occurrence of superconductivity in cuprates are enumerated. There is a minimum of seven, which are discussed in some detail. They may be taken as a recipe in the search for superconductors at elevated temperature with other transition-metal chalcogenide compounds. (orig.)

  3. Reaction ability of nitrosyl group in transition metal complexes

    Transformations of the intraspheric nitrosyl group in complexes of transition metals are reviewed. All the reactions involving these groups are divided into two types: reactions associated with the electrophilic properties of the nitrosyl group; reactions associated with the nucleophilic properties of the nitrosyl group. Attempts to correlate the reactivity of the nitrosyl group with its structure and spectral characteristics are considered

  4. Transport properties of transition metal impurities on gold nanowires

    Pontes, Renato B.; da Silva, Edison Z.; Fazzio, Adalberto; da Silva, Antônio J. R.

    2009-03-01

    Performing first principles density functional theory (DFT) we calculated the electronic and transport properties of a Au thin nanowire with transition metal atoms (Mn, Fe, Ni or Co) bridging the two sides of the Au nanowire. We will show that these systems have strong spin dependent transport properties and that the local symmetry can dramatically change them, leading to a significant spin polarized conductance. This spin dependent transport is also associated with the transition metal in the nanowire, in particular with the d-level positioning. Using Co, for example [1], when the symmetry permits the mixing between the wire s-orbitals with the transition metal d-states, there are interference effects that resemble Fano-like resonances with an anisotropy of 0.07 at the Fermi level. On the other hand, if this symmetry decouples such states, we simply have a sum of independent transmission channels and the calculated anisotropy was 0.23. The anisotropies for the other transition metals, as well as calculated transmittances for two Co impurities will also be presented [1] R. B. Pontes, E. Z. da Silva, A. Fazzio and Antônio J. R. da Silva, J. Am. Chem. Soc. 130 (30), 9897-903, 2008

  5. The Electrochemical Synthesis of Transition-Metal Acetylacetonates

    Long, S. R.; Browning, S. R.; Lagowski, J. J.

    2008-01-01

    The electrochemical synthesis of transition-metal acetylacetonates described here can form the basis of assisting in the transformation of an entry-level laboratory course into a research-like environment where all members of a class are working on the same problem, but where each member has a personal responsibility for the synthesis and…

  6. Electron-Hole Liquids in Transition Metal Oxide Heterostructures

    Millis, Andrew J.; Schlom, Darrell G.

    2010-01-01

    Appropriately designed transition metal oxide heterostructures involving small band gap Mott insulators are argued to support spatially separated electron and hole gasses at equilibrium. Spatial separations and carrier densities favoring the formation of excitonic states are achievable. The excitonic states may exhibit potentially novel properties. Energetic estimates are given, candidate material systems are discussed, and the possibility of large photvoltaic effects is mentioned

  7. Reactions of transition metal complexes with cyclic ethers

    Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

  8. Surface segregation energies in transition-metal alloys

    Ruban, Andrei; Skriver, Hans Lomholt; Nørskov, Jens Kehlet

    1999-01-01

    to the electrostatic potential and energy. We use the database to establish the major factors which govern surface segregation in transition metal alloys. We find that the calculated trends are well described by Friedel's rectangular state density model and that the few but significant deviations...

  9. The order parameter and susceptibility of the 3D Ising-like system in an external field near the phase transition point

    M.P. Kozlovskii

    2010-01-01

    Full Text Available The present work is devoted to the investigation of the 3D Ising-like model in the presence of an external field in the vicinity of critical point. The method of collective variables is used. General expressions for the order parameter and susceptibility are calculated as functions of temperature and the external field as well as scaling functions of that are explicitly obtained. The results are compared with the ones obtained within the framework of parametric representation of the equation of state and Monte Carlo simulations. New expression for the exit point from critical regime of the order parameter fluctuations is proposed and used for the calculation.

  10. Hydrothermal Synthesis, Crystal Structure and Characterization of a Microporous 3D Pillared-Layer 3d-4f Copper-Holmium Heterometallic Coordination Polymer

    A microporous 3D pillared-layer 3d-4f (Cu+-Ho3+) coordination polymer based on the linkages of 2D wavelike Ho-carboxylate layers and 1D Cu4Br4 inorganic chains in centipede-type structure by IN. pillars has been obtained. Furthermore, the magnetic properties of this complex have been investigated. Our results provide an intriguing example of 3D 3d-4f PCPs and further demonstrate that the pillared-layer approach can be used for constructing novel 3D 3d-4f PCPs. There has been more and more interest in recent years in the design and synthesis of porous coordination polymers (PCPs) not only for their fascinating structural diversity but also for their potential applications as functional materials in magnetism, molecular adsorption, gas storage, ion exchange, catalysis and separation. Up to now, almost all approaches to the construction of porous materials have focused on the 3D monometallic PCPs. However, the preparation of hetero-metallic PCPs especially containing lanthanide (Ln) and transition metal (TM) ions has been drawn less attention. A pillared-layer approach to the construction of 3D 3d-4f coordination polymers upon the connections of Ln-carboxylate layers and TM-inorganic motifs by organic pillars via coordination bonding has been reported. In most such 3D pillared-layer 3d-4f structures, TM-inorganic layers/chains generally obstruct the development of channels based on the pores formed by Ln-carboxylate layers

  11. Estimating the acidity of transition metal hydride and dihydrogen complexes by adding ligand acidity constants.

    Morris, Robert H

    2014-02-01

    A simple equation (pKa(THF) = ∑AL + Ccharge + Cnd + Cd6) can be used to obtain an estimate of the pKa of diamagnetic transition metal hydride and dihydrogen complexes in tetrahydrofuran, and, by use of conversion equations, in other solvents. It involves adding acidity constants AL for each of the ligands in the 5-, 6-, 7-, or 8-coordinate conjugate base complex of the hydride or dihydrogen complex along with a correction for the charge (Ccharge = -15, 0 or 30 for x = +1, 0 or -1 charge, respectively) and the periodic row of the transition metal (Cnd = 0 for 3d or 4d metal, 2 for 5d metal) as well as a correction for d(6) octahedral acids (Cd6 = 6 for d(6) metal ion in the acid, 0 for others) that are not dihydrogen complexes. Constants AL are provided for 13 commonly occurring ligand types; of these, nine neutral ligands are correlated with Lever's electrochemical ligand parameters EL. This method gives good estimates of the over 170 literature pKa values that range from less than zero to 50 with a standard deviation of 3 pKa units for complexes of the metals chromium to nickel, molybdenum, ruthenium to palladium, and tungsten to platinum in the periodic table. This approach allows a quick assessment of the acidity of hydride complexes found in nature (e.g., hydrogenases) and in industry (e.g., catalysis and hydrogen energy applications). The pKa values calculated for acids that have bulky or large bite angle chelating ligands deviate the most from this correlation. The method also provides an estimate of the base strength of the deprotonated form of the complex. PMID:24410025

  12. Pressure-induced phase transitions and metallization in VO2

    Bai, Ligang; Li, Quan; Corr, Serena A.; Meng, Yue; Park, Changyong; Sinogeikin, Stanislav V.; Ko, Changhyun; Wu, Junqiao; Shen, Guoyin

    2015-03-01

    We report the results of pressure-induced phase transitions and metallization in VO2 based on synchrotron x-ray diffraction, electrical resistivity, and Raman spectroscopy. Our isothermal compression experiments at room temperature and 383 K show that the room temperature monoclinic phase (M 1 ,P 21/c ) and the high-temperature rutile phase (R ,P 42/m n m ) of VO2 undergo phase transitions to a distorted M 1 monoclinic phase (M 1' ,P 21/c ) above 13.0 GPa and to an orthorhombic phase (CaCl2-like, P n n m ) above 13.7 GPa, respectively. Upon further compression, both high-pressure phases transform into a new phase (phase X ) above 34.3 and 38.3 GPa at room temperature and 383 K, respectively. The room temperature M 1 -M 1' phase transition structurally resembles the R -CaCl2 phase transition at 383 K, suggesting a second-order displacive type of transition. Contrary to previous studies, our electrical resistivity results, Raman measurements, as well as ab initio calculations indicate that the new phase X , rather than the M 1' phase, is responsible for the metallization under pressure. The metallization mechanism is discussed based on the proposed crystal structure.

  13. Electrocatalysis using transition metal carbide and oxide nanocrystals

    Regmi, Yagya N.

    Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel

  14. Preparation of nanoporous metal foam from high nitrogen transition metal complexes

    Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

    2006-11-28

    Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

  15. Empirical prediction of optical transitions in metallic armchair SWCNTs

    G. R. Ahmed Jamal

    2015-12-01

    Full Text Available In this work, a quick and effective method to calculate the second and third optical transition energies of metallic armchair single-wall carbon nanotubes (SWCNT is presented. In this proposed method, the transition energy of any armchair SWCNT can be predicted directly by knowing its one chiral index as both of its chiral indices are same. The predicted results are compared with recent experimental data and found to be accurate over a wide diameter range from 2 to 4.8 nm. The empirical equation proposed here is also compared with that proposed in earlier works. The proposed way may help the research works or applications where information of optical transitions of armchair metallic nanotubes is needed.

  16. Transition Metal Nitrides for Electrocatalytic Energy Conversion: Opportunities and Challenges.

    Xie, Junfeng; Xie, Yi

    2016-03-01

    Electrocatalytic energy conversion has been considered as one of the most efficient and promising pathways for realizing energy storage and energy utilization in modern society. To improve electrocatalytic reactions, specific catalysts are needed to lower the overpotential. In the search for efficient alternatives to noble metal catalysts, transition metal nitrides have attracted considerable interest due to their high catalytic activity and unique electronic structure. Over the past few decades, numerous nitride-based catalysts have been explored with respect to their ability to drive various electrocatalytic reactions, such as the hydrogen evolution reaction and the oxygen evolution reaction to achieve water splitting and the oxygen reduction reaction coupled with the methanol oxidation reaction to construct fuel cells or rechargeable Li-O2 batteries. This Minireview provides a brief overview of recent progress on electrocatalysts based on transition metal nitrides, and outlines the current challenges and future opportunities. PMID:26494184

  17. Towards understanding a mechanism for reversible hydrogen storage: theoretical study of transition metal catalysed dehydrogenation of sodium alanate.

    Ljubić, Ivan; Clary, David C

    2010-04-28

    On the basis of density functional theory and coupled-cluster CCSD(T) calculations we propose a mechanism of the dehydrogenation of transition metal doped sodium alanate. Insertion of two early 3d-transition metals, scandium and titanium, both of which are promising catalysts for reversible hydrogen storage in light metal hydrides, is compared. The mechanism is deduced from studies on the decomposition of a model system consisting of one transition metal atom and two NaAlH(4) units. Subsequently, the significance of such minimal cluster model systems to the real materials is tested by embedding the systems into the surface of the NaAlH(4) crystal. It is found that the dehydrogenation proceeds via breaking of the bridge H-Al bond and consequent formation of intermediate coordination compounds in which the H(2) molecule is side-on (eta(2)-) bonded to the transition metal centre. The total barrier to the H(2) release is thus dependent upon both the strength of the Al-H bond to be broken and the depth of the coordinative potential. The analogous mechanism applies for the recognized three successive dehydrogenation steps. The gas-phase model structures embedded into the surface of the NaAlH(4) crystal exhibit an unambiguous kinetic stability and their general geometric features remain largely unchanged. PMID:20379493

  18. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 μB depending on the substrate orientation. The largest induced magnetic moment of about 0.46 μB is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition metals (Tc, Ru, Rh, to

  19. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    Al-Zubi, Ali

    2010-12-22

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 {mu}{sub B} depending on the substrate orientation. The largest induced magnetic moment of about 0.46 {mu}{sub B} is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition

  20. The transition to the metallic state in low density hydrogen

    McMinis, Jeremy; Morales, Miguel A. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Ceperley, David M. [Department of Physics, University of Illinois, Urbana, Illinois 61801 (United States); Kim, Jeongnim [Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-11-21

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work, we use diffusion quantum Monte Carlo to benchmark the transition between paramagnetic and anti-ferromagnetic body centered cubic atomic hydrogen in its ground state. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of r{sub s} = 2.27(3) a{sub 0}. We compare our results to previously reported density functional theory, Hedin’s GW approximation, and dynamical mean field theory results.

  1. 3D Spectroscopic Instrumentation

    Bershady, Matthew A

    2009-01-01

    In this Chapter we review the challenges of, and opportunities for, 3D spectroscopy, and how these have lead to new and different approaches to sampling astronomical information. We describe and categorize existing instruments on 4m and 10m telescopes. Our primary focus is on grating-dispersed spectrographs. We discuss how to optimize dispersive elements, such as VPH gratings, to achieve adequate spectral resolution, high throughput, and efficient data packing to maximize spatial sampling for 3D spectroscopy. We review and compare the various coupling methods that make these spectrographs ``3D,'' including fibers, lenslets, slicers, and filtered multi-slits. We also describe Fabry-Perot and spatial-heterodyne interferometers, pointing out their advantages as field-widened systems relative to conventional, grating-dispersed spectrographs. We explore the parameter space all these instruments sample, highlighting regimes open for exploitation. Present instruments provide a foil for future development. We give an...

  2. 3D Projection Installations

    Halskov, Kim; Johansen, Stine Liv; Bach Mikkelsen, Michelle

    2014-01-01

    Three-dimensional projection installations are particular kinds of augmented spaces in which a digital 3-D model is projected onto a physical three-dimensional object, thereby fusing the digital content and the physical object. Based on interaction design research and media studies, this article...... contributes to the understanding of the distinctive characteristics of such a new medium, and identifies three strategies for designing 3-D projection installations: establishing space; interplay between the digital and the physical; and transformation of materiality. The principal empirical case, From...... Fingerplan to Loop City, is a 3-D projection installation presenting the history and future of city planning for the Copenhagen area in Denmark. The installation was presented as part of the 12th Architecture Biennale in Venice in 2010....

  3. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

    2016-01-01

    The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

  4. Analysis of Metal Selective Sintering 3D Printing Atmosphere Protection System%金属选区烧结3D打印气氛保护系统分析

    李金梁; 王洪波; 张凯

    2016-01-01

    为了保证金属选区烧结3D 打印的成型质量,就要给金属选区烧结过程中气氛保护,从而防止金属在烧结过程中氧化。本文从理论上分析了金属选区烧结3D打印机气氛保护系统的原理及构造,以及相应的气氛保护技术指标和经验数据,对增材制造成型技术的有发展提供借鉴和参考。%In order to ensure the forming quality of 3D printing in metal selective sintering process , it is to protect the metal during the sintering process , so as to prevent the metal from oxidation during the sintering process . The paper theoretically analyzed the principle and structure of the metal selective sintering 3D printer atmosphere protection system , and the corresponding atmosphere protection technology index and data of experience , which provide reference and reference to increase in material fabrication technology of development .

  5. Herramientas SIG 3D

    Francisco R. Feito Higueruela

    2010-04-01

    Full Text Available Applications of Geographical Information Systems on several Archeology fields have been increasing during the last years. Recent avances in these technologies make possible to work with more realistic 3D models. In this paper we introduce a new paradigm for this system, the GIS Thetrahedron, in which we define the fundamental elements of GIS, in order to provide a better understanding of their capabilities. At the same time the basic 3D characteristics of some comercial and open source software are described, as well as the application to some samples on archeological researchs

  6. Bootstrapping 3D fermions

    Iliesiu, Luca; Kos, Filip; Poland, David; Pufu, Silviu S.; Simmons-Duffin, David; Yacoby, Ran

    2016-03-01

    We study the conformal bootstrap for a 4-point function of fermions in 3D. We first introduce an embedding formalism for 3D spinors and compute the conformal blocks appearing in fermion 4-point functions. Using these results, we find general bounds on the dimensions of operators appearing in the ψ × ψ OPE, and also on the central charge C T . We observe features in our bounds that coincide with scaling dimensions in the GrossNeveu models at large N . We also speculate that other features could coincide with a fermionic CFT containing no relevant scalar operators.

  7. Interaktiv 3D design

    Villaume, René Domine; Ørstrup, Finn Rude

    2002-01-01

    Projektet undersøger potentialet for interaktiv 3D design via Internettet. Arkitekt Jørn Utzons projekt til Espansiva blev udviklet som et byggesystem med det mål, at kunne skabe mangfoldige planmuligheder og mangfoldige facade- og rumudformninger. Systemets bygningskomponenter er digitaliseret som...... 3D elementer og gjort tilgængelige. Via Internettet er det nu muligt at sammenstille og afprøve en uendelig  række bygningstyper som  systemet blev tænkt og udviklet til....

  8. 3D Dental Scanner

    Kotek, L.

    2015-01-01

    This paper is about 3D scan of plaster dental casts. The main aim of the work is a hardware and software proposition of 3D scan system for scanning of dental casts. There were used camera, projector and rotate table for this scanning system. Surface triangulation was used, taking benefits of projections of structured light on object, which is being scanned. The rotate table is controlled by PC. The camera, projector and rotate table are synchronized by PC. Controlling of stepper motor is prov...

  9. TOWARDS: 3D INTERNET

    Ms. Swapnali R. Ghadge

    2013-01-01

    In today’s ever-shifting media landscape, it can be a complex task to find effective ways to reach your desired audience. As traditional media such as television continue to lose audience share, one venue in particular stands out for its ability to attract highly motivated audiences and for its tremendous growth potential the 3D Internet. The concept of '3D Internet' has recently come into the spotlight in the R&D arena, catching the attention of many people, and leading to a lot o...

  10. 3D打印技术在金属成形领域的应用和展望%Application and Prospect of 3 D Printing in Metal Forming

    谭丽斌; 余心宏

    2015-01-01

    3D printing technology is not only a new precision forming technology, but also the core technology of the third industrial revolution, which plays an important role in the metal forming field. Due to the unique advantages of 3D printing, such as the fast processing speed, the high materials utilization, and unrestricted forming shape, it can be widely applied. The current research status of the process, materials and new-high forming devices for 3D printing in China and other countries were introduced in this article. From the market shares of 3D printing, the development direction of 3D printing was prospected.%3D打印技术是新型精密成形技术,也是第三次工业革命的核心技术,在金属成形领域发挥着重要作用. 3D打印由于加工速度快、材料利用率高、成形件形状不受限制的优势,应用领域相对广泛. 文中重点介绍国内外3D打印的工艺研究现状、材料研究现状以及新型高端成形设备,从3D打印所占据市场份额出发,展望其发展前景.

  11. Adhesion and friction of transition metals in contact with non-metallic hard materials

    An investigation was conducted to examine the adhesion and friction behavior of transition metals in contact with various non-metallic hard materials and the nature of the metal transfer to the hard materials. Sliding friction experiments were conducted with the metals yttrium, titanium, tantalum, zirconium, vanadium, neodymium, iron, cobalt, nickel, tungsten, platinum, rhenium, ruthenium and rhodium in sliding contact with single-crystal diamond, silicon carbide, pyrolytic boron nitride and ferrite. All experiments were conducted under the following conditions: loads, 0.05-0.3 N; sliding velocities, 3 x 10-3 and 0.7 x 10-3 m min-1; in a vacuum of 10-8 Pa; at room temperature. Auger electron spectroscopy analysis was conducted with the metals and non-metals to determine the surface chemistry and the degree of surface cleanness. The results of the investigation indicate the adhesion and friction of the transition metals in contact with diamond, silicon carbide, boron nitride and ferrite are related to the relative chemical activity of the metals. The more chemically active the metal, the higher the coefficient of friction and the greater the amount of transfer to the non-metals. (Auth.)

  12. An Anderson Impurity Model for Efficient Sampling of Adiabatic Potential Energy Surfaces of Transition Metal Complexes

    La Bute-Montiago X; Cox, D L

    2004-01-01

    We present a model intended for rapid sampling of ground and excited state potential energy surfaces for first-row transition metal active sites. The method is computationally inexpensive and is suited for dynamics simulations where (1) adiabatic states are required "on-the-fly" and (2) the primary source of the electronic coupling between the diabatic states is the perturbative spin-orbit interaction among the 3d electrons. The model Hamiltonian we develop is a variant of the Anderson impurity model and achieves efficiency through a physically motivated basis set reduction based on the large value of the d-d Coulomb interaction U_{d} and a Lanczos matrix diagonalization routine to solve for eigenvalues. The model parameters are constrained by fits to the partial density of states (PDOS) obtained from ab initio density functional theory calculations. For a particular application of our model we focus on electron-transfer occuring between cobalt ions solvated by ammonium, incorporating configuration interactio...

  13. Transition-metal-catalyzed C-S bond coupling reaction.

    Lee, Chin-Fa; Liu, Yi-Chen; Badsara, Satpal Singh

    2014-03-01

    Sulfur-containing molecules such as thioethers are commonly found in chemical biology, organic synthesis, and materials chemistry. While many reliable methods have been developed for preparing these compounds, harsh reaction conditions are usually required in the traditional methods. The transition metals have been applied in this field, and the palladium-catalyzed coupling of thiols with aryl halides and pseudo halides is one of the most important methods in the synthesis of thioethers. Other metals have also been used for the same purpose. Here, we summarize recent efforts in metal-catalyzed C-S bond cross-coupling reactions, focusing especially on the coupling of thiols with aryl- and vinyl halides based on different metals. PMID:24443103

  14. Highest performance in 3D metal cutting at smallest footprint: benchmark of a robot based system vs. parameters of gantry systems

    Scheller, Torsten; Bastick, André; Michel-Triller, Robert; Manzella, Christon

    2014-02-01

    In the automotive industry as well as in other industries ecological aspects regarding energy savings are driving new technologies and materials, e.g. lightweight materials as aluminium or press hardened steels. Processing such parts especially complex 3D shaped parts laser manufacturing has become the key process offering highest efficiency. The most established systems for 3D cutting applications are based on gantry systems. The disadvantage of those systems is their huge footprint to realize the required stability and work envelope. Alternatively a robot based system might be of advantage if accuracy, speed and overall performance would be capable processing automotive parts. With the BIM "beam in motion" system, JENOPTIK Automatisierungstechnik GmbH has developed a modular robot based laser processing machine, which meets all OEM specs processing press hardened steel parts. A benchmark of the BIM versus a gantry system was done regarding all required parameters to fulfil OEM specifications for press hardened steel parts. As a result a highly productive, accurate and efficient system can be described based on one or multiple robot modules working simultaneously together. The paper presents the improvements on the robot machine concept BIM addressed in 2012 [1] leading to an industrial proven system approach for the automotive industry. It further compares the performance and the parameters for 3D cutting applications of the BIM system versus a gantry system by samples of applied parts. Finally an overview of suitable applications for processing complex 3D parts with high productivity at small footprint is given.

  15. The pressure-induced Mott Transition in transition-metal iodides

    Pasternak, M.P. (Tel Aviv Univ. (Israel). School of Physics and Astronomy); Taylor, R.D. (Los Alamos National Lab., NM (USA)); Jeanloz, R. (California Univ., Berkeley, CA (USA). Dept. of Geology and Geophysics)

    1991-01-01

    Many of the Transition Metal (TM) compounds, because of exchange and correlation interactions within the narrow and poorly overlapping d-bands, become antiferromagnetic insulators, the Mott Insulators (MI). The properties of the MI and their gradual transition into the non-correlated metallic state (the Mott Transition) are of crucial important for the elucidation of HTS materials features in particular and to magnetism in general. The transition of the MI into a metal can be achieved either by doping or by high pressure. To yield the definitive data on the Mott transition high pressure work on well characterized materials should be sought. The present studies provide for the first time extensive information on the Mott-Hubbard gap closure induced by high pressure. High pressure studies using Diamond Anvil Cells were conducted in several (TM)I{sub 2} compounds. They all have layered structures and other antiferromagnetically at ambient pressure. {sup 129}I Moessbauer Spectroscopy (MS) was used to study the properties of the (TM){sup 2+} sublattice magnetization as a function of pressure and temperature, and X-ray diffraction was used to look for possible crystallographic transitions and to obtain the equation of state. Results show that the high pressure transition at P{sub c} from a magnetic to a non-magnetic state is not accompanied by crystallographic changes. Previous studies{sup 1} with NiI{sub 2} have confirmed the presence of a metallic state at P > P{sub c}. Inherent to the pressure behavior of the magnetic state is the gradual increase of T{sub N} in all cases and a slight increase in the TM{sup 2+} moments with pressure increase. The collapse of the magnetic state is abrupt for some cases (NiI{sub 2}) and gradual for others (CoI{sub 2}), indicative of different band-overlap mechanisms. 2 refs., 5 figs.

  16. Tangible 3D Modelling

    Hejlesen, Aske K.; Ovesen, Nis

    2012-01-01

    This paper presents an experimental approach to teaching 3D modelling techniques in an Industrial Design programme. The approach includes the use of tangible free form models as tools for improving the overall learning. The paper is based on lecturer and student experiences obtained through...

  17. Shaping 3-D boxes

    Stenholt, Rasmus; Madsen, Claus B.

    2011-01-01

    Enabling users to shape 3-D boxes in immersive virtual environments is a non-trivial problem. In this paper, a new family of techniques for creating rectangular boxes of arbitrary position, orientation, and size is presented and evaluated. These new techniques are based solely on position data...

  18. 3D Harmonic Echocardiography:

    M.M. Voormolen

    2007-01-01

    textabstractThree dimensional (3D) echocardiography has recently developed from an experimental technique in the ’90 towards an imaging modality for the daily clinical practice. This dissertation describes the considerations, implementation, validation and clinical application of a unique

  19. Structural relationships in complex hydrides of the late transition metals

    Literature data on complex hydrides of the late transition metals (groups 7-10), such as the hydrogen storage material Mg2NiH4, are reviewed with respect to order-disorder phase transitions and structural relationships. They are analysed in terms of crystallographic group-subgroup trees and their use in understanding the different crystal structures from a symmetry point of view is demonstrated. New data are presented on the low temperature behaviour of magnesium iridium hydrides and strontium rhodium hydrides studied by powder X-ray diffraction. (orig.)

  20. Pressure-induced phase transitions and metallization in VO2

    Bai, Ligang; Li, Quan; Corr, Serena A; Meng, Yue; Park, Changyong; Sinogeikin, Stanislav V.; Ko, Changhyun; Wu, Junqiao; Shen, Guoyin

    2015-01-01

    We report the results of pressure-induced phase transitions and metallization in VO2 based on synchrotron x-ray diffraction, electrical resistivity, and Raman spectroscopy. Our isothermal compression experiments at room temperature and 383 K show that the room temperature monoclinic phase (M1,P21/c) and the high-temperature rutile phase (R,P42/mnm) of VO2 undergo phase transitions to a distorted M1 monoclinic phase (M1′,P21/c) above 13.0 GPa and to an orthorhombic phase (CaCl2-like, Pnnm) abo...

  1. An Alternative Approach to the Teaching of Systematic Transition Metal Chemistry.

    Hathaway, Brian

    1979-01-01

    Presents an alternative approach to teaching Systematic Transition Metal Chemistry with the transition metal chemistry skeleton features of interest. The "skeleton" is intended as a guide to predicting the chemistry of a selected compound. (Author/SA)

  2. Nonlinear d10-ML2 Transition-Metal Complexes

    Wolters, Lando P.; Bickelhaupt, F. Matthias

    2013-01-01

    We have investigated the molecular geometries of a series of dicoordinated d10-transition-metal complexes ML2 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+; L=NH3, PH3, CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand–metal–ligand (L–M–L) angle: this angle varies from 180° to 128.6° as a function of the metal as well as the ligands. Our main objective is to present a detailed explanation why ML2 complexes can become bent...

  3. Multireference Character for 4d Transition Metal-Containing Molecules.

    Wang, Jiaqi; Manivasagam, Sivabalan; Wilson, Angela K

    2015-12-01

    Four diagnostic criteria have been examined to identify the suitability of single-reference wave function-based quantum chemistry methods for a set of 118 4d transition metal species. These diagnostics include the weight of the leading configuration of the CASSCF wave function, C0(2); the Frobenius norm of the coupled cluster amplitude vector related to single excitations, T1; the matrix 2-norm of the coupled cluster T1 amplitude vector arising from coupled cluster calculations, D1; and the percent total atomization energy, %TAE, corresponding to a relationship between energies determined with CCSD and CCSD(T) calculations. New criteria, namely, T1 ≥ 0.045, D1 ≥ 0.120, and %TAE ≥ 10%, are herein proposed as a gauge for 4d transition metal-containing molecules to predict the possible need to employ multireference (MR) wave function-based methods to describe energetic and spectroscopic properties. PMID:26642991

  4. On thermal lattice dilatation of some transition metal compounds

    The report deals with the thermal lattice dilatation of cubic transition metal compounds. The thermal dilatation is determined through the variation of the lattice constants. The measurements are carried out 'in situ' by use of a high-temperature X-ray diffractometer chamber. The evaluation relates to both the linear thermal expansion coefficient α and, for some compounds, the specific heat at constant volume Csub(V) and the Grueneisen constant γ. In general a higher thermal dilatation is observed for nitrides than for carbides with the compounds formed by the transition metals belonging to the IVA and VA groups. The influence exerted by vacancies and by the oxygen dissolved in the lattice on the thermal dilatation of carbonitrides of zirconium, hafnium and tantalum is explained by the more pronounced anharmonic character of atomic vibrations in the crystal lattice. (orig.)

  5. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    Vora, Hitesh D.; Rajamure, Ravi Shanker; Roy, Anurag; Srinivasan, S. G.; Sundararajan, G.; Banerjee, Rajarshi; Dahotre, Narendra B.

    2016-05-01

    Various physical and chemical properties of surface and subsurface regions of Al can be improved by the formation of transition metal intermetallic phases (Al x TM y ) via coating of the transition metal (TM). The lower equilibrium solid solubility of TM in Al (additive manufacturing approach can effectively synthesize TM intermetallic coatings on the surface of Al. The focus of the present work included the development of process control to achieve thermodynamic and kinetic conditions necessary for desirable physical, microstructural and compositional attributes. A multiphysics finite element model was developed to predict the temperature profile, cooling rate, melt depth, dilution of W in Al matrix and corresponding micro-hardness in the coating, and the interface between the coating and the base material and the base material.

  6. Quantum superconductor-metal transition in a proximity array

    Feigel' man, M V; Larkin, A I; Skvortsov, M A [L D Landau Institute for Theoretical Physics, Russian Academy of Sciences, ul. Kosygina 2, 117940 Moscow (Russian Federation)

    2001-10-01

    A theory of the zero-temperature superconductor-metal transition is developed for an array of superconductive islands (of size d) coupled via a disordered two-dimensional conductor with the dimensionless conductance g = h/e{sup 2} R{sub {open_square}} >> 1. At T = 0 macroscopically superconductive state of the array with lattice spacing b >> d is destroyed at g < g{sub c} {approx} 0.1 ln{sup 2} (b/d). At high temperatures the normal-state resistance between neighboring islands at b = b{sub c} is much smaller than R{sub Q} = h/4e{sup 2}. (5. superconductor-metal-insulator transitions)

  7. Engineering skyrmions in transition-metal multilayers for spintronics

    Dupé, B.; Bihlmayer, G.; Böttcher, M.; Blügel, S.; Heinze, S.

    2016-06-01

    Magnetic skyrmions are localized, topologically protected spin structures that have been proposed for storing or processing information due to their intriguing dynamical and transport properties. Important in terms of applications is the recent discovery of interface stabilized skyrmions as evidenced in ultra-thin transition-metal films. However, so far only skyrmions at interfaces with a single atomic layer of a magnetic material were reported, which greatly limits their potential for application in devices. Here we predict the emergence of skyrmions in [4d/Fe2/5d]n multilayers, that is, structures composed of Fe biatomic layers sandwiched between 4d and 5d transition-metal layers. In these composite structures, the exchange and the Dzyaloshinskii-Moriya interactions that control skyrmion formation can be tuned separately by the two interfaces. This allows engineering skyrmions as shown based on density functional theory and spin dynamics simulations.

  8. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    Vora, Hitesh D.; Rajamure, Ravi Shanker; Roy, Anurag; Srinivasan, S. G.; Sundararajan, G.; Banerjee, Rajarshi; Dahotre, Narendra B.

    2016-07-01

    Various physical and chemical properties of surface and subsurface regions of Al can be improved by the formation of transition metal intermetallic phases (Al x TM y ) via coating of the transition metal (TM). The lower equilibrium solid solubility of TM in Al (additive manufacturing approach can effectively synthesize TM intermetallic coatings on the surface of Al. The focus of the present work included the development of process control to achieve thermodynamic and kinetic conditions necessary for desirable physical, microstructural and compositional attributes. A multiphysics finite element model was developed to predict the temperature profile, cooling rate, melt depth, dilution of W in Al matrix and corresponding micro-hardness in the coating, and the interface between the coating and the base material and the base material.

  9. Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides

    Mak, Kin Fai; Shan, Jie

    2016-04-01

    Recent advances in the development of atomically thin layers of van der Waals bonded solids have opened up new possibilities for the exploration of 2D physics as well as for materials for applications. Among them, semiconductor transition metal dichalcogenides, MX2 (M = Mo, W; X = S, Se), have bandgaps in the near-infrared to the visible region, in contrast to the zero bandgap of graphene. In the monolayer limit, these materials have been shown to possess direct bandgaps, a property well suited for photonics and optoelectronics applications. Here, we review the electronic and optical properties and the recent progress in applications of 2D semiconductor transition metal dichalcogenides with emphasis on strong excitonic effects, and spin- and valley-dependent properties.

  10. Structural models for amorphous transition metal binary alloys

    A dense random packing of 445 hard spheres with two different diameters in a concentration ratio of 3 : 1 was hand-built to simulate the structure of amorphous transition metal-metalloid alloys. By introducing appropriate pair potentials of the Lennard-Jones type, the structure is dynamically relaxed by minimizing the total energy. The radial distribution functions (RDF) for amorphous Fe0.75P0.25, Ni0.75P0.25, Co0.75P0.25 are obtained and compared with the experimental data. The calculated RDF's are resolved into their partial components. The results indicate that such dynamically constructed models are capable of accounting for some subtle features in the RDF of amorphous transition metal-metalloid alloys

  11. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    Vora, Hitesh D.; Rajamure, Ravi Shanker; Roy, Anurag; Srinivasan, S. G.; Sundararajan, G.; Banerjee, Rajarshi; Dahotre, Narendra B.

    2016-07-01

    Various physical and chemical properties of surface and subsurface regions of Al can be improved by the formation of transition metal intermetallic phases (Al x TM y ) via coating of the transition metal (TM). The lower equilibrium solid solubility of TM in Al (engineering via a laser-aided additive manufacturing approach can effectively synthesize TM intermetallic coatings on the surface of Al. The focus of the present work included the development of process control to achieve thermodynamic and kinetic conditions necessary for desirable physical, microstructural and compositional attributes. A multiphysics finite element model was developed to predict the temperature profile, cooling rate, melt depth, dilution of W in Al matrix and corresponding micro-hardness in the coating, and the interface between the coating and the base material and the base material.

  12. Engineering skyrmions in transition-metal multilayers for spintronics.

    Dupé, B; Bihlmayer, G; Böttcher, M; Blügel, S; Heinze, S

    2016-01-01

    Magnetic skyrmions are localized, topologically protected spin structures that have been proposed for storing or processing information due to their intriguing dynamical and transport properties. Important in terms of applications is the recent discovery of interface stabilized skyrmions as evidenced in ultra-thin transition-metal films. However, so far only skyrmions at interfaces with a single atomic layer of a magnetic material were reported, which greatly limits their potential for application in devices. Here we predict the emergence of skyrmions in [4d/Fe2/5d]n multilayers, that is, structures composed of Fe biatomic layers sandwiched between 4d and 5d transition-metal layers. In these composite structures, the exchange and the Dzyaloshinskii-Moriya interactions that control skyrmion formation can be tuned separately by the two interfaces. This allows engineering skyrmions as shown based on density functional theory and spin dynamics simulations. PMID:27257020

  13. Metal-insulator and charge ordering transitions in oxide nanostructures

    Singh, Sujay Kumar

    Strongly correlated oxides are a class of materials wherein interplay of various degrees of freedom results in novel electronic and magnetic phenomena. Vanadium oxides are widely studied correlated materials that exhibit metal-insulator transitions (MIT) in a wide temperature range from 70 K to 380 K. In this Thesis, results from electrical transport measurements on vanadium dioxide (VO2) and vanadium oxide bronze (MxV 2O5) (where M: alkali, alkaline earth, and transition metal cations) are presented and discussed. Although the MIT in VO2 has been studied for more than 50 years, the microscopic origin of the transition is still debated since a slew of external parameters such as light, voltage, and strain are found to significantly alter the transition. Furthermore, recent works on electrically driven switching in VO2 have shown that the role of Joule heating to be a major cause as opposed to electric field. We explore the mechanisms behind the electrically driven switching in single crystalline nanobeams of VO2 through DC and AC transport measurements. The harmonic analysis of the AC measurement data shows that non-uniform Joule heating causes electronic inhomogeneities to develop within the nanobeam and is responsible for driving the transition in VO2. Surprisingly, field assisted emission mechanisms such as Poole-Frenkel effect is found to be absent and the role of percolation is also identified in the electrically driven transition. This Thesis also provides a new insight into the mechanisms behind the electrolyte gating induced resistance modulation and the suppression of MIT in VO2. We show that the metallic phase of VO2 induced by electrolyte gating is due to an electrochemical process and can be both reversible and irreversible under different conditions. The kinetics of the redox processes increase with temperature; a complete suppression of the transition and the stabilization of the metallic phase are achievable by gating in the rutile metallic phase

  14. 金属零件3D打印技术的应用研究%The Applications and Progress of Manufacturing of Metal Parts by 3 D Printing Technology

    曾光; 韩志宇; 梁书锦; 张鹏; 陈小林; 张平祥

    2014-01-01

    Manufacturing of metal parts by 3D printing technology, as the most advanced and potential technology of 3D printing technologies, presents the most important direction of modern advanced manufacturing technologies .With the de-velopment of science and technology constantly demanding for materials , utilizing the rapid proto-typing technology to pro-duce metal functional parts directly will be the main research direction.3D printing technology is rapidly changing our tra-ditional production mode and life style.3D printing manufacturing technology, which is networked and personalized, will drive the third industrial revolution.Laser engineered net shaping (LENS), selective laser melting (SLM) and electron beam selective melting ( EBSM) are the typical representatives of the metal parts 3D printing technology.Based on the three types of technologies, the metal parts 3D printing technology and its basic principles and application fields are intro-duced.At last, the development prospect of the printing technology is discussed .%金属零件3D打印技术作为整个3D打印体系中最为前沿和最具潜力的技术,是目前先进制造技术的重要发展方向。随着科技发展对材料的不断需求,利用快速成形技术直接制造金属功能零件将会成为该技术的主要发展方向。3D打印技术正在快速改变着人们传统的生产方式和生活方式。以数字化、网络化、个性化、定制化为特点的3D打印制造技术被外界认为将推动第三次工业革命。激光工程化净成形技术(LENS),激光选区熔化技术(SLM)及电子束选区熔化技术(EBSM)3种技术是金属零件3D打印技术的典型代表。对金属零件3D打印技术,包括基本的技术原理及其技术应用领域进行了介绍,最后对金属零件3D打印技术的发展进行了展望。

  15. Synthesis and Characterization of Few Layer Semiconducting Transition Metal Dichalcogenides

    Mann, John Calif

    2013-01-01

    The intense interest in graphene as the prototypical 2D electronic material has recently been accompanied by the investigation of layered transition metal dichalcogenides (TMDC), most notably MoS2 and MoSe2. Like graphene, they can be prepared in a stable form down to monolayer thickness. These materials provide favorable mechanical properties similar to graphene, but exhibit an intrinsic indirect band gap that crossovers to a direct band gap in the monolayer limit without the need for nanos...

  16. Ab initio calculations of temperature dependent resistivity for transition metals

    Wagenknecht, D.; Turek, Ilja; Carva, K.

    Praha : Matfyzpress, 2015 - (Šafránková, J.; Pavlů, J.), s. 42-47 ISBN 978-80-7378-311-2. [Week of Doctoral Students 2015. Praha (CZ), 02.06.2015-04.06.2015] R&D Projects: GA ČR GA15-13436S Institutional support: RVO:68081723 Keywords : electrical resistivity * temperature dependence * transition metals Subject RIV: BM - Solid Matter Physics ; Magnetism

  17. Applications of Transition Metals in Organic Synthesis and Polymerization

    Praveen; K.Tandon; Manish; Srivastava; Santosh; B.Singh

    2007-01-01

    1 Results Classic oxidants require rigorous control of the experimental conditions added with the problem of lack of selectivity. Catalysis by transition metals with environmentally safe oxidants provides synthetic routes to minimize pollution by giving environmental benign by-products. Fe (Ⅵ) is a powerful and a selective oxidant with Fe(Ⅲ) as a by-product, while hydrogen peroxide is clean with water as the only by-product. Separation of sodium or potassium ferrates requires tedious processes. Associat...

  18. Excitonic linewidth and coherence lifetime in monolayer transition metal dichalcogenides

    Selig, Malte; Berghäuser, Gunnar; Raja, Archana; Nagler, Philipp; Schüller, Christian; Heinz, Tony F.; Korn, Tobias; Chernikov, Alexey; Malic, Ermin; Knorr, Andreas

    2016-01-01

    Atomically thin transition metal dichalcogenides (TMDs) are direct-gap semiconductors with strong light-matter and Coulomb interaction. The latter accounts for tightly bound excitons, which dominate the optical properties of these technologically promising materials. Besides the optically accessible bright excitons, these systems exhibit a variety of dark excitonic states. They are not visible in optical spectra, but can strongly influence the coherence lifetime and the linewidth of the emiss...

  19. Two dimensional transition metal dichalcogenides grown by chemical vapor deposition

    Tsang, Ka-yi; 曾家懿

    2014-01-01

    An atomically thin film of semiconducting transition metal dichalcogenides (TMDCs) is emerging as a class of key materials in chemistry and physics due to their remarkable chemical and electronic properties. The TMDCs are layered materials with weak out-of-plane van der Waals (vdW) interaction and strong in-plane covalent bonding enabling scalable exfoliation into two-dimensional (2D) layers of atomic thickness. The growth techniques to prepare these 2D TMDC materials in high yield and large ...

  20. Planar defects and dislocations in transition metal disilicides

    Paidar, Václav

    Boston: John Wiley & Sons, 2013 - (Marquis, F.), s. 431-437 ISBN 978-1-63266-000-8. [Pacific Rim International Congress on Advanced Materials and Processing 2013 /8./ (PRICM-8). Waikoloa (US), 04.08.2013-09.08.2013] R&D Projects: GA AV ČR IAA100100920 Grant ostatní: AV ČR(CZ) M100411202 Institutional support: RVO:68378271 Keywords : transition metal disilicides * dislocation cores * stacking faults Subject RIV: BM - Solid Matter Physics ; Magnetism