In Vitro Biocompatibility of Si Alloyed Multi-Principal Element Carbide Coatings

PubMed Central

Vladescu, Alina; Titorencu, Irina; Dekhtyar, Yuri; Jinga, Victor; Pruna, Vasile; Balaceanu, Mihai; Dinu, Mihaela; Pana, Iulian; Vendina, Viktorija

2016-01-01

In the current study, we have examined the possibility to improve the biocompatibility of the (TiZrNbTaHf)C through replacement of either Ti or Ta by Si. The coatings were deposited on Si and 316L stainless steel substrates by magnetron sputtering in an Ar+CH4 mixed atmosphere and were examined for elemental composition, chemical bonds, surface topography, surface electrical charge and biocompatible characteristics. The net surface charge was evaluated at nano and macroscopic scale by measuring the electrical potential and work function, respectively. The biocompatible tests comprised determination of cell viability and cell attachment to the coated surface. The deposited coatings had C/(metal+Si) ratios close to unity, while a mixture of metallic carbide, free-carbon and oxidized species formed on the film surface. The coatings’ surfaces were smooth and no influence of surface roughness on electrical charge or biocompatibility was found. The biocompatible characteristics correlated well with the electrical potential/work function, suggesting a significant role of surface charge in improving biocompatibility, particularly cell attachment to coating's surface. Replacement of either Ti or Ta by Si in the (TiZrNbTaHf)C coating led to an enhanced surface electrical charge, as well as to superior biocompatible properties, with best results for the (TiZrNbSiHf)C coating. PMID:27571361

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor.

PubMed

von Rohr, Fabian; Winiarski, Michał J; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-11-15

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.

A model for Nb-Zr-REE-Ga enrichment in Lopingian altered alkaline volcanic ashes: Key evidence of H-O isotopes

NASA Astrophysics Data System (ADS)

Dai, Shifeng; Nechaev, Victor P.; Chekryzhov, Igor Yu.; Zhao, Lixin; Vysotskiy, Sergei V.; Graham, Ian; Ward, Colin R.; Ignatiev, Alexander V.; Velivetskaya, Tatyana A.; Zhao, Lei; French, David; Hower, James C.

2018-03-01

Clay-altered volcanic ash with highly-elevated concentrations of Nb(Ta), Zr(Hf), rare earth elements (REE), and Ga, is a new type of critical metal deposit with high commercial prospects that has been discovered in Yunnan Province, southwest China. Previous studies showed that the volcanic ashes had been subjected to hydrothermal fluids, the nature of which, however, is not clear. Here we show that the volcanic ashes were originated from alkaline magmatism, followed by a continuous hydrothermal-weathering process. Heated meteoric waters, which were sourced from acidic rains and mixed with CO2 from degassing of the Emeishan plume, have caused partial, but widespread, acidic leaching of Nb, Ta, Zr, Hf, REE, and Ga into ground water and residual enrichment of these elements, along with Al and Ti, in the deeply altered rocks. Subsequent alteration occurring under cooler, neutral or alkaline conditions, caused by water-rock interaction, resulted in precipitation of the leached critical metals in the deposit. Polymetallic mineralization of similar origin may be found in other continental regions subjected to explosive alkaline volcanism associated with deep weathering in humid conditions.

Search for New Superconductors for Energy and Power Applications

DTIC Science & Technology

2014-10-21

superconductors, borides , carbides, silicides, and chalcogenides. In addition, a number of thin film systems have been explored: A15s, superlattices, arrays of...YBa2Cu3O7 Bi2Se3 Eu-Si-C ErRh4B4 Bi2Sr2CaCu2O8 (UD, OD) Sb2Se3 V-Si-C (Ga,Mn)As CuO ZrSe2 Sm-Si-C Hf(FeCo)P Y1-xCaxCrO3 Fe-Te-Se BORIDES Hf-Fe-C-P...Physics, Warsaw, Poland Table III New superconductors, discovered by UCSD MURI team. BORIDES Tc (K) Nb0.9Zr0.1B 11.2 ZrNbxB 9.0 ZrVxB 9.0

Effect of component substitution on the atomic dynamics in glass-forming binary metallic melts

NASA Astrophysics Data System (ADS)

Nowak, B.; Holland-Moritz, D.; Yang, F.; Voigtmann, Th.; Evenson, Z.; Hansen, T. C.; Meyer, A.

2017-08-01

We investigate the substitution of early transition metals (Zr, Hf, and Nb) in Ni-based binary glass-forming metallic melts and the impact on structural and dynamical properties by using a combination of neutron scattering, electrostatic levitation (ESL), and isotopic substitution. The self-diffusion coefficients measured by quasielastic neutron scattering (QENS) identify a sluggish diffusion as well as an increased activation energy by almost a factor of 2 for Hf35Ni65 compared to Zr36Ni64 . This finding can be explained by the locally higher packing density of Hf atoms in Hf35Ni65 compared to Zr atoms in Zr36Ni64 , which has been derived from interatomic distances by analyzing the measured partial structure factors. Furthermore, QENS measurements of liquid Hf35Ni65 prepared with 60Ni , which has a vanishing incoherent scattering cross section, have demonstrated that self-diffusion of Hf is slowed down compared to the concentration weighted self-diffusion of Hf and Ni. This implies a dynamical decoupling between larger Hf and smaller Ni atoms, which can be related to a saturation effect of unequal atomic nearest-neighbor pairs, that was observed recently for Ni-rich compositions in Zr-Ni metallic melts. In order to establish a structure-dynamics relation, measured partial structure factors have been used as an input for mode-coupling theory (MCT) of the glass transition to calculate self-diffusion coefficients for the different atomic components. Remarkably, MCT can reproduce the increased activation energy for Hf35Ni65 as well as the dynamical decoupling between Hf and Ni atoms.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

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

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Alloy design for intrinsically ductile refractory high-entropy alloys

NASA Astrophysics Data System (ADS)

Sheikh, Saad; Shafeie, Samrand; Hu, Qiang; Ahlström, Johan; Persson, Christer; Veselý, Jaroslav; Zýka, Jiří; Klement, Uta; Guo, Sheng

2016-10-01

Refractory high-entropy alloys (RHEAs), comprising group IV (Ti, Zr, Hf), V (V, Nb, Ta), and VI (Cr, Mo, W) refractory elements, can be potentially new generation high-temperature materials. However, most existing RHEAs lack room-temperature ductility, similar to conventional refractory metals and alloys. Here, we propose an alloy design strategy to intrinsically ductilize RHEAs based on the electron theory and more specifically to decrease the number of valence electrons through controlled alloying. A new ductile RHEA, Hf0.5Nb0.5Ta0.5Ti1.5Zr, was developed as a proof of concept, with a fracture stress of close to 1 GPa and an elongation of near 20%. The findings here will shed light on the development of ductile RHEAs for ultrahigh-temperature applications in aerospace and power-generation industries.

NMR study of B-2p Fermi-level density of states in the transition metal diborides

NASA Astrophysics Data System (ADS)

Lue, C. S.; Lai, W. J.

2005-04-01

We present a systematic study of the AlB2-type transition metal diborides by measuring the 11B NMR spin-lattice relaxation rate on TiB2, VB2, ZrB2, NbB2, HfB2, as well as TaB2. For all studied materials, the observed relaxation at B nuclei is mainly due to the p-electrons. The comparison with theoretical calculations allows the experimental determination of the partial B-2p Fermi-level density of states (DOS). In addition, the extracted B-2p Fermi-level DOS values in TiB2, ZrB2, and HfB are consistently smaller than in VB2, NbB2, and TaB2. We connect this trend to the rigid-band scenario raised by band structure calculations.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

PubMed Central

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-01-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials. PMID:27803330

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

DOE PAGES

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; ...

2016-11-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Ceramic plasma-sprayed coating of melting crucibles for casting metal fuel slugs

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

K.H. Kim; C.T. Lee; C.B. Lee

2013-10-01

Thermal cycling and melt reaction studies of ceramic coatings plasma-sprayed on Nb substrates were carried out to evaluate the performance of barrier coatings for metallic fuel casting applications. Thermal cycling tests of the ceramic plasma-sprayed coatings to 1450 degrees C showed that HfN, TiC, ZrC, and Y2O3 coating had good cycling characteristics with few interconnected cracks even after 20 cycles. Interaction studies by 1550 degrees C melt dipping tests of the plasma-sprayed coatings also indicated that HfN and Y2O3 do not form significant reaction layer between U–20 wt.% Zr melt and the coating layer. Plasma-sprayed Y2O3 coating exhibited the mostmore » promising characteristics among HfN, TiC, ZrC, and Y2O3 coating.« less

Adsorption and diffusion of Au atoms on the (001) surface of Ti, Zr, Hf, V, Nb, Ta, and Mo carbides.

PubMed

Florez, Elizabeth; Viñes, Francesc; Rodriguez, Jose A; Illas, Francesc

2009-06-28

The adsorption of atomic Au on the (001) surface of TiC, ZrC, HfC, VC, NbC, TaC, and delta-MoC and the mechanism of diffusion of this adatom through the surface have been studied in terms of a periodic density functional theory based approach. In all the cases, the Au adsorption energies are in the range of 1.90-2.35 eV. The moderately large adsorption energies allow the Au diffusion before desorption could take place. For TiC(001), ZrC(001), and HfC(001), atomic Au is adsorbed directly on top of C atoms and diffusion takes place along the diagonal of the squares formed by M-C-M-C atoms with the transition state located above the hollow sites. For the rest of transition metal carbides the situation is less simple with the appearance of more than one stable adsorption site, as for NbC and TaC, of a small energy barrier for diffusion around the most stable adsorption site and of a more complex diffusion pathway. The small energy barrier for diffusion around the most stable site will result in a highly mobile Au species which could be observed in scanning tunnel microscope experiments. After depositing Au on metal-carbide surfaces, there is a noticeable charge transfer from the substrate to the adsorbed Au atom. The electronic perturbations on Au increase when going from TiC to ZrC or TaC. Our results indicate that metal carbides should be better supports for the chemical activation of Au than metal oxides.

Effect of Cold Deformation and Annealing on the Microstructure and Tensile Properties of a HfNbTaTiZr Refractory High Entropy Alloy

NASA Astrophysics Data System (ADS)

Senkov, O. N.; Pilchak, A. L.; Semiatin, S. L.

2018-07-01

The microstructure and tensile properties of HfNbTaTiZr after cold working and annealing were investigated. Cold work was introduced by axial compression followed by rolling resulting in a total thickness reduction of 89 pct without any evidence of cracking. The cold-worked material retained a single-phase microstructure and had a room temperature tensile yield stress σ 0.2 = 1438 MPa, peak true stress σ p = 1495 MPa, and true fracture strain ɛ f = 5 pct. Annealing at 800 °C for up to 256 hours resulted in the precipitation of Nb and Ta rich particles with a BCC crystal structure inside a Hf-and-Zr-enriched BCC matrix. The second phase particles nucleated heterogeneously inside deformation bands and slip lines and coarsened during annealing. Analysis of the coarsening behavior suggested that kinetics were controlled by the diffusion of Nb and Ta. In the two-phase material, σ 0.2 and σ p decreased from 1159 to 1071 MPa and from 1174 to 1074 MPa, respectively, with an increase in particle diameter from 0.18 to 0.72 μm, while ɛ f remained between 5 and 8 pct. Full recrystallization and normal grain growth, with the activation energy of 238 kJ/mol and activation volume of 5.3 to 9.6 m3/mol, occurred during annealing above 1000 °C. After heat treatment at this temperature, the alloy was characterized by a single-phase BCC structure with σ 0.2 = 1110 to 1115 MPa, σ p = 1160 to 1195 MPa, and ɛ f = 12 to 19 pct with the maximum values attained after annealing for 1 hour.

Effect of Cold Deformation and Annealing on the Microstructure and Tensile Properties of a HfNbTaTiZr Refractory High Entropy Alloy

NASA Astrophysics Data System (ADS)

Senkov, O. N.; Pilchak, A. L.; Semiatin, S. L.

2018-05-01

The microstructure and tensile properties of HfNbTaTiZr after cold working and annealing were investigated. Cold work was introduced by axial compression followed by rolling resulting in a total thickness reduction of 89 pct without any evidence of cracking. The cold-worked material retained a single-phase microstructure and had a room temperature tensile yield stress σ 0.2 = 1438 MPa, peak true stress σ p = 1495 MPa, and true fracture strain ɛ f = 5 pct. Annealing at 800 °C for up to 256 hours resulted in the precipitation of Nb and Ta rich particles with a BCC crystal structure inside a Hf-and-Zr-enriched BCC matrix. The second phase particles nucleated heterogeneously inside deformation bands and slip lines and coarsened during annealing. Analysis of the coarsening behavior suggested that kinetics were controlled by the diffusion of Nb and Ta. In the two-phase material, σ 0.2 and σ p decreased from 1159 to 1071 MPa and from 1174 to 1074 MPa, respectively, with an increase in particle diameter from 0.18 to 0.72 μm, while ɛ f remained between 5 and 8 pct. Full recrystallization and normal grain growth, with the activation energy of 238 kJ/mol and activation volume of 5.3 to 9.6 m3/mol, occurred during annealing above 1000 °C. After heat treatment at this temperature, the alloy was characterized by a single-phase BCC structure with σ 0.2 = 1110 to 1115 MPa, σ p = 1160 to 1195 MPa, and ɛ f = 12 to 19 pct with the maximum values attained after annealing for 1 hour.

Geochemical characteristics of aluminum depleted and undepleted komatiites and HREE-enriched low-Ti tholeiites, western Abitibi greenstone belt: A heterogeneous mantle plume-convergent margin environment

NASA Astrophysics Data System (ADS)

Fan, J.; Kerrich, R.

1997-11-01

A compositionally diverse suite of komatiites, komatiitic basalts, and basalts coexist in the Tisdale volcanic assemblage of the late-Archean (˜2.7 Ga) Abitibi greenstone belt. The komatiites are characterized by a spectrum of REE patterns, from low total REE contents (9 ppm) and pronounced convex-up patterns to greater total REE (18 ppm) and approximately flat-distributions. Thorium and niobium are codepleted with LREE. Komatiites with the most convex-up patterns have low Al 2O 3 (4.7 wt%) contents and Al 2O 3/TiO 2(12) ratios; they are interpreted to be the Al-depleted variety of komatiite derived from a depleted mantle source. Those komatiites and komatiitic basalts with flatter REE patterns are characterized by greater Al 2O 3 (7.0 wt%) and near chondritic Al 2O 3/TiO 2 (20) ratios; they are interpreted to be Al-undepleted komatiites generated from trace element undepleted mantle. For the komatiites and komatiitic basalts collectively, Gd/Ybn ratios are negatively correlated with La/Smn, but positively with MgO and Ni. The spectrum of patterns is interpreted as mixing between Al, HREE, Y-depleted, and Sc-depleted komatiites and Al-undepleted komatiites in a heterogeneous mantle plume. Auminum-depleted komatiites are characterized by negative Zr and Hf anomalies, consistent with majorite garnet-liquid D's for HFSE and REEs, signifying melt segregation at depths of >400 km. Tisdale Al-undepleted komatiites and komatiitic basalts have small negative to zero Zr(Hf)/MREE fractionation, signifying melt segregation in or above the garnet stability field. Collectively, the komatiites have correlations of Zr/Zr∗ and Hf/Hf ∗ with Gd/Ybn, and hence the Zr(Hf)/MREE fractionations are unlikely to have stemmed from alteration or crustal contamination. Two types of basalts are present. Type I basalts are Mg-tholeiites with near flat REE and primitive mantle normalized patterns, compositionally similar to abundant Mg-tholeiites associated with both Al-undepleted and Al-depleted komatiites in the Abitibi belt. They have absolute concentrations and ratios of most moderately and highly compatible elements comparable to N- MORB (Zr ˜79 vs. 74, Y ˜30 vs. 28, and Zr/Y = 2.4-2.9 vs. 2.6 ), but are relatively less depleted in highly incompatible elements and lack positive Nb or P anomalies. Type II basalts are relatively aluminous (Al 2O 3 ˜ 16 wt%), with high Al 2O 3/TiO 2 (24-28) ratios. They are characterized by low Th, Nb, and LREE contents at eight to ten times chondrite, with slightly convex-up LREE patterns ( La/Smn = 0.86-0.99 ), but strongly fractionated and enriched HREEs, Y, and Sc, where Gd/Ybn = 0.50-0.55 and consistently positive Zr(Hf)/MREEs anomalies. These basalts are tentatively interpreted as low-Ti tholeiites formed in a convergent margin setting with second stage melting, induced by fluids and melts enriched in incompatible elements and Zr(Hf) relative to MREEs, of a mantle source depleted during first stage melting. They are analogous to the Phanerozoic low-Ti tholeiite - boninite association. Accordingly the Tisdale volcanic sequence records a plume-convergent margin interaction. New analyses of Al-undepleted komatiites from the classical locality at Pyke Hill in Munro Township confirm the presence of small positive anomalies of P, Zr, and Hf, with Zr/Hf ratios generally < 36. These signatures are similar in spinifex and cumulate zones signifying that they are unlikely to have resulted from alteration. The data were generated by INAA and ICP-MS using both HFHNO 3 dissolution and Na 2O 2 sinter. The lack of LREE enrichment with negative Nb, Ta, P, and Ti anomalies in any of the Tisdale or Munro komatiites confirms an intraoceanic setting for the volcanic stage of the Western Abitibi greenstone belt.

Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Shi, Wenwu; Wang, Zhiguo

2018-05-01

The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m‑1. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

High thermoelectric figure of merit by resonant dopant in half-Heusler alloys

NASA Astrophysics Data System (ADS)

Chen, Long; Liu, Yamei; He, Jian; Tritt, Terry M.; Poon, S. Joseph

2017-06-01

Half-Heusler alloys have been one of the benchmark high temperature thermoelectric materials owing to their thermal stability and promising figure of merit ZT. Simonson et al. early showed that small amounts of vanadium doped in Hf0.75Zr0.25NiSn enhanced the Seebeck coefficient and correlated the change with the increased density of states near the Fermi level. We herein report a systematic study on the role of vanadium (V), niobium (Nb), and tantalum (Ta) as prospective resonant dopants in enhancing the ZT of n-type half-Heusler alloys based on Hf0.6Zr0.4NiSn0.995Sb0.005. The V doping was found to increase the Seebeck coefficient in the temperature range 300-1000 K, consistent with a resonant doping scheme. In contrast, Nb and Ta act as normal n-type dopants, as evident by the systematic decrease in electrical resistivity and Seebeck coefficient. The combination of enhanced Seebeck coefficient due to the presence of V resonant states and the reduced thermal conductivity has led to a state-of-the-art ZT of 1.3 near 850 K in n-type (Hf0.6Zr0.4)0.99V0.01NiSn0.995Sb0.005 alloys.

A new strategy to design eutectic high-entropy alloys using simple mixture method

DOE PAGES

Jiang, Hui; Han, Kaiming; Gao, Xiaoxia; ...

2018-01-13

Eutectic high entropy alloys (EHEAs) hold promising industrial application potential, but how to design EHEA compositions remains challenging. In the present work, a simple and effective strategy by combining mixing enthalpy and constituent binary eutectic compositions was proposed to design EHEA compositions. This strategy was then applied to a series of (CoCrFeNi)M x (M = Nb, Ta, Zr, Hf) HEAs, leading to the discovery of new EHEAs, namely, CoCrFeNiNb 0.45, CoCrFeNiTa 0.4, CoCrFeNiZr 0.55 and CoCrFeNiHf 0.4. The microstructure of these new EHEAs comprised of FCC and Laves phases in the as-cast state. In conclusion, the experimental result shows thatmore » this new alloy design strategy can be used to locate new EHEAs effectively.« less

Ab Initio Predictions of Strong Interfaces in Transition-Metal Carbides and Nitrides for Superhard Nanocomposite Coating Applications

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

Hu, Chongze; Huang, Jingsong; Sumpter, Bobby G.

Conceiving strong interfaces represents an effective direction in the development of superhard nanocomposite materials for practical applications in protective coatings. Additionally, in the pursuit of engineering strong nanoscale interfaces between cubic rock-salt (B1) domains, we investigate using density functional theory (DFT) coherent interface models designed based on hexagonal (HX) NiAs and WC structures, as well as experiment. The DFT screening of a collection of transition-metal (M = Zr, Hf, Nb, Ta) carbides and nitrides indicates that the interface models provided by the HX polymorphs store little coherency strain and develop an energetic advantage as the valence-electron concentration increases. Finally, ourmore » result suggests that harnessing the polymorphism encountered in transition-metal (M = Zr, Hf, Nb, Ta) carbides and nitrides for interface design represents a promising strategy for advancing superhard nanomaterials.« less

Ab Initio Predictions of Strong Interfaces in Transition-Metal Carbides and Nitrides for Superhard Nanocomposite Coating Applications

DOE PAGES

Hu, Chongze; Huang, Jingsong; Sumpter, Bobby G.; ...

2018-04-19

Conceiving strong interfaces represents an effective direction in the development of superhard nanocomposite materials for practical applications in protective coatings. Additionally, in the pursuit of engineering strong nanoscale interfaces between cubic rock-salt (B1) domains, we investigate using density functional theory (DFT) coherent interface models designed based on hexagonal (HX) NiAs and WC structures, as well as experiment. The DFT screening of a collection of transition-metal (M = Zr, Hf, Nb, Ta) carbides and nitrides indicates that the interface models provided by the HX polymorphs store little coherency strain and develop an energetic advantage as the valence-electron concentration increases. Finally, ourmore » result suggests that harnessing the polymorphism encountered in transition-metal (M = Zr, Hf, Nb, Ta) carbides and nitrides for interface design represents a promising strategy for advancing superhard nanomaterials.« less

A new strategy to design eutectic high-entropy alloys using simple mixture method

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

Jiang, Hui; Han, Kaiming; Gao, Xiaoxia

Eutectic high entropy alloys (EHEAs) hold promising industrial application potential, but how to design EHEA compositions remains challenging. In the present work, a simple and effective strategy by combining mixing enthalpy and constituent binary eutectic compositions was proposed to design EHEA compositions. This strategy was then applied to a series of (CoCrFeNi)M x (M = Nb, Ta, Zr, Hf) HEAs, leading to the discovery of new EHEAs, namely, CoCrFeNiNb 0.45, CoCrFeNiTa 0.4, CoCrFeNiZr 0.55 and CoCrFeNiHf 0.4. The microstructure of these new EHEAs comprised of FCC and Laves phases in the as-cast state. In conclusion, the experimental result shows thatmore » this new alloy design strategy can be used to locate new EHEAs effectively.« less

Two-dimensional nitrides as highly efficient potential candidates for CO2 capture and activation.

PubMed

Morales-Salvador, Raul; Morales-García, Ángel; Viñes, Francesc; Illas, Francesc

2018-06-13

The performance of novel two-dimensional nitrides in carbon capture and storage (CCS) is analyzed for a broad range of pressures and temperatures. Employing an integrated theoretical framework where CO2 adsorption/desorption rates on the M2N (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) surfaces are derived from transition state theory and density functional theory based calculations, the present theoretical simulations consistently predict that, depending on the particular composition, CO2 can be strongly adsorbed and even activated at temperatures above 1000 K. For practical purposes, Ti2N, Zr2N, Hf2N, V2N, Nb2N, and Ta2N are predicted as the best suited materials for CO2 activation. Moreover, the estimated CO2 uptake of 2.32-7.96 mol CO2 kg-1 reinforces the potential of these materials for CO2 abatement.

Low-cost, high-strength Fe--Ni--Cr alloys for high temperature exhaust valve application

DOEpatents

Muralidharan, Govindarajan

2017-09-05

An Fe--Ni--Cr alloy is composed essentially of, in terms of wt. %: 2.4 to 3.7 Al, up to 1.05 Co, 14.8 to 15.9 Cr, 25 to 36 Fe, up to 1.2 Hf, up to 4 Mn, up to 0.6 Mo, up to 2.2 Nb, up to 1.05 Ta, 1.9 to 3.6 Ti, up to 0.08 W, up to 0.03 Zr, 0.18 to 0.27 C, up to 0.0015 N, balance Ni, wherein, in terms of atomic percent: 8.5.ltoreq.Al+Ti+Zr+Hf+Ta.ltoreq.11.5, 0.53.ltoreq.Al/(Al+Ti+Zr+Hf+Ta).ltoreq.0.65, and 0.16.ltoreq.Cr/(Fe+Ni+Cr+Mn).ltoreq.0.21, the alloy being essentially free of Cu, Si, and V.

Preconcentration of Zr, Hf, Nb, Ta and W in seawater using solid-phase extraction on TSK-8-hydroxyquinoline resin and determination by inductively coupled plasma-mass spectrometry.

PubMed

Firdaus, M Lutfi; Norisuye, Kazuhiro; Sato, Taishi; Urushihara, Shouhei; Nakagawa, Yusuke; Umetani, Shigeo; Sohrin, Yoshiki

2007-02-05

Here, we present the first simultaneous preconcentration and determination of ultratrace (pmol kg(-1) level) Zr, Hf, Nb, Ta and W in seawater, both in the form of dissolved and acid-dissolvable species. 8-Hydroxyquinoline (8HQ) bonded covalently to a vinyl polymer resin, TSK-8HQ, was used in a chelating adsorbent column to concentrate the metals. The greatest advantage of this resin is its endurance to 5M HF, since this is an effective eluent for all five metals. The analytes were successfully concentrated from 250 mL seawater with a 50-fold concentration factor through the column extraction and evaporation. The detection limit was 0.009-0.15 pmol kg(-1). The procedure blank determined using ultra pure water as a sample was 0.005-0.37 pmol kg(-1). The five metals were quantitatively recovered from seawater with good precision (2-4%). The effect of sample pH, sample flow rate, eluent composition and sample pretreatment were carefully studied. This method was applied to seawater.

The high field strength element budget of atmospheric aerosols (puy de Dôme, France)

NASA Astrophysics Data System (ADS)

Vlastelic, Ivan; Suchorski, Krzysztof; Sellegri, Karine; Colomb, Aurélie; Nauret, François; Bouvier, Laetitia; Piro, Jean-Luc

2015-10-01

High field strength elements (HFSE), including Zr, Hf, Nb, Ta and Ti have low solubility in aqueous fluids and partition into dense and resistant minerals. HFSE proved useful in studying terrestrial weathering and sediment transport, but little is known about their behavior during atmospheric processes, which play an important role in global sedimentary cycles. The atmospheric budget of HFSE is evaluated from the sequential dissolution of aerosol samples collected between 2011 and 2014 at puy de Dôme (1465 m elevation, French Massif Central). Aerosols were sampled during nighttime, while the site is generally located above the planetary boundary layer. Systematic, partial recovery of HFSE during gentle dissolution of aerosols indicates that resistant minerals are ubiquitous in air samples. Total dissolution of aerosols in pressure vessels reveals that Zr and Hf occur on average in sub-crustal abundance, which is consistent with the sampling site being dominantly influenced by oceanic air masses depleted in zircons. Conversely, zircon excess occasionally occurs in continental air masses, in particular those originating from northern Africa. Overall, the Hf/Nd ratio, a proxy for zircon fractionation, varies from 0.26 to 3.94 times the Upper Continental Crust (UCC) value, encompassing the range of worldwide loess. This wide compositional range is consistent with (1) the occurrence of coarse zircons (10-30 μm) in dust source, with possible local enrichments relative to bulk UCC in residual wind-winnowed soils, and (2) gravitational settling of coarse zircons during long-distance (>ca. 1000 km) transport. Niobium and Ta are systematically more abundant (by a mean factor of ∼3) in puy de Dôme aerosols than expected from average crustal or soil concentrations. The volume-weighted average Nb/Ta ratio of 15.5 ± 2.6 (1σ) is also higher than in bulk UCC (11.4-13.3). The positive Nb-Ta anomaly of free troposphere aerosols unlikely reflects a net Nb-Ta enrichment but might result from loss of more water-soluble elements during weathering of aerosols in clouds. Depletion in Zr-Hf (coarse zircons settling) and Nb-Ta enrichment (cloud processing) might occur during large-scale transport of mineral dust over ocean basins, which could explain the peculiar HFSE distribution in some Hawaiian soils showing inputs of Asian dust.

Anion photoelectron spectroscopy of germanium and tin clusters containing a transition- or lanthanide-metal atom; MGe(n)- (n = 8-20) and MSn(n)- (n = 15-17) (M = Sc-V, Y-Nb, and Lu-Ta).

PubMed

Atobe, Junko; Koyasu, Kiichirou; Furuse, Shunsuke; Nakajima, Atsushi

2012-07-14

The electronic properties of germanium and tin clusters containing a transition- or lanthanide-metal atom from group 3, 4, or 5, MGe(n) (M = Sc, Ti, V, Y, Zr, Nb, Lu, Hf, and Ta) and MSn(n) (M = Sc, Ti, Y. Zr, and Hf), were investigated by anion photoelectron spectroscopy at 213 nm. In the case of the group 3 elements Sc, Y, and Lu, the threshold energy of electron detachment of MGe(n)(-) exhibits local maxima at n = 10 and 16, while in the case of the group 4 elements Ti, Zr, and Hf, it exhibits a local minimum only at n = 16, associated with the presence of a small bump in the spectrum. A similar behavior is observed for MSn(n)(-) around n = 16, and these electronic characteristics of MGe(n) and MSn(n) are closely related to those of MSi(n). Compared to MSi(n), however, the larger cavity size of a Ge(n) cage allows metal atom encapsulation at a smaller size n. A cooperative effect between the electronic and geometric structures of clusters with a large cavity of Ge(16) or Sn(16) is discussed together with the results of experiments that probe their geometric stability via their reactivity to H(2)O adsorption.

Microstructural investigation of plastically deformed Ti{sub 20}Zr{sub 20}Hf{sub 20}Nb{sub 20}Ta{sub 20} high entropy alloy by X-ray diffraction and transmission electron microscopy

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

Dirras, G., E-mail: dirras@univ-paris13.fr; Gubicza, J.; Heczel, A.

2015-10-15

The microstructure evolution in body-centered cubic (bcc) Ti{sub 20}Zr{sub 20}Hf{sub 20}Nb{sub 20}Ta{sub 20} high entropy alloy during quasi-static compression test was studied by X-ray line profile analysis (XLPA) and transmission electron microscopy (TEM). The average lattice constant and other important parameters of the microstructure such as the mean crystallite size, the dislocation density and the edge/screw character of dislocations were determined by XLPA. The elastic anisotropy factor required for XLPA procedure was determined by nanoindentation. XLPA shows that the crystallite size decreased while the dislocation density increased with strain during compression, and their values reached about 39 nm and 15more » × 10{sup 14} m{sup −2}, respectively, at a plastic strain of ~ 20%. It was revealed that with increasing strain the dislocation character became more screw. This can be explained by the reduced mobility of screw dislocations compared to edge dislocations in bcc structures. These observations are in line with TEM investigations. The development of dislocation density during compression was related to the yield strength evolution. - Highlights: • Ti{sub 20}Zr{sub 20}Hf{sub 20}Nb{sub 20}Ta{sub 20} high entropy alloy was processed by arc-melting. • The mechanical was evaluated by RT compression test. • The microstructure evolution was studied by XLPA and TEM. • With increasing strain the dislocation character became more screw. • The yield strength was related to the development of the dislocation density.« less

Thermal expansion of quaternary nitride coatings

NASA Astrophysics Data System (ADS)

Tasnádi, Ferenc; Wang, Fei; Odén, Magnus; Abrikosov, Igor A.

2018-04-01

The thermal expansion coefficient of technologically relevant multicomponent cubic nitride alloys are predicted using the Debye model with ab initio elastic constants calculated at 0 K and an isotropic approximation for the Grüneisen parameter. Our method is benchmarked against measured thermal expansion of TiN and Ti(1-x)Al x N as well as against results of molecular dynamics simulations. We show that the thermal expansion coefficients of Ti(1-x-y)X y Al x N (X  =  Zr, Hf, Nb, V, Ta) solid solutions monotonously increase with the amount of alloying element X at all temperatures except for Zr and Hf, for which they instead decrease for y≳ 0.5 .

Extended HFSE systematics of Apollo samples - wrenching further Secrets from the Lunar Mantle

NASA Astrophysics Data System (ADS)

Thiemens, M. M.; Sprung, P.; Munker, C.

2016-12-01

As Earth's intimate companion, the Moon provides a close extraterrestrial view on planetary differentiation. In turn, investigating chemical and isotopic compositions of lunar rocks for traces of a putative crystallizing Lunar Magma Ocean (LMO) provides a better understanding of the evolution and differentiation of infant planetary bodies.We expand on high-precision extended High Field Strength Element (HFSE) observations of Münker [1]. In detail, we investigate if the HFSE systematics of low- and high- Ti basalts, KREEPy basalts and breccias, soils, and ferroan anorthosites (FAN) are consistent with their formation from the LMO (FAN, KREEP) or mantle sources comprising mixtures of primary LMO products [2] (mare basalts). Of particular interest is the recently discovered dependence of HFSE partitioning on the Ti-concentration of co-existing melts [3] and that of W partitioning on oxygen fugacity [3,4].Our data form a positively correlated array in Zr/Hf vs. Nb/Ta space, similar to previous high-precision [1] but unlike lower-precision data. The HFSE systematics of different rock types from the Apollo missions mostly form distinct groups. High-Ti and some Apollo 12 low-Ti mare basalts form the lower end of the array, KREEPy samples its upper end. Low Zr/Nb in most high-Ti mare basalts and the globally highest Hf/W confirm involvement of Ti-rich-oxide-bearing cumulates in high-Ti formation [e.g., 1,2]. No global lunar trends exist for Hf/W vs. Zr/Nb. Overall, the composition of KREEPy samples agrees reasonably well with model KREEP-compositions assuming a LMO below IW-1 [1,4].Clearly distinct groupings observed for the various rock types and the lack of a global trend in Hf/W vs. Zr/Nb calls for melting of distinct ultramafic sources [1]. The HFSE systematics of Apollo rocks tend to support a LMO scenario, setting the stage for more detailed petrogenetic modeling. Initial modeling suggests that the lunar mantle must possess residual metal to reconcile the HFSE systematics of Apollo rocks within an LMO-scenario, providing an alternative explanation for the very low abundances of HSE in the lunar crust [5].[1] Münker, C. (2010) GCA 74, 7340-7361. [2] Snyder et al. (1992) GCA 56, 3809-3823. [3] Leitzke et al. (in press) Chem. Geol. [4] Fonseca et al. (2014) EPSL 404, 1-13. [5] Day & Walker (2015) EPSL 423, 114-124

Purification of nuclear grade Zr scrap as the high purity dense Zr deposits from Zirlo scrap by electrorefining in LiF-KF-ZrF4 molten fluorides

NASA Astrophysics Data System (ADS)

Park, Kyoung Tae; Lee, Tae Hyuk; Jo, Nam Chan; Nersisyan, Hayk H.; Chun, Byong Sun; Lee, Hyuk Hee; Lee, Jong Hyeon

2013-05-01

Zirconium (Zr) has commonly been used as a cladding material of nuclear fuel. Moreover, it is regarded as the only material that can be used for nuclear fuel cladding because it has the lowest neutron capture cross section of any metal element and because it has high corrosion resistance and size stability. In this study, Hf-free Zr tubes (Zr-1Nb-1Sn-0.1Fe) were used as anode materials and electrorefining was performed in a LiF-KF eutectic 6 wt.% ZrF4 molten fluoride salt system. As a result of electrolysis, Zr scrap metal was recycled into pure Zr with low levels of impurities, and the size and density of the Zr deposit was controlled using applied current density.

Lanthanide Contraction as a Design Factor for High-Performance Half-Heusler Thermoelectric Materials.

PubMed

Liu, Yintu; Fu, Chenguang; Xia, Kaiyang; Yu, Junjie; Zhao, Xinbing; Pan, Hongge; Felser, Claudia; Zhu, Tiejun

2018-06-25

Forming solid solutions, as an effective strategy to improve thermoelectric performance, has a dilemma that alloy scattering will reduce both the thermal conductivity and carrier mobility. Here, an intuitive way is proposed to decouple the opposite effects, that is, using lanthanide contraction as a design factor to select alloying atoms with large mass fluctuation but small radius difference from the host atoms. Typical half-Heusler alloys, n-type (Zr,Hf)NiSn and p-type (Nb,Ta)FeSb solid solutions, are taken as paradigms to attest the validity of this design strategy, which exhibit greatly suppressed lattice thermal conductivity and maintained carrier mobility. Furthermore, by considering lanthanide contraction, n-type (Zr,Hf)CoSb-based alloys with high zT of ≈1.0 are developed. These results highlight the significance of lanthanide contraction as a design factor in enhancing the thermoelectric performance and reveal the practical potential of (Zr,Hf)CoSb-based half-Heusler compounds due to the matched n-type and p-type thermoelectric performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure, Tensile and Creep Properties of Ta20Nb20Hf20Zr20Ti20 High Entropy Alloy

PubMed Central

Larianovsky, Natalya; Katz-Demyanetz, Alexander; Eshed, Eyal; Regev, Michael

2017-01-01

This paper examines the microstructure and mechanical properties of Ta20Nb20Hf20Zr20Ti20. Two casting processes, namely, gravity casting and suction-assisted casting, were applied, both followed by Hot Isostatic Pressing (HIP). The aim of the current study was to investigate the creep and tensile properties of the material, since the literature review revealed no data whatsoever regarding these properties. The main findings are that the HIP process is responsible for the appearance of a Hexagonal Close Packed (HCP) phase that is dispersed differently in these two castings. The HIP process also led to a considerable increase in the mechanical properties of both materials under compression, with values found to be higher than those reported in the literature. Contrary to the compression properties, both materials were found to be highly brittle under tension, either during room temperature tension tests or creep tests conducted at 282 °C. Fractography yielded brittle fracture without any evidence of plastic deformation prior to fracture. PMID:28773245

Compressive creep behavior of alloys based on B2 FeAl

NASA Technical Reports Server (NTRS)

Mantravadi, N.; Vedula, K.; Gaydosh, D.; Titran, R. H.

1986-01-01

Alloys based on FeAl are attractive alternate materials for environmental resistance at intermediate temperatures. Addition of small amounts of Nb, Hf, Ta, Mo, Zr, and B were shown to improve the compressive creep of this alloy at 1100 K. Boron, in particular, was found to have a synergistic effect along with Zr in providing properties substantially better than the binary alloy. This improvement seems to be related to the higher activation energy found for this alloy, suggesting a modification in the diffusion behavior due to the alloying additions.

Compressive creep behavior of alloys based on B2 FeAl

NASA Technical Reports Server (NTRS)

Mantravadi, N.; Vedula, K.; Gaydosh, D.; Titran, R. H.

1987-01-01

Alloys based on FeAl are attractive alternative materials for environmental resistance at intermediate temperatures. Addition of small amounts of Nb, Hf, Ta, Mo, Zr, and B were shown to improve the compressive creep of this alloy at 1100 K. Boron, in particular, was found to have a synergistic effect along with Zr in providing properties substantially better than the binary alloy. This improvement seems to be related to the higher activation energy found for this alloy, suggesting a modification in the diffusion behavior due to the alloying additions.

Transport and magnetic properties of HITPERM alloys

NASA Astrophysics Data System (ADS)

Pekala, K.; Latuch, J.; Pekala, M.; Skorvanek, I.; Jaskiewicz, P.

2003-02-01

Nanocrystalline HITPERM alloys Fe44.6Co43.3X7.4B3.7Cu1 (X = Nb, Zr, Hf) prepared by crystallization of amorphous precursors are studied by magnetization and electrical resistivity measurements for the first time. Structural and magnetic components of the electrical resistivity are separated. The electrical resistivity of the nanocrystalline α' (FeCo) phase calculated using the Maxwell Garnett relation proves strong electron scattering on the grain boundaries. The temperature variation of the crystalline fraction during the first crystallization stage is calculated for the Hf based alloy.

Polyorganometallosiloxane-2- or -4-pyridine coatings

DOEpatents

Sugama, Toshifumi

1997-01-01

A new family of polyorganometallosiloxane-2- or -4-pyridine compounds are provided for corrosion resistant coatings on light metals such as aluminum, magnesium, zinc, steel and their allows. The novel compounds contain backbones modified by metal alkoxides, metallocenes and metallophthalocyanates where the metal is Zr, Ti, Mo, V, Hf, Nb, Si, B and combinations thereof. Methods of making the new compounds are also provided.

Fluorite transition metal hydride induced destabilization of the MgH2 system in MgH2/TMH2 multilayers ( TM=Sc , Ti, V, Cr, Y, Zr, Nb, La, Hf)

NASA Astrophysics Data System (ADS)

Tao, S. X.; Notten, P. H. L.; van Santen, R. A.; Jansen, A. P. J.

2010-09-01

The structural changes in MgH2 induced by contact with fluorite transition metal hydrides ( TMH2 , TM=Sc , Ti, V, Cr, Y, Zr, Nb, La, Hf) have been studied using density-functional theory calculations. Models of MgH2(rutile)/TiH2(fluorite) and MgH2(fluorite)/TiH2(fluorite) multilayers with different Mg:TM ratios have been designed. With a fixed thickness of the TMH2 layer, structure transformation of MgH2 from rutile to fluorite occurs with a decrease in thickness of the MgH2 layer. The hydrogen desorption energy from the fluorite MgH2 layer in the multilayers is significantly lower than that of the bulk rutile MgH2 . The structural deformation of the MgH2 layer due to the strain induced by TMH2 is found to be responsible for the destabilization of the Mg-H bond: the more structural deformation, the more destabilization of the Mg-H. Our results provide an important insight for the development of new hydrogen-storage materials with desirable thermodynamic properties.

Polyorganometallosiloxane-2- or -4-pyridine coatings

DOEpatents

Sugama, T.

1997-12-30

A new family of polyorganometallosiloxane-2- or -4-pyridine compounds are provided for corrosion resistant coatings on light metals such as aluminum, magnesium, zinc, steel and their alloys. The novel compounds contain backbones modified by metal alkoxides, metallocenes and metallophthalocyanates where the metal is Zr, Ti, Mo, V, Hf, Nb, Si, B and combinations thereof. Methods of making the new compounds are also provided. 13 figs.

Nanostructured multielement (TiHfZrNbVTa)N coatings before and after implantation of N+ ions (1018 cm-2): Their structure and mechanical properties

NASA Astrophysics Data System (ADS)

Pogrebnjak, A. D.; Bondar, O. V.; Borba, S. O.; Abadias, G.; Konarski, P.; Plotnikov, S. V.; Beresnev, V. M.; Kassenova, L. G.; Drodziel, P.

2016-10-01

Multielement high entropy alloy (HEA) nitride (TiHfZrNbVTa)N coatings were deposited by vacuum arc and their structural and mechanical stability after implantation of high doses of N+ ions, 1018 cm-2, were investigated. The crystal structure and phase composition were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy, while depth-resolved nanoindentation tests were used to determine the evolution of hardness and elastic modulus along the implantation depth. XRD patterns show that coatings exhibit a main phase with fcc structure, which preferred orientation varies from (1 1 1) to (2 0 0), depending on the deposition conditions. First-principles calculations reveal that the presence of Nb atoms could favor the formation of solid solution with fcc structure in multielement HEA nitride. TEM results showed that amorphous and nanostructured phases were formed in the implanted coating sub-surface layer (∼100 nm depth). Concentration of nitrogen reached 90 at% in the near-surface layer after implantation, and decreased at higher depth. Nanohardness of the as-deposited coatings varied from 27 to 38 GPa depending on the deposition conditions. Ion implantation led to a significant decrease of the nanohardness to 12 GPa in the implanted region, while it reaches 24 GPa at larger depths. However, the H/E ratio is ⩾0.1 in the sub-surface layer due to N+ implantation, which is expected to have beneficial effect on the wear properties.

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

Qu, Wentao; Sun, Xuguang; Yuan, Bifei

The microstructures, phase transformations and shape memory properties of Ti-30Zr-xNb (x = 5, 7, 9, 13 at.%) alloys were investigated. The X-ray diffraction and transmission electron microscopy observations showed that the Ti-30Zr-5Nb, Ti-30Zr-7/9Nb and Ti-30Zr-13Nb alloys were composed of the hcp α′-martensite, orthorhombic α″-martensite and β phases, respectively. The results indicated the enhanced β-stabilizing effect of Nb in Ti-30Zr-xNb alloys than that in Ti-Nb alloys due to the high content of Zr. The differential scanning calorimetry test indicated that the Ti-30Zr-5Nb alloy displayed a reversible transformation with a high martensitic transformation start temperature of 776 K and a reverse martensiticmore » transformation start temperature (A{sub s}) of 790 K. For the Ti-30Zr-7Nb and Ti-30Zr-9Nb alloys, the martensitic transformation temperatures decreased with the increasing Nb content. Moreover, an ω phase transformation occurred in the both alloys upon heating at a temperature lower than the corresponding A{sub s}, which is prompted by more addition of Nb. Although the critical stress in tension of the three martensitic alloys decreased with increasing Nb content, the Ti-30Zr-9Nb alloy showed a critical stress of as high as 300 MPa. Among all the alloys, the Ti-30Zr-9Nb alloy exhibited the maximum shape memory effect of 1.61%, due to the lowest critical stress for the martensite reorientation. - Highlights: •Ti-30Zr-5Nb alloy is composed of hcp α′-martensite with the M{sub s} of 776 K. •Ti-30Zr-7Nb and Ti-30Zr-9Nb alloys are predominated by orthorhombic α″-martensite. •Ti-30Zr-13Nb alloy consists of a single β phase due to the β-stabilizing effect of Nb. •The martensitic transformation temperatures decrease with increasing Nb content. •Ti-30Zr-9Nb alloy shows the maximum shape memory effect of 1.61%.« less

Step tunneling enhanced asymmetry in metal-insulator-insulator-metal (MIIM) diodes for rectenna applications

NASA Astrophysics Data System (ADS)

Alimardani, N.; Conley, J. F.

2013-09-01

We combine nanolaminate bilayer insulator tunnel barriers (Al2O3/HfO2, HfO2/Al2O3, Al2O3/ZrO2) deposited via atomic layer deposition (ALD) with asymmetric work function metal electrodes to produce MIIM diodes with enhanced I-V asymmetry and non-linearity. We show that the improvements in MIIM devices are due to step tunneling rather than resonant tunneling. We also investigate conduction processes as a function of temperature in MIM devices with Nb2O5 and Ta2O5 high electron affinity insulators. For both Nb2O5 and Ta2O5 insulators, the dominant conduction process is established as Schottky emission at small biases and Frenkel-Poole emission at large biases. The energy depth of the traps that dominate Frenkel-Poole emission in each material are estimated.

Molecular dynamics simulation of liquid structure for undercooled Zr-Nb alloys assisted with electrostatic levitation experiments

NASA Astrophysics Data System (ADS)

Yang, S. J.; Hu, L.; Wang, L.; Wei, B.

2018-06-01

The liquid structures of undercooled Zr90Nb10, Zr70Nb30 and Zr50Nb50 alloys were studied by molecular dynamics simulation combined with electrostatic levitation experiments. The densities of three alloys were measured by electrostatic levitation to modify the Zr-Nb potential functions by adjusting parameters in potential functions. In simulation, the atomic packing in Zr-Nb alloys was more ordered at lower temperatures. The Voronoi tessellation analyses indicated Nb-centered clusters were easier to form than Zr-centered clusters although the Nb content was less than 50%. The partial pair distribution functions showed that the interactions among Zr atoms are quite different to that among Nb atoms.

Parametric Study of Amorphous High-Entropy Alloys formation from two New Perspectives: Atomic Radius Modification and Crystalline Structure of Alloying Elements

NASA Astrophysics Data System (ADS)

Hu, Q.; Guo, S.; Wang, J. M.; Yan, Y. H.; Chen, S. S.; Lu, D. P.; Liu, K. M.; Zou, J. Z.; Zeng, X. R.

2017-01-01

Chemical and topological parameters have been widely used for predicting the phase selection in high-entropy alloys (HEAs). Nevertheless, previous studies could be faulted due to the small number of available data points, the negligence of kinetic effects, and the insensitivity to small compositional changes. Here in this work, 92 TiZrHfM, TiZrHfMM, TiZrHfMMM (M = Fe, Cr, V, Nb, Al, Ag, Cu, Ni) HEAs were prepared by melt spinning, to build a reliable and sufficiently large material database to inspect the robustness of previously established parameters. Modification of atomic radii by considering the change of local electronic environment in alloys, was critically found out to be superior in distinguishing the formation of amorphous and crystalline alloys, when compared to using atomic radii of pure elements in topological parameters. Moreover, crystal structures of alloying element were found to play an important role in the amorphous phase formation, which was then attributed to how alloying hexagonal-close-packed elements and face-centered-cubic or body-centered-cubic elements can affect the mixing enthalpy. Findings from this work not only provide parametric studies for HEAs with new and important perspectives, but also reveal possibly a hidden connection among some important concepts in various fields.

Permian magmatic sequences of the Bilihe gold deposit in central Inner Mongolia, China: Petrogenesis and tectonic significance

NASA Astrophysics Data System (ADS)

Liu, Chunhua; Nie, Fengjun

2015-08-01

The Bilihe gold deposit is located in the eastern section of the Ondor Sum-Yanji Suture at the southern margin of the Xing'an-Mongolian Orogenic Belt (XMOB) and the northern margin of the North China Craton (NCC), central Inner Mongolia. The magmatic rocks in the ore district are generally high-K calc-alkaline, enriched in LREE, Zr, and Hf, and depleted in HREE, Nb, Ta, and P. The magmatic evolution sequences are norite gabbro → granodiorite porphyry → granite or norite gabbro → andesite → dacite porphyry → granodiorite, which show a trend of decreasing TiO2, FeO, MgO, CaO, and P2O5 with increasing SiO2. In the Bilihe ore district, hydrothermal processes were coeval with granitic magmatism for a period of ~ 17 Myr (272-255 Ma). The ages of the granite, granodiorite porphyry, granodiorite, and dacite porphyry are 271.5-264.1 Ma, 269.8-255.8 Ma, 268.3 Ma, and 268.6-259.4 Ma, respectively. The magmatic rocks contain magmatic, hydrothermal, and magmatic-hydrothermal zircons. The magmatic zircons have δCe > 4, La < 3 ppm, and SmN/LaN > 2.5; the hydrothermal zircons have δCe < 4, La > 3 ppm, and SmN/LaN < 2.5. The Nb/Ta and Zr/Hf ratios of granodiorite are 12.7-14.99 and 40.2-46.56, respectively. The Zr/Hf ratios successively increase in the sequence of granite (27.4-29.02) → granodiorite porphyry (29.19-32.18) → dacite porphyry (33.54-38.5) → norite gabbro (36.75-38.37), and their Nb/Ta ratios are 9.09-12.38. Zircons in granodiorite yield ε Hf (t) values of - 0.29 to - 56 (n = 13) and 2.07-7.62 (n = 5), and they give a Hf two-stage model age (tDM2) of 807-4765 Ma. The ε Hf (t) values of the zircons in granite, granodiorite porphyry, and dacite porphyry are - 0.46 to 8.03, 3.17 to 10.32, and - 0.78 to 6.58, respectively, and their Hf tDM2 ages are 787-1324 Ma, 638-1091 Ma, and 868-1343 Ma, respectively. Dehydration partial melting of subducted oceanic crust resulted in the formation of dacite porphyry; partial melting of depleted mantle resulted in the formation of norite gabbro; mixing of depleted mantle and lower crust resulted in the formation of granodiorite porphyry; partial melting of lower crust resulted in the formation of granite; and mixing of lower crust and old upper crust resulted in the formation of granodiorite. Magmatic rocks in the ore district with ages of 272-255 Ma were formed during the late stages of closure of the Paleoasian Ocean; i.e., during the transformation from a collisional to extensional setting.

The distribution of zirconium and hafnium in terrestrial rocks, meteorites and the moon

NASA Technical Reports Server (NTRS)

Ehmann, W. D.; Chyi, L. L.; Garg, A. N.; Ali, M. Z.

1979-01-01

It is shown that Zr and Hf are not always fractionated in terrestrial igneous differentiation or regional metamorphism. Data do support a Zr-Hf fractionation in the differentiation of the alkali olivine magma at St. Helena Island. A strong Zr-Hf fractionation exists among lunar rocks and minerals. Ilmenite is an excellent concentrator of Zr and Hf and always exhibits high Zr/Hf ratios. Chondritic meteorites exhibit rather uniform Zr abundances and Zr/Hf ratios but a distinct Zr-Hf fractionation is observed among the eucrite and diogenite achondrites.

Screening on binary Ti alloy with excellent mechanical property and castability for dental prosthesis application

PubMed Central

Li, H. F.; Qiu, K. J.; Yuan, W.; Zhou, F. Y.; Wang, B. L.; Li, L.; Zheng, Y. F.; Liu, Y. H.

2016-01-01

In the present study, the microstructure, mechanical property, castability, corrosion behavior and in vitro cytocompatibility of binary Ti–2X alloys with various alloying elements, including Ag, Bi, Ga, Ge, Hf, In, Mo, Nb, Sn and Zr, were systematically investigated, in order to assess their potential applications in dental field. The experimental results showed that all binary Ti‒2X alloys consisted entirely α–Ti phase. The tensile strength and microhardness of Ti were improved by adding alloying elements. The castability of Ti was significantly improved by separately adding 2 wt.% Bi, Ga, Hf, Mo, Nb, Sn and Zr. The corrosion resistance of Ti in both normal artificial saliva solution (AS) and extreme artificial saliva solution (ASFL, AS with 0.2 wt.% NaF and 0.3 wt.% lactic acid) has been improved by separately adding alloying elements. In addition, the extracts of studied Ti‒2X alloys produced no significant deleterious effect to both fibroblasts L929 cells and osteoblast-like MG63 cells, indicating a good in vitro cytocompatibility, at the same level as pure Ti. The combination of enhanced mechanical properties, castability, corrosion behavior, and in vitro cytocompatibility make the developed Ti‒2X alloys have great potential for future stomatological applications. PMID:27874034

Corrosion behavior and oxide properties of Zr 1.1 wt%Nb 0.05 wt%Cu alloy

NASA Astrophysics Data System (ADS)

Park, Jeong-Yong; Choi, Byung-Kwon; Yoo, Seung Jo; Jeong, Yong Hwan

2006-12-01

The corrosion behavior and oxide properties of Zr-1.1 wt%Nb-0.05 wt%Cu (ZrNbCu) and Zircaloy-4 have been investigated. The corrosion rate of the ZrNbCu alloy was much lower than that of the Zirclaoy-4 in the 360 °C water and 360 °C PWR-simulating loop condition without a neutron flux and it was increased with an increase of the final annealing temperature from 470 °C to 570 °C. TEM observations revealed that the precipitates in the ZrNbCu were β-Nb and ZrNbFe-precipitate with β-Nb being more frequently observed and that the precipitates were more finely distributed in the ZrNbCu alloy. It was also observed that the oxides of the ZrNbCu and Zircaloy-4 consisted of two and seven layers, respectively, after 1000 days in the PWR-simulating loop condition and that the thickness of a fully-developed layer was higher in the ZrNbCu than in the Zircaloy-4. It was also found that the β-Nb in ZrNbCu was oxidized more slowly when compared to the Zr(Fe, Cr) 2 in Zirclaoy-4 when the precipitates in the oxide were observed by TEM. Cracks were observed in the vicinity of the oxidized Zr(Fe, Cr) 2, while no cracks were formed near β-Nb which had retained a metallic state. From the results obtained, it is suggested that the oxide formed on the ZrNbCu has a more protective nature against a corrosion when compared to that of the Zircaloy-4.

THERMODYNAMIC PROPERTIES OF Zr AND Hf HALIDES (in Rumanian)

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

Lungu, S.N.

1962-01-01

The following standard heats of formation were found: ZrCl/sub 3/, 178.6 plus or minus 3.2; ZrCl/sub 2/, 124.3 plus or minus 3; ZrBr/sub 3/, 151 plus or minus 7; Zr Br/sbu 2/, 100 plus or minus 6; ZrI/sub 3/, 103 plus or minus 6; ZrI/sub 2/, 68 plus or minus 4; and HfCl/sub 4/, 239.4 plus or minus 5.5; HfCl/sub 3/, 186.6; HfCl/sub 2/, 130; HfBr/sub 4/, 200; HfBr/sub 3/, 157; HfBr / sub 2/, 108; HfI/sub 4/, 140; HfI/sub 3/, 113; and HfI/sub 2/, 72 kcal/mole. (R.V.J.)

Tracking magmatic processes through Zr/Hf ratios in rocks and Hf and Ti zoning in zircons: An example from the Spirit Mountain batholith, Nevada

USGS Publications Warehouse

Lowery, Claiborne L.E.; Miller, C.F.; Walker, B.A.; Wooden, J.L.; Mazdab, F.K.; Bea, F.

2006-01-01

Zirconium and Hf are nearly identical geochemically, and therefore most of the crust maintains near-chondritic Zr/Hf ratios of ???35-40. By contrast, many high-silica rhyolites and granites have anomalously low Zr/Hf (15-30). As zircon is the primary reservoir for both Zr and Hf and preferentially incorporates Zr, crystallization of zircon controls Zr/ Hf, imprinting low Zr/Hf on coexisting melt. Thus, low Zr/Hf is a unique fingerprint of effective magmatic fractionation in the crust. Age and compositional zonation in zircons themselves provide a record of the thermal and compositional histories of magmatic systems. High Hf (low Zr/ Hf) in zircon zones demonstrates growth from fractionated melt, and Ti provides an estimate of temperature of crystallization (TTiZ) (Watson and Harrison, 2005). Whole-rock Zr/Hf and zircon zonation in the Spirit Mountain batholith, Nevada, document repeated fractionation and thermal fluctuations. Ratios of Zr/Hf are ???30-40 for cumulates and 18-30 for high-SiO2 granites. In zircons, Hf (and U) are inversely correlated with Ti, and concentrations indicate large fluctuations in melt composition and TTiZ (>100??C) for individual zircons. Such variations are consistent with field relations and ion-probe zircon geochronology that indicate a >1 million year history of repeated replenishment, fractionation, and extraction of melt from crystal mush to form the low Zr/Hf high-SiO2 zone. ?? 2006 The Mineralogical Society.

The Middle Triassic evolution of the Bangong-Nujiang Tethyan Ocean: evidence from analyses of OIB-type basalts and OIB-derived phonolites in northern Tibet

NASA Astrophysics Data System (ADS)

Fan, Jian-Jun; Li, Cai; Liu, Jin-Heng; Wang, Ming; Liu, Yi-Ming; Xie, Chao-Ming

2017-12-01

In this paper, we present new major and trace element chemical data for the basalts and phonolites of the Nare ocean island fragment (NaOI), as well as zircon U-Pb age data and Hf isotope compositions for the NaOI phonolites in the middle segment of the Bangong-Nujiang Suture Zone, northern Tibet. Our aim is to assess the genesis of these rocks and to reconstruct the Middle Triassic evolution of the Bangong-Nujiang Tethyan Ocean (BNTO). The NaOI retains an ocean island-type double-layered structure comprising a basaltic basement and an oceanic sedimentary cover sequence (conglomerate and limestone, the latter accompanied by layers of erupted phonolite near the top of the sequence). The basalts in the NaOI are enriched in light rare earth elements and high field strength elements (Nb, Ta, Zr, Hf, and Ti), and they exhibit chondrite-normalized REE patterns and primitive mantle-normalized trace element patterns similar to those of ocean island basalts. Taking into consideration their high Dy/Yb, Sm/Yb, and La/Sm ratios, we conclude that the NaOI basalts were derived from the partial melting of garnet peridotite in the mantle. The NaOI phonolites have LREE-enriched chondrite-normalized REE patterns with negative Eu anomalies (Eu/Eu* = 0.41-0.43) and primitive mantle-normalized trace element patterns with enrichments in Nb, Ta, Zr, and Hf, and depletions in Ba, U, Sr, P, and Ti. Given the high contents of Nb (172-256 ppm), Ta (11.8-16.0 ppm), Zr (927-1117 ppm), and Hf (20.8-26.9 ppm), and the very low contents of MgO (0.11-0.25 wt%), the very low Mg# values (5-10), and the near-zero contents of Cr (1.27-7.59 ppm), Ni (0.43-7.19 ppm), and Co (0.11-0.38 ppm), and the small and homogeneously positive ɛ Hf(t) values (+ 4.9 to + 9.5), we infer that the NaOI phonolites were formed by the fractional crystallization of an OIB-derived mafic parent magma. The phonolites of the NaOI contain zircons that yielded U-Pb ages of 239 and 242 Ma, indicating that the NaOI formed during the Middle Triassic. These data, combined with data from modern ocean islands (e.g., Canary Islands, Cape Verde, Fernando de Noronha, Tristan da Cunha, and Gough in the Atlantic Ocean, and Society and Austral-Cook in the Pacific Ocean), lead us to infer that the BNTO was open for a long time before the Middle Triassic, and that the ocean had already developed into a mature ocean with a thick oceanic lithosphere by at least the Middle Triassic.

The characterisation of second phases in the Zr-Nb and Zr-Nb-Sn-Fe alloys: A critical review

NASA Astrophysics Data System (ADS)

Harte, Allan; Griffiths, Malcolm; Preuss, Michael

2018-07-01

The nature and evolution of the Fe environment in Zr-Nb and Zr-Nb-Sn-Fe systems is essential to alloy performance during corrosion, hardening and irradiation-induced growth. Unfortunately, there is ambiguity in the literature regarding the characterisation of secondary phases in these systems. The presence, or not, of Fe in β-Nb phase has been a source of disagreement. In ternary ZrNbFe intermetallics, identical compositions have been designated as Zr(Nb,Fe)2 or (Zr,Nb)3Fe. We show that while Zr(Nb,Fe)2 is commonly reported, it is not always justified. The cubic phase (Zr,Nb)2Fe is easily identified, but its composition is more variable after low temperature heat treatments. We demonstrate the need for correlative approaches in the assessment of phase composition, crystallography and local Fe environment under different heat treatment regimes. Irradiation effects allow us to draw clues regarding phase designation, but there is diverse behaviour under irradiation due to initial phase composition, irradiation dose rate and temperature.

Geochemical insights into the lithology of mantle sources for Cenozoic alkali basalts in West Qinling, China

NASA Astrophysics Data System (ADS)

Dai, Li-Qun; Zheng, Fei; Zhao, Zi-Fu; Zheng, Yong-Fei

2018-03-01

Although alkali basalts are common in oceanic islands and continental rifts, the lithology of their mantle sources is still controversial. While the peridotite is usually viewed as a common source lithology, there are increasing studies suggesting significant contributions from ultramafic metasomatites such as carbonated peridotite, pyroxenite and hornblendite to the origin of alkali basalts. The present study indicates that carbonated peridotite plus hornblendite would have served as the mantle sources of Cenozoic alkali basalts from the West Qinling orogen in China. The target basalts show low SiO2 contents of 36.9 to 40.8 wt% and highly variable Na2O + K2O contents from 0.86 to 4.77 wt%, but high CaO contents of 12.5 to 16.3 wt% and CaO/Al2O3 ratios of 1.42 to 2.19. They are highly enriched in the majority of incompatible trace elements, but depleted in Rb, K, Pb, Zr, Hf, and Ti. Furthermore, they exhibit high (La/Yb)N, Zr/Hf, Ce/Pb and Nb/Ta ratios, but low Ti/Eu and Hf/Sm ratios. Generally, with increasing (La/Yb)N and CaO/Al2O3 ratios, their Ti/Eu and Hf/Sm ratios decrease whereas their Zr/Hf, Ce/Pb and Nb/Ta ratios increase. These major and trace element features are similar to those of carbonatites and hornblendite-derived melts to some extent, but significantly different from those of mid-ocean ridge basalts (MORB). This suggests that the alkali basalts would be originated from metasomatic mantle sources. A comparison of the major-trace elements in the alkali basalts with those of some representative mantle-derived melts indicates that the source lithology of alkali basalts is a kind of ultramafic metasomatites that are composed of carbonated peridotite and hornblendite. Such metasomatites would be generated by reaction of the depleted MORB mantle peridotite with hydrous, carbonate-bearing felsic melts derived from partial melting of the subducted Paleotethyan oceanic crust. Therefore, the melt-peridotite reaction at the slab-mantle interface in the Paleotethyan subduction channel plays the key role in transferring the geochemical signatures from the subducted Paleotethyan oceanic crust to the alkali basalts in the fossil convergent plate margin.

Effects of thermomechanical processing on the microstructure and mechanical properties of Nb-1Zr-C alloys

NASA Technical Reports Server (NTRS)

Titran, Robert H.; Uz, Mehmet

1996-01-01

A systematic study to evaluate the effects of thermomechanical processing on the microstructure and mechanical properties of Nb-1Zr alloy sheet containing 0.06 and 0.1 wt.%C (PWC-11) was conducted and compared to the results of Nb-1Zr. Coarse orthorhombic Nb2C precipitates were present in all the cast, extruded and cold rolled Nb-Zr samples containing C. After high temperature (greater than 0.5 T(sub m)) exposure (with or without applied stress), the Nb2C transforms to very fine and extremely stable FCC (Zr, Nb)C dispersoid, resulting in a highly creep resistant material. Only ZrO2 precipitates were found in Nb-1Zr. The creep strength of the 0.06C and the 0.1C carbide strengthened alloys were much superior to Nb-1Zr. At 1350 K the strength of the 0.06C alloy was about three times that of Nb-1Zr, while the 0.1C alloy had about five times the creep stress capability of Nb-1Zr. The tensile strength, long term creep strength, and stability of the microstructure of the PWC-11 sheet appear to be independent of the number of 1900 K extrusions performed prior to cold rolling. The microhardness of these single, double and triple extnided PWC-11 sheets also were comparable. The tensile strength of PWC-11 and Nb-1Zr at room temperature and 1350 K were comparable.

Development and fabrication of insulator seals for thermionic diodes

NASA Technical Reports Server (NTRS)

Poirier, V. L.

1972-01-01

Eight different types of cermet seals for thermionic diodes were investigated: (1) 1 micron Al2O3 with Nb spheres; (2) 200 A Al2O3 with Nb spheres; (3) 1 micron Al2O3 with Nb 1% Zr spheres; (4) 200 A Al2O3 with Nb 1% Zr spheres; (5) Pure Y2O3 with Nb 1% Zr spheres; (6) Y2O3 3% ZrO2 with Nb 1% Zr spheres; (7) Y2O3 10% ZrO2 with Nb 1% Zr spheres; and (8) ZrO2 12% Y2O3 with Nb 1% Zr spheres. Investigations were made to determine the most favorable fabrication techniques and the effect of the bonding cycle, (length of bonding time and shutdown sequences). The analysis of the seals included tensile test, vacuum test, electrical test and metallurgical examination. At the conclusion of the development phase, 36 seals were fabricated for delivery for evaluation.

General facile approach to transition-metal oxides with highly uniform mesoporosity and their application as adsorbents for heavy-metal-ion sequestration.

PubMed

Seisenbaeva, Gulaim A; Daniel, Geoffrey; Kessler, Vadim G; Nedelec, Jean-Marie

2014-08-18

Mesoporous powders of transition-metal oxides, TiO2, ZrO2, HfO2, Nb2O5, and Ta2O5, pure from organic impurities were produced by a rapid single-step thermohydrolytic approach. The obtained materials display an impressively large active surface area and sharp pore-size distribution, being composed of partially coalesced uniform nanoparticles with crystalline cores and amorphous shells. They reveal extremely high adsorption capacity in removal of Cr(VI) anions from solutions (25.8 for TiO2, 73.0 for ZrO2, and 74.7 mg g(-1) for Nb2O5 in relation to the Cr2O7(2-) anion), making them very attractive as adsorbents in water remediation applications. The difference in adsorption capacities for the studied oxides may be explained by variation in surface hydration and surface-charge distribution. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of [Li]/[Nb] ratio on composition and defect structure of Zr:Yb:Tm:LiNbO3 crystals

NASA Astrophysics Data System (ADS)

Liu, Chunrui; Dai, Li; Wang, Luping; Shao, Yu; Yan, Zhehua; Xu, Yuheng

2018-04-01

Zr:Yb:Tm:LiNbO3 crystals with various [Li]/[Nb] ratios (0.946, 1.05, 1.20 and 1.38) were grown by the Czochralski technique. Distribution coefficients of Zr4+, Yb3+ and Tm3+ ions were analyzed by the inductively coupled plasma-atomic emission spectrometer (ICP-AES). The influence of [Li]/[Nb] ratio on the composition and defect structure of Zr:Yb:Tm:LiNbO3 crystals was investigated by X-ray diffraction and IR transmission spectrum. The results show that as the [Li]/[Nb] ratio increases in the melt, the distribution coefficients of Yb3+ and Tm3+ ions both increase while that of Zr4+ ion deceases. When the [Li]/[Nb] ratio increases to 1.20 in the melt, Zr:Yb:Tm:LiNbO3 crystal is nearly stoichiometric. In addition, when the [Li]/[Nb] ratio reaches up to 1.38, NbLi4+ are completely replaced and Li+ starts to impel the Zr4+, Yb3+ and Tm3+ into the normal Li sites.

Atomic and electronic basis for the serrations of refractory high-entropy alloys

NASA Astrophysics Data System (ADS)

Wang, William Yi; Shang, Shun Li; Wang, Yi; Han, Fengbo; Darling, Kristopher A.; Wu, Yidong; Xie, Xie; Senkov, Oleg N.; Li, Jinshan; Hui, Xi Dong; Dahmen, Karin A.; Liaw, Peter K.; Kecskes, Laszlo J.; Liu, Zi-Kui

2017-06-01

Refractory high-entropy alloys present attractive mechanical properties, i.e., high yield strength and fracture toughness, making them potential candidates for structural applications. Understandings of atomic and electronic interactions are important to reveal the origins for the formation of high-entropy alloys and their structure-dominated mechanical properties, thus enabling the development of a predictive approach for rapidly designing advanced materials. Here, we report the atomic and electronic basis for the valence-electron-concentration-categorized principles and the observed serration behavior in high-entropy alloys and high-entropy metallic glass, including MoNbTaW, MoNbVW, MoTaVW, HfNbTiZr, and Vitreloy-1 MG (Zr41Ti14Cu12.5Ni10Be22.5). We find that the yield strengths of high-entropy alloys and high-entropy metallic glass are a power-law function of the electron-work function, which is dominated by local atomic arrangements. Further, a reliance on the bonding-charge density provides a groundbreaking insight into the nature of loosely bonded spots in materials. The presence of strongly bonded clusters and weakly bonded glue atoms imply a serrated deformation of high-entropy alloys, resulting in intermittent avalanches of defects movement.

Critical Assessment 14: High Entropy Alloys and Their Development as Structural Materials (Postprint)

DTIC Science & Technology

2015-01-01

Mn and Cu or on refractory metals such as V, Cr, Ti, Mo, Nb , Ta, W, Zr and Hf.5,6 The compound forming elements Al and Ti are often added to both...additional properties include environmental resistance , processibil- ity, appearance (for architectural uses) and low cost. Workhardening and solid...be successful, and some work already reports on the corrosion resistance , oxidation behaviour and wear properties of structural HEAs.5 High entropy

Mineral chemistry and geochemistry of ophiolitic metaultramafics from Um Halham and Fawakhir, Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Abdel-Karim, Abdel-Aal M.; Ali, Shehata; El-Shafei, Shaimaa A.

2018-03-01

This study is focused on ophiolitic metaultramafics from Um Halham and Fawakhir, Central Eastern Desert of Egypt. The rocks include serpentinized peridotites, serpentinites together with talc- and quartz-carbonates. The primary spinel relict is Al-chromite [Cr# > 60], which is replaced by Cr-magnetite during metamorphism. The high Cr# of Al-chromites resembles supra-subduction zone (SSZ) peridotites and suggests derivation from the deeper portion of the mantle section with boninitic affinity. These mantle rocks equilibrated with boninitic melt have been generated by high melting degrees. The estimated melting degrees ( 19-24%) lie within the range of SSZ peridotites. The high Cr# of spinel and Fo content of olivine together with the narrow compositional range suggest a mantle residual origin. Serpentinized peridotite and serpentinites have low Al2O3/SiO2 ratios (mostly < 0.03) like fore-arc mantle wedge serpentinites and further indicate that their mantle protolith had experienced partial melting before serpentinization process. Moreover, they have very low Nb, Ta, Zr and Hf concentrations along with sub-chondritic Nb/Ta (0.3-16) and Zr/Hf (mostly 1-20) ratios further confirming that their mantle source was depleted by earlier melting extraction event. The high chondrite normalized (La/Sm)N ratios (average 10) reflect input of subduction-related slab melts/fluids into their mantle source.

Origin of Permian OIB-like basalts in NW Thailand and implication on the Paleotethyan Ocean

NASA Astrophysics Data System (ADS)

Wang, Yuejun; He, Huiying; Zhang, Yuzhi; Srithai, Boontarika; Feng, Qinglai; Cawood, Peter A.; Fan, Weiming

2017-03-01

The basaltic rocks in NW Thailand belong to part of giant Southeast Asian igneous zone that delineates the extension of the Paleotethyan Ocean from SW China into NW Thailand. The Chiang Mai basaltic samples from the Chiang Dao, Fang, Lamphun and Ban Sahakorn sections are divisible into two groups of high-iron basalt. Group 1 has SiO2 of 38.30-49.18 wt.%, FeOt of 13.09-25.37 wt.%, MgO of 8.38-1.60 wt.%, TiO2 of 3.92-6.30 wt.%, which is rarely observed in nature. Group 2 shows SiO2 = 44.71-49.21 wt.%, FeOt = 10.88-14.34 wt.%, MgO = 5.24-16.11 wt.%, TiO2 = 2.22-3.07 wt.% and mg# = 44-70. Olivine and pyroxene are responsible for the fractionation of the Group 2 magma whereas low oxygen fugacity during the late-stage differentiation of the Group 1 magma prolonged fractionation of ilmenite and magnetite. The onset of ilmenite and magnetite fractionations controls the distinct differentiation commencing at MgO = 7 wt.%. Both groups show similar REE and primitive mantle-normalized patterns with insignificant Eu, Nb-Ta and Zr-Hf anomalies. They have similar Nd isotopic compositions with εNd (t) values ranging from + 2.8 to + 3.7 and similar Nb/La, Nb/U, Th/La, Zr/Nb, Th/Ta, La/Yb, Nb/Th, Nb/Y and Zr/Y, resembling those of OIB-like rocks. The representative basaltic sample yields the argon plateau age of 282.3 ± 1.4 Ma, suggestive of Early Permian origin. Our data argue for Group 1 and Group 2 are coeval in the intra-oceanic seamount setting within the Paleotethyan Ocean, which at least continued till 283 Ma. These data, along with other observations, suggest that the Inthanon zone defines the main Paleotethyan suture zone, which northerly links with the Changning-Menglian suture zone in SW China.

Aqueous Isolation of 17-Nuclear Zr-/Hf- Oxide Clusters during the Hydrothermal Synthesis of ZrO2/HfO2.

PubMed

Sung, Qing; Liu, Caiyun; Zhang, Guanyun; Zhang, Jian; Tung, Chen-Ho; Wang, Yifeng

2018-06-21

Novel 17-nuclear Zr-/Hf- oxide clusters ({Zr17} and {Hf17}) are isolated from aqueous systems. In the clusters, Zr/Hf ions are connected via μ3-O, μ3-OH and μ2-OH linkages into a pinwheel core which is wrapped with SO42-, HCOO- and aqua ligands. Octahedral hexanuclear Zr-/Hf- oxide clusters ({Zr6}oct and {Hf6}oct) are also isolated from the same hydrothermal system by decreasing the synthesis temperature. Structural analysis, synthetic conditions, vibrational spectra and ionic conductivity of the clusters are studied. Structural studies and synthesis inspection suggest that formation of {Zr6}oct and {Zr17} involves assembly of the same transferable building blocks, but the condensation degree and thermodynamic stability of the products increase with hydrothermal temperature. The role of {Zr6}oct and {Zr17} in the formation of ZrO2 nanocrystals are then discussed in the scenario of nonclassical nucleation theory. Besides, the Zr-oxide clusters exhibit ionic conductivity due to the mobility of protons. This study not only adds new members to the Zr-/Hf- oxide cluster family, but also establishes a connection from Zr4+ ions to ZrO2 in the hydrothermal preparation of zirconium oxide nanomaterials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural, microstructural and thermal analysis of U-(6-x)Zr-xNb alloys (x = 0, 2, 4, 6)

NASA Astrophysics Data System (ADS)

Kaity, Santu; Banerjee, Joydipta; Parida, S. C.; Bhasin, Vivek

2018-06-01

Uranium-rich U-Zr-Nb alloy is considered as a good alternative fuel for fast reactors from the perspective of excellent dimensional stability and desired thermo-physical properties to achieve higher burnup. Detailed investigations related to the structural and microstructural characterization, thermal expansion, phase transformation, microhardness were carried out on U-6Zr, U-4Zr-2Nb, U-2Zr-4Nb and U-6Nb alloys (composition in wt%) where the total amount of alloying elements was restricted to 6 wt%. Structural, microstructural and thermal analysis studies revealed that these alloys undergo a series of transformations from high temperature bcc γ-phase to a variety of equilibrium and intermediate phases depending upon alloy composition, cooling rate and quenching. The structural analysis was carried out by Rietveld refinement. The data of U-Nb and U-Zr-Nb alloys have been highlighted and compared with binary U-Zr alloy.

Effect of Zr substitution on the thermal and mechanical properties of Rh3A (A=Nb,Ta) - A theoretical study

NASA Astrophysics Data System (ADS)

Manjula, M.; Sundareswari, M.; Viswanathan, E.

2018-04-01

The present study focuses upon the thermal and mechanical properties of Rh3ZrxA1-x (A= Nb,Ta) ternary alloys using ab initio density functional theory where Nb/Ta is substituted by Zr. These ternary alloys were investigated for the first time using elastic moduli, hardness, Debye temperature, Debye average velocity and Gruneisen parameter. Further the ductile/brittle analysis was made by using Cauchy pressure, degree of brittleness and Poisson's ratio. Systematic addition of Zr with Rh3Nb/Ta shows that Rh3Zr0.75Nb0.25, Rh3Zr0.875Nb0.125 and Rh3Zr0.875Ta0.125combinations are more ductile. Further the melting temperature of Rh3Zr0.75Nb0.25(2227 K), Rh3Zr0.875Nb0.125(2200 K) and Rh3Zr0.875Ta0.125 (2134 K) alloys are nearer to those of their parent binary alloys namely Rh3Nb (2636 K) and Rh3Ta (2562 K). Their corresponding density values (10.84 gm/cm3, 10.77 gm/cm3 and 11.09 gm/cm3) are found to be much less than those of their parent materials.

Transformation behavior of the γU(Zr,Nb) phase under continuous cooling conditions

NASA Astrophysics Data System (ADS)

Komar Varela, C. L.; Gribaudo, L. M.; González, R. O.; Aricó, S. F.

2014-10-01

The selected alloy for designing a high-density monolithic-type nuclear fuel with U-Zr-Nb alloy as meat and Zry-4 as cladding, has to remain in the γU(Zr,Nb) phase during the whole fabrication process. Therefore, it is necessary to define a range of concentrations in which the γU(Zr,Nb) phase does not decompose under the process conditions. In this work, several U alloys with concentrations between 28.2-66.9 at.% Zr and 0-13.3 at.% Nb were fabricated to study the possible transformations of the γU(Zr,Nb) phase under different continuous cooling conditions. The results of the electrical resistivity vs temperature experiments are presented. For a cooling rate of 4 °C/min a linear regression was determined by fitting the starting decomposition temperature as a function of Nb concentration. Under these conditions, a concentration of 45.3 at.% Nb would be enough to avoid any transformation of the γU(Zr,Nb) phase. In experiments that involve higher cooling conditions, it has been determined that this concentration can be halved.

3D surface topography study of the biofunctionalized nanocrystalline Ti-6Zr-4Nb/Ca-P

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

Jakubowicz, J., E-mail: jaroslaw.jakubowicz@put.poznan.pl; Adamek, G.; Jurczyk, M.U.

2012-08-15

In this work surface of the sintered Ti-6Zr-4Nb nanocrystalline alloy was electrochemically biofunctionalized. The porous surface was produced by anodic oxidation in 1 M H{sub 3}PO{sub 4} + 2%HF electrolyte at 10 V for 30 min. Next the calcium-phosphate (Ca-P) layer was deposited, onto the formed porous surface, using cathodic potential - 5 V kept for 60 min in 0.042 M Ca(NO{sub 3}){sub 2} + 0.025 M (NH{sub 4}){sub 2}HPO{sub 4} + 0.1 M HCl electrolyte. The deposited Ca-P layer anchored in the pores. The biofunctionalized surface was studied by XRD, SEM and EDS. In vitro tests culture of normalmore » human osteoblast (NHOst) cells showed very good cells proliferation, colonization and multilayering. Using optical profiler, roughness and hybrid 3D surface topography parameters were estimated. Correlation between surface composition, morphology, roughness and biocompatibility results was done. It has been shown by us that surface with appropriate chemical composition and topography, after combined electrochemical anodic and cathodic surface treatment, supports osteoblast adhesion and proliferation. 3D topography measurements using optical profiler play a key role in the biomaterials surface analysis. - Highlights: Black-Right-Pointing-Pointer Nanocrystalline Ti-6Zr-4Nb/Ca-P material was produced for hard tissue implant applications. Black-Right-Pointing-Pointer Calcium-phosphate results in surface biofunctionalization. Black-Right-Pointing-Pointer The biofunctionalized surface shows good in-vitro behavior.« less

Electrical and Magnetic Properties of Binary Amorphous Transition Metal Alloys.

NASA Astrophysics Data System (ADS)

Liou, Sy-Hwang

The electrical, superconductive and magnetic properties of several binary transition metal amorphous and metastable crystalline alloys, Fe(,x)Ti(,100-x) (30 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Zr(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 93), Fe(,x)Hf(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Nb(,100 -x) (22 (LESSTHEQ) x (LESSTHEQ) 85), Ni(,x)Nb(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 80), Cu(,x)Nb(,100-x) (10 (LESSTHEQ) x (LESSTHEQ) 90) were studied over a wide composition range. Films were made using a magnetron sputtering system, and the structure of the films was investigated by energy dispersive x-ray diffraction. The composition region of each amorphous alloys system was determined and found in good agreement with a model proposed by Egami and Waseda. The magnetic properties and hyperfine interactions in the films were investigated using a conventional Mossbauer spectrometer and a ('57)Co in Rh matrix source. In all Fe-early transition metal binary alloys systems, Fe does not retain its moment in the low iron concentration region and the result is that the critical concentration for magnetic order (x(,c)) is much larger than anticipated from percolation considerations. A direct comparison between crystalline alloys and their amorphous counterparts of the same composition illustrate no clear correlation between crystalline and amorphous states. Pronounced discontinuities in the magnetic properties with variation in Fe content of all Fe-early transition metal alloys at phase boundaries separating amorphous and crystalline states have been observed. This is caused by the differences in the atomic arrangement and the electronic structure between crystalline and amorphous solids. The temperature dependence of resistivity, (rho)(T), of several binary amorphous alloys of Fe-TM (where TM = Ti, Zr, Hf, Nb etc.) has been studied from 2K to 300K. The Fe-poor (x < x(,c)) samples and the Fe-rich (x > x(,c)) samples have distinctive differences in (rho)(T) at low temperature (below 30K). All the magnetic samples show a logarithmic dependence at low temperature that can be described by Kondo scattering. In addition, there is a change in slope of (rho)(T) at a temperature close to the magnetic ordering temperature, indicating a contribution attributed to magnetic ordering. Several Nb-based amorphous alloys (Fe-Nb, Ni-Nb, Cu-Nb) have also been systematically studied. The effect of the magnetic species on superconductivity is investigated. The value of superconducting transition temperature (T(,s)) increases linearly with increasing Nb concentration. (Abstract shortened with permission of author.).

Characteristics of high-k gate dielectric formed by the oxidation of sputtered Hf/Zr/Hf thin films on the Si substrate

NASA Astrophysics Data System (ADS)

Kim, H. D.; Roh, Y.; Lee, J. E.; Kang, H.-B.; Yang, C.-W.; Lee, N.-E.

2004-07-01

We have investigated the effects of high temperature annealing on the physical and electrical properties of multilayered high-k gate oxide [HfSixOy/HfO2/intermixed-layer(IL)/ZrO2/intermixed-layer(IL)/HfO2] in metal-oxide-semiconductor device. The multilayered high-k films were formed after oxidizing the Hf/Zr/Hf films deposited directly on the Si substrate. The subsequent N2 annealing at high temperature (>= 700 °C) not only results in the polycrystallization of the multilayered high-k films, but also causes the diffusion of Zr. The latter transforms the HfSixOy/HfO2/IL/ZrO2/IL/HfO2 film into the Zr-doped HfO2 film, and improves electrical properties in general. However, the thin SiOx interfacial layer starts to form if annealing temperature increases over 700 °C, deteriorating the equivalent oxide thickness. .

Geochemical variations in aeolian mineral particles from the Sahara-Sahel Dust Corridor.

PubMed

Moreno, Teresa; Querol, Xavier; Castillo, Sonia; Alastuey, Andrés; Cuevas, Emilio; Herrmann, Ludger; Mounkaila, Mohammed; Elvira, Josep; Gibbons, Wes

2006-10-01

The Sahara-Sahel Dust Corridor runs from Chad to Mauritania and expels huge amounts of mineral aerosols into the Atlantic Ocean. Data on samples collected from Algeria, Chad, Niger, and Western Sahara illustrate how corridor dust mineralogy and chemistry relate to geological source and weathering/transport history. Dusts sourced directly from igneous and metamorphic massifs are geochemically immature, retaining soluble cations (e.g., K, Na, Rb, Sr) and accessory minerals containing HFSE (e.g., Zr, Hf, U, Th) and REE. In contrast, silicate dust chemistry in desert basins (e.g., Bodélé Depression) is influenced by a longer history of transport, physical winnowing (e.g., loss of Zr, Hf, Th), chemical leaching (e.g., loss of Na, K, Rb), and mixing with intrabasinal materials such as diatoms and evaporitic salts. Mineral aerosols blown along the corridor by the winter Harmattan winds mix these basinal and basement materials. Dusts blown into the corridor from sub-Saharan Africa during the summer monsoon source from deeply chemically weathered terrains and are therefore likely to be more kaolinitic and stripped of mobile elements (e.g., Na, K, Mg, Ca, LILE), but retain immobile and resistant elements (e.g., Zr, Hf, REE). Finally, dusts blown southwestwards into the corridor from along the Atlantic Coastal Basin will be enriched in carbonate from Mesozoic-Cenozoic marine limestones, depleted in Th, Nb, and Ta, and locally contaminated by uranium-bearing phosphate deposits.

Enhancement of wear and corrosion resistance of low modulus β-type Zr-20Nb-xTi (x=0, 3) dental alloys through thermal oxidation treatment.

PubMed

Zhang, Jianfeng; Gan, Xiaxia; Tang, Hongqun; Zhan, Yongzhong

2017-07-01

In order to obtain material with low elastic modulus, good abrasion resistance and high corrosion stability as screw for dental implant, the biomedical Zr-20Nb and Zr-20Nb-3Ti alloy with low elastic modulus were thermal oxidized respectively at 700°C for 1h and 600°C for 1.25h to obtain the compact oxidized layer to improve its wear resistance and corrosion resistance. The results show that smooth compact oxidized layer (composed of monoclinic ZrO 2 , tetragonal ZrO 2 and 6ZrO 2 -Nb 2 O 5 ) with 22.6μm-43.5μm thickness and 1252-1306HV hardness can be in-situ formed on the surface of the Zr-20Nb-xTi (x=0, 3). The adhesion of oxidized layers to the substrates is determined to be 58.35-66.25N. The oxidized Zr-20Nb-xTi alloys reveal great improvement of the pitting corrosion resistance in comparison with the un-oxidized alloys. In addition, the oxidized Zr-20Nb-3Ti exhibits sharply reduction of the corrosion rates and the oxidized Zr-20Nb shows higher corrosion rates than un-oxidized alloys, which is relevant with the content of the t-ZrO 2 . Wear test in artificial saliva demonstrates that the wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) are superior to pure Ti. All of the un-oxidized Zr-20Nb-xTi (x=0, 3) alloys suffer from serious adhesive wear due to its high plasticity. Because of the protection from compact oxide layer with high adhesion and high hardness, the coefficients of friction and wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) alloys decrease 50% and 95%, respectively. The defects on the oxidized Zr-20Nb have a negative effect on the friction and wear properties. In addition, after the thermal oxidation, compression test show that elastic modulus and strength of Zr-20Nb-xTi (x=0, 3) increase slightly with plastic deformation after 40% of transformation. Furthermore, stripping of the oxidized layer from the alloy matrix did not occur during the whole experiments. As the surface oxidized Zr-20Nb-3Ti alloy has a combination of excellent performance such as high chemical stability, good wear resistance performance and low elastic modulus, moderate strength, it is considered an alternative material as dental implant. Copyright © 2017 Elsevier B.V. All rights reserved.

Dopant occupancy and exposure energy in Hf:Nd:LiNbO3 crystal as a function of [Li]/[Nb] ratios

NASA Astrophysics Data System (ADS)

Dai, Li; Liu, Chunrui; Han, Xianbo; Yan, Zhehua; Tan, Chao; Wang, Luping; Xu, Yuheng

2017-09-01

A series of Hf: Nd: LiNbO3 crystals with various [Li]/[Nb] ratios ([Li]/[Nb] = 0.94, 1.05, 1.20, 1.38) in the melt were grown by conventional Czochralski technique. The distribution coefficients of Hf4+ and Nd3+ ions were recorded by an inductively coupled plasma-atomic emission spectrometer (ICP-AES). The effective distribution coefficient of Hf4+ is reduced and that of Nd3+ is increased with the increase of [Li]/[Nb] ratio in the melts. In all cases, the effective distribution coefficients is less than 1. The IR transmission spectroscopy of the Hf: Nd: LiNbO3 crystals were measured, getting the results that Hf: Yb: Ho: LiNbO3 crystals with 1.05 [Li]/[Nb] ratios was the stoichiometric. The optical damage resistance ability of Hf:Nd:LiNbO3 crystals were studied by light-induced scattering exposure energy flux threshold method and it increases with the increasing of [Li]/[Nb] ratios. When the [Li]/[Nb] ratio is 1.38 in the melt (the sample 4#), the exposure energy achieves 687.35 J/cm2, approximately 441 folds than that of the sample 1# ([Li]/[Nb] = 0.94) in magnitude.

National Hypersonic Science Center for Materials and Structures

DTIC Science & Technology

2014-08-31

Hence, ( Zr , Nb )B2 showed improved oxidation resistance compared to pure ZrB2. 9.2 Effects of W Additives on Oxide Scale Thickness and the...TM Additives on Oxide Scale Growth on ZrB2 The oxidation behavior of ( Zr , Nb )B2 ceramics was studied to determine the effect of Nb on the thickness...and morphology of the oxide scales on ZrB2 [B6]. At 1500 °C, exposure to air resulted in the formation of a two-layer oxide scale structure on ( Zr , Nb

The influence of Zr substitution for Nb on the corrosion behaviors of the Ni-Nb-Zr bulk metallic glasses

NASA Astrophysics Data System (ADS)

Li, DengKe; Zhu, ZhengWang; Zhang, HaiFeng; Wang, AiMin; Hu, ZhuangQi

2012-12-01

The influence of Zr content on corrosion behaviors of the Ni61.5Nb38.5- x Zr x ( x=1, 3, 5, 7, 9 at.%) bulk metallic glasses (BMGs) in 1 M HCl aqueous solution was investigated by potentiodynamic polarization measurements and X-ray photo-electron spectroscopy (XPS). It was found that these BMG alloys possess superior corrosion resistance, that is, with large passive region of about 1.5 V and low passive current density (as low as 0.05 Am-2 for Ni61.5Nb31.5Zr7). XPS analysis indicates that the high corrosion resistance is attributed to the formation of Nb- and Zr-enriched surface films formed in the aggressive acid solution. The Zr substitution for Nb effectively reduces the Ni content, particularly the metallic state Ni content in the surface films, which depresses the electrical conduction of the surface films and reduces the passive current density, thus leading to the enhancement of the corrosion resistance of these Ni-Nb-Zr BMGs. These alloys may potentially be useful for engineering applications.

Strengthening mechanisms, creep, and fatigue processes in dispersion-hardened niobium alloy. Final scientific report, 1 Feb 89-31 Jan 92

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

Mukherjee, A.K.; Gibeling, J.C.

The creep and fatigue properties of pure Nb and Nb-l%Zr alloy were investigated. A model was developed based on the migration of subgrain boundary that can explain the anomalous primary creep transients found in Nb-l%Zr alloy, due to coarsening of subgrain structure. TEM investigations confirmed that such subgrain coarsening occurs during primary creep of Nb-l%Zr. Baseline low cycle fatigue studies of Nb and Nb-l%Zr were completed. Cyclic hardening is observed and there is a microplastic plateau in Nb. The Nb-1%Zr is stronger in cyclic deformation than Nb, with little influence of strain rate. The deformation in the alloy at bothmore » high and low strain rates is controlled by the interaction between gliding edge dislocation and solute atoms.« less

Mn-coatings on the micro-pore formed Ti-29Nb-xHf alloys by RF-magnetron sputtering for dental applications

NASA Astrophysics Data System (ADS)

Park, Seon-Yeong; Choe, Han-Cheol

2018-02-01

In this study, Mn-coatings on the micro-pore formed Ti-29Nb-xHf alloys by RF-magnetrons sputtering for dental applications were studied using different experimental techniques. Mn coating films were formed on Ti-29Nb-xHf alloys by a radio frequency magnetron sputtering technique for 0, 1, 3, and 5 min at 45 W. The microstructure, composition, and phase structure of the coated alloys were examined by optical microscopy, field emission scanning electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The microstructure of Ti-29Nb alloy showed α" phase in the needle-like structure and Ti-29Nb-15Hf alloy showed β phase in the equiaxed structure. As the sputtering time increased, the circular particles of Mn coatings on the Ti-29Nb alloy increased at inside and outside surfaces. As the sputtering time increased, [Mn + Ca/P] ratio of the plasma electrolytic oxidized films in Ti- 29Nb-xHf alloys increased. The corrosion potential (Ecorr) of Mn coatings on the Ti-29Nb alloy showed higher than that of Mn coatings on the Ti-29Nb-15Hf alloy. The passive current density (Ipass) of the Mn coating on the Ti-29Nb alloy and Mn coatings on the Ti-29Nb-15Hf alloy was less noble than the non-Mn coated Ti-29Nb and Ti-29Nb-15Hf alloys surface.

Properties of binary transition-metal arsenides (TAs)

NASA Astrophysics Data System (ADS)

Saparov, Bayrammurad; Mitchell, Jonathan E.; Sefat, Athena S.

2012-08-01

We present thermodynamic and transport properties of transition-metal (T) arsenides, TAs, with T = Sc to Ni (3d), Zr, Nb, Ru (4d), Hf and Ta (5d). Characterization of these binaries is carried out with powder x-ray diffraction, temperature- and field-dependent magnetization and resistivity, temperature-dependent heat capacity, Seebeck coefficient, and thermal conductivity. All binaries show metallic behavior except TaAs and RuAs. TaAs, NbAs, ScAs and ZrAs are diamagnetic, while CoAs, VAs, TiAs, NiAs and RuAs show approximately Pauli paramagnetic behavior. FeAs and CrAs undergo antiferromagnetic ordering below TN ≈ 71 K and TN ≈ 260 K, respectively. MnAs is a ferromagnet below TC ≈ 317 K and undergoes hexagonal-orthorhombic-hexagonal transitions at TS ≈ 317 K and 384 K, respectively. For TAs, Seebeck coefficients vary between + 40 and - 40 μV K-1 in the 2-300 K range, whereas thermal conductivity values stay below 18 W m-1 K-1. The Sommerfeld coefficients γ are less than 10 mJ K-2 mol-1. At room temperature with application of 8 T magnetic field, large positive magnetoresistance is found for TaAs (˜25%), MnAs (˜90%) and NbAs (˜75%).

Effect of thermo-mechanical processing on microstructure and mechanical properties of U - Nb - Zr alloys: Part 2 - U - 3 wt % Nb - 9 wt % Zr and U - 9 wt% Nb - 3 wt% Zr

NASA Astrophysics Data System (ADS)

Morais, Nathanael Wagner Sales; Lopes, Denise Adorno; Schön, Cláudio Geraldo

2018-04-01

The present work is the second and final part of an extended investigation on Usbnd Nb - Zr alloys. It investigates the effect of mechanical processing routes on microstructure of alloys U - 3 wt % Nb - 9 wt % Zr and U - 9 wt% Nb - 3 wt% Zr, through X-ray diffraction and scanning electron microscopy, completing the investigation, which started with alloy U - 6 wt% Nb - 6 wt% Zr in part 1. Mechanical properties are determined using microhardness and bending tests and correlated with the developed microstructures. The results show that processing sequence, in particular the inclusion of a 1000 °C heat treatment step, affects significantly the microstructure and mechanical properties of these alloys alloy in different ways. Microstructural characterization shows that both alloys present significant volume fraction of precipitates of a body-centered cubic (BCC) γ-Nb-Zr rich phase in addition the uranium-rich matrix. Bending tests show that sample ductility does not correlate necessarily with hardness and that the key factor appears to be the amount of the γ-Nb-Zr precipitates, which controls the matrix microstructure. Samples with a monoclinic α″ cellular microstructure and/or with the tetragonally-distorted BCC phase (γ0), although not strictly ductile, showed the largest allowed strains-before-break and complete elastic recovery of the broken pieces, pointing out to the macroscopic observation of superelasticity.

Variations of trace element concentration of magnetite and ilmenite from the Taihe layered intrusion, Emeishan large igneous province, SW China: Implications for magmatic fractionation and origin of Fe-Ti-V oxide ore deposits

NASA Astrophysics Data System (ADS)

She, Yu-Wei; Song, Xie-Yan; Yu, Song-Yue; He, Hai-Long

2015-12-01

In situ LA-ICP-MS trace elemental analysis has been applied to magnetite and ilmenite of the Taihe layered intrusion, Emeishan large igneous province, SW China, in order to understand better fractionation processes of magma and origin of Fe-Ti-V oxide ore deposits. The periodic reversals in Mg, Ti, Mn in magnetite and Mg, Sc in ilmenite are found in the Middle Zone of the intrusion and agree with fractionation trends as recorded by olivine (Fo), plagioclase (An) and clinopyroxene (Mg#) compositions. These suggest the Taihe intrusion formed from open magma chamber processes in a magma conduit with multiple replenishments of more primitive magmas. The V and Cr of magnetite are well correlated with V and Cr of clinopyroxene indicating that they became liquidus phases almost simultaneously at an early stage of magma evolution. Ilmenite from the Middle and Upper Zones shows variable Cr, Ni, V, Mg, Nb, Ta and Sc contents indicating that ilmenite at some stratigraphic levels crystallized slightly earlier than magnetite and clinopyroxene. The early crystallization of magnetite and ilmenite is the result of the high FeOt and TiO2 contents in the parental magma. The ilmenite crystallization before magnetite in the Middle and Upper Zones can be attributed to higher TiO2 content of the magma due to the remelting of pre-existing ilmenite in a middle-level magma chamber. Compared to the coeval high-Ti basalts, the relatively low Zr, Hf, Nb and Ta contents in both magnetite and ilmenite throughout the Taihe intrusion indicate that they crystallized from Fe-Ti-(P)-rich silicate magmas. Positive correlations of Ti with Mg, Mn, Sc and Zr of magnetite, and Zr with Sc, Hf and Nb of ilmenite also suggest that magnetite and ilmenite crystallized continuously from the homogeneous silicate magma rather than an immiscible Fe-rich melt. Therefore, frequent replenishments of Fe-Ti-(P)-rich silicate magma and gravitational sorting and settling are crucial for the formation the massive and apatite-rich disseminated ores in the Lower and Middle Zones of the Taihe intrusion.

Non-Contact Tabletop Mechanical Testing of Ultra-High Temperature Ceramics

DTIC Science & Technology

2012-05-01

class of refractory materials including transition metal borides , carbides and nitrides e.g. ZrB2l HfB2) ZrC, HfC, TaC, HfN and ZrN. They recently...ike oxidizing atmospheres, at very high temperatures Refractory borides like ZrB2 and HfB2 have extremely high melting temperatures (over 3000°C...But borides are very poor in oxidation resistance, due to the nature of thär oxides Non-protective ZrCfe or Hf02 and volatile liquid B203. Addition

Progressive enrichment of arc magmas caused by the subduction of seamounts under Nishinoshima volcano, Izu-Bonin Arc, Japan

NASA Astrophysics Data System (ADS)

Sano, Takashi; Shirao, Motomaro; Tani, Kenichiro; Tsutsumi, Yukiyasu; Kiyokawa, Shoichi; Fujii, Toshitsugu

2016-06-01

The chemical composition of intraplate seamounts is distinct from normal seafloor material, meaning that the subduction of seamounts at a convergent margin can cause a change in the chemistry of the mantle wedge and associated arc magmas. Nishinoshima, a volcanic island in the Izu-Bonin Arc of Japan, has been erupting continuously over the past 2 years, providing an ideal opportunity to examine the effect of seamount subduction on the chemistry of arc magmas. Our research is based on the whole-rock geochemistry and the chemistry of minerals within lavas and air-fall scoria from Nishinoshima that were erupted before 1702, in 1973-1974, and in 2014. The mineral phases within the analyzed samples crystallized under hydrous conditions (H2O = 3-4 wt.%) at temperatures of 970 °C-990 °C in a shallow (3-6 km depth) magma chamber. Trace element data indicate that the recently erupted Nishinoshima volcanics are much less depleted in the high field strength elements (Nb, Ta, Zr, Hf) than other volcanics within the Izu-Bonin Arc. In addition, the level of enrichment in the Nishinoshima magmas has increased in recent years, probably due to the addition of material from HIMU-enriched (i.e., high Nb/Zr and Ta/Hf) seamounts on the Pacific Plate, which is being subducted westwards beneath the Philippine Sea Plate. This suggests that the chemistry of scoria from Nishinoshima volcano records the progressive addition of components derived from subducted seamounts.

Investigation of (Ti-Zr-Hf-V-Nb)N Multicomponent Nanostructured Coatings before and after Thermal Annealing by Nuclear Physics Methods of Analysis

NASA Astrophysics Data System (ADS)

Pogrebnjak, A. D.; Beresnev, V. M.; Bondar', A. V.; Kaverin, M. V.; Ponomarev, A. G.

2013-10-01

(Ti-Zr-Hf-V-Nb)N multicomponent nanostructured coatings with thickness of 1.0-1.4 μm synthesized by the method of cathode arc-vapor deposition at temperatures of 250-300°С are investigated by various mutually complementary methods of elemental structural analysis using slow positron beams (SPB), proton microbeam based particle-induced x-ray emission (μ-PIXE), energy-dispersive x-ray spectroscopy (EDS) and scanning electron microscopy (SEM) analyses based on electron micro- and nanobeams, x-ray diffraction (XRD) method of phase structural analysis, and the "a-sin2φ" method of measuring a stressed-strained state (x-ray tensometry). The elemental composition, microstructure, residual stress in nanograins, profiles of defect and atom distributions with depth and over the coating surface in 3D-representation are studied for these coatings, and their phase composition, severely strained state, and composition of coatings before and after annealing at Tann = 600°С for annealing time τ = 30 min are investigated. It is demonstrated that the oxidation resistance of the examined coatings can be significantly increased by high-temperature annealing that leads to the formation of elastic severely strained compression state of the coating. Redistribution of elements and defects, their segregation near the interface boundaries and around grains and subgrains in the process of thermostimulated diffusion, and termination of spinodal segregation without considerable change of the average nanograin size are revealed.

Geochemistry and mineralogy of the older (> 40 ka) ignimbrites in the Campanian Plain, southern Italy

NASA Astrophysics Data System (ADS)

Belkin, Harvey E.; Raia, Federica; Rolandi, Giuseppe; Jackson, John C.; de Vivo, Benedetto

2010-05-01

The Campanian Plain in southern Italy has been volcanically active during the last 600 ka. The largest and best known eruption at 39 ka formed the Campanian Ignimbrite (CI), which has the largest volume (~310 km3) and the greatest areal extent. However, significant, but scattered deposits of older ignimbrites underlie the CI and document a long history of trachytic eruptions. We examined the geochemistry and mineralogy of 11 older ignimbrite strata by optical petrography, electron microprobe, scanning electron microscope, X-ray diffraction, and various whole-rock geochemical techniques. Strata at Durazzano (116.1 ka), Moschiano (184.7 ka), Seiano Valley A (245.9 ka), Seiano Valley B (289.6 ka), Taurano 7 (205.6 and 210.4 ka), Taurano 9 (183.8 ka), and Taurano 14 (157.4 ka) have been previously dated by the 40Ar/39Ar technique (Rolandi et al., 2003, Min. & Pet., 79) on hand-picked sanidine. The older ignimbrites are trachytic, but are highly altered with LOI from 8 to 17 wt%. Whole-rock compositions reflect variable element mobility during weathering; TiO2, Al2O3, Fe-oxide, and CaO tend to be enriched relative to average CI composition, whereas Na2O and K2O are depleted. X-ray diffraction identified major chabazite, kaolinite, and illite-smectite alteration products in some samples. The phenocryst mineralogy in all of the strata is typical for trachyte magma and consists of plagioclase (~An80 to ~An40), potassium feldspar (~Or50 to ~Or80), biotite (TiO2 = ~4.6 wt%, BaO = ~0.70 wt%, F = ~0.65 wt%), diopside (~Ca47Mg48Fe5 to ~Ca48Mg34Fe18), titanomagnetite, and uncommon Ca-amphibole. Relatively immobile trace elements Zr, Hf, Nb, and Th display similar abundance, linear trends, and ratios as those measured in the Campanian Ignimbrite: Th/Hf = ~4, Zr/Hf = ~50, and Zr/Nb = ~6. The similarity of trace element systematics and phenocryst mineralogy among the Campanian Ignimbrite and the older ignimbrites suggests that the magmagenesis processes and parental source have been relatively constant during the long period of trachyte volcanism in the Campanian Plain.

Color tone and interfacial microstructure of white oxide layer on commercially pure Ti and Ti-Nb-Ta-Zr alloys

NASA Astrophysics Data System (ADS)

Miura-Fujiwara, Eri; Mizushima, Keisuke; Watanabe, Yoshimi; Kasuga, Toshihiro; Niinomi, Mitsuo

2014-11-01

In this study, the relationships among oxidation condition, color tone, and the cross-sectional microstructure of the oxide layer on commercially pure (CP) Ti and Ti-36Nb-2Ta-3Zr-0.3O were investigated. “White metals” are ideal metallic materials having a white color with sufficient strength and ductility like a metal. Such materials have long been sought for in dentistry. We have found that the specific biomedical Ti alloys, such as CP Ti, Ti-36Nb-2Ta-3Zr-0.3O, and Ti-29Nb-13Ta-4.6Zr, form a bright yellowish-white oxide layer after a particular oxidation heat treatment. The brightness L* and yellowness +b* of the oxide layer on CP Ti and Ti-36Nb-2Ta-3Zr-0.3O increased with heating time and temperature. Microstructural observations indicated that the oxide layer on Ti-29Nb-13Ta-4.6Zr and Ti-36Nb-2Ta-3Zr-0.3O was dense and firm, whereas a piecrust-like layer was formed on CP Ti. The results obtained in this study suggest that oxide layer coating on Ti-36Nb-2Ta-3Zr-0.3O is an excellent technique for dental applications.

Phase composition, microstructure, and mechanical properties of porous Ti-Nb-Zr alloys prepared by a two-step foaming powder metallurgy method.

PubMed

Rao, X; Chu, C L; Zheng, Y Y

2014-06-01

Porous Ti-Nb-Zr alloys with different porosities from 6.06 to 62.8% are prepared by a two-step foaming powder metallurgy method using TiH2, Nb, and Zr powders together with 0 to 50wt% of NH4HCO3. The effects of the amounts of Nb and Zr as well as the sintering temperature (1473 to 1673K) on their phase composition, porosity, morphology, and mechanical characteristics are investigated. By controlling the porosity, Nb and Zr concentrations as well as the sintering temperature, porous Ti-Nb-Zr alloys with different mechanical properties can be obtained, for example, the hardness between 290 and 63HV, the compressive strength between 1530.5 and 73.4MPa, and the elastic modulus between 10.8 and 1.2GPa. The mechanical properties of the sintered porous Ti-Nb-Zr alloys can be tailored to match different requirements for the human bones and are thus potentially useful in the hard tissue implants. Copyright © 2014 Elsevier Ltd. All rights reserved.

Nanostructured Ti-Zr-Pd-Si-(Nb) bulk metallic composites: Novel biocompatible materials with superior mechanical strength and elastic recovery.

PubMed

Hynowska, A; Blanquer, A; Pellicer, E; Fornell, J; Suriñach, S; Baró, M D; Gebert, A; Calin, M; Eckert, J; Nogués, C; Ibáñez, E; Barrios, L; Sort, J

2015-11-01

The microstructure, mechanical behaviour, and biocompatibility (cell culture, morphology, and cell adhesion) of nanostructured Ti45 Zr15 Pd35- x Si5 Nbx with x = 0, 5 (at. %) alloys, synthesized by arc melting and subsequent Cu mould suction casting, in the form of rods with 3 mm in diameter, are investigated. Both Ti-Zr-Pd-Si-(Nb) materials show a multi-phase (composite-like) microstructure. The main phase is cubic β-Ti phase (Im3m) but hexagonal α-Ti (P63/mmc), cubic TiPd (Pm3m), cubic PdZr (Fm3m), and hexagonal (Ti, Zr)5 Si3 (P63/mmc) phases are also present. Nanoindentation experiments show that the Ti45 Zr15 Pd30 Si5 Nb5 sample exhibits lower Young's modulus than Ti45 Zr15 Pd35 Si5 . Conversely, Ti45 Zr15 Pd35 Si5 is mechanically harder. Actually, both alloys exhibit larger values of hardness when compared with commercial Ti-40Nb, (HTi-Zr-Pd-Si ≈ 14 GPa, HTi-Zr-Pd-Si-Nb ≈ 10 GPa and HTi-40Nb ≈ 2.7 GPa). Concerning the biological behaviour, preliminary results of cell viability performed on several Ti-Zr-Pd-Si-(Nb) discs indicate that the number of live cells is superior to 94% in both cases. The studied Ti-Zr-Pd-Si-(Nb) bulk metallic system is thus interesting for biomedical applications because of the outstanding mechanical properties (relatively low Young's modulus combined with large hardness), together with the excellent biocompatibility. © 2014 Wiley Periodicals, Inc.

A theoretical investigation of mixing thermodynamics, age-hardening potential, and electronic structure of ternary M11–xM2xB2 alloys with AlB2 type structure

PubMed Central

Alling, B.; Högberg, H.; Armiento, R.; Rosen, J.; Hultman, L.

2015-01-01

Transition metal diborides are ceramic materials with potential applications as hard protective thin films and electrical contact materials. We investigate the possibility to obtain age hardening through isostructural clustering, including spinodal decomposition, or ordering-induced precipitation in ternary diboride alloys. By means of first-principles mixing thermodynamics calculations, 45 ternary M11–xM2xB2 alloys comprising MiB2 (Mi = Mg, Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta) with AlB2 type structure are studied. In particular Al1–xTixB2 is found to be of interest for coherent isostructural decomposition with a strong driving force for phase separation, while having almost concentration independent a and c lattice parameters. The results are explained by revealing the nature of the electronic structure in these alloys, and in particular, the origin of the pseudogap at EF in TiB2, ZrB2, and HfB2. PMID:25970763

The behaviour of REE and Zr-Hf fractionation in the volcanic waters of Nevado del Ruiz system (Colombia)

NASA Astrophysics Data System (ADS)

Inguaggiato, Claudio; Censi, Paolo; Zuddas, Pierpaolo; Makario Londoño, John; Chacón, Zoraida; Alzate, Diego; Brusca, Lorenzo; D'Alessandro, Walter

2015-04-01

The geochemical behaviour of Rare Earth Element (REE), Zr and Hf have been investigated in the thermal waters of Nevado del Ruiz volcanic system. These fluids are characterised by a wide range of pH ranging between 1.0 and 8.8. The acidic waters are sulphate dominated with different Cl/SO4 ratios. The Nevado del Ruiz waters allowed to investigate the behaviour of investigated elements in a wide spectrum of pH and chemical composition of water. The important role of the pH and the ionic complexes have been evidenced in the distribution of REE, Zr and Hf in the aqueous phase. The pH rules the precipitation of authigenic oxyhydroxides of Fe, Al producing changes in REE, Zr, Hf amount and strong anomalies of Cerium and Europium. Y-Ho and Zr-Hf (twin pairs) have different behaviour in strong acidic waters with respect to the water with higher pH. Yttrium and Ho have the same behaviour of Zr and Hf in waters with pH near neutral-to-neutral, showing super-chondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate suggesting an enhanced scavenging of Ho and Hf respect to Y and Zr, leading to super-chondritic ratios. In acidic waters a different behaviour of twin pairs occurs with chondritic Y/Ho ratios (reflecting the Y/Ho ratio of average local rock) and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf have been investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anions chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH<3.6. In strong acidic waters, a different fractionation of Zr and Hf have been recognised as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.

(Nbx, Zr1-x)4AlC3 MAX Phase Solid Solutions: Processing, Mechanical Properties, and Density Functional Theory Calculations.

PubMed

Lapauw, Thomas; Tytko, Darius; Vanmeensel, Kim; Huang, Shuigen; Choi, Pyuck-Pa; Raabe, Dierk; Caspi, El'ad N; Ozeri, Offir; To Baben, Moritz; Schneider, Jochen M; Lambrinou, Konstantina; Vleugels, Jozef

2016-06-06

The solubility of zirconium (Zr) in the Nb4AlC3 host lattice was investigated by combining the experimental synthesis of (Nbx, Zr1-x)4AlC3 solid solutions with density functional theory calculations. High-purity solid solutions were prepared by reactive hot pressing of NbH0.89, ZrH2, Al, and C starting powder mixtures. The crystal structure of the produced solid solutions was determined using X-ray and neutron diffraction. The limited Zr solubility (maximum of 18.5% of the Nb content in the host lattice) in Nb4AlC3 observed experimentally is consistent with the calculated minimum in the energy of mixing. The lattice parameters and microstructure were evaluated over the entire solubility range, while the chemical composition of (Nb0.85, Zr0.15)4AlC3 was mapped using atom probe tomography. The hardness, Young's modulus, and fracture toughness at room temperature as well as the high-temperature flexural strength and E-modulus of (Nb0.85, Zr0.15)4AlC3 were investigated and compared to those of pure Nb4AlC3. Quite remarkably, an appreciable increase in fracture toughness was observed from 6.6 ± 0.1 MPa/m(1/2) for pure Nb4AlC3 to 10.1 ± 0.3 MPa/m(1/2) for the (Nb0.85, Zr0.15)4AlC3 solid solution.

Ferroelectric performances and crystal structures of (Pb, La)(Zr, Ti, Nb)O{sub 3}

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

Kitamura, Naoto; Division of Ecosystem Research, Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510; Mizoguchi, Takuma

2014-02-15

In this study, we focused on Nb and La substituted Pb(Zr, Ti)O{sub 3}: i.e., (Pb, La)(Zr, Ti, Nb)O{sub 3}. As for the samples, dependences of ferroelectric properties on La and Nb compositions were examined. In addition, the crystal structures were analyzed by the Rietveld method, and then a relationship between the metal compositions and the crystal structures were discussed. From P–E hysteresis loop measurements, it was found that the remanant polarization of Pb(Zr, Ti)O{sub 3} was increased by both the La and Nb substitutions although the heavy substitution of La had an undesirable effect. It was also indicated that themore » Curie temperature decreased with increasing La content. The Rietveld analysis using synchrotron X-ray diffraction patterns demonstrated that the structure distortion was relaxed by the La and Nb substitutions. Such a change in the crystals was well consistent with the harmful effects on the Curie temperature and the remanent polarization by the heavy La substitution. - Graphical abstract: Rietveld refinement pattern of 2 mol% PbSiO{sub 3}-added Pb{sub 0.95}La{sub 0.05}Zr{sub 0.50}Ti{sub 0.45}Nb{sub 0.05}O{sub 3} (synchrotron X-ray diffraction). Display Omitted - Highlights: • (Pb,La)(Zr,Ti,Nb)O{sub 3} were successfully synthesized. • Remanant polarization of Pb(Zr,Ti)O{sub 3} was improved by substitutions of La and Nb. • Crystal structures of (Pb,La)(Zr,Ti,Nb)O{sub 3} were refined and the distortions were estimated.« less

High-field superconductivity in the Nb-Ti-Zr ternary system

NASA Astrophysics Data System (ADS)

Ralls, K. M.; Rose, R. M.; Wulff, J.

1980-06-01

Resistive critical current densities, critical fields, and normal-state electrical resistivities were obtained at 4.2 °K for 55 alloys in the Nb-Ti-Zr ternary alloy system, excepting Ti-Zr binary compositions. The resistive critical field as a function of ternary composition has a saddle point between the Nb-Ti and Nb-Zr binaries, so that ternary alloying in this system is not expected to result in higher critical fields than the binary alloys.

Corrosion-Resistant Ti- xNb- xZr Alloys for Nitric Acid Applications in Spent Nuclear Fuel Reprocessing Plants

NASA Astrophysics Data System (ADS)

Manivasagam, Geetha; Anbarasan, V.; Kamachi Mudali, U.; Raj, Baldev

2011-09-01

This article reports the development, microstructure, and corrosion behavior of two new alloys such as Ti-4Nb-4Zr and Ti-2Nb-2Zr in boiling nitric acid environment. The corrosion test was carried out in the liquid, vapor, and condensate phases of 11.5 M nitric acid, and the potentiodynamic anodic polarization studies were performed at room temperature for both alloys. The samples subjected to three-phase corrosion testing were characterized using scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDAX). As Ti-2Nb-2Zr alloy exhibited inferior corrosion behavior in comparison to Ti-4Nb-4Zr in all three phases, weldability and heat treatment studies were carried out only on Ti-4Nb-4Zr alloy. The weldability of the new alloy was evaluated using tungsten inert gas (TIG) welding processes, and the welded specimen was thereafter tested for its corrosion behavior in all three phases. The results of the present investigation revealed that the newly developed near alpha Ti-4Nb-4Zr alloy possessed superior corrosion resistance in all three phases and excellent weldability compared to conventional alloys used for nitric acid application in spent nuclear reprocessing plants. Further, the corrosion resistance of the beta heat-treated Ti-4Nb-4Zr alloy was superior when compared to the sample heat treated in the alpha + beta phase.

Enhanced electronic and optical properties of three TMD heterobilayers.

PubMed

Rehman, Shafiq Ur; Ding, Z J

2018-06-20

The physical and chemical properties of monolayers can be tuned by selective combinations so as to be useful for device applications. Here we present a density functional theory study on the structural, electronic and optical properties of three transition metal dichalcogenide (TMD) heterobilayers, ZrS2/HfS2, ZrSe2/HfSe2 and SnS2/SnSe2. These heterobilayers are predicted to be energetically and dynamically stable structures. The band structure calculation result shows that ZrS2/HfS2, ZrSe2/HfSe2 and SnS2/SnSe2 heterobilayers are semiconductors with indirect band gaps. The efficient charge carrier separation in ZrS2/HfS2 and ZrSe2/HfSe2 heterobilayers indicates that they can be employed in energy harvesting devices. Contrary to the previous report on the ZrS2/HfS2 heterobilayer, we found it to have an intrinsic type-II band alignment which is required in p-n junction diodes and tunnel field effect transistors, and the same behavior was observed in ZrSe2/HfSe2 and SnS2/SnSe2 for the first time. The ZrS2/HfS2 and ZrSe2/HfSe2 heterobilayers reveal enhanced optical absorption both in the ultraviolet and visible regions as compared to their respective monolayers, whereas the parallel and perpendicular part of the optical absorption of the SnS2/SnSe2 heterobilayer revealed an anisotropic behavior; the perpendicular part is largely improved in the higher energy region, and the parallel part of the optical absorption is improved in the ultraviolet region.

Microstructure and Room Temperature Properties of a High-Entropy TaNbHfZrTi Alloy (Postprint)

DTIC Science & Technology

2014-04-01

ANSI Std. Z39-18 O.N. Senkov et al . / Journal of Alloys and Compounds 509 (2011) 6043–6048 6045 Fig. 3. SEM backscatter electron images of a...Senkov et al . / Journal of Alloys and Compounds 509 (2011) 6043–6048 Here ci is the atomic fraction of element i. The calculated (Calc.) amix is given...O.N. Senkov et al . / Journal of Alloys and Compounds 509 (2011) 6043–6048 6047 Table 4 Relative atomic size difference, ıaij (underlined numbers), and

Water vapor effect on high-temperature oxidation behavior of Fe3Al intermetallics

PubMed Central

Chevalier, Sebastian; Juzon, Pitor; Przybylski, Kazimierz; Larpin, Jean-Pierre

2009-01-01

Fe3Al intermetallics (Fe3Al, Fe3Al-Zr, Fe3Al-Zr,Mo and Fe3Al-Zr, Mo, Nb) were oxidized at 950 °C in dry and humid (11 vol% water) synthetic air. Thermogravimetric measurements showed that the oxidation rates of the tested intermetallics were lower in humid air than in dry air (especially for Fe3Al-Zr, Mo and Fe3Al-Zr, Mo, Nb). The addition of small amounts of Zr, Mo or Nb improved the kinetics compared with that of the undoped Fe3Al. Fe3Al showed massive spallation, whereas Fe3Al-Zr, Fe3Al-Zr, Mo and Fe3Al-Zr, Mo, Nb produced a flat, adherent oxide layer. The rapid transformation of transient alumina into alpha alumina may explain the decrease in the oxidation rate in humid air. PMID:27877306

Fabrication and Characterization of Novel Refractory Coatings Using Combinatorial Nanocalorimetry

DTIC Science & Technology

2015-07-21

The report summarizes the results of solid-state reaction in Zr /B and Zr /B4C multilayers, oxidation of ZrB2, the effect of Nb and C doping on the...oxidation resistance of the coatings at temperatures below 1000 K, but the temperature-dependence of the diffusion rate constant suggests that Nb ...28 B4. Zr -B- Nb oxidation

Microstructure and Properties of a Refractory NbCrMo0.5Ta0.5ZrTi Alloy (Preprint)

DTIC Science & Technology

2011-10-01

slightly enriched with Nb , Mo and Ta and depleted with Zr and Cr, and its lattice parameter after HIP was a = 324.76 ± 0.16 pm. The BCC2 phase was...FCC phase was highly enriched with Cr and it was identified as a Laves C15 phase, ( Zr ,Ta)(Cr,Mo, Nb )2, with the lattice parameter a = 733.38 ± 0.18 pm...with Nb , Mo and Ta and depleted with Zr and Cr, and its lattice parameter after HIP was a = 324.76 ± 0.16 pm. The BCC2 phase was enriched with Zr and Ti

Mechanical Properties of Low-Density, Refractory Multi-Principal Element Alloys of the Cr-Nb-Ti-V-Zr System (Postprint)

DTIC Science & Technology

2014-04-01

PROPERTIES OF LOW-DENSITY, REFRACTORY MULTI-PRINCIPAL ELEMENT ALLOYS OF THE Cr– Nb –Ti–V– Zr SYSTEM (POSTPRINT) 5a. CONTRACT NUMBER In-house 5b...element alloys of the Cr– Nb –Ti–V– Zr systemO.N. Senkov n, S.V. Senkova, D.B. Miracle, C. Woodward Air Force Research Laboratory, Materials and...densities below 7.0 g/cm3 have recently been produced by alloying Nb (rNb¼8.57 g/cm3) with four low density refractory elements, V (rV¼6.11 g/cm3), Zr

Surface phenomena of hydroxyapatite film on the nanopore formed Ti-29Nb-xZr alloy by anodization for bioimplants.

PubMed

Kim, Eun-Ju; Jeong, Yong-Hoon; Choe, Han-Cheol

2013-03-01

In this study, surface phenomena of hydroxyapatite (HA) film on the nanopore formed Ti-29Nb-xZr alloy by anodization for bioimplants have been investigated by electron beam physical vapor deposition (EB-PVD), field emission scanning electron microscope (FE-SEM), X-ray diffractometer (XRD), potentiostat and contact angle. The microstructure of Ti-29Nb-xZr alloys exhibited equiaxed structure and alpha" phase decreased, whereas beta phase increased as Zr content increased. The increment of Zr contents in HA coated nanotubular Ti-29Nb-xZr alloys showed good corrosion potential in 0.9% NaCI solution. The wettability of HA coated nanotubular surface was higher than that of non-coated samples.

Evolution of interphase and intergranular strain in zirconium-niobium alloys during deformation at room temperature

NASA Astrophysics Data System (ADS)

Cai, Song

Zr-2.5Nb is currently used for pressure tubes in the CANDU (CANada Deuterium Uranium) reactor. A complete understanding of the deformation mechanism of Zr-2.5Nb is important if we are to accurately predict the in-reactor performance of pressure tubes and guarantee normal operation of the reactors. This thesis is a first step in gaining such an understanding; the deformation mechanism of ZrNb alloys at room temperature has been evaluated through studying the effect of texture and microstructure on deformation. In-situ neutron diffraction was used to monitor the evolution of the lattice strain of individual grain families along both the loading and Poisson's directions and to track the development of interphase and intergranular strains during deformation. The following experiments were carried out with data interpreted using elasto-plastic modeling techniques: (1) Compression tests of a 100%betaZr material at room temperature. (2) Tension and compression tests of hot rolled Zr-2.5Nb plate material. (3) Compression of annealed Zr-2.5Nb. (4) Cyclic loading of the hot rolled Zr-2.5Nb. (5) Compression tests of ZrNb alloys with different Nb and oxygen contents. The experimental results were interpreted using a combination of finite element (FE) and elasto-plastic self-consistent (EPSC) models. The phase properties and phase interactions well represented by the FE model, the EPSC model successfully captured the evolution of intergranular constraint during deformation and provided reasonable estimates of the critical resolved shear stress and hardening parameters of different slip systems under different conditions. The consistency of the material parameters obtained by the EPSC model allows the deformation mechanism at room temperature and the effect of textures and microstructures of ZrNb alloys to be understood. This work provides useful information towards manufacturing of Zr-2.5Nb components and helps in producing ideal microstructures and material properties for pressure tubes. Also it is helpful in guiding the development of new materials for the next generation of nuclear reactors. Furthermore, the large data set obtained from this study can be used in evaluation and improving current and future polycrystalline deformation models.

Mixing effects in a ternary Hf-Zr-Ni metallic melt

NASA Astrophysics Data System (ADS)

Nowak, B.; Holland-Moritz, D.; Yang, F.; Evenson, Z.; Meyer, A.

2018-03-01

We study the effect of the substitution of Zr by Hf on the dynamical behavior in the Zr36Ni64 melt. A reduced measured self-diffusion coefficient and a higher measured melt viscosity for an increased amount of Hf were observed. The ternary Hf10Zr25Ni65 melt, which exhibits a pronounced deviation from Arrhenius behavior over a studied temperature range of 550 K, can be accurately described by the scaling law of mode-coupling theory (MCT) with almost equal parameters for the self-diffusion and the viscosity. Although we only substitute alloy components with a nearly equal atomic size and the measured overall packing fraction remains almost unchanged, the dynamics in Hf10Zr25Ni65 are slower compared to Zr36Ni64 . This corresponds also to a higher critical temperature Tc and might be induced by different chemical interactions in the melts. The increased Tc results in a significantly smaller difference between liquidus and critical temperature Δ TLC=TL-Tc for the ternary melt in comparison with Zr36Ni64 , which may favor the glass formation in the Hf10Zr25Ni65 melt.

Optical and structural characterization of Nb, Zr, Nb/Zr, Zr/Nb thin films on Si3N4 membranes windows

NASA Astrophysics Data System (ADS)

Jimenez, K.; Gaballah, A. E. H.; Ahmed, Nadeem; Zuppella, P.; Nicolosi, P.

2017-05-01

High brilliance sources in the EUV spectral range such as Synchrotron and Free Electron Lasers (FEL) are widely used in multiple scientific and technological applications thanks to their peculiar characteristics. One main technical problem of FEL is related to the rejection of high harmonics, seed laser, first stage photons, and diffuse light; in order to improve the quality of the beam delivered by these sources, a suitable optical system acting as band-pass filters is necessary. In this paper we discuss the optical and structure characterization of Nb/Zr and Zr/Nb self-stand transmittance filters, designed for 4.5 nm-20 nm wavelength ranges. In order to understand the properties of these bilayers filters, a campaign of measurements has been planned to be performed on Zr and Nb films on Si3N4 membrane windows and silicon substrates, deposited with e- beam deposition technique. Comparison of the results has been planned too. IMD transmittance and reflectance simulations, together with preliminary AFM and reflectance measurements will be shown in this work.

The petrogenesis of island arc basalts from Gunung Slamet volcano, Indonesia: Trace element and 87Sr /86Sr contraints

NASA Astrophysics Data System (ADS)

Vukadinovic, Danilo; Nicholls, Ian A.

1989-09-01

Selected major and trace elements, rare earth element (REE) and 87Sr /86Sr data are presented for arc basalts from Gunung Slamet volcano, Java, Indonesia. On the basis of stratigraphy, trace element content, Zr/Nb, and 87Sr /86Sr ratios, Slamet basalts can be broadly categorized into high abundance magma (HAM) and low abundance magma (LAM) types. Provided the quantities of 'immobile' trace elements (in aqueous systems) such as Nb, Hf and Zr in the mantle wedge and ensuing magmas are unaffected by additions from subducted lithosphere or overlying arc crust, a model may be developed whereby LAM are generated by higher degrees of melting in the mantle wedge (13%) compared to HAM (7%). Hf/Nb or Zr/Nb ratio systematics indicate that prior to metasomatism by the underlying lithosphere, the Slamet mantle wedge was similar in chemical character to transitional-MORB source mantle. Conversely, examination of immobile/mobile incompatible trace element ratios (IMITER) provide clues to the nature of the metasomatizing agent, most likely derived from the subducted slab (basalts and sediments). HAM have constant IMITER ( e.g.Nb/U, Zr/K), whereas LAM show a negative correlation between IMITER and 87Sr /86Sr . Metasomatism of the mantle wedge was modelled by interaction with either a slab-derived-melt or -aqueous fluid. Yb/Sr and 87Sr /86Sr ratios from Slamet basalts and oceanic sediments suggest that 'bulk' mixing of the latter into the mantle wedge is unlikely. Instead, sediments probably interact with overlying mantle in the same way that subducted basalts do-either as melts or fluids. In the case of slab-derived melts mixing with 'pristine' mantle, good agreement with back-calculated values for HAM and LAM sources can be achieved only if a residual phase such as rutile persists in the subducting lithosphere. In the case of fluids, excellent agreement with back-calculated values is obtained for all elements except heavy REE. It is tentatively suggested that aqueous slab-derived fluids, relatively rich in mobile incompatible elements, are the probable metasomatizing agent responsible for the chemical characteristics, particularly low IMITER, of Slamet and other island arc basalts (IAB). Because the mobilities/solubilities of Sr in high pressure and temperature fluids are poorly known, the modelled subduction fluids are not necessarily efficient at raising 87Sr /86Sr in the overlying mantle wedge. As a result, positive correlations between e.g.Ba/La vs. 87Sr /86Sr need not be observed in arc suites, especially if the relative mobilities of Sr, Ba, and La are dependent upon intensive parameters during metasomatism. Assimilation of arc crust by uprising magmas (up to ~14% of crustal Sr) can account for the range of 87Sr /86Sr in HAM. However, calculating the amounts of arc crustal assimilation by uprising magmas is poorly constrained since such modelling is highly dependent upon previous estimates of the degree of metasomatism undergone by the mantle wedge.

Paleozoic mafic-intermediate intrusions (320-287 Ma) in the Kalatongke area, southern Altai, NW China: Products of protracted magmatism in a convergent tectonic setting

NASA Astrophysics Data System (ADS)

Qian, Zhuangzhi; Duan, Jun; Li, Chusi; Xu, Gang; Feng, Yanqing; Ren, Meng

2018-06-01

Numerous small mafic-intermediate intrusions are present in the Kalatongke area in the southern part of the Paleozoic Altai Orogenic Belt, NW China. Previous studies reveal that most of these intrusions were emplaced at ∼287 Ma, broadly coeval with the eruption of alkaline flood basalts at ⩽282 Ma in the Tarim Craton. The similar ages have led some researchers to believe that the Tarim flood basalts and the Kalatongke mafic-intermediate intrusions are related to the same mantle plume. New and existing geochronological and geochemical data for the mafic-intermediate intrusions in the Kalatongke area together do not support such interpretation. Most of the intrusions in this small area (4.5 × 2 km) were emplaced at ∼287 Ma but our new data reveal that older intrusive rocks with zircon U-Pb ages from 290 ± 1.5 to 320 ± 2 Ma are also present. The temporal and spatial distribution of these intrusions does not show a hotspot track as expected by the mantle plume model. The intrusive rocks have similar Nd-Hf isotope compositions (εNd = 3-9, εHf = 15-19) and are all characterized by light REE enrichments relative to heavy REE, plus pronounced negative Nb-Ta anomalies. The oldest intrusion (∼320 Ma) also shows negative Zr-Hf anomalies, which are common in arc basalts but absent in continental flood basalts. The results of mixing calculations based on Sr-Nd-Hf isotopes and selected trace elements (Th, Nb and Yb) indicate that the parental magmas for these intrusions were all enriched in Th and depleted in Nb prior to crustal contamination, similar to the magmas generated in a convergent tectonic setting from subduction to post-subduction elsewhere in the world. The results from this study remind us that temporal correlation is not a reliable tool to determine the size of a mantle plume.

Fuel element design for the enhanced destruction of plutonium in a nuclear reactor

DOEpatents

Crawford, Douglas C.; Porter, Douglas L.; Hayes, Steven L.; Hill, Robert N.

1999-01-01

A uranium-free fuel for a fast nuclear reactor comprising an alloy of Pu, Zr and Hf, wherein Hf is present in an amount less than about 10% by weight of the alloy. The fuel may be in the form of a Pu alloy surrounded by a Zr--Hf alloy or an alloy of Pu--Zr--Hf or a combination of both.

Chlorine mobility during annealing in N2 in ZrO2 and HfO2 films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Ferrari, S.; Scarel, G.; Wiemer, C.; Fanciulli, M.

2002-12-01

Atomic layer deposition (ALD) growth of high-κ dielectric films (ZrO2 and HfO2) was performed using ZrCl4, HfCl4, and H2O as precursors. In this work, we use time of flight secondary ion mass spectrometry to investigate the chlorine distribution in ALD grown ZrO2 and HfO2 films, and its evolution during rapid thermal processes in nitrogen atmosphere. Chlorine outdiffusion is found to depend strongly upon annealing temperature and weakly upon the annealing time. While in ZrO2 chlorine concentration is significantly decreased already at 900 °C, in HfO2 it is extremely stable, even at temperatures as high as 1050 °C.

Design lateral heterostructure of monolayer ZrS2 and HfS2 from first principles calculations

NASA Astrophysics Data System (ADS)

Yuan, Junhui; Yu, Niannian; Wang, Jiafu; Xue, Kan-Hao; Miao, Xiangshui

2018-04-01

The successful fabrication of two-dimensional lateral heterostructures (LHS's) has opened up unprecedented opportunities in material science and device physics. It is therefore highly desirable to search for more suitable materials to create such heterostructures for next-generation devices. Here, we investigate a novel lateral heterostructure composed of monolayer ZrS2 and HfS2 based on density functional theory. The phonon dispersion and ab initio molecular dynamics analysis indicate its good kinetic and thermodynamic stability. Remarkably, we find that these lateral heterostructures exhibit an indirect to direct bandgap transition, in contrast to the intrinsic indirect bandgap nature of ZrS2 and HfS2. The type-II alignment and chemical bonding across the interline have also been revealed. The tensile strain is proved to be an efficient way to modulate the band structure. Finally, we further discuss other three stable lateral heterostructures: (ZrSe2)2(HfSe2)2 LHS, (ZrS2)2(ZrSe2)2 LHS and (HfS2)2(HfSe2)2 LHS. Generally, the lateral heterostructures of monolayer ZrS2 and HfS2 are of excellent electrical properties, and may find potential applications for future electronic devices.

Site Preference of Ternary Alloying Additions to AuTi

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

2006-01-01

Atomistic modeling of the site substitution behavior of several alloying additions, namely. Na, Mg, Al, Si. Sc, V, Cr, Mn. Fe, Co, Ni, Cu, Zn, Y, Zr. Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, and Pt in B2 TiAu is reported. The 30 elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice. Results of large scale simulations are also presented, distinguishing between additions that remain in solution from those that precipitate a second phase.

Computational Material Modeling of Hydrated Cement Paste Calcium Silicate Hydrate (C-S-H) Chemistry Structure - Influence of Magnesium Exchange on Mechanical Stiffness: C-S-H Jennite

DTIC Science & Technology

2015-04-27

MODELING OF C-S-H Material chemistry level modeling following the principles and techniques commonly grouped under Computational Material Science is...Henmi, C. and Kusachi, I. Monoclinic tobermorite from fuka, bitchu-cho, Okoyama Perfecture. Japan J. Min. Petr. Econ . Geol. (1989)84:374-379. [22...31] Liu, Y. et al. First principles study of the stability and mechanical properties of MC (M=Ti, V, Zr, Nb, Hf and Ta) compounds. Journal of Alloys and Compounds. (2014) 582:500-504. 10

Evolution of the lunar highland crust

NASA Technical Reports Server (NTRS)

Taylor, S. R.; Bence, A. E.

1975-01-01

The evolution of three distinct element associations in the lunar highland crust is discussed in terms of the Taylor-Jakes model which involves melting of most of the moon during accretion. Sources for (1) high Ca, Al, Sr, Eu, (2) high Mg and Cr, and (3) high K, REE, Zr, Hf, Nb are suggested. Bombardment by large projectiles during the differentiation process causes melting and mixing, which produces a wide range of compositions in the crust. The formation of dunite, troctolite, high-, medium-, and low-K Fra Mauro basalts, and rocks close to the olivine-spinel-plagioclase peritectic point is considered.

Magmatic evolution of the Jbel Boho alkaline complex in the Bou Azzer inlier (Anti-Atlas/Morocco) and its relation to REE mineralization

NASA Astrophysics Data System (ADS)

Benaouda, Rachid; Holzheid, Astrid; Schenk, Volker; Badra, Lakhlifi; Ennaciri, Aomar

2017-05-01

The Jbel Boho complex (Anti-Atlas/Morocco) is an alkaline magmatic complex that was formed during the Precambrian-Cambrian transition, contemporaneous with the lower early Cambrian dolomite sequence. The complex consists of a volcanic sequence comprising basanites, trachyandesites, trachytes and rhyolites that is intruded by a syenitic pluton. Both the volcanic suite and the pluton are cut by later microsyenitic and rhyolitic dykes. Although all Jbel Boho magmas were probably ultimately derived from the same, intraplate or plume-like source, new geochemical evidence supports the concept of a minimum three principal magma generations having formed the complex. Whereas all volcanic rocks (first generation) are LREE enriched and appear to be formed by fractional crystallization of a mantle-derived magma, resulting in strong negative Eu anomalies in the more evolved rocks associated with low Zr/Hf and Nb/Ta values, the younger syenitic pluton displays almost no negative Eu anomaly and very high Zr/Hf and Nb/Ta. The syenite is considered to be formed by a second generation of melt and likely formed through partial melting of underplated mafic rocks. The syenitic pluton consists of two types of syenitic rocks; olivine syenite and quartz syenite. The presence of quartz and a strong positive Pb anomaly in the quartz syenite contrasts strongly with the negative Pb anomaly in the olivine syenite and suggests the latter results from crustal contamination of the former. The late dyke swarm (third generation of melt) comprises microsyenitic and subalkaline rhyolitic compositions. The strong decrease of the alkali elements, Zr/Hf and Nb/Ta and the high SiO2 contents in the rhyolitic dykes might be the result of mineral fractionation and addition of mineralizing fluids, allowing inter-element fractionation of even highly incompatible HFSE due to the presence of fluorine. The occurrence of fluorite in some volcanic rocks and the Ca-REE-F carbonate mineral synchysite in the dykes with very high LREE contents (Ce ∼720 ppm found in one rhyolitic dyke) suggest the fluorine-rich nature of this system and the role played by addition of mineralizing fluids. The REE mineralization expressed as synchysite-(Ce) is detected in a subalkaline rhyolitic dyke (with ΣLREE = 1750 ppm) associated with quartz, chlorite and occasionally with Fe-oxides. The synchysite mineralization is probably the result of REE transport by acidic hydrothermal fluids as chloride complex and their neutralization during fluid-rock interaction. The major tectonic change from compressive to extensional regime in the late Neoproterozoic induced the emplacement of voluminous volcaniclastic series of the Ediacran Ouarzazate Group. The alkaline, within-plate nature of the Jbel Boho igneous complex implies that this extensional setting continued during the early Cambrian.

Origin and evolution of rare amphibole-bearing mantle peridotites from Wilcza Góra (SW Poland), Central Europe

NASA Astrophysics Data System (ADS)

Matusiak-Małek, Magdalena; Puziewicz, Jacek; Ntaflos, Theodoros; Grégoire, Michel; Kukuła, Anna; Wojtulek, Piotr Marian

2017-08-01

Mantle xenoliths in the 20 Ma Wilcza Góra basanite (Lower Silesia, NE Bohemian Massif) are mostly harzburgites, some with amphibole which is exceptional in the region. Forsterite content in olivine defines two Groups of peridotites: Group A (Fo89.1-91.5) and Group B (Fo84.2-89.2). Hornblende-clinopyroxenite, websterite and one composite xenolith consisting of dunite, olivine-hornblendite and pyroxene-hornblende-peridotite contain olivine with Fo77.3-82.5 and are classified as Group C. Group A xenoliths contain Al-poor orthopyroxene and some contain LREE-enriched clinopyroxene with negative Ti, Zr-Hf and Nb-Ta anomalies. Spinel (Cr# 0.57-0.68) is scarce in Group A, and Cr-rich pargasite occurs in only two xenoliths. Group B xenoliths contain less magnesian orthopyroxene and clinopyroxene. The REE patterns of Group B clinopyroxene are convex downward, less enriched in LREE and have smaller negative Ti, Zr-Hf and Nb-Ta anomalies than those in Group A. The Cr# in Group B spinel is 0.26-0.56, while pargasite is Ti-rich and Cr-poor. Clinopyroxene from Group C is low magnesian, slightly enriched in LREE and has no negative Ti, Zr-Hf and Nb-Ta anomalies. Group C pargasite is rich in Ti and poor in Cr. Equilibration temperatures recorded in all groups vary within the range of 905-970 °C. Xenoliths from Wilcza Góra record a polyphase lithospheric mantle evolution, starting with melting which extracted ca. 30% melt from the protolith and left a harzburgite residuum depleted in Al, lacking clinopyroxene and containing rare Cr-rich spinel. This residuum was later overprinted by chromatographic metasomatism by carbonated hydrous silicate melt related to Cenozoic volcanism. The metasomatic agent was locally hydrous enough to enable amphibole to crystallize. The Group C pyroxenites formed directly from the metasomatic melt or during peridotite-melt reactions at high melt-rock ratio. The melt is inferred to have percolated through the wall-rock peridotite, decreasing its amount and changing composition (and that of the crystallizing clinopyroxene and amphibole) as it differentiated chromatographically from Groups B to A. Enrichment in carbonatite component occurred in the further parts of a chromatographic column. Group B peridotites closest to the source of the metasomatic agent were percolated by an iron-rich melt. The latter, aside from crystallizing clinopyroxene and amphibole, caused Fe-enrichment in the host harzburgite. Such a metasomatic history is typical for the lithospheric mantle located beneath the northern margin of the Bohemian Massif, but Wilcza Góra is the only locality, where activity of a hydrous metasomatic agent is recorded. Thus, the lithospheric mantle in this area was affected by mafic silicate metasomatic agents of variable compositions.

Mechanical properties and bio-tribological behaviors of novel beta-Zr-type Zr-Al-Fe-Nb alloys for biomedical applications.

PubMed

Hua, Nengbin; Chen, Wenzhe; Zhang, Lei; Li, Guanghui; Liao, Zhenlong; Lin, Yan

2017-07-01

The present study prepares novel Zr 70+x Al 5 Fe 15-x Nb 10 (x=0, 5) alloys by arc-melting for potential biomedical application. The mechanical properties and bio-tribological behaviors of the Zr-based alloys are evaluated and compared with biomedical pure Zr. The as-prepared alloys exhibit a microstructure containing a micrometer-sized dendritic beta-Zr phase dispersed in a Zr 2 Fe-typed matrix. It is found that increasing the content of Zr is favorable for the mechanical compatibility with a combination of low Young's modulus, large plasticity, and high compressive strength. The wear resistance of the Zr-Al-Fe-Nb alloys in air and phosphate buffer saline (PBS) solution is superior to that of pure Zr. The wear mechanism of Zr-based alloys sliding in air is controlled by oxidation and abrasive wear whereas that sliding in PBS is controlled by synergistic effects of the abrasive and corrosive wear. Electrochemical measurements demonstrate that the Zr-based alloys are corrosion resistant in PBS. Their bio-corrosion resistance is improved with the increase in Zr content, which is attributed to the enrichment in Zr and decrease in Al concentration in the surface passive film of alloys. The Zr 75 Al 5 Fe 10 Nb 10 exhibits the best corrosion resistance in PBS, which contributes to its superior wear resistance in a simulated body environment. The combination of good mechanical properties, corrosion resistance, and biotribological behaviors of the Zr-Al-Fe-Nb alloys offers them potential advantages in biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Are new TiNbZr alloys potential substitutes of the Ti6Al4V alloy for dental applications? An electrochemical corrosion study.

PubMed

Ribeiro, Ana Lúcia Roselino; Hammer, Peter; Vaz, Luís Geraldo; Rocha, Luís Augusto

2013-12-01

The main aim of this work was to assess the electrochemical behavior of new Ti35Nb5Zr and Ti35Nb10Zr alloys in artificial saliva at 37 °C to verify if they are indicated to be used as biomaterials in dentistry as alternatives to Ti6Al4V alloys in terms of corrosion protection efficiency of the material. Electrochemical impedance spectroscopy (EIS) experiments were carried out for different periods of time (0.5-216 h) in a three-electrode cell, where the working electrode (Ti alloys) was exposed to artificial saliva at 37 °C. The near-surface region of the alloys was investigated using x-ray photoelectron spectroscopy (XPS). All alloys exhibited an increase in corrosion potential with the immersion time, indicating the growth and stabilization of the passive film. Ti35Nb5Zr and Ti6Al4V alloys had their EIS results interpreted by a double-layer circuit, while the Ti35Nb10Zr alloy was modeled by a one-layer circuit. In general, the new TiNbZr alloys showed similar behavior to that observed for the Ti6Al4V. XPS results suggest, in the case of the TiNbZr alloys, the presence of a thicker passive layer containing a lower fraction of TiO2 phase than that of Ti6Al4V. After long-term immersion, all alloys develop a calcium phosphate phase on the surface. The new TiNbZr alloys appear as potential candidates to be used as a substitute to Ti6Al4V in the manufacturing of dental implant-abutment sets.

Comparisons of immersion and electrochemical properties of highly biocompatible Ti-15Zr-4Nb-4Ta alloy and other implantable metals for orthopedic implants

NASA Astrophysics Data System (ADS)

Okazaki, Yoshimitsu; Nagata, Hiroyuki

2012-12-01

Metal release from implantable metals and the properties of oxide films formed on alloy surfaces were analyzed, focusing on the highly biocompatible Ti-15Zr-4Nb-4Ta alloy. The thickness and electrical resistance (Rp) of the oxide film on such an alloy were compared with those of other implantable metals. The quantity of metal released during a 1-week immersion test was considerably smaller for the Ti-15Zr-4Nb-4Ta than the Ti-6Al-4V alloy. The potential (E10) indicating a current density of 10 μA cm-2 estimated from the anodic polarization curve was significantly higher for the Ti-15Zr-4Nb-4Ta than the Ti-6Al-4V alloy and other metals. Moreover, the oxide film (4-7 nm thickness) formed on the Ti-15Zr-4Nb-4Ta surface is electrochemically robust. The oxide film mainly consisted of TiO2 with small amounts of ZrO2, Nb2O5 and Ta2O5 that made the film electrochemically stable. The Rp of Ti-15Zr-4Nb-4Ta was higher than that of Ti-6Al-4V, i.e. 0.9 Ω cm2 in 0.9% NaCl and 1.3 Ω cm2 in Eagle's medium. This Rp was approximately five-fold higher than that of stainless steel, which has a history of more than 40 years of clinical use in the human body. Ti-15Zr-4Nb-4Ta is a potential implant material for long-term clinical use. Moreover, E10 and Rp were found to be useful parameters for assessing biological safety.

Effects of processing and prolonged high temperature exposure on the microstructure of Nb-1Zr-C sheet

NASA Technical Reports Server (NTRS)

Uz, Mehmet; Titran, R. H.

1993-01-01

High temperature stability of the microstructure of Nb-1Zr sheet containing 0.1 and 0.06 wt. percent C was studied as affected by processing and prolonged 1350 K exposure with and without applied stress. Sheets were fabricated by cold rolling bars that were single-, double-, or triple-extruded at 1900 K. Creep samples were double-annealed (1 h at 1755 K + 2 h at 1475 K) prior to testing at 1350 K and 10,000 - 34,500 h. The microstructures of the as-cast, extruded, rolled, DA, and crept samples were characterized using various metallographic and analytical methods. The precipitates were rather coarse Nb2C initially, but transformed to finer (less than or equal to 1 micron) carbides of (Zr, Nb)C with each subsequent high temperature process. The grain size, and the relative amount and morphology of (Zr, Nb)C were found to be affected by the number of extrusions and to some extent by C-content. However, the microstructures of all the crept samples were similar with (Zr, Nb)C distributed throughout the matrix indicating that prolonged exposure to 1350 K gave rise to complete transformation of Nb2C to (Zr, Nb)C regardless of the processing history. These and other observations are presented with the emphasis on the correlation between processing, microstructure, and creep properties.

Gas Phase Chromatography of some Group 4, 5, and 6 Halides

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

Sylwester, Eric Robert

1998-10-01

Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr 4, HfBr 4, RfBr 4, NbBr 5, TaOBr 3, HaCl 5, WBr 6, FrBr, and BiBr 3. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography.more » Adsorption Enthalpy (ΔH a) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔH a was observed: RfBr 4 > ZrBr 4 > HfBr 4. The ΔH a values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of 261Rf was performed. 261Rf was produced via the 248Cm( 18O, 5n) reaction and observed with a half-life of 74 -6 +7 seconds, in excellent agreement with the previous measurement of 78 -6 +11 seconds. We recommend a new half-life of 75±7 seconds for 261Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant temperature) gas phase chromatography instrument to a thermochromatographic (variable temperature) instrument have been completed. Thermochromatography is a technique that can be used to study the volatility and ΔH a of longer-lived isotopes off-line, Future work will include a comparison between the two techniques and the use of thermochromatography to study isotopes in a wider range of half-lives and molecular structures.« less

Variation of Nb-Ta, Zr-Hf, Th-U and K-Cs in two diabase-granophyre suites

USGS Publications Warehouse

Gottfried, D.; Greenland, L.P.; Campbell, E.Y.

1968-01-01

Concentrations of Nb, Ta, Zr, Hf, Th, U and Cs have been determined in samples of igneous rocks representing the diabase-granophyre suites from Dillsburg, Pennsylvania, and Great Lake, Tasmania. Niobium and tantalum have a three to fourfold increase with differentiation in each of the suites. The chilled margin of the Great Lake intrusion contains half the niobium and tantalum content (5.3 ppm and 0.4 ppm, respectively) of the chilled basalt from Dillsburg (10 ppm and 0.9 ppm, respectively). The twofold difference between the suites is correlated with differences in their titanium content. The average Nb Ta ratios for each suite are similar: 13.5 for the Great Lake suite, and 14.4 for the Dillsburg suite. The zirconium content of the two suites is essentially the same and increases from 50 to 60 ppm in the chilled margins to 240-300 ppm in the granophyres. Hafnium is low in the early formed rocks (0.5 -1.5 ppm and achieves a maximum in the granophyres (5-8 ppm). The Zr Hfratio decreases from 68 to 33 with progressive differentiation. In the Dillsburg suite thorium and uranium increase from 2.6 ppm and 0.6 ppm, respectively, in the chilled samples to 11.8 ppm and 3.1 ppm in the granophyres. The chilled margin of the Great Lake suite contains 3.2 ppm thorium and 9.8 ppm uranium; the granophyre contains 11.2 ppm thorium and 2.8 ppm uranium. The average Th U ratios of the Dillsburg and Great Lake suites are nearly the same-4.1 and 4.4, respectively. Within each suite the Th U ratio remains quite constant. Cesium and the K Cs ratio do not vary systematically in the Dillsburg suite possibly because of redistribution or loss of cesium by complex geologic processes. Except for the chilled margin of the Great Lake suite, the variation of Cs and the K Cs ratio are in accord with theoretical considerations. Cesium increases from about 0.6 ppm in the lower zone to 3.5 ppm in the granophyre; the K Cs ratio varies from 10 ?? 103 in the lower zone to 6 ?? 103 in the granophyre. A comparison of the abundance of some of these elements is made with those reported on oceanic tholeiites from the Atlantic and Pacific oceans. Trace elements with large ionic radii (Th, U, Cs) are present in significantly greater concentrations in the two continental tholeiitic series than in the oceanic tholeiites. However, this does not seem to be true for lithophilic elements of smaller ionic radii (Zr and Nb). These trace element distribution patterns, when considered with other minor element and isotopic studies, indicate that 1. (1) crustal contamination does not entirely account for differences between continental and oceanic tholeiites, and 2. (2) the oceanic tholeiites do not necessarily delimit the geochemical characteristics of the mantle. ?? 1968.

Fuel element design for the enhanced destruction of plutonium in a nuclear reactor

DOEpatents

Crawford, D.C.; Porter, D.L.; Hayes, S.L.; Hill, R.N.

1999-03-23

A uranium-free fuel for a fast nuclear reactor comprising an alloy of Pu, Zr and Hf, wherein Hf is present in an amount less than about 10% by weight of the alloy. The fuel may be in the form of a Pu alloy surrounded by a Zr--Hf alloy or an alloy of Pu--Zr--Hf or a combination of both. 7 figs.

Davinciite, Na12K3Ca6Fe{3/2+}Zr3(Si26O73OH)Cl2, a New K,Na-Ordered mineral of the eudialyte group from the Khibiny Alkaline Pluton, Kola Peninsula, Russia

NASA Astrophysics Data System (ADS)

Khomyakov, A. P.; Nechelyustov, G. N.; Rastsvetaeva, R. K.; Rozenberg, K. A.

2013-12-01

This paper presents a description of a new zirconosilicate of the eudialyte group, which was named davinciite in honor of Leonardo da Vinci (1452-1519), a famous Italian scientist, painter, sculptor and architect. The new mineral has been found in hyperagpaitic pegmatite at the Rasvumchorr Mountain, Khibiny Pluton, Kola Peninsula, as relict inclusions, up to 1-2 mm in size in a rastsvetaevite matrix. It is associated with nepheline, sodalite, potassium feldspar, delhayelite, aegirine, shcherbakovite, villiaumite, nitrite, nacaphite, rasvumite, and djerfisherite. Davinciite is dark lavender and transparent, with a vitreous luster and white streak. The new mineral is brittle, with conchoidal fracture; the Mohs' hardness is 5. No indications of cleavage or parting were observed. The measured density is 2.82(2) g/cm3 (volumetric method); the calculated density is 2.848 g/cm3. Davinciite is optically uniaxial, positive; ω = 1.603(2), ɛ = 1.605(2). It is nonpleochroic and nonfluorescent in UV light. The new mineral slowly breaks down and gelates in 50% HCl and HNO3. It is trigonal, space group R3m. The unit-cell dimensions are a = 14.2956(2), c = 30.0228(5) Å, V=5313.6(2) Å3. The strongest reflections in the X-ray powder diffraction pattern [ d, Å ( I, %) ( hkl)] are as follows: 2.981(100)(315), 2.860(96)(404), 4.309(66)(205), 3.207(63)(208), 6.415(54)(104), 3.162(43)(217). The chemical composition (electron microprobe, H2O calculated from X-ray diffraction data) is as follows, wt %: 12.69 Na2O, 3.53 K2O, 11.02 CaO, 0.98 SrO, 0.15 BaO, 5.33 FeO, 0.37 MnO, 0.07 Al2O3, 51.20 SiO2, 0.39 TiO2, 11.33 ZrO2, 0.21HfO2, 0.09 Nb2O5, 1.89 Cl, 0.93H2O, -O = Cl2 0.43; total is 99.75. The empirical formula calculated on the basis of Si + Al + Zr + Hf + Ti + Nb = 29 ( Z = 3) is (Na1l.75Sr0.29Ba0.03)Σ12.07(K2.28Na0.72)Σ3Ca5.99(Fe2.26Mn0.16)Σ2.42(Zr2.80Ti0.15Hf0.03Nb0.02) Σ3(Si1.96Al0.04)Σ2[Si3O9]2 [Si9O27]2[(OH)1.42O0.58]Σ2[Cl1.62(H2O)0.38]Σ2 · 0.48H2O. The simplified formula is Na12K3Ca6Fe{3/2+}Zr3(Si26O73OH)Cl2. The IR-spectrum is given and the crystal structure is described. The position of davinciite in the crystal chemical taxonomy of the eudialyte group is shown, and its relationships with the other eudialyte-group minerals (acentric eudialyte, andrianovite, and kentbrooksite) are characterized. The type material of davinciite is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.

Multifunctional Beta Ti Alloy with Improved Specific Strength

NASA Astrophysics Data System (ADS)

Park, Chan Hee; Hong, Jae-Keun; Lee, Sang Won; Yeom, Jong-Taek

2017-12-01

Gum metals feature properties such as ultrahigh strength, ultralow elastic modulus, superelasticity, and superplasticity. They are composed of elements from Groups 4 and 5 of the periodic table and exist when the valance electron concentration (\\overline{e/a}) is 4.24; the bond order (\\overline{Bo}) is 2.87; and the "d" electron-orbital energy level (\\overline{Md}) is 2.45 eV. Typical compositions include Ti-23Nb-2Zr-0.7Ta-O and Ti-12Ta-9Nb-6Zr-3 V-O, which contain large amounts of heavy Group-5 elements such as Nb and Ta. In the present study, to improve the specific strength of a multifunctional beta Ti alloy, three alloys (Ti-20Nb-5Zr-1Fe-O, Ti-12Zr-10Mo-4Nb-O, and Ti-24Zr-9Cr-3Mo-O) were designed by satisfying the above three requirements while adding Fe, Mo, and Cr, which are not only lightweight but also have strong hardening effects. Microstructural and mechanical property analyses revealed that Ti-20Nb-5Zr-1Fe-O has a 25% higher specific strength than gum metal while maintaining an ultralow elastic modulus.

Microstructure research for ferroelectric origin in the strained Hf0.5Zr0.5O2 thin film via geometric phase analysis

NASA Astrophysics Data System (ADS)

Bi, Han; Sun, Qingqing; Zhao, Xuebing; You, Wenbin; Zhang, David Wei; Che, Renchao

2018-04-01

Recently, non-volatile semiconductor memory devices using a ferroelectric Hf0.5Zr0.5O2 film have been attracting extensive attention. However, at the nano-scale, the phase structure remains unclear in a thin Hf0.5Zr0.5O2 film, which stands in the way of the sustained development of ferroelectric memory nano-devices. Here, a series of electron microscopy evidences have illustrated that the interfacial strain played a key role in inducing the orthorhombic phase and the distorted tetragonal phase, which was the origin of the ferroelectricity in the Hf0.5Zr0.5O2 film. Our results provide insight into understanding the association between ferroelectric performances and microstructures of Hf0.5Zr0.5O2-based systems.

Conjoint corrosion and wear in titanium alloys.

PubMed

Khan, M A; Williams, R L; Williams, D F

1999-04-01

When considering titanium alloys for orthopaedic applications it is important to examine the conjoint action of corrosion and wear. In this study we investigate the corrosion and wear behaviour of Ti-6Al-4V, Ti-6Al-7Nb and Ti-13Nb-13Zr in phosphate buffered saline (PBS), bovine albumin solutions in PBS and 10% foetal calf serum solutions in PBS. The tests were performed under four different conditions to evaluate the influence of wear on the corrosion and corrosion on the wear behaviour as follows: corrosion without wear, wear-accelerated corrosion, wear in a non-corrosive environment and wear in a corrosive environment. The corrosion behaviour was investigated using cyclic polarisation studies to measure the ability of the surface to repassivate following breakdown of the passive layer. The properties of the repassivated layer were evaluated by measuring changes in the surface hardness of the alloys. The amount of wear that had occurred was assessed from weight changes and measurement of the depth of the wear scar. It was found that in the presence of wear without corrosion the wear behaviour of Ti-13Nb-13Zr was greater than that of Ti-6Al-7Nb or Ti-6Al-4V and that in the presence of proteins the wear of all three alloys is reduced. In the presence of corrosion without wear Ti-13Nb-13Zr was more corrosion resistant than Ti-6Al-7Nb which was more corrosion resistant than Ti-6Al-4V without proteins whereas in the presence of protein the corrosion resistance of Ti-13Nb-13Zr and Ti-6Al-7Nb was reduced and that of Ti-6Al-4V increased. In the presence of corrosion and wear the corrosion resistance of Ti-13Nb-13Zr is higher than that of Ti-6Al-7Nb or Ti-6Al-4V in PBS but in the presence of proteins the corrosion resistance of Ti-13Nb-13Zr and Ti-6Al-7Nb are very similar but higher than that of Ti-6Al-4V. The wear of Ti-13Nb-13Zr is lower than that of Ti-6Al-7Nb and Ti-6Al-4V with or without the presence of proteins in a corrosive environment. Therefore the overall degradation when both corrosion and wear processes are occurring is lowest for Ti-13Nb-13Zr and highest for Ti-6Al-4V and the presence of proteins reduces the degradation of all three alloys.

Discovery of a Superconducting High-Entropy Alloy

NASA Astrophysics Data System (ADS)

Koželj, P.; Vrtnik, S.; Jelen, A.; Jazbec, S.; Jagličić, Z.; Maiti, S.; Feuerbacher, M.; Steurer, W.; Dolinšek, J.

2014-09-01

High-entropy alloys (HEAs) are multicomponent mixtures of elements in similar concentrations, where the high entropy of mixing can stabilize disordered solid-solution phases with simple structures like a body-centered cubic or a face-centered cubic, in competition with ordered crystalline intermetallic phases. We have synthesized an HEA with the composition Ta34Nb33Hf8Zr14Ti11 (in at. %), which possesses an average body-centered cubic structure of lattice parameter a =3.36 Å. The measurements of the electrical resistivity, the magnetization and magnetic susceptibility, and the specific heat revealed that the Ta34Nb33Hf8Zr14Ti11 HEA is a type II superconductor with a transition temperature Tc≈7.3 K, an upper critical field μ0Hc2≈8.2 T, a lower critical field μ0Hc1≈32 mT, and an energy gap in the electronic density of states (DOS) at the Fermi level of 2Δ ≈2.2 meV. The investigated HEA is close to a BCS-type phonon-mediated superconductor in the weak electron-phonon coupling limit, classifying it as a "dirty" superconductor. We show that the lattice degrees of freedom obey Vegard's rule of mixtures, indicating completely random mixing of the elements on the HEA lattice, whereas the electronic degrees of freedom do not obey this rule even approximately so that the electronic properties of a HEA are not a "cocktail" of properties of the constituent elements. The formation of a superconducting gap contributes to the electronic stabilization of the HEA state at low temperatures, where the entropic stabilization is ineffective, but the electronic energy gain due to the superconducting transition is too small for the global stabilization of the disordered state, which remains metastable.

Electric resistivity and thermoelectricity of Ni-Nb-Zr and Ni-Nb-Zr-H glassy alloys

NASA Astrophysics Data System (ADS)

Fukuhara, Mikio; Inoue, Akihisa

2010-09-01

Electric resistivity ρ and thermoelectric power S of Ni 36Nb 24Zr 40 and (Ni 0.36Nb 0.24Zr 0.4) 90H 10 glassy alloys were investigated in temperature region between 1.5 and 300 K. After resistivity curves of both alloys increase gradually with decreasing temperature down to around 6 K, they dropped suddenly and then reached zero resistivity at 2.1 K, leading to superconductivity. Linear curve with negative TCR of ρ vs T2 and slight increase of S/ T in temperature region down to around 6 K clearly reveal Fermi-liquid phenomenon in electronic state for both alloys independent of hydrogen content.

Zirconium and hafnium fractionation in differentiation of alkali carbonatite magmatic systems

NASA Astrophysics Data System (ADS)

Kogarko, L. N.

2016-05-01

Zirconium and hafnium are valuable strategic metals which are in high demand in industry. The Zr and Hf contents are elevated in the final products of magmatic differentiation of alkali carbonatite rocks in the Polar Siberia region (Guli Complex) and Ukraine (Chernigov Massif). Early pyroxene fractionation led to an increase in the Zr/Hf ratio in the evolution of the ultramafic-alkali magmatic system due to a higher distribution coefficient of Hf in pyroxene with respect to Zr. The Rayleigh equation was used to calculate a quantitative model of variation in the Zr/Hf ratio in the development of the Guli magmatic system. Alkali carbonatite rocks originated from rare element-rich mantle reservoirs, in particular, the metasomatized mantle. Carbonated mantle xenoliths are characterized by a high Zr/Hf ratio due to clinopyroxene development during metasomatic replacement of orthopyroxene by carbonate fluid melt.

Statistical Modeling of Zr/Hf Extraction using TBP-D2EHPA Mixtures

NASA Astrophysics Data System (ADS)

Rezaeinejhad Jirandehi, Vahid; Haghshenas Fatmehsari, Davoud; Firoozi, Sadegh; Taghizadeh, Mohammad; Keshavarz Alamdari, Eskandar

2012-12-01

In the present work, response surface methodology was employed for the study and prediction of Zr/Hf extraction curves in a solvent extraction system using D2EHPA-TBP mixtures. The effect of change in the levels of temperature, nitric acid concentration, and TBP/D2EHPA ratio (T/D) on the Zr/Hf extraction/separation was studied by the use of central composite design. The results showed a statistically significant effect of T/D, nitric acid concentration, and temperature on the extraction percentage of Zr and Hf. In the case of Zr, a statistically significant interaction was found between T/D and nitric acid, whereas for Hf, both interactive terms between temperature and T/D and nitric acid were significant. Additionally, the extraction curves were profitably predicted applying the developed statistical regression equations; this approach is faster and more economical compared with experimentally obtained curves.

Enhancement of thermoelectric figure-of-merit at low temperatures by titanium substitution for hafnium in n-type half-Heuslers Hf0.75-xTixZr0.25NiSn0.99Sb0.01

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

Joshi, Giri; Dahal, Tulashi; Chen, Shuo

The effect of titanium (Ti) substitution for hafnium (Hf) on thermoelectric properties of (Hf, Zr)-based n-type half-Heuslers: Hf0.75-xTixZr0.25NiSn0.99Sb0.01, has been studied. The samples are made by arc melting followed by ball milling and hot pressing via the nanostructuring approach. A peak thermoelectric figure-of-merit (ZT) of ~1.0 is achieved at 500 °C in samples with a composition of Hf0.5Zr0.25Ti0.25NiSn0.99Sb0.01 due to a slight increase in carrier concentration and also a lower thermal conductivity caused by Ti. The ZT values below 500 °C of hot pressed Hf0.5Zr0.25Ti0.25NiSn0.99Sb0.01 samples are significantly higher than those of the same way prepared Hf0.75Zr0.25NiSn0.99Sb0.01 samples at eachmore » temperature, which are very much desired for mid-range temperature applications such as waste heat recovery in automobiles.« less

Enhancement of thermoelectric figure-of-merit at low temperatures by titanium substitution for hafnium in n-type half-Heuslers Hf0.75-xTixZr0.25NiSn0.99Sb0.01

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

Joshi, Giri; Dahal, Tulashi; Chen, Shuo

The effect of titanium (Ti) substitution for hafnium (Hf) on thermoelectric properties of (Hf, Zr)-based n-type half-Heuslers: Hf 0.75-xTi xZr 0.25NiSn 0.99Sb 0.01, has been studied. The samples are made by arc melting followed by ball milling and hot pressing via the nanostructuring approach. A peak thermoelectric figure-of-merit (ZT) of ~1.0 is achieved at 500 °C in samples with a composition of Hf 0.5Zr 0.25Ti 0.25NiSn 0.99Sb 0.01 due to a slight increase in carrier concentration and also a lower thermal conductivity caused by Ti. TheZT values below 500 °C of hot pressed Hf 0.5Zr 0.25Ti 0.25NiSn 0.99Sb 0.01 samplesmore » are significantly higher than those of the same way prepared Hf 0.75Zr 0.25NiSn 0.99Sb 0.01samples at each temperature, which are very much desired for mid-range temperature applications such as waste heat recovery in automobiles.« less

Observations of a Cast Cu-Cr-Zr Alloy

NASA Technical Reports Server (NTRS)

Ellis, David L.

2006-01-01

Prior work has demonstrated that Cu-Cr-Nb alloys have considerable advantages over the copper alloys currently used in regeneratively cooled rocket engine liners. Observations indicated that Zr and Nb have similar chemical properties and form very similar compounds. Glazov and Zakharov et al. reported the presence of Cr2Zr in Cu-Cr-Zr alloys with up to 3.5 wt% Cr and Zr though Zeng et al. calculated that Cr2Zr could not exist in a ternary Cu-Cr-Zr alloy. A cast Cu-6.15 wt% Cr-5.25 wt% Zr alloy was examined to determine if the microstructure developed would be similar to GRCop-84 (Cu-6.65 wt% Cr-5.85 wt% Nb). It was observed that the Cu-Cr-Zr system did not form any Cr2Zr even after a thermal exposure at 875 C for 176.5 h. Instead the alloy consisted of three phases: Cu, Cu5Zr, and Cr.

Effects of Dopant on the Dielectric Properties of CaZrO3 Ceramic Sintered in a Reducing Atmosphere

NASA Astrophysics Data System (ADS)

Lee, W. S.; Su, C. Y.; Lee, Y. C.; Lin, S. P.; Yang, Tony

2006-07-01

In this study, the influence of CaZrO3 doped with three dopants, SiO2, MnO, and Nb2O5, and then sintered in a reducing atmosphere on microstructure, phase formation, and electrical properties is investigated. SiO2 plays the role of sintering aid to enhance the density of CaZrO3 leading to better performance of electrical properties as a function of SiO2 content. MnO, and Nb2O5 were incorporated into the Zr-site of CaZrO3 to make stoichometric CaZrO3 into non-stoichiometric CaZrO3 with Zr excess resulting in the formation of a second phase, CaZr4O9, which has a lower dielectric constant (13) in comparison with that of the main phase of CaZrO3 (32). Thus, the dielectric constant of CaZrO3 doped with Nb2O5, or MnO is decreased markedly. In addition, Mn+2 incorporated into Zr-sites of CaZrO3 plays the role of acceptor, which compensates for the number of conduction electrons and contributes to better performance of electrical properties such as insulation resistance and \\tanδ. Conversely, Nb+5 incorporated into Zr-sites of CaZrO3 plays the role of donor and provides more conduction electrons, leading to poor performance of electrical properties.

Thermal stability and specular reflection behaviour of CoNbZr-based bottom spin valves with nano-oxide layer

NASA Astrophysics Data System (ADS)

Kim, Jong Soo; Lee, Seong-Rae

2004-06-01

The thermal stability and specularity aspects of a CoNbZr-based bottom spin valve (SV) employing a nano-oxide layer (NOL) were investigated. The magnetoresistance (MR) ratio of the as-deposited CoNbZr-based bottom SV increased by 62% (from 6.3 to 10.2%) with incorporation of the NOL. The enhancement of the MR ratio was considered to be due to the specular effect ( increased from 0.722 to 1.363 cm) of the NOL. The MR ratio of a Ta-based bottom SV decreased by about 45% (from 6.9 to 3.8%) when the samples were annealed at 300 °C for 240 min. By contrast, the MR ratio of the CoNbZr-based bottom SV with NOL increase d by 14 % (from 10.2 to 11.7%). The root mean square roughness value of the CoNbZr layer (0.07 nm) was superior to that of the Ta layer (0.43 nm). Although Mn in IrMn diffused out to the surface through the active layers resulting in the formation of Mn oxide at the surface in the CoNbZr-based bottom SV, no trace of Mn was found in the active layers and no significant degradation occurred.

Thermal stability of the microstructure of an aged Nb-Zr-C alloy

NASA Technical Reports Server (NTRS)

Uz, Mehmet; Titran, Robert H.

1990-01-01

The effects of thermal aging with and without an applied stress on the microstructure of a Nb-Zr-C alloy containing 0.9 wt percent Zr and 0.06 wt percent C were studied. Chemical analysis, metallographic examination, energy dispersive x-ray spectra of the bulk material, and chemical and x-ray analyses of the phase-extracted residue were used to characterize the microstructure. The samples examined were from a creep strength study involving hot and cold working, and various combinations of exposure to temperatures ranging from 1350 to 1755 K with and without applied load for times as long as 34,000 plus hours. The results showed that the initial microstructure consisted primarily of orthorombic precipitates of Nb sub 2 C which were partially or completely transformed to face-centered cubic carbides of nb and Zr, (Zr, Nb)C, upon prolonged exposure to elevated temperatures. Furthermore, it was found that the microstructure of the alloy is extremely stable owing to the very finely distributed precipitates throughout its matrix and along the grain boundaries. The lattice parameters of the cubic carbides were determed to vary from 0.458 to 0.465 nm as the Zr/Nb ratio varied from 38/62 to 75/25.

Development of Ti-Nb-Zr alloys with high elastic admissible strain for temporary orthopedic devices.

PubMed

Ozan, Sertan; Lin, Jixing; Li, Yuncang; Ipek, Rasim; Wen, Cuie

2015-07-01

A new series of beta Ti-Nb-Zr (TNZ) alloys with considerable plastic deformation ability during compression test, high elastic admissible strain, and excellent cytocompatibility have been developed for removable bone tissue implant applications. TNZ alloys with nominal compositions of Ti-34Nb-25Zr, Ti-30Nb-32Zr, Ti-28Nb-35.4Zr and Ti-24.8Nb-40.7Zr (wt.% hereafter) were fabricated using the cold-crucible levitation technique, and the effects of alloying element content on their microstructures, mechanical properties (tensile strength, yield strength, compressive yield strength, Young's modulus, elastic energy, toughness, and micro-hardness), and cytocompatibilities were investigated and compared. Microstructural examinations revealed that the TNZ alloys consisted of β phase. The alloy samples displayed excellent ductility with no cracking, or fracturing during compression tests. Their tensile strength, Young's modulus, elongation at rupture, and elastic admissible strain were measured in the ranges of 704-839 MPa, 62-65 GPa, 9.9-14.8% and 1.08-1.31%, respectively. The tensile strength, Young's modulus and elongation at rupture of the Ti-34Nb-25Zr alloy were measured as 839 ± 31.8 MPa, 62 ± 3.6 GPa, and 14.8 ± 1.6%, respectively; this alloy exhibited the elastic admissible strain of approximately 1.31%. Cytocompatibility tests indicated that the cell viability ratios (CVR) of the alloys are greater than those of the control group; thus the TNZ alloys possess excellent cytocompatibility. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Electroforming and Switching in Oxides of Transition Metals: The Role of Metal Insulator Transition in the Switching Mechanism

NASA Astrophysics Data System (ADS)

Chudnovskii, F. A.; Odynets, L. L.; Pergament, A. L.; Stefanovich, G. B.

1996-02-01

Electroforming and switching effects in sandwich structures based on anodic films of transition metal oxides (V, Nb, Ti, Fe, Ta, W, Zr, Hf, Mo) have been studied. After being electroformed, some materials exhibited current-controlled negative resistance with S-shapedV-Icharacteristics. For V, Fe, Ti, and Nb oxides, the temperature dependences of the threshold voltage have been measured. As the temperature increased,Vthdecreased to zero at a critical temperatureT0, which depended on the film material. Comparison of theT0values with the temperatures of metal-insulator phase transition for some compounds (Tt= 120 K for Fe3O4, 340 K for VO2, ∼500 K for Ti2O3, and 1070 K for NbO2) showed that switching was related to the transition in the applied electric field. Channels consisting of the above-mentioned lower oxides were formed in the initial anodic films during the electroforming. The possibility of formation of these oxides with a metal-insulator transition was confirmed by thermodynamic calculations.

High Nb, Ta, and Al creep- and oxidation-resistant austenitic stainless steel

DOEpatents

Brady, Michael P [Oak Ridge, TN; Santella, Michael L [Knoxville, TN; Yamamoto, Yukinori [Oak Ridge, TN; Liu, Chain-tsuan [Oak Ridge, TN

2010-07-13

An austenitic stainless steel HTUPS alloy includes, in weight percent: 15 to 30 Ni; 10 to 15 Cr; 2 to 5 Al; 0.6 to 5 total of at least one of Nb and Ta; no more than 0.3 of combined Ti+V; up to 3 Mo; up to 3 Co; up to 1 W; up to 0.5 Cu; up to 4 Mn; up to 1 Si; 0.05 to 0.15 C; up to 0.15 B; up to 0.05 P; up to 1 total of at least one of Y, La, Ce, Hf, and Zr; less than 0.05 N; and base Fe, wherein the weight percent Fe is greater than the weight percent Ni wherein said alloy forms an external continuous scale comprising alumina, nanometer scale sized particles distributed throughout the microstructure, said particles comprising at least one composition selected from the group consisting of NbC and TaC, and a stable essentially single phase fcc austenitic matrix microstructure, said austenitic matrix being essentially delta-ferrite-free and essentially BCC-phase-free.

Characterization of Ceramic Plasma-Sprayed Coatings, and Interaction Studies Between U-Zr Fuel and Ceramic Coated Interface at an Elevated Temperature

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

Ki Hwan Kim; Chong Tak Lee; R. S. Fielding

2011-08-01

Candidate coating materials for re-usable metallic nuclear fuel crucibles, HfN, TiC, ZrC, and Y2O3, were plasma-sprayed onto niobium substrates. The coating microstructure and the thermal cycling behavior were characterized, and U-Zr melt interaction studies carried out. The Y2O3 coating layer had a uniform thickness and was well consolidated with a few small pores scattered throughout. While the HfN coating was not well consolidated with a considerable amount of porosity, but showed somewhat uniform thickness. Thermal cycling tests on the HfN, TiC, ZrC, and Y2O3 coatings showed good cycling characteristics with no interconnected cracks forming even after 20 cycles. Interaction studiesmore » done on the coated samples by dipping into a U-20wt.%Zr melt indicated that HfN and Y2O3 did not form significant reaction layers between the melt and the coating while the TiC and the ZrC coatings were significantly degraded. Y2O3 exhibited the most promising performance among HfN, TiC, ZrC, and Y2O3 coatings.« less

Experimental Determination of Impurity and Interdiffusion Coefficients in Seven Ti and Zr Binary Systems Using Diffusion Multiples

NASA Astrophysics Data System (ADS)

Chen, Zhangqi; Liu, Zi-Kui; Zhao, Ji-Cheng

2018-05-01

Diffusion coefficients of seven binary systems (Ti-Mo, Ti-Nb, Ti-Ta, Ti-Zr, Zr-Mo, Zr-Nb, and Zr-Ta) at 1200 °C, 1000 °C, and 800 °C were experimentally determined using three Ti-Mo-Nb-Ta-Zr diffusion multiples. Electron probe microanalysis (EPMA) was performed to collect concentration profiles at the binary diffusion regions. Forward simulation analysis (FSA) was then applied to extract both impurity and interdiffusion coefficients in Ti-rich and Zr-rich part of the bcc phase. Excellent agreements between our results and most of the literature data validate the high-throughput approach combining FSA with diffusion multiples to obtain a large amount of systematic diffusion data, which will help establish the diffusion (mobility) databases for the design and development of biomedical and structural Ti alloys.

Experimental Determination of Impurity and Interdiffusion Coefficients in Seven Ti and Zr Binary Systems Using Diffusion Multiples

NASA Astrophysics Data System (ADS)

Chen, Zhangqi; Liu, Zi-Kui; Zhao, Ji-Cheng

2018-07-01

Diffusion coefficients of seven binary systems (Ti-Mo, Ti-Nb, Ti-Ta, Ti-Zr, Zr-Mo, Zr-Nb, and Zr-Ta) at 1200 °C, 1000 °C, and 800 °C were experimentally determined using three Ti-Mo-Nb-Ta-Zr diffusion multiples. Electron probe microanalysis (EPMA) was performed to collect concentration profiles at the binary diffusion regions. Forward simulation analysis (FSA) was then applied to extract both impurity and interdiffusion coefficients in Ti-rich and Zr-rich part of the bcc phase. Excellent agreements between our results and most of the literature data validate the high-throughput approach combining FSA with diffusion multiples to obtain a large amount of systematic diffusion data, which will help establish the diffusion (mobility) databases for the design and development of biomedical and structural Ti alloys.

Comparison of bio-mineralization behavior of Ti-6Al-4V-1Nb and Zr-1Nb nano-tubes formed by anodization

NASA Astrophysics Data System (ADS)

Choi, Yong; Hong, Sun I.

2014-12-01

Nano-tubes of titanium and zirconium alloys like Ti-6Al-4V-1Nb and Zr-1Nb were prepared by anodization followed by coating with hydroxylapatite (HA) and their bio-mineralization behaviors were compared to develop a bio-compatible material for implants in orthopedics, dentistry and cardiology. Ti-6Al-4V-1Nb weight gain in a simulated body solution increased gradually. The bigger tube diameter was, the heavier HA was deposited. Surface roughness of both alloys increased highly with the increasing diameter of nano-tube. Their surface roughness decreased by HA deposition due to the removal of the empty space of the nano-tubes. Zr-1Nb alloy had faster growth of nano-tubes layers more than Ti-6Al-4V-1Nb alloy.

On the Effects of Hot Forging and Hot Rolling on the Microstructural Development and Mechanical Response of a Biocompatible Ti Alloy

PubMed Central

Okazaki, Yoshimitsu

2012-01-01

Zr, Nb, and Ta as alloying elements for Ti alloys are important for attaining superior corrosion resistance and biocompatibility in the long term. However, note that the addition of excess Nb and Ta to Ti alloys leads to higher manufacturing cost. To develop low-cost manufacturing processes, the effects of hot-forging and continuous-hot-rolling conditions on the microstructure, mechanical properties, hot forgeability, and fatigue strength of Ti-15Zr-4Nb-4Ta alloy were investigated. The temperature dependences with a temperature difference (ΔT) from β-transus temperature (Tβ) for the volume fraction of the α- and β-phases were almost the same for both Ti-15Zr-4Nb-4Ta and Ti-6Al-4V alloys. In the α-β-forged Ti-15Zr-4Nb-4Ta alloy, a fine granular α-phase structure containing a fine granular β-phase at grain boundaries of an equiaxed α-phase was observed. The Ti-15Zr-4Nb-4Ta alloy billet forged at Tβ-(30 to 50) °C exhibited high strength and excellent ductility. The effects of forging ratio on mechanical strength and ductility were small at a forging ratio of more than 3. The maximum strength (σmax) markedly increased with decreasing testing temperature below Tβ. The reduction in area (R.A.) value slowly decreased with decreasing testing temperature below Tβ. The temperature dependences of σmax for the Ti-15Zr-4Nb-4Ta and Ti-6Al-4V alloys show the same tendency and might be caused by the temperature difference (ΔT) from Tβ. It was clarified that Ti-15Zr-4Nb-4Ta alloy could be manufactured using the same manufacturing process as for previously approved Ti-6Al-4V alloy, taking into account the difference (ΔT) between Tβ and heat treatment temperature. Also, the manufacturing equivalency of Ti-15Zr-4Nb-4Ta alloy to obtain marketing approval of implants was established. Thus, it was concluded that continuous hot rolling is useful for manufacturing α-β-type Ti alloy.

Influence of Group IV and V Alloying Elements on the Microstructure Engineering and Deformation Behavior in Tantalum Carbides

DTIC Science & Technology

2015-04-06

materials is a mix of covalent, metallic and ionic resulting in high hardness as well as good thermal and electrical conductivity [4-7]. The materials...difficulty in capturing the out-of-plane sigma bonds. Both these deficiencies are well known. Table A.1: Properties of the pure elements Property Ti Zr ...Hf V Nb Ta Graphite Diamond a (Å) 2.93 3.23 3.19 2.98 3.33 3.31 2.47 3.57 c (Å) 4.62 5.18 5.05 7.72 Ecoh (eV) 5.31 6.33 6.48 5.37 6.93 8.20

Membranes for separation of carbon dioxide

DOEpatents

Ku, Anthony Yu-Chung [Rexford, NY; Ruud, James Anthony [Delmar, NY; Ramaswamy, Vidya [Niskayuna, NY; Willson, Patrick Daniel [Latham, NY; Gao, Yan [Niskayuna, NY

2011-03-01

Methods for separating carbon dioxide from a fluid stream at a temperature higher than about 200.degree. C. with selectivity higher than Knudsen diffusion selectivity include contacting a porous membrane with the fluid stream to preferentially transport carbon dioxide. The porous membrane includes a porous support and a continuous porous separation layer disposed on a surface of the porous support and extending between the fluid stream and the porous support layer. The porous support comprises alumina, silica, zirconia, stabilized zirconia, stainless steel, titanium, nickel-based alloys, aluminum-based alloys, zirconium-based alloys or a combination thereof. Median pore size of the porous separation layer is less than about 10 nm, and the porous separation layer comprises titania, MgO, CaO, SrO, BaO, La.sub.2O.sub.3, CeO.sub.2, HfO.sub.2, Y.sub.2O.sub.3, VO.sub.z, NbO.sub.z, TaO.sub.z, ATiO.sub.3, AZrO.sub.3, AAl.sub.2O.sub.4, A.sup.1FeO.sub.3, A.sup.1MnO.sub.3, A.sup.1CoO.sub.3, A.sup.1NiO.sub.3, A.sup.2HfO.sub.3, A.sup.3 CeO.sub.3, Li.sub.2ZrO.sub.3, Li.sub.2SiO.sub.3, Li.sub.2TiO.sub.3, Li.sub.2HfO.sub.3, A.sup.4N.sup.1.sub.yO.sub.z, Y.sub.xN.sup.1.sub.yO.sub.z, La.sub.xN.sup.1.sub.yO.sub.z, HfN.sup.2.sub.yO.sub.z, or a combination thereof; wherein A is La, Mg, Ca, Sr or Ba; A.sup.1 is La, Ca, Sr or Ba; A.sup.2 is Ca, Sr or Ba; A.sup.3 is Sr or Ba; A.sup.4 is Mg, Ca, Sr, Ba, Ti or Zr; N.sup.1 is V, Nb, Ta, Cr, Mo, W, Mn, Si or Ge; N.sup.2 is V, Mo, W or Si; x is 1 or 2; y ranges from 1 to 3; and z ranges from 2 to 7.

Constraints on Hf and Zr mobility in high-sulfidation epithermal systems: formation of kosnarite, KZr2(PO4)3, in the Chaquicocha gold deposit, Yanacocha district, Peru

NASA Astrophysics Data System (ADS)

Deditius, Artur P.; Utsunomiya, Satoshi; Sanchez-Alfaro, Pablo; Reich, Martin; Ewing, Rodney C.; Kesler, Stephen E.

2015-04-01

We report the first occurrence of Hf-rich kosnarite [K(Hf,Zr)2(PO4)3], space group R- 3c, Z = 6, in the giant Chaquicocha high-sulfidation epithermal gold deposit in the Yanacocha mining district, Peru. Kosnarite crystals are small (<100 μm) and occur in 2-3-mm-thick veins that cut intensively silicified rocks. The paragenesis includes a first stage of As-free pyrite and quartz (plus gratonite and rutile), followed by trace metal-rich pyrite [(Fe,As,Pb,Au)S2] and secondary Fe sulfates. Kosnarite is associated with quartz and is clearly late within the paragenetic sequence. Electron microprobe analyses (EMPA) of kosnarite show relatively high concentrations of HfO2 and Rb2O (7.61 and 1.05 wt.%, respectively). The re-calculated chemical formulas of kosnarite vary from KΣ1.00(Zr1.93Na0.01Hf0.01Mn0.01)Σ1.96(P3.04O4)Σ3 to (K0.92Rb0.05Na0.03)Σ1.00(Zr1.81Hf0.19)Σ2.00 [(P2.98Si0.02As0.01)Σ3.01O4]Σ3, where Hf and Rb are most likely incorporated according to a coupled substitution of Hf4+ + Rb+ ⇔ Zr4+ + K+. Back-scattered electron (BSE) images and elemental mapping of kosnarite reveal that Hf and Rb are enriched in 2-10-μm-wide oscillatory and/or sector zones. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observations of such zones reveal a pattern of alternating, 5-50-nm-thick, Hf-rich and Zr-rich nanozones. These high-resolution observations indicate that the incorporation of Hf does not appear to cause significant distortion in the kosnarite structure. Semiquantitative TEM-energy-dispersive X-ray spectrometry (EDS) analyses of the nano-layers show up to 22 wt.% of HfO2, which corresponds to 31 mol% of the hypothetical, KHf2(PO4)3, end-member. The presence of kosnarite in the advanced argillic alteration zone at Yanacocha is indicative of Hf and Zr mobility under highly acidic conditions and points towards an unforeseen role of phosphates as sinks of Zr and Hf in high-sulfidation epithermal environments. Finally, potentially new geochronological applications of highly insoluble vein kosnarite, including Rb-Sr dating, may provide further age constraints in pervasively altered areas where other isotopic systems might have been reset.

Early paleozoic granodioritic plutons in the Shedong W-Mo ore district, Guangxi, southern China: Products of re-melting of middle Proterozoic crust due to magma underplating

NASA Astrophysics Data System (ADS)

Jiang, Xingzhou; Kang, Zhiqiang; Xu, Jifeng; Feng, Zuohai; Pang, Chongjin; Fang, Guicong; Wu, Jiachang; Xiong, Songquan

2017-06-01

The Shedong W-Mo ore district in the south-central Dayaoshan Uplift of Guangxi, southern China hosts the Baoshan and Pingtoubei deposits, both of which occur in granodioritic plutons. Zircon U-Pb dating of granodiorites and its mafic microgranular enclaves (MMEs) in the Baoshan deposit yielded ages of 439.8 ± 3.2 and 441.1 ± 2.2 Ma, respectively. Granodiorites have moderate SiO2 (54.5-63.0 wt.%) and high Al2O3 (15.4-17.8 wt.%) contents, wide variations in major element ratios, significant rare earth element fractionation, and small negative Eu anomalies. They are rich in Th, U, Zr, and Hf, and depleted in Ba, Nb, and Ti. Their initial 87Sr/86Sr, εNd(t), and εHf(t) values are in the range of 0.7086-0.7091, -5.2 to -6.6 and -6.3 to +1.6, respectively. Rounded or lenticular MMEs have relatively low silica and high mafic components, depletion in Eu, Sr, and Zr, and marked negative Eu anomalies. Rb/Sr and Nb/Ta ratios, and εNd(t) and εHf(t) values of the MMEs are higher than those of host granodiorites, indicating a different magmatic source. Zircon U-Pb dating of the unexposed granodiorite porphyry in the Pingtoubei deposit yielded an age of 440.0 ± 1.7 Ma. The granodiorite porphyries have high SiO2 and low K2O, FeOT, and MgO contents, with similar trace element features to the granodiorites at the Baoshan deposit, although the former has small negative Eu anomalies. Its initial 87Sr/86Sr values range from 0.7162 to 0.7173, εNd(t) values from -8.7 to -12.3, and εHf(t) values from -7.8 to +1.3, indicative of a crustal source. Nd and Hf two-stage model ages of the granodiorites, MMEs, and granodiorite porphyries have a narrow range between 1.3 and 2.2 Ga. We propose that the granodiorites and MMEs at the Baoshan deposit were produced through re-melting of middle Proterozoic crust as a result of underplating of mantle-derived magmas in a transitional compression-to-extension tectonic setting. Mantle-derived magmas provided the heat and material for the formation of the granodiorites and MMEs.

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

Qu, Wentao, E-mail: wtqu@xsyu.edu.cn

The phase transformation and microstructures of the deformed Ti-30Zr-5Nb shape memory alloy were investigated. The X-ray diffraction measurements indicated that the Ti-30Zr-5Nb alloy was composed of a single orthorhombic α″-martensite phase. The alloy exhibited one yielding behavior in the tensile test, with a critical stress of ~ 600 MPa and a tensile strain of approximately 15%. A shape memory recovery accompanied by a permanent strain was exhibited in the deformed alloys when heated at 873 K. The permanent strain increased with increasing pre-strain. The microstructure evolution of the deformed alloy was investigated by transmission electron microscopy. The results showed thatmore » the martensite reorientation occurred and the dislocations were generated during deformation. The alloy displayed a reversible martensite transformation start temperature as high as 763 K. However, no strain-induced martensite stabilization was found in the deformed alloy with different pre-strain levels, potentially because the large chemical energy of the Ti-30Zr-5Nb alloy depressed the effects of the elastic energy and the dissipative energy. - Highlights: • Ti-30Zr-5Nb alloy is composed of single orthorhombic α″-martensite phase with M{sub s} of 721 K. • No martensite stabilization has been found in Ti-30Zr-5Nb alloy with different pre-strain. • Ti-30Zr-5Nb shows the maximum shape memory effect of 2.75% with a pre-strain of 8%.« less

RESEARCH ON PHYSICAL AND CHEMICAL PRINCIPLES AFFECTING HIGH TEMPERATURE MATERIALS FOR ROCKET NOZZLES. Quarterly Progress Report, April 1, 1963-June 30, 1963

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

Lowrie, R.

1963-10-31

The development and properties of refractory materials are described. Corrosion of zirconium carbide, niobium carbide, and niobium carbide-zirconium carbide systems by carbon dioxide and hydrochloric acid at 2250 deg C is reported. Corrosion of silver-tungsten alloys by carbon dioxide and oxygen at 2150 to 2440 deg K is summarized. Measurements of pyrolytic and ZTA graphite corrosion by carbon dioxide and oxygen at 2100 to 2800 deg K are shown. At 2300 deg C the rate of formation of methane from graphite and hydrogen is greatly reduced by the addition of helium, at constant hydrogen pressure. Up to 2000 deg Cmore » the effect of helium is small. The pyrolysis of methane on graphite at 2000 deg C is tabulated. Oxidation of tungsten to form WO/sub 2/ and WO/sub 3/ is reported. Vaporization of hafnium borides at 2297 to 2538 deg K is analyzed. The lattice parameters of ZrB/sub 2/ at of TiN/sub 0.6/ and TiN/sub 0.75/ are discussed. Powder metallurgical techniques are used to prepare TiB/sub 2/, ZrB/sub 2/, HfB/ sub 2/, NbB/sub 2/, a nd TaB/sub 2/ for detailed x-ray characterization. The electric conductivity of NbC-ZrC systems is reported. General descriptions are given of analytical techniques for free carbon in carbides and spectrographic methods for metallic impurities in carbides and borides. Preliminary roomtemperature measurements are reported of the elastic properties of polycrystalline ZrB/sub 2/. Titanium carbide is brazed to tungsten with a platinum-boron system. A largegrained polycrystalline specimen of ZrC is plastically deformed in creep at 2134 deg C. Metallographic and x-ray examinations of polycrystalline TiC specimens deformed in creep reveal an increasing development with deformation of subgrains having preferred orientation. (N.W.R.)« less

Electric Properties of Pb(Sb1/2Nb1/2)O3 PbTiO3 PbZrO3 Ceramics

NASA Astrophysics Data System (ADS)

Kawamura, Yasushi; Ohuchi, Hiromu

1994-09-01

Solid-solution ceramics of ternary system xPb(Sb1/2Nb1/2)O3 yPbTiO3 zPbZrO3 were prepared by the solid-state reaction of powder materials. Ceramic, electric, dielectric and piezoelectric properties and crystal structures of the system were studied. Sintering of the system xPb(Sb1/2Nb1/2)O3 yPbTiO3 zPbZrO3 is much easier than that of each end composition, and well-sintered high-density ceramics were obtained for the compositions near the morphotropic transformation. Piezoelectric ceramics with high relative dielectric constants, high radial coupling coefficient and low resonant resistance were obtained for the composition near the morphotropic transformation. The composition Pb(Sb1/2Nb1/2)0.075Ti0.45Zr0.475O3 showed the highest dielectric constant (ɛr=1690), and the composition Pb(Sb1/2Nb1/2)0.05Ti0.45Zr0.5O3 showed the highest radial coupling coefficient (kp=64%).

Importance of nanoparticles and colloids from volcanic ash for riverine transport of trace elements to the ocean: evidence from glacial-fed rivers after the 2010 eruption of Eyjafjallajökull Volcano, Iceland.

PubMed

Tepe, Nathalie; Bau, Michael

2014-08-01

Volcanic ashes are often referenced as examples for natural nanoparticles, yet the particle size distribution <1000 nm is only rarely documented. We here report results of a geochemical study of glacial-fed rivers, glacial surface runoff, glacial base flow, and pure glacial meltwater from southern Iceland, that had been sampled 25 days after the explosive eruptions at Eyjafjallajökull in 2010. In addition to the dissolved concentrations of rare earth elements (REE), Zr, Hf, Nb, and Th in the 450 nm-filtered waters, we also studied the respective filter residues (river particulates >450 nm) and volcanic ash. In spite of the low solubilities and high particle-reactivities of the elements studied, most water samples show high dissolved concentrations, such as up to 971 ng/kg of Ce and 501 ng/kg of Zr. Except for the pure glacial meltwater and glacial base flow, all waters display the same shale-normalized REE patterns with pronounced light and heavy REE depletion and positive Eu anomalies. While such patterns are unusual for river waters, they are similar to those of the respective river particulates and the volcanic ash, though at different concentration levels. The distribution of dissolved Zr, Hf, Nb, and Th in the waters also matches that of filter residues and ash. This strongly suggests that in all 450 nm-filtered river waters, the elements studied are associated with solid ash particles smaller than 450 nm. This reveals that volcanic ash-derived nanoparticles and colloids are present in these glacial-fed rivers and that such ultrafine particles control the trace element distribution in the surface runoff. Subsequent to explosive volcanic eruptions, these waters provide terrigenous input from landmasses to estuaries, that is characterized by a unique trace element signature and that subsequent to modification by estuarine processes delivers a pulse of nutrients to coastal seawater in regions not affected by plume fall-out. Copyright © 2014 Elsevier B.V. All rights reserved.

Siudaite, Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O: a new eudialyte-group mineral from the Khibiny alkaline massif, Kola Peninsula

NASA Astrophysics Data System (ADS)

Chukanov, Nikita V.; Rastsvetaeva, Ramiza K.; Kruszewski, Łukasz; Aksenov, Sergey M.; Rusakov, Vyacheslav S.; Britvin, Sergey N.; Vozchikova, Svetlana A.

2018-03-01

The new eudialyte-group mineral siudaite, ideally Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O, was discovered in a peralkaline pegmatite situated at the Eveslogchorr Mt., Khibiny alkaline massif, Kola Peninsula, Russia. The associated minerals are aegirine, albite, microcline, nepheline, astrophyllite, and loparite-(Ce). Siudaite forms yellow to brownish-yellow equant anhedral grains up to 1.5 cm across. Its lustre is vitreous, and the streak is white. Cleavage is none observed. The Mohs' hardness is 4½. Density measured by hydrostatic weighing is 2.96(1) g/cm3. Density calculated using the empirical formula is equal to 2.973 g/cm3. Siudaite is nonpleochroic, optically uniaxial, negative, with ω = 1.635(1) and ɛ = 1.626(1) (λ = 589 nm). The IR spectrum is given. The chemical composition of siudaite is (wt%; electron microprobe, H2O determined by HCN analysis): Na2O 8.40, K2O 0.62, CaO 9.81, La2O3 1.03, Ce2O3 1.62, Pr2O3 0.21, Nd2O3 0.29, MnO 6.45, Fe2O3 4.51. TiO2 0.54, ZrO2 11.67, HfO2 0.29, Nb2O5 2.76, SiO2 47.20, Cl 0.54, H2O 3.5, -O = Cl - 0.12, total 99.32. According to Mössbauer spectroscopy data, all iron is trivalent. The empirical formula (based on 24.5 Si atoms pfu, in accordance with structural data) is [Na7.57(H2O)1.43]Σ9(Mn1.11Na0.88Ce0.31La0.20Nd0.05Pr0.04K0.41)Σ3(H2O)1.8(Ca5.46Mn0.54)Σ6(Fe3+ 1.76Mn2+ 1.19)Σ2.95Nb0.65(Ti0.20Si0.50)Σ0.71(Zr2.95Hf0.04Ti0.01)Σ3Si24.00Cl0.47O70(OH)2Cl0.47·1.82H2O. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is trigonal, space group R3m, with a = 14.1885(26) Å, c = 29.831(7) Å, V = 5200.8(23) Å3 and Z = 3. Siudaite is chemically related to georgbarsanovite and is its analogue with Fe3+-dominant M2 site. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.38 (60) (-114), 4.29 (55) (-225), 3.389 (47) (131), 3.191 (63) (-228). 2.963 (100) (4-15), 2.843 (99) (-444), 2.577 (49) (3-39). Siudaite is named after the Polish mineralogist and geochemist Rafał Siuda (b. 1975).

Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, John H.

1993-01-01

El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

Excellent glass forming ability and plasticity in high entropy Zr20Ti20Hf20M20Be20 (M = Cu, Ni, Co) alloys

NASA Astrophysics Data System (ADS)

Zong, Haitao; Geng, Chenchen; Kang, Chaoyang; Cao, Guohua; Bian, Linyan; Li, Lixin; Zhang, Baoqing; Li, Ming

2018-03-01

We reported here the studies of a series of Zr20Ti20Hf20M20Be20 (M = Cu, Ni and Co) quinary high entropy bulk metallic glasses. Glasses with critical diameters (Dc) of 3 mm, 8 mm and 5 mm, respectively has been successfully fabricated by copper mold casting. Strikingly, a plastic strain of 11.6% is achieved in the Zr20Ti20Hf20Cu20Be20 metallic glass. The dynamic fragility the Zr20Ti20Hf20Cu20Be20 alloy is determined from calorimetric measurements. The excellent plasticity is explained to be attributed to relatively higher fragility.

An intermetallic powder-in-tube approach to increased flux-pinning in Nb 3Sn by internal oxidation of Zr

DOE PAGES

Motowidlo, Leszek R.; Lee, P. J.; Tarantini, C.; ...

2017-11-28

We report on the development of multifilamentary Nb 3Sn superconductors by a versatile powder-in-tube technique (PIT) that demonstrates a simple pathway to a strand with a higher density of flux-pinning sites that has the potential to increase critical current density beyond present levels. The approach uses internal oxidation of Zr-alloyed Nb tubes to produce Zr oxide particles within the Nb 3Sn layer that act as a dispersion of artificial pinning centres (APCs). In this design, SnO 2 powder is mixed with Cu 5Sn 4 powder within the PIT core that supplies the Sn for the A15 reaction with Nb1Zr filamentmore » tubes. Initial results show an average grain size of ~38 nm in the A15 layer, compared to the 90–130 nm of typical APC-free high-J c strands made by conventional PIT or Internal Sn processing. Furthermore, there is a shift in the peak of the pinning force curve from H/H irr of ~0.2 to ~0.3 and the pinning force curves can be deconvoluted into grain boundary and point-pinning components, the point-pinning contribution dominating for the APC Nb-1wt%Zr strands.« less

An intermetallic powder-in-tube approach to increased flux-pinning in Nb3Sn by internal oxidation of Zr

NASA Astrophysics Data System (ADS)

Motowidlo, L. R.; Lee, P. J.; Tarantini, C.; Balachandran, S.; Ghosh, A. K.; Larbalestier, D. C.

2018-01-01

We report on the development of multifilamentary Nb3Sn superconductors by a versatile powder-in-tube technique (PIT) that demonstrates a simple pathway to a strand with a higher density of flux-pinning sites that has the potential to increase critical current density beyond present levels. The approach uses internal oxidation of Zr-alloyed Nb tubes to produce Zr oxide particles within the Nb3Sn layer that act as a dispersion of artificial pinning centres (APCs). In this design, SnO2 powder is mixed with Cu5Sn4 powder within the PIT core that supplies the Sn for the A15 reaction with Nb1Zr filament tubes. Initial results show an average grain size of ˜38 nm in the A15 layer, compared to the 90-130 nm of typical APC-free high-J c strands made by conventional PIT or Internal Sn processing. There is a shift in the peak of the pinning force curve from H/H irr of ˜0.2 to ˜0.3 and the pinning force curves can be deconvoluted into grain boundary and point-pinning components, the point-pinning contribution dominating for the APC Nb-1wt%Zr strands.

An intermetallic powder-in-tube approach to increased flux-pinning in Nb 3Sn by internal oxidation of Zr

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

Motowidlo, Leszek R.; Lee, P. J.; Tarantini, C.

We report on the development of multifilamentary Nb 3Sn superconductors by a versatile powder-in-tube technique (PIT) that demonstrates a simple pathway to a strand with a higher density of flux-pinning sites that has the potential to increase critical current density beyond present levels. The approach uses internal oxidation of Zr-alloyed Nb tubes to produce Zr oxide particles within the Nb 3Sn layer that act as a dispersion of artificial pinning centres (APCs). In this design, SnO 2 powder is mixed with Cu 5Sn 4 powder within the PIT core that supplies the Sn for the A15 reaction with Nb1Zr filamentmore » tubes. Initial results show an average grain size of ~38 nm in the A15 layer, compared to the 90–130 nm of typical APC-free high-J c strands made by conventional PIT or Internal Sn processing. Furthermore, there is a shift in the peak of the pinning force curve from H/H irr of ~0.2 to ~0.3 and the pinning force curves can be deconvoluted into grain boundary and point-pinning components, the point-pinning contribution dominating for the APC Nb-1wt%Zr strands.« less

New intermetallic MIrP (M=Ti, Zr, Nb, Mo) and MgRuP compounds related with MoM'P (M'=Ni and Ru) superconductor

NASA Astrophysics Data System (ADS)

Kito, Hijiri; Iyo, Akira; Wada, Toshimi

2011-01-01

Using a cubic-anvil high-pressure apparatus, ternary iridium phosphides MIrP (M=Ti, Zr, Nb, Mo) and MgRuP have been prepared by reaction of stoichiometric amounts of each metal and phosphide powders at around 2 Gpa and above 1523 K for the first time. The structure of these compounds prepared at high-pressure has been characterized by X-ray powder diffraction. Diffraction lines of these compounds are assigned by the index of the Co2Si-type structure. The electrical resistivity and the d.c magnetic susceptibility of MIrP (M=Ti, Zr, Nb, Mo) have measured at low temperatures. Unfortunately, no superconducting transition for MIrP (M=Ti, Zr, Nb, Mo) and MgRuP are observed down to 2 K.

Reduced sediment melting at 7.5-12 GPa: phase relations, geochemical signals and diamond nucleation

NASA Astrophysics Data System (ADS)

Brey, G. P.; Girnis, A. V.; Bulatov, V. K.; Höfer, H. E.; Gerdes, A.; Woodland, A. B.

2015-08-01

Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5-12 GPa and 800-1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325-394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite-siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at <9 GPa and the hydrous aluminosilicates topaz-OH and phase egg at >10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000-1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich (<10 wt% SiO2) at 800-1000 °C to volatile-rich silicate liquids (up to 40 wt% SiO2) at high temperatures. Trace elements were analyzed in melts and crystalline phases by LA ICP MS. The garnet-melt and clinopyroxene-melt partition coefficients are in general consistent with results from the literature for volatile-free systems and silicocarbonate melts derived by melting carbonated peridotites. Most trace elements are strongly incompatible in kyanite and silica polymorphs ( D < 0.01), except for V, Cr and Ni, which are slightly compatible in kyanite ( D > 1). Aragonite and Fe-Mg carbonate have very different REE partition coefficients ( D Mst-Sd/L ~ 0.01 and D Arg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in incompatible elements and displays a pronounced negative Ta-Nb anomaly but no Zr-Hf anomaly. Although all experiments were conducted in the diamond stability field, only graphite was observed in low-temperature experiments. Spontaneous diamond nucleation and the complete transformation of graphite to diamond were observed at temperatures above 1200-1300 °C. We speculate that the observed character of graphite-diamond transformation is controlled by relationships between the kinetics of metastable graphite dissolution and diamond nucleation in a hydrous silicocarbonate melt that is oversaturated in C.

Electrochemical studies on zirconium and its biocompatible alloys Ti-50Zr at.% and Zr-2.5Nb wt.% in simulated physiologic media.

PubMed

Oliveira, Nilson T C; Biaggio, Sonia R; Rocha-Filho, Romeu C; Bocchi, Nerilso

2005-09-01

Different electrochemical studies were carried out for Zr and its biocompatible alloys Ti-50Zr at.% and Zr-2.5Nb wt.% in solutions simulating physiologic media, Ringer and PBS (phosphate buffered saline) solutions. The results from rest-potential measurements showed that the three materials are spontaneously passivated in both solutions and that the Ti-50Zr alloy has the greatest tendency for spontaneous oxide formation. Some corrosion parameters (such as the pitting and repassivation potentials) were obtained via cyclic voltammetry in both solutions, revealing that the Ti-50Zr has the best corrosion protection while Zr has the worst. On the other hand, the pre-anodization (up to 8 V vs. SCE) of the alloys in a 0.15 mol/L Na2SO4 solution led to a significant improvement in their protection against pitting corrosion when exposed to the Ringer solution. Elemental analyses by EDX showed that during pitting corrosion, there is no preferential corrosion of any of the alloying elements (Zr, Ti, Nb). Copyright (c) 2005 Wiley Periodicals, Inc.

Petrogenesis and tectonic implications of the Yadong leucogranites, southern Himalaya

NASA Astrophysics Data System (ADS)

Gou, Zhengbin; Zhang, Zeming; Dong, Xin; Xiang, Hua; Ding, Huixia; Tian, Zuolin; Lei, Hengcong

2016-07-01

The leucogranites in the Higher Himalayan Sequence (HHS) provide a probe to elucidate the crustal melting of continental collisional orogen. An integrated geochemical and geochronological study of the Yadong leucogranites, southern Himalaya, shows that these rocks have relatively high SiO2 contents of 69.77 to 75.32 wt.% and alumina saturation index (A/CNK) of 1.09-1.40, typical of peraluminous granites. They show moderately fractionated REE patterns with negative Eu anomalies, and are characterized by enriched LILE (Rb and Cs) and depleted HFSE (Zr, Hf, Nb and Ta). LA-ICP-MS U-Pb zircon dating of ten samples yields crystallization ages ranging from 21.0 to 11.7 Ma. The zircons have variable εHf(t) values of - 26.3 to - 3.5 and corresponding Hf two-stage model ages of 2.77-1.33 Ga. The present study reveals that the muscovite-biotite leucogranites (2ML) have higher TiO2, MgO, CaO, Sr, Ba and Zr contents, lower Rb/Sr ratios than the tourmaline-muscovite leucogranites (TML). Zircon and monazite saturation thermometry results show that the melt temperatures (681-784 °C) of the 2ML are 20-80 °C higher than those (663-705 °C) of the TML. Combining with previous results, we propose that the TML were derived from the muscovite-dehydration melting, whereas the 2ML dominantly resulted from the biotite-dehydration melting during the prograde metamorphism of the pelitic and felsic granulites of the HHS. Therefore, the Himalayan leucogranites were probably formed during the subduction of the Indian crust following the India and Asia collision.

Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high-k atomic layer deposition

NASA Astrophysics Data System (ADS)

Jeloaica, L.; Estève, A.; Djafari Rouhani, M.; Estève, D.

2003-07-01

The initial stage of atomic layer deposition of HfO2, ZrO2, and Al2O3 high-k films, i.e., the decomposition of HfCl4, ZrCl4, and Al(CH3)3 precursor molecules on an OH-terminated SiO2 surface, is investigated within density functional theory. The energy barriers are determined using artificial activation of vibrational normal modes. For all precursors, reaction proceeds through the formation of intermediate complexes that have equivalent formation energies (˜-0.45 eV), and results in HCl and CH4 formation with activation energies of 0.88, 0.91, and 1.04 eV for Hf, Zr, and Al based precursors, respectively. The reaction product of Al(CH3)3 decomposition is found to be more stable (by -1.45 eV) than the chemisorbed intermediate complex compared to the endothermic decomposition of HfCl4 and ZrCl4 chemisorbed precursors (0.26 and 0.29 eV, respectively).

Effect of annealing temperature on microstructure and superelastic properties of a Ti-18Zr-4.5Nb-3Sn-2Mo alloy.

PubMed

Fu, Jie; Kim, Hee Young; Miyazaki, Shuichi

2017-01-01

In this study a new superelastic Ti-18Zr-4.5Nb-3Sn-2Mo alloy was prepared by adding 2at% of Mo as a substitute for Nb to the Ti-18Zr-11Nb-3Sn alloy, and heat treatment at different temperatures was conducted. The temperature dependence of superelasticity and annealing texture was investigated. Texture showed a dependence of annealing temperature: the specimen annealed at 923K for 0.3ks exhibited {113} β <47¯1> β type texture which was similar to the deformation texture, while specimens annealed at 973, 1073K, and 1173K showed {001} β <110> β type recrystallization texture which was preferable for recovery strain. The largest recovery strain of 6.2%, which is the same level as that of the Ti-18Zr-11Nb-3Sn alloy, was obtained in the specimen annealed at 1173K for 0.3ks due to the well-developed {001} β <110> β type recrystallization texture. The Ti-18Zr-3Nb-3Sn-2Mo alloy presented a higher tensile strength compared with the Ti-18Zr-11Nb-3Sn alloy when heat treated at 1173K for 0.3ks, which was due to the solid solution strengthening effect of Mo. Annealing at 923K for 0.3ks was effective in obtaining a good combination of a high strength as 865MPa and a large recovery strain as 5.6%. The high recovery strain was due to the high stress at which the maximum recovery stain was obtained which was attributed to the small grain size formed at low annealing temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electronic Transport Behaviors due to Charge Density Waves in Ni-Nb-Zr-H Glassy Alloys

NASA Astrophysics Data System (ADS)

Fukuhara, Mikio; Umemori, Yoshimasa

2013-11-01

The amorphous Ni-Nb-Zr-H glassy alloy containing subnanometer-sized icosahedral Zr5 Nb5Ni3 clusters exhibited four types of electronic phenomena: a metal/insulator transition, an electric current-induced voltage oscillation (Coulomb oscillation), giant capacitor behavior and an electron avalanche with superior resistivity. These findings could be excluded by charge density waves that the low-dimensional component of clusters, in which the atoms are lined up in chains along the [130] direction, plays important roles in various electron transport phenomena.

Nickel aluminide alloy suitable for structural applications

DOEpatents

Liu, Chain T.

1998-01-01

Alloys for use in structural applications based upon NiAl to which are added selected elements to enhance room temperature ductility and high temperature strength. Specifically, small additions of molybdenum produce a beneficial alloy, while further additions of boron, carbon, iron, niobium, tantalum, zirconium and hafnium further improve performance of alloys at both room temperature and high temperatures. A preferred alloy system composition is Ni--(49.1.+-.0.8%)Al--(1.0.+-.0.8%)Mo--(0.7.+-.0.5%)Nb/Ta/Zr/Hf--(nearly zero to 0.03%)B/C, where the % is at. % in each of the concentrations. All alloys demonstrated good oxidation resistance at the elevated temperatures. The alloys can be fabricated into components using conventional techniques.

Effect of minor reactive metal additions on fracture toughness of iron: 12-percent nickel alloy at-196 deg and 25 deg C

NASA Technical Reports Server (NTRS)

Witzke, W. R.; Stephens, J. R.

1976-01-01

The slow bend precracked Charpy fracture toughness and tensile behavior of arc-melted and hot-rolled Fe-12Ni alloys containing up to 4 atomic percent reactive metal additions were determined at -196 C and 25 C after water quenching from three annealing temperatures. The fracture toughness of Fe-12Ni at -196 C was improved by small amounts of Al, Ce, Hf, La, Nb, Ta, Ti, V, Y, and Zr, but not by Si. Cryogenic toughness was improved up to 7.5 times that of binary Fe-12Ni and varied with the reactive metal, its concentration, and the annealing temperature.

Devices capable of removing silicon and aluminum from gaseous atmospheres

DOEpatents

Spengler, Charles J.; Singh, Prabhakar

1989-01-01

An electrochemical device is made of a containment vessel (30) optional ceramic material within the containment vessel and including one or more electrochemical cells (10), the cells containing a porous exposed electrode (11) in contact with a solid electrolyte, where at least one of the exposed electrode, the containment vessel, and the optional ceramic material contains a deposit selected from metal oxide and metal salt capable of forming a metal oxide upon heating, where the metal is selected from the group consisting of Ce, Sm, Mg, Be, Ca, Sr, Ti, Zr, Hf, Y, La, Pr, Nb, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, and their mixtures.

Microstructure and Phase Stability of Single Crystal NiAl Alloyed with Hf and Zr

NASA Technical Reports Server (NTRS)

Locci, I. E.; Dickerson, R. M.; Garg, A.; Noebe, R. D.; Whittenberger, J. D.; Nathal, M. V.; Darolia, R.

1996-01-01

Six near stoichiometric, NiAl single-crystal alloys, with 0.05-1.5 at.% of Hf and Zr additions plus Si impurities, were microstructurally analyzed in the as-cast, homogenized, and aged conditions. Hafnium-rich interdendritic regions, containing the Heusler phase (Ni2AlHf), were found in all the as-cast alloys containing Hf. Homogenization heat treatments partially reduced these interdendritic segregated regions. Transmission electron microscopy (TEM) observations of the as-cast and homogenized microstructures revealed the presence of a high density of fine Hf (or Zr) and Si-rich precipitates. These were identified as G-phase, Nil6X6Si7, or as an orthorhombic NiXSi phase, where X is Hf or Zr. Under these conditions the expected Heusler phase (beta') was almost completely absent. The Si responsible for the formation of the G and NiHfSi phases is the result of molten metal reacting with the Si-containing crucible used during the casting process. Varying the cooling rates after homogenization resulted in the refinement or complete suppression of the G and NiHfSi phases. In some of the alloys studied, long-term aging heat treatments resulted in the formation of Heusler precipitates, which were more stable at the aging temperature and coarsened at the expense of the G-phase. In other alloys, long-term aging resulted in the formation of the NiXSi phase. The stability of the Heusler or NiXSi phases can be traced to the reactive element (Hf or Zr) to silicon ratio. If the ratio is high, then the Heusler phase appears stable after long time aging. If the ratio is low, then the NiHfSi phase appears to be the stable phase.

Effects of the accumulated annealing parameter on the corrosion characteristics of a Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy

NASA Astrophysics Data System (ADS)

Baek, Jong Hyuk; Jeong, Yong Hwan; Kim, In Sup

2000-07-01

Corrosion behavior, hydrogen pickup, oxide microstructure, and precipitate characterization have been studied in order to investigate the effect of the accumulated annealing parameter on the corrosion characteristics in a Zr-Nb-Sn-Fe-Cr alloy. An autoclave corrosion test was carried out in 400°C steam for 300 days on the Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy, which had been given 18 different accumulated annealing parameters. The corrosion rate increased with increasing the accumulated annealing parameter. To investigate the crystal structure of oxide layer, the corroded specimens were prepared to have an equal oxide thickness (˜1.6 μm) by controlling exposure time. The relative fraction of tetragonal ZrO 2 also decreased gradually with increasing accumulated annealing parameter. From the hydrogen analysis of the corroded samples for 300 days, it was observed that, with increasing the size of precipitates, the hydrogen pickup was enhanced. It was revealed from transmission electron microscope (TEM) observation of the oxide that the larger precipitates still remained to be oxidized in the oxide layer and had undergone a reduction of Fe/Cr ratio from 2.1 to 1.5. The oxidation of the precipitates in the oxide gave rise to a volume expansion at the precipitate-oxide interface. This volume change could lead to the transformation in the oxide phase from tetragonal ZrO 2 to monoclinic ZrO 2 and in oxide structure from columnar grain to equiaxed grain. The precipitate in a Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy is composed of Nb, Fe, and Cr and the Nb content in the precipitate increase with increasing accumulated annealing parameter. Thus, it can be thought that Nb within precipitates plays a key role in the microstructural change of oxide.

Two-Dimensional Nb-Based M 4 C 3 Solid Solutions (MXenes)

DOE PAGES

Yang, Jian; Naguib, Michael; Ghidiu, Michael; ...

2015-10-15

Two new two-dimensional Nb 4C 3-based solid solutions (MXenes), (Nb 0.8,Ti 0.2) 4C 3T x and (Nb 0.8,Zr 0.2) 4C 3T x (where T is a surface termination) were synthesizedas confirmed by X-ray diffractionfrom their corresponding MAX phase precursors (Nb 0.8,Ti 0.2) 4AlC 3 and (Nb 0.8,Zr 0.2) 4AlC 3. In our report we discuss Zr-containing MXene. We also studied intercalation of Li ions into these two compositions, and Nb 4C 3T x in order to determine the potential of those materials for energy storage applications. Lithiation and delithiation peaks at 2.26 and 2.35 V, respectively, appeared in the casemore » of Nb 4C 3T x, but were not present in Nb 2CT x. After 20 cycles at a rate of C/4, the specific capacities of (Nb 0.8,Ti 0.2) 4C 3T xand (Nb 0.8,Ti 0.2) 4C 3T x were 158 and 132 mAh/g, respectively, both slightly lower than the capacity of Nb 4C 3T x.« less

Oxidation of ZrB2-and HfB2-Based Ultra-High Temperature Ceramics: Effects of Ta Additions

NASA Technical Reports Server (NTRS)

Opila, Elizabeth; Levine, Stanley; Lorinez, Jonathan

2003-01-01

Several compositions of ZrB2- and HfB2-based Ultra-High Temperature Ceramics (UHTC) were oxidized in stagnant air at 1627 C in ten minute cycles for times up to 100 minutes. These compositions include: ZrB2 - 20v% SiC, HfB2 - 20v% SiC, ZrB2 - 20v% SiC - 20v% TaSi2, ZrB2 - 33v% SiC, HfB2 - 20v% SiC - 20v% TaSi2, and ZrB2 - 20v% SiC - 20v% TaC. The weight change due to oxidation was recorded. The ZrB2 - 20v% SiC - 20v% TaSi2 composition was also oxidized in stagnant air at 1927 C and in an arc jet atmosphere. Samples were analyzed after oxidation by x-ray diffraction, field emission scanning electron microscopy, and energy dispersive spectroscopy to determine the reaction products and to observe the microstructure. The ZrB2 - 20v% SiC - 20v% TaSi2 showed the lowest oxidation rate at 1627 C, but performed poorly under the more extreme tests due to liquid phase formation. Effects of Ta-additions on the oxidation of the diboride-based UHTC are discussed.

Experimental determination of the phase relationships in Zr/2.5 8.0 at% Nb/0 6.7 at% Al alloys with 750 at ppm 0 and 250 at ppm N between 730 900° C

NASA Astrophysics Data System (ADS)

Peruzzi, A.; Bolcich, J.

1990-11-01

Zr alloys with 2.5 to 8.0 at% Nb and 0 to 6.7 at% Al were subjected to dynamic and static treatments between 730-900° C and studied by qualitative and quantitative optical metallography, electrical resistance, X-ray diffractometry and electron microanalysis. The experimental data were analyzed by taking into account the effects of oxygen and nitrogen impurities. The main results for Zn-Nb-Al alloys with 750 at ppm O and 250 at ppm N are the following: (i) Equilibrium relationships are established between the α (hcp), β (bcc) and Zr 3Al (Cu 3Au) phases along isothermal sections at 730, 771 and 800°C. (ii) The β/ α + β boundaries are determined along iso-aluminum vertical sections at 6.7, 3.3 and 0 at% Al. (iii) The addition of Al to Zr-Nb alloys increases the solubility of Nb in the α phase, its maximum value at 730° C being about 0.7-0.8 at% for 4 at% Al. (iv) Solubility values for Al in the α-phase of Zr-Al were estimated by extrapolation from ternary alloys. These estimates help to solve an existing discrepancy in the Zr-Al system.

Processing and microstructure of Nb-1 percent Zr-0.1 percent C alloy sheet

NASA Technical Reports Server (NTRS)

Uz, Mehmet; Titran, Robert H.

1992-01-01

A systematic study was carried out to evaluate the effects of processing on the microstructure of Nb-1 wt. pct. Zr-0.1 wt. pct. C alloy sheet. The samples were fabricated by cold rolling different sheet bars that were single-, double- or triple-extruded at 1900 K. Heat treatment consisted on one- or two-step annealing of different samples at temperatures ranging from 1350 to 1850 K. The assessment of the effects of processing on microstructure involved characterization of the precipitates including the type, crystal structure, chemistry and distribution within the material as well as an examination of the grain structure. A combination of various analytical and metallographic techniques were used on both the sheet samples and the residue extracted from them. The results show that the relatively coarse orthorhombic Nb2C carbides in the as-rolled samples transformed to rather fine cubic monocarbides of Nb and Zr with varying Zr/Nb ratios upon subsequent heat treatment. The relative amount of the cubic carbides and the Zr/Nb ratio increased with increasing number of extrusions prior to cold rolling. Furthermore, the size and the aspect ratio of the grains appear to be strong functions of the processing history of the material. These and other results obtained will be presented with the emphasis on a possible relationship between processing and microstructure.

Primary radiation damage of Zr-0.5%Nb binary alloy: atomistic simulation by molecular dynamics method

NASA Astrophysics Data System (ADS)

Tikhonchev, M.; Svetukhin, V.; Kapustin, P.

2017-09-01

Ab initio calculations predict high positive binding energy (˜1 eV) between niobium atoms and self-interstitial configurations in hcp zirconium. It allows the expectation of increased niobium fraction in self-interstitials formed under neutron irradiation in atomic displacement cascades. In this paper, we report the results of molecular dynamics simulation of atomic displacement cascades in Zr-0.5%Nb binary alloy and pure Zr at the temperature of 300 K. Two sets of n-body interatomic potentials have been used for the Zr-Nb system. We consider a cascade energy range of 2-20 keV. Calculations show close estimations of the average number of produced Frenkel pairs in the alloy and pure Zr. A high fraction of Nb is observed in the self-interstitial configurations. Nb is mainly detected in single self-interstitial configurations, where its fraction reaches tens of percent, i.e. more than its tenfold concentration in the matrix. The basic mechanism of this phenomenon is the trapping of mobile self-interstitial configurations by niobium. The diffusion of pure zirconium and mixed zirconium-niobium self-interstitial configurations in the zirconium matrix at 300 K has been simulated. We observe a strong dependence of the estimated diffusion coefficients and fractions of Nb in self-interstitials produced in displacement cascades on the potential.

High Mn austenitic stainless steel

DOEpatents

Yamamoto, Yukinori [Oak Ridge, TN; Santella, Michael L [Knoxville, TN; Brady, Michael P [Oak Ridge, TN; Maziasz, Philip J [Oak Ridge, TN; Liu, Chain-tsuan [Knoxville, TN

2010-07-13

An austenitic stainless steel alloy includes, in weight percent: >4 to 15 Mn; 8 to 15 Ni; 14 to 16 Cr; 2.4 to 3 Al; 0.4 to 1 total of at least one of Nb and Ta; 0.05 to 0.2 C; 0.01 to 0.02 B; no more than 0.3 of combined Ti+V; up to 3 Mo; up to 3 Co; up to 1W; up to 3 Cu; up to 1 Si; up to 0.05 P; up to 1 total of at least one of Y, La, Ce, Hf, and Zr; less than 0.05 N; and base Fe, wherein the weight percent Fe is greater than the weight percent Ni, and wherein the alloy forms an external continuous scale including alumina, nanometer scale sized particles distributed throughout the microstructure, the particles including at least one of NbC and TaC, and a stable essentially single phase FCC austenitic matrix microstructure that is essentially delta-ferrite-free and essentially BCC-phase-free.

Effect of structural evolution on mechanical properties of ZrO2 coated Ti-6Al-7Nb-biomedical application

NASA Astrophysics Data System (ADS)

Zalnezhad, E.

2016-05-01

Zirconia (ZrO2) nanotube arrays were fabricated by anodizing pure zirconium (Zr) coated Ti-6Al-7Nb in fluoride/glycerol electrolyte at a constant potential of 60 V for different times. Zr was deposited atop Ti-6Al-7Nb via a physical vapor deposition magnetron sputtering (PVDMS) technique. Structural investigations of coating were performed utilizing X-ray diffraction (XRD) analysis. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to characterize the morphology and microstructure of coatings. Unannealed ZrO2 nanotube arrays were amorphous. Monoclinic and tetragonal ZrO2 appeared when the coated substrates were heat treated at 450 °C and 650 °C, while monoclinic ZrO2 was found at 850 °C and 900 °C. Mechanical properties, including nanohardness and modulus of elasticity, were evaluated at different annealing temperatures using a nanoindentation test. The nanoindentation results show that the nanohardness and modulus of elasticity for Ti-6AL-7Nb increased by annealing ZrO2 coated substrate at 450 °C. The nanohardness and modulus of elasticity for coated substrate decreased with annealing temperatures of 650, 850, and 900 °C. At an annealing temperature of 900 °C, cracks in the ZrO2 thin film coating occurred. The highest nanohardness and elastic modulus values of 6.34 and 218 GPa were achieved at an annealing temperature of 450 °C.

Lattice Thermal Conductivity of Ultra High Temperature Ceramics (UHTC) ZrB2 and HfB2 from Atomistic Simulations

NASA Technical Reports Server (NTRS)

Lawson, JOhn W.; Daw, Murray S.; Bauschlicher, Charles W.

2011-01-01

Ultra high temperature ceramics (UHTC) including ZrB2 and HfB2 are candidate materials for applications in extreme environments because of their high melting point, good mechanical properties and reasonable oxidation resistance. Unlike many ceramics, these materials have high thermal conductivity which can be advantageous, for example, to reduce thermal shock. Recently, we developed Tersoff style interatomic potentials for both ZrB2 and HfB2 appropriate for atomistic simulations. As an application, Green-Kubo molecular dynamics simulations were performed to evaluate the lattice thermal conductivity for single crystals of ZrB2 and HfB2. The atomic mass difference in these binary compounds leads to oscillations in the time correlation function of the heat current. Results at room temperature and at elevated temperatures will be reported.

Discovery of ferromagnetism with large magnetic anisotropy in ZrMnP and HfMnP

DOE PAGES

Lamichhane, Tej N.; Taufour, Valentin; Masters, Morgan W.; ...

2016-08-29

Here, ZrMnP and HfMnP single crystals are grown by a self-flux growth technique, and structural as well as temperature dependent magnetic and transport properties are studied. Both compounds have an orthorhombic crystal structure. ZrMnP and HfMnP are ferromagnetic with Curie temperatures around 370 K and 320 K, respectively. The spontaneous magnetizations of ZrMnP and HfMnP are determined to be 1.9 μ B/f.u. and 2.1 μ B/f.u., respectively, at 50 K. The magnetocaloric effect of ZrMnP in terms of entropy change (Δ S) is estimated to be –6.7 kJ m –3 K –1 around 369 K. The easy axis of magnetizationmore » is [100] for both compounds, with a small anisotropy relative to the [010] axis. At 50 K, the anisotropy field along the [001] axis is ~4.6 T for ZrMnP and ~10 T for HfMnP. Such large magnetic anisotropy is remarkable considering the absence of rare-earth elements in these compounds. The first principle calculation correctly predicts the magnetization and hard axis orientation for both compounds, and predicts the experimental HfMnP anisotropy field within 25%. More importantly, our calculations suggest that the large magnetic anisotropy comes primarily from the Mn atoms, suggesting that similarly large anisotropies may be found in other 3d transition metal compounds.« less

First principles study of structural, electronic and optical properties of perovskites CaZrO3 and CaHfO3 in cubic phase

NASA Astrophysics Data System (ADS)

Hoat, D. M.; Silva, J. F. Rivas; Blas, A. Méndez

2018-07-01

In this work, we present the first principles calculations for structural, electronic and optical properties of perovskites CaZrO3 and CaHfO3 using the full-potential linearized augmented plane wave method (FP-LAPW) within the framework of density functional theory (DFT) as implemented in WIEN2k package. The exchange-correlation potential is treated with local density approximation (LDA) and generalized gradient approximation (GGA-PBE and PBESol). Additionally, the Tran Blaha modified Becke-Johnson exchange potential (mBJ) also is employed for electronic and optical calculations due to that it gives very accurate band gap of solids. Our obtained structural parameters are in good agreement with experimental datas and other theoretical results. The energy band gap obtained with mBJ is 4.56 eV for CaZrO3 and 5.27 eV for CaHfO3. The hybridization of states of O atom with those of Zr and Hf atoms in CaZrO3 and CaHfO3, respectively, is observed. The spin-orbit coupling effect on electronic properties of considered compounds also is investigated. Finally, the linear optical properties of CaZrO3 and CaHfO3 are derived from their complex dielectric function calculated with mBJ potential for wide energy range up to 45 eV, and all of them analyzed in details.

Electronic structure study of Ce1-xAxO2 (A = Zr & Hf) nanoparticles: NEXAFS and EXAFS investigations.

PubMed

Sharma, Aditya; Varshney, Mayora; Shin, Hyun-Joon; Park, Yong Jun; Kim, Min-Gyu; Ha, Tae-Kyun; Chae, Keun Hwa; Gautam, Sanjeev

2014-10-07

Single phase nanoparticles (NPs) of CeO2, Ce0.5Zr0.5O2, Ce0.5Hf0.5O2 and Ce0.5Hf0.25Zr0.25O2 were successfully synthesized by co-precipitation method at constant pH and temperature. The X-ray diffraction results revealed that the additive atoms did not segregate to form secondary phases but led to grain size variation in the NPs. The 10 Dq values in the near edge X-ray absorption fine structure (NEXAFS) spectra at the O K-edge did not vary in the same way as the average grain size was changed for the doped CeO2 NPs. The deconvolution of Ce M5-edge and detailed analysis of O K pre-edge peak have shown the higher Ce(+3)/(Ce(+3) + Ce(+4)) ratio in the Zr- and Hf-doped samples. The local atomic structure around the Ce, Zr and Hf atoms was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy at Ce K-edge, Zr K-edge and Hf L3-edge, respectively, and the EXAFS data were fitted with the theoretical calculations. The 4f occupancy, Ce(+3)/(Ce(+3) + Ce(+4)) ratio of Ce ions, coordination number of Ce and Ce-Ce/Ce-O bond distances were sensitive to the additive atoms but not explicitly changed according to the grain size variation in the NPs.

Zirconium, hafnium, and rare earth element partition coefficients for ilmenite and other minerals in high-Ti lunar mare basalts - An experimental study

NASA Technical Reports Server (NTRS)

Mckay, G.; Wagstaff, J.; Yang, S.-R.

1986-01-01

Partition coefficients were determined for Gd, Lu, Hf and Zr among ilmenite, armalcolite, and synthetic high-Ti mare basaltic melts at temperatures from 1122 deg to 1150 deg, and at oxygen fugacities of IW x 10 exp 0.5, by in situ analysis with an electron microprobe, using samples doped to present concentration levels. Coefficients for Zr were also measured for samples containing 600-1600 ppm Zr using this microprobe. In addition, coefficients were determined for Hf and Zr between chromian ulvospinel and melt, for Hf between pigeonite and melt, and for Lu between olivine and melt by microprobe analysis of samples doped to present levels. Values measured using the microprobe were in agreement with the values measured by analyzing mineral separates from the same run products by isotope dilution. Coefficient values for ilmenite are less than 0.01 for the LREE, are around 0.1 for the HREE, and are several times greater than this for Zr and Hf.

Effect of atomic size on undercoolability of binary solid solution alloy liquids with Zr, Ti, and Hf using electrostatic levitation

NASA Astrophysics Data System (ADS)

Jeon, S.; Kang, D.-H.; Lee, Y. H.; Lee, S.; Lee, G. W.

2016-11-01

We investigate the relationship between the excess volume and undercoolability of Zr-Ti and Zr-Hf alloy liquids by using electrostatic levitation. Unlike in the case of Zr-Hf alloy liquids in which sizes of the constituent atoms are matched, a remarkable increase of undercoolability and negative excess volumes are observed in Zr-Ti alloy liquids as a function of their compositional ratios. In this work, size mismatch entropies for the liquids were obtained by calculating their hard sphere diameters, number densities, and packing fractions. We also show that the size mismatch entropy, which arises from the differences in atomic sizes of the constituent elements, plays an important role in determining the stabilities of metallic liquids.

Preparation and electrochemical properties of Zr-site substituted Li7La3(Zr2-xMx)O12 (M = Ta, Nb) solid electrolytes

NASA Astrophysics Data System (ADS)

Huang, Mian; Shoji, Mao; Shen, Yang; Nan, Ce-Wen; Munakata, Hirokazu; Kanamura, Kiyoshi

2014-09-01

Li7La3Zr2O12 (LLZ) solid electrolytes with Zr site partially substituted by Ta and Nb elements were prepared via the conventional solid-state reaction. All the compositions could lead to the cubic garnet-type structure after sintering at 1150 °C. The use of γ-Al2O3 as a sintering aid in the preparation of doped LLZ was studied. It was shown that Al could help to improve the micro-structure for Nb doping, but not necessary for Ta doping. The Ta and Nb doping enhanced the ionic conductivity at 25 °C to 4.09 × 10-4 S cm-1 and 4.50 × 10-4 S cm-1, respectively. A conductivity as high as 1.23 × 10-3 S cm-1 was obtained when measured at 50 °C in air for the Nb-doped LLZ. All-solid-state batteries with LLZTa and LLZNb solid electrolytes were assembled and tested. The cyclic voltammetry (CV) measurement indicated the successful working of the batteries.

Mass measurements of neutron-deficient Y, Zr, and Nb isotopes and their impact on rp and νp nucleosynthesis processes

NASA Astrophysics Data System (ADS)

Xing, Y. M.; Li, K. A.; Zhang, Y. H.; Zhou, X. H.; Wang, M.; Litvinov, Yu. A.; Blaum, K.; Wanajo, S.; Kubono, S.; Martínez-Pinedo, G.; Sieverding, A.; Chen, R. J.; Shuai, P.; Fu, C. Y.; Yan, X. L.; Huang, W. J.; Xu, X.; Tang, X. D.; Xu, H. S.; Bao, T.; Chen, X. C.; Gao, B. S.; He, J. J.; Lam, Y. H.; Li, H. F.; Liu, J. H.; Ma, X. W.; Mao, R. S.; Si, M.; Sun, M. Z.; Tu, X. L.; Wang, Q.; Yang, J. C.; Yuan, Y. J.; Zeng, Q.; Zhang, P.; Zhou, X.; Zhan, W. L.; Litvinov, S.; Audi, G.; Uesaka, T.; Yamaguchi, Y.; Yamaguchi, T.; Ozawa, A.; Fröhlich, C.; Rauscher, T.; Thielemann, F.-K.; Sun, B. H.; Sun, Y.; Dai, A. C.; Xu, F. R.

2018-06-01

Using isochronous mass spectrometry at the experimental storage ring CSRe in Lanzhou, the masses of 82Zr and 84Nb were measured for the first time with an uncertainty of ∼10 keV, and the masses of 79Y, 81Zr, and 83Nb were re-determined with a higher precision. The latter are significantly less bound than their literature values. Our new and accurate masses remove the irregularities of the mass surface in this region of the nuclear chart. Our results do not support the predicted island of pronounced low α separation energies for neutron-deficient Mo and Tc isotopes, making the formation of Zr-Nb cycle in the rp-process unlikely. The new proton separation energy of 83Nb was determined to be 490(400) keV smaller than that in the Atomic Mass Evaluation 2012. This partly removes the overproduction of the p-nucleus 84Sr relative to the neutron-deficient molybdenum isotopes in the previous νp-process simulations.

Effect of transition metal impurities on the strength of grain boundaries in vanadium

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

Wu, Xuebang; Kong, Xiang-Shan; You, Yu-Wei

2016-09-07

Effects of 3d (Ti-Ni), 4d (Zr-Pd), and 5d (Hf-Pt) transition metal impurities on strength of two representative vanadium grain boundaries (GBs), symmetric Σ3(111) and asymmetric Σ5(210), were studied by first-principles calculations within the framework of the Rice-Wang thermodynamic model and within the computational tensile test. The desirable elements to increase the GB cohesion were predicted based on their segregation and strengthening behaviors across the different GB sites. It reveals that the elements Ti, Zr, Hf, Nb, and Ta are good choices for the GB cohesion enhancers. In addition, the GB strengthening by solutes is sensitive to the GB structures. Themore » elements Cr, Mn, Fe, Co, and Ni decrease the GB strength of the Σ3(111) GB but they can increase the cohesion of the Σ5(210) GB. Furthermore, the origin of Ti-induced change of the GB strength was uncovered by analyzing the atomic bonds and electronic structures as well as the tensile strength. This work provides a theoretical guidance to screen promising alloying elements in V-based materials with improved resistance to GB decohesion and also helps us to understand the formation mechanism of Ti-rich precipitates in the V-Cr-Ti alloys under neutron or ion irradiation environments.« less

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2.

PubMed

Perevalov, T V; Islamov, D R; Gritsenko, V A; Prosvirin, I P

2018-05-11

The electronic structure of oxygen-deficient Hf 0.5 Zr 0.5 O 2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf 0.5 Zr 0.5 O 2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf 0.5 Zr 0.5 O 2 : an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf 0.5 Zr 0.5 O 2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

Grain size engineering for ferroelectric Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films by an insertion of Al{sub 2}O{sub 3} interlayer

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

Kim, Han Joon; Park, Min Hyuk; Kim, Yu Jin

2014-11-10

The degradation of ferroelectric (FE) properties of atomic layer deposited Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films with increasing thickness was mitigated by inserting 1 nm-thick Al{sub 2}O{sub 3} interlayer at middle position of the thickness of the FE film. The large P{sub r} of 10 μC/cm{sup 2}, which is 11 times larger than that of single layer Hf{sub 0.5}Zr{sub 0.5}O{sub 2} film with equivalent thickness, was achieved from the films as thick as 40 nm. The Al{sub 2}O{sub 3} interlayer could interrupt the continual growth of Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films, and the resulting decrease of grain size prevented the formation of non-ferroelectricmore » monoclinic phase. The Al{sub 2}O{sub 3} interlayer also largely decreased the leakage current of the Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films.« less

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2

NASA Astrophysics Data System (ADS)

Perevalov, T. V.; Islamov, D. R.; Gritsenko, V. A.; Prosvirin, I. P.

2018-05-01

The electronic structure of oxygen-deficient Hf0.5Zr0.5O2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf0.5Zr0.5O2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf0.5Zr0.5O2: an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf0.5Zr0.5O2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

Titanite-scale insights into multi-stage magma mixing in Early Cretaceous of NW Jiaodong terrane, North China Craton

NASA Astrophysics Data System (ADS)

Jiang, Peng; Yang, Kui-Feng; Fan, Hong-Rui; Liu, Xuan; Cai, Ya-Chun; Yang, Yue-Heng

2016-08-01

The Early Cretaceous Guojialing-type granodiorites in northwestern Jiaodong terrane carry significant records for strong mantle-crust interaction during the destruction of North China Craton (NCC); however, the definite petrogenetic mechanism and detailed magmatic process remain an enigma. Titanite in igneous rocks can serve as an effective petrogenetic indicator. Here, we present integrated geochronological and geochemical studies on titanites from Guojialing-type granodiorites and their dioritic enclaves to constrain their petrogenesis. Titanites from granodiorites (G-type) and plagioclase-rich dioritic enclaves (E-type-I) present an identical U-Pb age ( 130 Ma) and an indistinguishable wide range of Zr and total REEs contents, and Th/U ratios. However, these two types of titanites exhibit distinct micro-scale textures and geochemical compositions. G-type titanites are characterized by oscillatory zonings with two Light BSE zones (LBZ) and two or three dark BSE zones, whereas E-type-I titanites are marked by core-mantle-rim zonings. Drastic increase of LREEs, Zr, Hf, and Fe and decrease of Nb, Ta, Al, and F contents are observed in LBZ of G-type titanites, whereas remarkable reduction of LREEs, Zr, and Hf and elevation of F contents are observed from the cores to the mantles of E-type-I titanites. Based on Zr-in-titanite thermometry, G-type titanites are interpreted to have experienced twice notable temperature increase, while E-type-I titanites are inferred to have undergone a rapid cooling process. Furthermore, we suggest that the drastic chemical changes in G-type and E-type-I titanites are ascribed to early-stage magma mixing between a colder felsic magma and a Fe-, REE-rich hotter dioritic magma. Compared to G-type and E-type-I titanites, titanites from plagioclase-poor dioritic enclaves (E-type-II) are characterized by their occurrence in interstitial space and present a relatively younger U-Pb age ( 128 Ma) and much narrower and lower range of Zr, total REEs contents, and Th/U ratios, but reveal high F contents (0.35-0.76 wt.%) and extreme high Nb/Ta ratios (up to 65.6). Such titanites are perceived to record late-stage mingling, during which F-rich and REE-poor hybrid granodioritic magma squeezed into the incompletely consolidated dioritic enclaves with accompanying fluid-rock interaction. Combining our results with previous isotopic studies, a new genetic model for Guojialing-type granodiorites is envisaged, which involves multi-stage magma mixing between Archean lower crust-derived felsic magma and mafic lower crust-derived dioritic magma, triggered by mantle-derived mafic magma underplating during the course of asthenospheric upwelling in Early Cretaceous. Such process further implicates the reactivation of Jiaodong lower crust during the destruction of NCC.

Structural and dielectric properties of thin ZrO2 films on silicon grown by atomic layer deposition from cyclopentadienyl precursor

NASA Astrophysics Data System (ADS)

Niinistö, J.; Putkonen, M.; Niinistö, L.; Kukli, K.; Ritala, M.; Leskelä, M.

2004-01-01

ZrO2 thin films with thicknesses below 20 nm were deposited by the atomic layer deposition process on Si(100) substrates at 350 °C. An organometallic precursor, Cp2Zr(CH3)2 (Cp=cyclopentadienyl, C5H5) was used as the zirconium source and water or ozone as oxygen source. The influence of oxygen source and substrate pretreatment on the dielectric properties of ZrO2 films was investigated. Structural characterization with high-resolution transmission electron microscopy was performed to films grown onto HF-etched or native oxide covered silicon. Strong inhibition of ZrO2 film growth was observed with the water process on HF-etched Si. Ozone process on HF-etched Si resulted in interfacial SiO2 formation between the dense and uniform film and the substrate while water process produced interfacial layer with intermixing of SiO2 and ZrO2. The effective permittivity of ZrO2 in Al/ZrO2/Si/Al capacitor structures was dependent on the ZrO2 layer thickness and oxygen source used. The interfacial layer formation increased the capacitance equivalent oxide thickness (CET). CET of 2.0 nm was achieved with 5.9 nm ZrO2 film deposited with the H2O process on HF-stripped Si. The ozone-processed films showed good dielectric properties such as low hysteresis and nearly ideal flatband voltage. The leakage current density was lower and breakdown field higher for the ozone-processed ZrO2 films.

Geochemistry of Zr, Hf, and REE in a wide spectrum of Eh and water composition: The case of Dead Sea Fault system (Israel)

NASA Astrophysics Data System (ADS)

Censi, P.; Raso, M.; Yechieli, Y.; Ginat, H.; Saiano, F.; Zuddas, P.; Brusca, L.; D'Alessandro, W.; Inguaggiato, C.

2017-03-01

Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the contrary, in waters where Eh < 0 values occur (Group 2), chondritic Zr/Hf values are found. Superchondritic Zr/Hf values are produced by the preferential Hf scavenging onto Fe-oxyhydroxides that is inhibited under reducing conditions consistent with the water oversaturation relative to pyrite. Redox conditions also influence the amplitude of Ce and Eu anomalies. Oxidized Group-1 waters show negative Ce anomalies related to the oxidative Ce scavenging as CeO2 onto Fe-oxyhydroxide. Reduced Group-2 waters show positive Eu anomaly values consistent with the larger Eu2+ concentration relative to Eu3+ in these waters suggested by model calculations. The higher stability of Eu2+ with respect to its trivalent neighbors along the REE series can explain the above mentioned positive Eu anomaly values. The middle-REE enrichment observed in shale-normalized REE patterns of studied waters can be ascribed to carbonate and/or gypsum dissolution.

Trace- and rare-earth element geochemistry and Pb-Pb dating of black shales and intercalated Ni-Mo-PGE-Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

NASA Astrophysics Data System (ADS)

Jiang, Shao-Yong; Chen, Yong-Quan; Ling, Hong-Fei; Yang, Jing-Hong; Feng, Hong-Zhen; Ni, Pei

2006-08-01

The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb-Pb isotope dating for the Ni-Mo-PGE-Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni-Mo-PGE-Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb-Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni-Mo-PGE-Au sulfide ores, and two Pb-Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni-Mo-PGE-Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.

Discovery of a superconducting high-entropy alloy.

PubMed

Koželj, P; Vrtnik, S; Jelen, A; Jazbec, S; Jagličić, Z; Maiti, S; Feuerbacher, M; Steurer, W; Dolinšek, J

2014-09-05

High-entropy alloys (HEAs) are multicomponent mixtures of elements in similar concentrations, where the high entropy of mixing can stabilize disordered solid-solution phases with simple structures like a body-centered cubic or a face-centered cubic, in competition with ordered crystalline intermetallic phases. We have synthesized an HEA with the composition Ta34Nb33Hf8Zr14Ti11 (in at. %), which possesses an average body-centered cubic structure of lattice parameter a=3.36  Å. The measurements of the electrical resistivity, the magnetization and magnetic susceptibility, and the specific heat revealed that the Ta34Nb33Hf8Zr14Ti11 HEA is a type II superconductor with a transition temperature Tc≈7.3  K, an upper critical field μ0H_c2≈8.2  T, a lower critical field μ0Hc1≈32  mT, and an energy gap in the electronic density of states (DOS) at the Fermi level of 2Δ≈2.2  meV. The investigated HEA is close to a BCS-type phonon-mediated superconductor in the weak electron-phonon coupling limit, classifying it as a "dirty" superconductor. We show that the lattice degrees of freedom obey Vegard's rule of mixtures, indicating completely random mixing of the elements on the HEA lattice, whereas the electronic degrees of freedom do not obey this rule even approximately so that the electronic properties of a HEA are not a "cocktail" of properties of the constituent elements. The formation of a superconducting gap contributes to the electronic stabilization of the HEA state at low temperatures, where the entropic stabilization is ineffective, but the electronic energy gain due to the superconducting transition is too small for the global stabilization of the disordered state, which remains metastable.

An experimental study of trace element partitioning between perovskite, hibonite and melt: Equilibrium values

NASA Technical Reports Server (NTRS)

Kennedy, A. K.; Lofgren, G. E.; Wasserburg, G. J.

1993-01-01

The presence of perovskite (CATiO3) and hibonite (Ca Al12O19) within different regions of Calcium-, Aluminum-rich Inclusions (CAI) and the trace element concentrations of these minerals in each circumstance, constrain models of precursor formation, nebular condensation, the thermal history of inclusions with relict perovskite and hibonite, and the formation of the Wark-Lovering rim. At present mineral/melt partition coefficient data for hibonite are limited to a few elements in simple experimental systems, or to those derived from hibonite-glass pairs in hibonite/glass microspherules. Similarly, there is only limited data on perovskite D that are applicable to meteorite compositions. Apart from the importance of partitioning studies to meteorite research, D values also are invaluable in the development of thermodynamic models, especially when data is available for a large number of elements that have different ionic charge and radii. In addition, study of the effect of rapid cooling on partitioning is crucial to our understanding of meteorite inclusions. To expand our knowledge of mineral/melt D for perovskite and hibonite, a study was instituted where D values are obtained in both equilibrium and dynamic cooling experiments. As an initial phase of this study mineral/melt D was measured for major elements (Ca, Mg, Al, Ti, and Si), 15 rare earth elements (La-Lu) and 8 other elements (Ba, Sr, U, Th, Nb, Zr, Hf, and Ge) in perovskite and hibonite grown under equilibrium conditions, in bulk compositions that are respectively similar to Compact Type A (CTA) CAI and to a hibonite/glass microspherule. Experimental mixes were doped with REE at 20-50x chondritic (ch) abundances, Ba at 50 ppm, Sr, Hf, Nb, and Zr at 100 ppm and, U and Th at 200 ppm. Trace element abundances were measured with the PANURGE ion microprobe. Major element compositions were obtained by electron microprobe analysis.

Extraction chromatography of the Rf homologs, Zr and Hf, using TEVA and UTEVA resins in HCl, HNO3, and H2SO4 media

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

Alfonso, M. C.; Bennett, M. E.; Folden, C. M.

2015-06-20

The extraction behavior of the Rf homologs, Zr and Hf, has been studied in HCl, HNO3, and H2SO4 media using TEVA (R) (a trioctyl and tridecyl methyl ammonium-based resin) and UTEVA (R) (a diamyl amylphosphonate-based resin). All six systems were considered for the future chemical characterization of Rf. Batch uptake studies were first performed to determine which systems could separate Zr and Hf and these results were used to determine what acid concentration range to focus on for the column studies. The batch uptake studies showed that UTEVA separates Zr and Hf in all media, while the intergroup separation wasmore » only observed in HCl media with TEVA. Both HCl systems showed viability for potential extraction chromatographic studies of Rf.« less

Reactive sputter deposition of metal oxide nanolaminates

NASA Astrophysics Data System (ADS)

Rubin Aita, Carolyn

2008-07-01

We discuss the reactive sputter deposition of metal oxide nanolaminates on unheated substrates using four archetypical examples: ZrO2 Al2O3, HfO2 Al2O3, ZrO2 Y2O3, and ZrO2 TiO2. The pseudobinary bulk phase diagrams corresponding to these nanolaminates represent three types of interfaces. I. Complete immiscibility (ZrO2 Al2O3 and HfO2 Al2O3). II. Complete miscibility (ZrO2 Y2O3). III. Limited miscibility without a common end-member lattice (ZrO2 TiO2). We found that, although reactive sputter deposition is a far-from-equilibrium process, thermodynamic considerations strongly influence both phase formation within layers and at interfaces. We show that pseudobinary phase diagrams can be used to predict interfacial cation mixing in the nanolaminates. However, size effects must be considered to predict specific structures. In the absence of pseudoepitaxy, size effects play a significant role in determining the nanocrystalline phases that form within a layer (e.g. tetragonal ZrO2, tetragonal HfO2, and orthorhombic HfO2) and at interfaces (e.g. monoclinic (Zr,Ti)O2). These phases are not bulk standard temperature and pressure phases. Their formation is understood in terms of self-assembly into the lowest energy structure in individual critical nuclei.

Geochronology, geochemistry, and Sr-Nd-Pb-Hf isotopes of the Zhunsujihua granitoid intrusions associated with the molybdenum deposit, northern Inner Mongolia, China: implications for petrogenesis and tectonic setting

NASA Astrophysics Data System (ADS)

Zhang, Xiaojun; Lentz, David R.; Yao, Chunliang; Liu, Rui; Yang, Zhen; Mei, Yanxiong; Fan, Xianwang; Huang, Fei; Qin, Ying; Zhang, Kun; Zhang, Zhenfei

2018-03-01

The Zhunsujihua porphyry molybdenum deposit, located in northern Inner Mongolia of China that belongs to Central-Asian Orogenic Belt (CAOB), is the only Mo deposit formed in the late Carboniferous in this area so far. Its mineralization is mainly restricted to the Zhunsujihua granitoid intrusions, which are composed of the main granodiorite (GD) and crosscutting, virtually coeval minor syn-ore leucogranite (LG) and diorite porphyry (DP) dykes. LA-ICP-MS zircon U-Pb dating yields crystallization ages of 300.0 ± 2.0, 299.3 ± 2.0, and 299.0 ± 2.6 Ma for the GD, LG, and DP, respectively. The major and trace element lithogeochemical data show that the GD and LG are metaluminous to weakly peraluminous, high-K calc-alkaline series with I-type granite characteristics, strongly oxidized, with low concentrations of Ba, Nb, Sr, P, and Ti and elevated K and Rb contents, indicating typical arc magmatic features. The LG is a product derived by extensive fractional crystallization of a parental magma similar to the GD as evident from the lower Eu/Eu*, Nb/Ta, Zr/Hf, and T Zr. The moderately altered DP exhibits high concentrations of K, Rb, Cs, LREE, Y, and low Sr/Y, with a positive ɛ Nd (300 Ma), which indicates a mantle or juvenile source associated with an arc setting. The Sr-Nd-Hf isotope data show low I Sr (0.70406-0.70461) and moderate ɛ Nd (300 Ma) (-0.9 to 1.5) for the GD and LG, and relatively high ɛ Hf (300 Ma) values (-3.6 to +11.2) for the GD, suggesting the magma mainly originated from the juvenile lower crust that was derived from depleted mantle, with a minor component of ancient continental crust. Lead isotope data have characteristics of a lower crust source with minor contamination by upper crustal material. Combined with previous research, the Zhunsujihua granitoid intrusions developed in an intracontinental volcanic arc (Uliastai) associated with northward subduction of the Paleo-Asian Ocean plate during late Carboniferous to early Permian; this suggests that the subduction of Paleo Asian Ocean may have continued to late Carboniferous, and the Hengenshan basin is probably closed during the early Permian. Fractional crystallization is the main evolutionary process of the felsic magma, which has played an important role in the Mo mineralization. The coeval DP may have provided additional heat for the extended evolution of the crystallizing felsic magma chamber.

Bone response to a novel Ti-Ta-Nb-Zr alloy.

PubMed

Stenlund, Patrik; Omar, Omar; Brohede, Ulrika; Norgren, Susanne; Norlindh, Birgitta; Johansson, Anna; Lausmaa, Jukka; Thomsen, Peter; Palmquist, Anders

2015-07-01

Commercially pure titanium (cp-Ti) is regarded as the state-of-the-art material for bone-anchored dental devices, whereas the mechanically stronger alloy (Ti-6Al-4V), made of titanium, aluminum (Al) and vanadium (V), is regarded as the material of choice for high-load applications. There is a call for the development of new alloys, not only to eliminate the potential toxic effect of Al and V but also to meet the challenges imposed on dental and maxillofacial reconstructive devices, for example. The present work evaluates a novel, dual-stage, acid-etched, Ti-Ta-Nb-Zr alloy implant, consisting of elements that create low toxicity, with the potential to promote osseointegration in vivo. The alloy implants (denoted Ti-Ta-Nb-Zr) were evaluated after 7 days and 28 days in a rat tibia model, with reference to commercially pure titanium grade 4 (denoted Ti). Analyses were performed with respect to removal torque, histomorphometry and gene expression. The Ti-Ta-Nb-Zr showed a significant increase in implant stability over time in contrast to the Ti. Further, the histological and gene expression analyses suggested faster healing around the Ti-Ta-Nb-Zr, as judged by the enhanced remodeling, and mineralization, of the early-formed woven bone and the multiple positive correlations between genes denoting inflammation, bone formation and remodeling. Based on the present experiments, it is concluded that the Ti-Ta-Nb-Zr alloy becomes osseointegrated to at least a similar degree to that of pure titanium implants. This alloy is therefore emerging as a novel implant material for clinical evaluation. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The Mechanical Properties and In Vitro Biocompatibility of PM-Fabricated Ti-28Nb-35.4Zr Alloy for Orthopedic Implant Applications.

PubMed

Xu, Wei; Li, Ming; Wen, Cuie; Lv, Shaomin; Liu, Chengcheng; Lu, Xin; Qu, Xuanhui

2018-03-30

A biocompatible Ti-28Nb-35.4Zr alloy used as bone implant was fabricated through the powder metallurgy process. The effects of mechanical milling and sintering temperatures on the microstructure and mechanical properties were investigated systematically, before in vitro biocompatibility of full dense Ti-28Nb-35.4Zr alloy was evaluated by cytotoxicity tests. The results show that the mechanical milling and sintering temperatures have significantly effects on the density and mechanical properties of the alloys. The relative density of the alloy fabricated by the atomized powders at 1500 °C is only 83 ± 1.8%, while the relative density of the alloy fabricated by the ball-milled powders can rapidly reach at 96.4 ± 1.3% at 1500 °C. When the temperature was increased to 1550 °C, the alloy fabricated by ball-milled powders achieve full density (relative density is 98.1 ± 1.2%). The PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C can achieve a wide range of mechanical properties, with a compressive yield strength of 1058 ± 35.1 MPa, elastic modulus of 50.8 ± 3.9 GPa, and hardness of 65.8 ± 1.5 HRA. The in vitro cytotoxicity test suggests that the PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C has no adverse effects on MC3T3-E1 cells with cytotoxicity ranking of 0 grade, which is nearly close to ELI Ti-6Al-4V or CP Ti. These properties and the net-shape manufacturability makes PM-fabricated Ti-28Nb-35.4Zr alloy a low-cost, highly-biocompatible, Ti-based biomedical alloy.

Comparison of Fatigue Properties and Fatigue Crack Growth Rates of Various Implantable Metals

PubMed Central

Okazaki, Yoshimitsu

2012-01-01

The fatigue strength, effects of a notch on the fatigue strength, and fatigue crack growth rate of Ti-15Zr-4Nb-4Ta alloy were compared with those of other implantable metals. Zr, Nb, and Ta are important alloying elements for Ti alloys for attaining superior long-term corrosion resistance and biocompatibility. The highly biocompatible Ti-15Zr-4Nb-4Ta alloy exhibited an excellent balance between strength and ductility. Its notched tensile strength was much higher than that of a smooth specimen. The strength of 20% cold-worked commercially pure (C.P.) grade 4 Ti was close to that of Ti alloy. The tension-to-tension fatigue strength of an annealed Ti-15Zr-4Nb-4Ta rod at 107 cycles was approximately 740 MPa. The fatigue strength of this alloy was much improved by aging treatment after solution treatment. The fatigue strengths of C.P. grade 4 Ti and stainless steel were markedly improved by 20% cold working. The fatigue strength of Co-Cr-Mo alloy was markedly increased by hot forging. The notch fatigue strengths of 20% cold-worked C.P. grade 4 Ti, and annealed and aged Ti-15Zr-4Nb-4Ta, and annealed Ti-6Al-4V alloys were less than those of the smooth specimens. The fatigue crack growth rate of Ti-15Zr-4Nb-4Ta was the same as that of Ti-6Al-4V. The fatigue crack growth rate in 0.9% NaCl was the same as that in air. Stainless steel and Co-Cr-Mo-Ni-Fe alloy had a larger stress-intensity factor range (ΔK) than Ti alloy.

Nonvolatile memories using deep traps formed in HfO2 by Nb ion implantation

NASA Astrophysics Data System (ADS)

Choul Kim, Min; Oh Kim, Chang; Taek Oh, Houng; Choi, Suk-Ho; Belay, K.; Elliman, R. G.; Russo, S. P.

2011-03-01

We report nonvolatile memories (NVMs) based on deep-energy trap levels formed in HfO2 by metal ion implantation. A comparison of Nb- and Ta-implanted samples shows that suitable charge-trapping centers are formed in Nb-implanted samples, but not in Ta-implanted samples. This is consistent with density-functional theory calculations which predict that only Nb will form deep-energy levels in the bandgap of HfO2. Photocurrent spectroscopy exhibits characteristics consistent with one of the trap levels predicted in these calculations. Nb-implanted samples showing memory windows in capacitance-voltage (V) curves always exhibit current (I) peaks in I-V curves, indicating that NVM effects result from deep traps in HfO2. In contrast, Ta-implanted samples show dielectric breakdowns during the I-V sweeps between 5 and 11 V, consistent with the fact that no trap levels are present. For a sample implanted with a fluence of 1013 Nb cm-2, the charge losses after 104 s are ˜9.8 and ˜25.5% at room temperature (RT) and 85°C, respectively, and the expected charge loss after 10 years is ˜34% at RT, very promising for commercial NVMs.

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Impact of mechanical stress on ferroelectricity in (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films

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

Shiraishi, Takahisa; Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577; Katayama, Kiliha

2016-06-27

To investigate the impact of mechanical stress on their ferroelectric properties, polycrystalline (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films were deposited on (111)Pt-coated SiO{sub 2}, Si, and CaF{sub 2} substrates with thermal expansion coefficients of 0.47, 4.5, and 22 × 10{sup −6}/ °C, respectively. In-plane X-ray diffraction measurements revealed that the (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films deposited on SiO{sub 2} and Si substrates were under in-plane tensile strain and that their volume fraction of monoclinic phase decreased as this strain increased. In contrast, films deposited on CaF{sub 2} substrates were under in-plane compressive strain, and their volume fraction of monoclinic phasemore » was the largest among the three kinds of substrates. The maximum remanent polarization of 9.3 μC/cm{sup 2} was observed for Pt/(Hf{sub 0.5}Zr{sub 0.5})O{sub 2}/Pt/TiO{sub 2}/SiO{sub 2}, while ferroelectricity was barely observable for Pt/(Hf{sub 0.5}Zr{sub 0.5})O{sub 2}/Pt/TiO{sub 2}/SiO{sub 2}/CaF{sub 2}. This result suggests that the in-plane tensile strain effectively enhanced the ferroelectricity of the (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films.« less

Atomistic study of the electronic contact resistivity between the half-Heusler alloys (HfCoSb, HfZrCoSb, HfZrNiSn) and the metal Ag

NASA Astrophysics Data System (ADS)

He, Yuping; Léonard, François; Spataru, Catalin D.

2018-06-01

Half-Heusler (HH) alloys have shown promising thermoelectric properties in the medium- and high-temperature range. To harness these material properties for thermoelectric applications, it is important to realize electrical contacts with low electrical contact resistivity. However, little is known about the detailed structural and electronic properties of such contacts and the expected values of contact resistivity. Here, we employ atomistic ab initio calculations to study electrical contacts in a subclass of HH alloys consisting of the compounds HfCoSb, HfZrCoSb, and HfZrNiSn. By using Ag as a prototypical metal, we show that the termination of the HH material critically determines the presence or absence of strong deformations at the interface. Our study includes contacts to doped materials, and the results indicate that the p -type materials generally form ohmic contacts while the n -type materials have a small Schottky barrier. We calculate the temperature dependence of the contact resistivity in the low- to medium-temperature range and provide quantitative values that set lower limits for these systems.

ZnO/(Hf,Zr)O2/ZnO-trilayered nanowire capacitor structure fabricated solely by metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Fujisawa, Hironori; Kuwamoto, Kei; Nakashima, Seiji; Shimizu, Masaru

2016-02-01

HfO2-based thin films are one of the key dielectric and ferroelectric materials in Si-CMOS LSIs as well as in oxide electronic nanodevices. In this study, we demonstrated the fabrication of a ZnO/(Hf,Zr)O2/ZnO-trilayered nanowire (NW) capacitor structure solely by metalorganic chemical vapor deposition (MOCVD). 15-nm-thick dielectric (Hf,Zr)O2 and 40-nm-thick top ZnO electrode layers were uniformly grown by MOCVD on a ZnO NW template with average diameter, length, and aspect ratio of 110 nm, 10 µm, and ˜90, respectively. The diameter and aspect ratio of the resultant trilayerd NWs are 200-300 nm and above 30, respectively. The crystalline phase of HfO2 and stacked the structure are also discussed.

Novel Electrochemical Test Bench for Evaluating the Functional Fatigue Life of Biomedical Alloys

NASA Astrophysics Data System (ADS)

Ijaz, M. F.; Dubinskiy, S.; Zhukova, Y.; Korobkova, A.; Pustov, Y.; Brailovski, V.; Prokoshkin, S.

2017-08-01

The aim of the present work was first to develop and validate a test bench that simulates the in vitro conditions to which the biomedical implants will be actually subjected in vivo. For the preliminary application assessments, the strain-controlled fatigue tests of biomedically pure Ti and Ti-Nb-Zr alloy in simulated body fluid were undertaken. The in situ open-circuit potential measurements from the test bench demonstrated a strong dependence on the dynamic cycling and kind of material under testing. The results showed that during fatigue cycling, the passive oxide film formed on the surface of Ti-Nb-Zr alloy was more resistant to fatigue degradation when compared with pure Ti. The Ti-Nb-Zr alloy exhibited prolonged fatigue life when compared with pure Ti. The fractographic features of both materials were also characterized using scanning electron microscopy. The electrochemical results and the fractographic evidence confirmed that the prolonged functional fatigue life of the Ti-Nb-Zr alloy is apparently ascribable to the reversible martensitic phase transformation.

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

Soares Azevedo e Silva, Paulo Ricardo, E-mail: paulori@alunos.eel.usp.br; Baldan, Renato, E-mail: renato@ppgem.eel.usp.br; Nunes, Carlos Angelo, E-mail: cnunes@demar.eel.usp.br

MAR-M247 superalloy has excellent mechanical properties and good oxidation resistance at elevated temperatures. Niobium is an element known as {gamma} Prime phase hardener in nickel-based superalloys, besides promoting homogeneous distribution of MC carbides. This work is inserted in a project that aims to evaluate the total replacement of tantalum by niobium atoms in MAR-M247 superalloy (10.2 Co, 10.2 W, 8.5Cr, 5.6 Al, 1.6 Nb, 1.4 Hf, 1.1 Ti, 0.7 Mo, 0.15 C, 0.06 Zr, 0.015 B, Ni balance-wt.%). Based on microstructural characterizations (SEM and FEG-SEM, both with EDS) of the as-cast material and heat-treated materials as well as utilizing Thermocalcmore » simulations and experiments of differential thermal analysis (DTA), heat-treatment at 1260 Degree-Sign C for 8 h was chosen as an ideal condition for the solution of Nb-modified MAR-M247 superalloy. The hardness of as-cast and ideally solution treated materials was 390 {+-} 14 HV and 415 {+-} 6 HV, respectively. - Highlights: Black-Right-Pointing-Pointer DTA and microstructure of MAR-M247(Nb) showed a good agreement with Thermocalc. Black-Right-Pointing-Pointer An ideal condition for solution heat-treatment of MAR-M247(Nb) is 1260 Degree-Sign C for 8 h. Black-Right-Pointing-Pointer It was an observed evidence of incipient melting in samples heat-treated at 1280 Degree-Sign C.« less

SYNTHESIS OF ZrI$sub 4$ AND HfI$sub 4$ BY HALOID EXCHANGE (in Russian)

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

Nisel'son, L.A.; Teslitskaya, M.V.; Shvedova, T.A.

1962-05-01

Syntheses of ZrI/sub 4/ and Hfl/sub 4/ by reactions of ZrCl/sub 4/ with SiI/sub 4/, Al/sub 2/I/sub 6/, HI, and Al/sub 2/Br and HfCl/sub 4/ with Al/sub 2 / I/sub 6/ are analyzed. The highest exchange yield was reached with /sub 4/ from ZrCl/sub 4/ and other admixtures was achieved by distillation. (R.V.J.)

Some properties of low-vapor-pressure braze alloys for thermionic converters

NASA Technical Reports Server (NTRS)

Bair, V. L.

1978-01-01

Property measurements were made for arc-melted, rod-shaped specimens. Density and dc electrical resistivity at 296 K were measured for various binary eutectic alloys. Thermal conductivity was inferred from the electrical conductivity using the Wiedemann, Franz, Lorenz relation. Linear thermal expansion from 293 K to two-thirds melting point, under a helium atmosphere, was measured for Zr, 21.7-wt percent Ru; Zr, 13-wt percent W; Zr, 22.3-wt percent Nb; Nb, 66.9-wt percent Ru; and Zr, 25.7-wt percent Ta.

Thermal properties of zirconium diboride -- transition metal boride solid solutions

NASA Astrophysics Data System (ADS)

McClane, Devon Lee

This research focuses on the thermal properties of zirconium diboride (ZrB2) based ceramics. The overall goal was to improve the understanding of how different transition metal (TM) additives influence thermal transport in ZrB2. To achieve this, ZrB2 with 0.5 wt% carbon, and 3 mol% of individual transition metal borides, was densified by hot-press sintering. The transition metals that were investigated were: Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The room temperature thermal diffusivities of the compositions ranged from 0.331 cm2/s for nominally pure ZrB2 to 0.105 cm2/s for (Zr,Cr)B2 and converged around 0.155cm2/s at higher temperatures for all compositions. Thermal conductivities were calculated from the diffusivities, using temperature-dependent values for density and heat capacity. The electron contribution to thermal conductivity was calculated from measured electrical resistivity according to the Wiedemann-Franz law. The phonon contribution to thermal conductivity was calculated by subtracting the electron contribution from the total thermal conductivity. Rietveld refinement of x-ray diffraction data was used to determine the lattice parameters of the compositions. The decrease in thermal conductivity for individual additives correlated directly to the metallic radius of the additive. Additional strain appeared to exist for additives when the stable TM boride for that metal had different crystal symmetries than ZrB2. This research provided insight into how additives and impurities affect thermal transport in ZrB2. The research potentially offers a basis for future modeling of thermal conductivity in ultra-high temperature ceramics based on the correlation between metallic radius and the decrease in thermal conductivity.

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

Thornburg, Nicholas E.; Nauert, Scott L.; Thompson, Anthony B.

Many industrially significant selective oxidation reactions are catalyzed by supported and bulk transition metal oxides. Catalysts for the synthesis of oxygenates, and especially for epoxidation, have predominantly focused on TiO x supported on or co-condensed with SiO 2, whereas much of the rest of Groups 4 and 5 have been less studied. We have recently demonstrated through periodic trends using a uniform molecular precursor that niobium(V)-silica catalysts reveal the highest activity and selectivity for efficient utilization of H 2O 2 for epoxidation across all of Groups 4 and 5. In this work, we graft a wide range of Nb(V) precursors,more » spanning surface densities of 0.07–1.6 Nb groups nm –2 on mesoporous silica, and we characterize these materials with UV–visible spectroscopy and Nb K-edge XANES. Further, we apply in situ chemical titration with phenylphosphonic acid (PPA) in the epoxidation of cis-cyclooctene by H 2O 2 to probe the numbers and nature of the active sites across this series and in a set of related Ti-, Zr-, Hf-, and Ta-SiO2 catalysts. By this method, the fraction of kinetically relevant NbO x species ranges from ~15% to ~65%, which correlates with spectroscopic evaluation of the NbO x sites. This titration leads to a single value for the average turnover frequency, on a per active site basis rather than a per Nb atom basis, of 1.4 ± 0.52 min –1 across the 21 materials in the series. These quantitative maps of structural properties and kinetic consequences link key catalyst descriptors of supported Nb-SiO 2 to enable rational design for next-generation oxidation catalysts.« less

Phase Structure and Site Preference Behavior of Ternary Alloying Additions to PdTi and PtTi Shape-Memory Alloys

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

2006-01-01

The phasc structure and concentration dependence of the lattice parameter and energy of formation of ternary Pd-'I-X and Pt-Ti-X alloys for a large number of ternary alloying additions X (X = Na, Mg, Al, Si, Sc. V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, Hf, Ta, W, Re, Os, Ir) are investigated with an atomistic modeling approach. In addition, a detailed description of the site preference behavior of such additions showing that the elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice is provided.

Oxidation of high-temperature intermetallics; Proceedings of the Workshop, Cleveland, OH, Sept. 22, 23, 1988

NASA Technical Reports Server (NTRS)

Grobstein, Toni (Editor); Doychak, Joseph (Editor)

1989-01-01

The present conference on the high-temperature oxidation behavior of aerospace structures-applicable intermetallic compounds discusses the influence of reactive-element additions on the oxidation of Ni3Al base alloys, the effect of Ni3Al oxidation below 850 C on fracture behavior, the oxidation of FeAl + Hf, Zr, and B, the synergistic effect of Al and Si on the oxidation resistance of Fe alloys, and pack cementation coatings of Cr-Al on Fe, Ni, and Co alloys. Also discussed are the formation of alumina on Nb- and Ti-base alloys, the oxidation behavior of titanium aluminide alloys, silicide coatings for refractory metals, the oxidation of chromium disilicide, and the oxidation behavior of nickel beryllides.

Testing Room-Temperature Ionic Liquid Solutions for Depot Repair of Aluminum Coatings

DTIC Science & Technology

2011-05-01

Ne 3 Na Mg IIIB IVB VB VIB VIIB ------ VIIIB ------ IB IIB Al Si P S Cl Ar 4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 5 Rb Sr Y Zr Nb Mo Tc...Ru Rh Pd Ag Cd In Sn Sb Te I Xe 6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 7 Fr Ra Ac Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th Pa U Np...Electroplating Bath Lid Arrangement ;:::::::::::=== Thermometer Purge gas vent Anode lead Cathode lead (Extractable from the lid) Purge feed gas

Nickel aluminide alloy suitable for structural applications

DOEpatents

Liu, C.T.

1998-03-10

Alloys are disclosed for use in structural applications based upon NiAl to which are added selected elements to enhance room temperature ductility and high temperature strength. Specifically, small additions of molybdenum produce a beneficial alloy, while further additions of boron, carbon, iron, niobium, tantalum, zirconium and hafnium further improve performance of alloys at both room temperature and high temperatures. A preferred alloy system composition is Ni--(49.1{+-}0.8%)Al--(1.0{+-}0.8%)Mo--(0.7 + 0.5%)Nb/Ta/Zr/Hf--(nearly zero to 0.03%)B/C, where the % is at. % in each of the concentrations. All alloys demonstrated good oxidation resistance at the elevated temperatures. The alloys can be fabricated into components using conventional techniques. 4 figs.

Strategy for stabilization of the antiferroelectric phase (Pbma) over the metastable ferroelectric phase (P2{sub 1}ma) to establish double loop hysteresis in lead-free (1−x)NaNbO{sub 3}-xSrZrO{sub 3} solid solution

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

Guo, Hanzheng, E-mail: hug17@psu.edu; Randall, Clive A.; Shimizu, Hiroyuki

A new lead-free antiferroelectric solid solution system, (1−x)NaNbO{sub 3}-xSrZrO{sub 3}, was rationalized through noting the crystal chemistry trend, of decreasing the tolerance factor and an increase in the average electronegativity of the system. The SrZrO{sub 3} doping was found to effectively stabilize the antiferroelectric (P) phase in NaNbO{sub 3} without changing its crystal symmetry. Preliminary electron diffraction and polarization measurements were presented which verified the enhanced antiferroelectricity. In view of our recent report of another lead-free antiferroelectric system (1−x)NaNbO{sub 3}-xCaZrO{sub 3} [H. Shimizu et al. “Lead-free antiferroelectric: xCaZrO{sub 3} - (1−x)NaNbO{sub 3} system (0 ≤ x ≤ 0.10),” Dalton Trans.more » (published online)], the present results point to a general strategy of utilizing tolerance factor to develop a broad family of new lead-free antiferroelectrics with double polarization hysteresis loops. We also speculate on a broad family of possible solid solutions that could be identified and tested for this important type of dielectric.« less

Processing of U-2.5Zr-7.5Nb and U-3Zr-9Nb alloys by sintering process

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

Dos Santos, A. M. M.; Ferraz, W. B.; Lameiras, F. S.

2012-07-01

To minimize the risk of nuclear proliferation, there is worldwide interest in reducing fuel enrichment of research and test reactors. To achieve this objective while still guaranteeing criticality and cycle length requirements, there is need of developing high density uranium metallic fuels. Alloying elements such as Zr, Nb and Mo are added to uranium to improve fuel performance in reactors. In this context, the Centro de Desenvolvimento da Tecnologia Nuclear (CDTN) is developing the U-2.5Zr-7.5Nb and U-3Zr-9Nb (weight %) alloys by the innovative process of sintering that utilizes raw materials in the form of powders. The powders were pressed atmore » 400 MPa and then sintered under a vacuum of about 1x10{sup -4} Torr at temperatures ranging from 1050 deg. to 1500 deg.C. The densities of the alloys were measured geometrically and by hydrostatic method and the phases identified by X ray diffraction (XRD). The microstructures of the pellets were observed by scanning electron microscopy (SEM) and the alloying elements were analyzed by energy dispersive X-ray spectroscopy (EDS). The results obtained showed the fuel density to slightly increase with the sintering temperature. The highest density achieved was approximately 80% of theoretical density. It was observed in the pellets a superficial oxide layer formed during the sintering process. (authors)« less

Tephra compositions from Late Quaternary volcanoes around the Antarctic Peninsula

NASA Astrophysics Data System (ADS)

Kraus, S.

2009-12-01

Crustal extension and rifting processes opened the Bransfield Strait between the South Shetland Islands and the Antarctic Peninsula during the last 4 Ma. Similar processes on the Peninsula's eastern side are responsible for volcanism along Larsen Rift. There are at least 11 volcanic centers with known or suspected Late Pleistocene / Holocene explosive activity (Fig. 1). Fieldwork was carried out on the islands Deception, Penguin, Bridgeman and Paulet, moreover at Melville Peak (King George Is.) and Rezen Peak (Livingston Is.). Of special importance is the second ever reported visit and sampling at Sail Rock, and the work on never before visited outcrops on the northern slopes and at the summit of Cape Purvis volcano (Fig. 1). The new bulk tephra ICP-MS geochemical data provide a reliable framework to distinguish the individual volcanic centers from each other. According to their Mg-number, Melville Peak and Penguin Island represent the most primitive magma source. Nb/Y ratios higher than 0.67 in combination with elevated Th/Yb and Ta/Yb ratios and strongly enriched LREE seem to be diagnostic to distinguish the volcanoes located along the Larsen Rift from those associated with Bransfield Rift. Sr/Y ratios discriminate between the individual Larsen Rift volcanoes, Paulet Island showing considerably higher values than Cape Purvis volcano. Along Bransfield Rift, Bridgeman Island and Melville Peak have notably lower Nb/Y and much higher Th/Nb than Deception Island, Penguin Island and Sail Rock. The latter displays almost double the Th/Yb ratio as compared to Deception Island, and also much higher LREE enrichment but extraordinarily low Ba/Th, discriminating it from Penguin Island. Such extremely low Ba/Th ratios are also typical for Melville Peak, but for none of the other volcanoes. Penguin Island has almost double the Ba/Th and Sr/Y ratios higher than any other investigated volcano. Whereas the volcanoes located in the northern part of Bransfield Strait have Zr/Hf ratios lower than N-MORB, all other volcanoes including the Larsen Rift centers display Zr/Hf higher than N-MORB. It is expected that the correlation of the new data with published data from tephra layers found in ice, lake and marine sediment cores will contribute to a better constrained timing of individual climatic events identified in the northern Antarctic Peninsula area. Late Quaternary volcanoes around the northern Antarctic Peninsula.

Composition, response to pressure, and negative thermal expansion in M IIB IVF 6 (M = Ca, Mg; B = Zr, Nb) [Composition, response to pressure, and negative thermal expansion in A IIB IVF 6; A - Ca, Mg, B - Zr, Nb

DOE PAGES

Hester, Brett R.; Hancock, Justin C.; Lapidus, Saul H.; ...

2016-12-27

CaZrF 6 has recently been shown to combine strong negative thermal expansion (NTE) over a very wide temperature range (at least 10–1000 K) with optical transparency from mid-IR into the UV range. Variable-temperature and high-pressure diffraction has been used to determine how the replacement of calcium by magnesium and zirconium by niobium(IV) modifies the phase behavior and physical properties of the compound. Similar to CaZrF 6, CaNbF 6 retains a cubic ReO 3-type structure down to 10 K and displays NTE up until at least 900 K. It undergoes a reconstructive phase transition upon compression to ~400 MPa at room temperature and pressure-induced amorphization above ~4 GPa. Prior to the first transition, it displays very strong pressure-induced softening. MgZrF 6 adopts a cubic ( Fmmore » $$\\bar{3}$$m) structure at 300 K and undergoes a symmetry-lowering phase transition involving octahedral tilts at ~100 K. Immediately above this transition, it shows modest NTE. Its’ thermal expansion increases upon heating, crossing through zero at ~500 K. Unlike CaZrF 6 and CaNbF 6, it undergoes an octahedral tilting transition upon compression (~370 MPa) prior to a reconstructive transition at ~1 GPa. Cubic MgZrF 6 displays both pressure-induced softening and stiffening upon heating. MgNbF 6 is cubic ( Fm$$\\bar{3}$$m) at room temperature, but it undergoes a symmetry-lowering octahedral tilting transition at ~280 K. It does not display NTE within the investigated temperature range (100–950 K). Furthermore the replacement of Zr(IV) by Nb(IV) leads to minor changes in phase behavior and properties, the replacement of the calcium by the smaller and more polarizing magnesium leads to large changes in both phase behavior and thermal expansion.« less

Composition, response to pressure, and negative thermal expansion in M IIB IVF 6 (M = Ca, Mg; B = Zr, Nb) [Composition, response to pressure, and negative thermal expansion in A IIB IVF 6; A - Ca, Mg, B - Zr, Nb

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

Hester, Brett R.; Hancock, Justin C.; Lapidus, Saul H.

CaZrF 6 has recently been shown to combine strong negative thermal expansion (NTE) over a very wide temperature range (at least 10–1000 K) with optical transparency from mid-IR into the UV range. Variable-temperature and high-pressure diffraction has been used to determine how the replacement of calcium by magnesium and zirconium by niobium(IV) modifies the phase behavior and physical properties of the compound. Similar to CaZrF 6, CaNbF 6 retains a cubic ReO 3-type structure down to 10 K and displays NTE up until at least 900 K. It undergoes a reconstructive phase transition upon compression to ~400 MPa at room temperature and pressure-induced amorphization above ~4 GPa. Prior to the first transition, it displays very strong pressure-induced softening. MgZrF 6 adopts a cubic ( Fmmore » $$\\bar{3}$$m) structure at 300 K and undergoes a symmetry-lowering phase transition involving octahedral tilts at ~100 K. Immediately above this transition, it shows modest NTE. Its’ thermal expansion increases upon heating, crossing through zero at ~500 K. Unlike CaZrF 6 and CaNbF 6, it undergoes an octahedral tilting transition upon compression (~370 MPa) prior to a reconstructive transition at ~1 GPa. Cubic MgZrF 6 displays both pressure-induced softening and stiffening upon heating. MgNbF 6 is cubic ( Fm$$\\bar{3}$$m) at room temperature, but it undergoes a symmetry-lowering octahedral tilting transition at ~280 K. It does not display NTE within the investigated temperature range (100–950 K). Furthermore the replacement of Zr(IV) by Nb(IV) leads to minor changes in phase behavior and properties, the replacement of the calcium by the smaller and more polarizing magnesium leads to large changes in both phase behavior and thermal expansion.« less

Chemistry of the subalkalic silicic obsidians

USGS Publications Warehouse

MacDonald, Ray; Smith, Robert L.; Thomas, John E.

1992-01-01

Nonhydrated obsidians are quenched magmatic liquids that record in their chemical compositions details of the tectonic environment of formation and of the differentiation mechanisms that affected their subsequent evolution. This study attempts to analyze, in terms of geologic processes, the compositional variations in the subalkalic silicic obsidians (Si02≥70 percent by weight, molecular (Na2O+K20)>Al2O3). New major- and trace-element determinations of 241 samples and a compilation of 130 published major-element analyses are reported and interpreted. Obsidians from five different tectonic settings are recognized: (1) primitive island arcs, (2) mature island arcs, (3) continental margins, (4) continental interiors, and (5) oceanic extensional zones. Tectonomagmatic discrimination between these groups is successfully made on Nb-Ta, Nb-FeOt and Th-Hf-Ta plots, and compositional ranges and averages for each group are presented. The chemical differences between groups are related to the type of crust in which magmas were generated. With increasingly sialic (continental type) crust, the obsidians show overall enrichment in F, Be, Li, Mo, Nb, Rb, Sn, Ta, U, W, Zn, and the rare-earth elements, and depletion in Mg, Ca, Ba, Co, Sc, Sr, and Zr. They become more potassic, have higher Fe/Mg and F/Cl ratios, and lower Zr/Hf, Nb/Ta, and Th/U ratios. Higher values of total rare-earth elements are accompanied by light rare-earth-element enrichment and pronounced negative Eu anomalies. An attempt is made to link obsidian chemistry to genetic mechanlism. Two broad groups of rocks are distinguished: one generated where crystal-liquid processes dominated (CLPD types), which are the products of crustal anatexis, possibly under conditions of low halogen fugacity, ± crystal fractionation ± magma mixing; and a second group represented by rocks formed in the upper parts of large magma chambers by interplays of crystal fractionation, volatile transfer, magma mixing, and possibly various liquid-state differentiation mechanisms, or in other words a complex interaction of petrogenetic processes (CIPP types). Such rocks may also form by volatile-fluxed partial melting of the wallrocks, and subsequent mixing into the magma reservoir. Compositional ranges and averages for CLPD and CIPP obsidians are given. It is shown by analogy with well-documented, zoned ash-flow ruffs that obsidians fractionated by CIPP have very low Mg, P, Ba, and Sr contents, flat rare-earth-element patterns with extensive Eu anomalies, low K/Rb and Zr/Nb ratios, and relatively high Na2O/K2O ratios. There is, however, considerable compositional overlap between CLPD and CIPP obsidians. The effects of magma mixing, assimilation, and vapor-phase transport in producing compositional variations in the obsidians are briefly assessed. The geochemistry of the subalkalic silicic obsidians is described on an element-by-element basis, in order to provide a database for silicic magma compositions that will hopefully contribute to studies of granitic rocks. Attempts are also made to isolate the geochemical effects of tectonic environment and genetic mechanism for each element, by comparison with data from crystal-liquid equilibria-controlled systems, from ash-flow sheets zoned by CIPP, and from mixed-magma series. A final tabulation relates the complexities of obsidian geochemistry to all the tectonic and genetic variables.

LA-ICP-MS analysis of trace elements in glass spherules of the El'gygytgyn impact structure, Siberia

NASA Astrophysics Data System (ADS)

Adolph, Leonie; Deutsch, Alex

2010-05-01

The 3.58±0.04 Ma old El'gygytgyn impact structure (Central Chukotka, NE Siberia) with a diameter of 18 km (Gurov and Gurova 1979, Layer 2000) is one of only two terrestrial craters with a volcanic target; therefore, analysis of its target and impact lithologies is of basic interest for comparative planetology. Lake El'gygytgyn is a very valuable climate archive in the Arctic as it was neither covered by glaciers (Melles et al. 2007) nor has the lake ever fallen dry. Climate and impact research were the rationale for the ICDP drilling project that finished successfully in spring 2009. Impactites like melt rocks and breccias are rarely found in outcrops yet are present in the 80 m terrace of Lake El'gygytgyn (Gurov and Gurova 1979). Numerous investigations on petrography, shock metamorphism, and geochemistry of impactites from El'gygytgyn have been published so far (e.g. Gurov et al. 2007). We report the first trace element data for seven 30- to 760-μm-sized impact glass spherules that have been collected about10 km off the crater center from a terrace deposit of the Enmyvaam River outside the crater rim. The spherules are translucent with colors ranging from amber, dark brown to nearly black; they contain a few circular bubbles, schlieren, and very rarely mineral clasts and breccia fragments. Major elements were measured with the JEOL JXA 8600 MX Superprobe, 31 trace elements were analyzed with the Finnigan Element2 LA-ICP-MS with 5 Hz, 8-9 J/cm2 at with Si as internal, and NIST612 as external standard (Institut f. Mineralogie, WWU Münster). The spot size was 60 μm. All spherules show a very homogeneous major and trace element distribution yet clear differences exist between the samples in the SiO2 content (in weight percent) 53-68: four of the glasses are dacitic, two andesitic, and one basaltic-andesitic in composition. In addition, MgO (2.1-9.2), K2O (0.6-3.3), and (in ppm) Ni (317-1096), Co (25-79), Zr (100-169), Rb (18-107), and Ba (459-1092) display wide ranges in concentration. The Ni/Co ratio is consistently high (11-14), the Zr/Hf ratio range between 36 and an anomalous high value of about 50, the Nb/Ta ratio vary from 17.6 to 14.9. The rare earth element distribution patterns are similar, yet samples with low SiO2 contents (53.1-58.4) have lower REE concentrations except for Eu. The new trace element data for impact glass lithologies from El'gygytgyn extent the range of known impactites (Gurov et al. 2007) into the field of more mafic compositions. Basalts to andesites are known to occur in the El'gygytgyn area, and obviously form the precursor lithologies for two of the spherules. All impact glass samples plot in the Zr-Ti-Y-diagram (in the tectonic setting for calc-alkaline rocks, as expected from the larger geological frame (Chekhovich et al. 1999), indicating that impact melting did not change the primary characteristics of the precursor rocks. In agreement with this setting are the Nb/Ta and Zr/Hf values although a Zr/Hf of 50 is remarkable. Origin and importance of the exceptional high Ni contents, in combination with high Ni/Co ratios are currently not understood. We exclude, however, technical reasons for these data as analyses of standard glass NIST 612 measured as unknown yielded satisfactory results.

Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-09-23

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate-Modified Niobium(V)-Silica Catalysts

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

Thornburg, Nicholas E.; Notestein, Justin M.

Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions.more » Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.« less

METHOD OF PRODUCING HAFNIUM-FREE "CRYSTAL-BAR" ZIRCONIUM FROM A CRUDE SOURCE OF ZIRCONIUM

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

Newnham, I.E.

1959-05-01

Production of Hf-free crystal-bar Zr is described. The crude source of Zr is carbided with carbon in a graphite resistance furnace, then treated with iodide to form ZrI/sub 4/. The ZrI/sub 4/ plus iodide impurities is heated with Zr powder in an evacuated vessel to 500 C. This causes ZrI/sub 3/ to form and be separated from the more volatile HfI/sub 4/ and AlI/sub 3/ which deposit on the condenserlid. The ZrI/sub 3/ is further separated from iodides of Fe, and V by heating to 350 C to re-form ZrI/sub 4/. The morevolatile ZrI/sub 4/ then is collected in puremore » form on another condenser-lid from which it can be removed and reduced to Zr. (T.R.H.)« less

Effect of Nb Content on Mechanical Behavior and Structural Properties of W/(Zr55Cu30Al10Ni5)100- x Nb x Composite

NASA Astrophysics Data System (ADS)

Mahmoodan, Morteza; Gholamipour, Reza; Mirdamadi, Shamseddin; Nategh, Said

2017-05-01

In the present study, (Zr55Cu30Al10Ni5)100- x Nb( x=0,1,2,3) bulk metallic glass matrix/tungsten wire composites were fabricated by infiltration process. Structural studies were investigated by scanning electron microscopy and X-ray diffraction method. Also, mechanical behaviors of the materials were analyzed using quasi-static compressive tests. Results indicated that the best mechanical properties i.e., 2105 MPa compressive ultimate strength and 28 pct plastic strain before failure, were achieved in the composite sample with X = 2. It was also found that adding Nb to the matrix modified interface structure in W fiber/(Zr55Cu30Al10Ni5)98Nb2 since the stable diffusion band formation acts as a functionally graded layer. Finally, the observation of multiple shear bands formation in the matrix could confirm the excellent plastic deformation behavior of the composite.

Effects of high pressure nitrogen annealing on ferroelectric Hf0.5Zr0.5O2 films

NASA Astrophysics Data System (ADS)

Kim, Taeho; Park, Jinsung; Cheong, Byoung-Ho; Jeon, Sanghun

2018-02-01

The effect of high-pressure nitrogen annealing at up to 50 atmospheres (atm) on Hf0.5Zr0.5O2 films at relatively low temperatures (450 °C) is analyzed using polarization-electric field curves, bipolar switching endurance measurements, grazing angle incidence X-ray diffraction, and piezoelectric force microscopy. Hf0.5Zr0.5O2 films annealed at 450 °C/50 atm have excellent characteristics, including remanent polarizations greater than 20 μC/cm2, a switching speed of 200 ns, and reliability, measured by sustained performance after 1010 bipolar switching cycles. The enhanced device features are attributed to the transition to the orthorhombic-phase from the tetragonal-phase of Hf0.5Zr0.5O2 at high pressure, which is also consistent with the results of "wake-up" analysis, and the variations of the pure polarization curves, extracted from the total displacement field under pressure.

Transition between strong and weak topological insulator in ZrTe5 and HfTe5

NASA Astrophysics Data System (ADS)

Fan, Zongjian; Liang, Qi-Feng; Chen, Y. B.; Yao, Shu-Hua; Zhou, Jian

2017-04-01

ZrTe5 and HfTe5 have attracted increasingly attention recently since the theoretical prediction of being topological insulators (TIs). However, subsequent works show many contradictions about their topolog-ical nature. Three possible phases, i.e. strong TI, weak TI, and Dirac semi-metal, have been observed in different experiments until now. Essentially whether ZrTe5 or HfTe5 has a band gap or not is still a question. Here, we present detailed first-principles calculations on the electronic and topological prop-erties of ZrTe5 and HfTe5 on variant volumes and clearly demonstrate the topological phase transition from a strong TI, going through an intermediate Dirac semi-metal state, then to a weak TI when the crystal expands. Our work might give a unified explain about the divergent experimental results and propose the crucial clue to further experiments to elucidate the topological nature of these materials.

On the Alloying and Properties of Tetragonal Nb5Si3 in Nb-Silicide Based Alloys

PubMed Central

Tsakiropoulos, Panos

2018-01-01

The alloying of Nb5Si3 modifies its properties. Actual compositions of (Nb,TM)5X3 silicides in developmental alloys, where X = Al + B + Ge + Si + Sn and TM is a transition and/or refractory metal, were used to calculate the composition weighted differences in electronegativity (Δχ) and an average valence electron concentration (VEC) and the solubility range of X to study the alloying and properties of the silicide. The calculations gave 4.11 < VEC < 4.45, 0.103 < Δχ < 0.415 and 33.6 < X < 41.6 at.%. In the silicide in Nb-24Ti-18Si-5Al-5Cr alloys with single addition of 5 at.% B, Ge, Hf, Mo, Sn and Ta, the solubility range of X decreased compared with the unalloyed Nb5Si3 or exceeded 40.5 at.% when B was with Hf or Mo or Sn and the Δχ decreased with increasing X. The Ge concentration increased with increasing Ti and the Hf concentration increased and decreased with increasing Ti or Nb respectively. The B and Sn concentrations respectively decreased and increased with increasing Ti and also depended on other additions in the silicide. The concentration of Sn was related to VEC and the concentrations of B and Ge were related to Δχ. The alloying of Nb5Si3 was demonstrated in Δχ versus VEC maps. Effects of alloying on the coefficient of thermal expansion (CTE) anisotropy, Young’s modulus, hardness and creep data were discussed. Compared with the hardness of binary Nb5Si3 (1360 HV), the hardness increased in silicides with Ge and dropped below 1360 HV when Al, B and Sn were present without Ge. The Al effect on hardness depended on other elements substituting Si. Sn reduced the hardness. Ti or Hf reduced the hardness more than Cr in Nb5Si3 without Ge. The (Nb,Hf)5(Si,Al)3 had the lowest hardness. VEC differentiated the effects of additions on the hardness of Nb5Si3 alloyed with Ge. Deterioration of the creep of alloyed Nb5Si3 was accompanied by decrease of VEC and increase or decrease of Δχ depending on alloying addition(s). PMID:29300327

Impact of Nb vacancies and p-type doping of the NbCoSn-NbCoSb half-Heusler thermoelectrics.

PubMed

Ferluccio, Daniella A; Smith, Ronald I; Buckman, Jim; Bos, Jan-Willem G

2018-02-07

The half-Heuslers NbCoSn and NbCoSb have promising thermoelectric properties. Here, an investigation of the NbCo 1+y Sn 1-z Sb z (y = 0, 0.05; 0 ≤ z ≤ 1) solid-solution is presented. In addition, the p-type doping of NbCoSn using Ti and Zr substitution is investigated. Rietveld analysis reveals the gradual creation of Nb vacancies to compensate for the n-type doping caused by the substitution of Sb in NbCoSn. This leads to a similar valence electron count (∼18.25) for the NbCo 1+y Sn 1-z Sb z samples (z > 0). Mass fluctuation disorder due to the Nb vacancies strongly decreases the lattice thermal conductivity from 10 W m -1 K -1 (z = 0) to 4.5 W m -1 K -1 (z = 0.5, 1). This is accompanied by a transition to degenerate semiconducting behaviour leading to large power factors, S 2 /ρ = 2.5-3 mW m -1 K -2 and figures of merit, ZT = 0.25-0.33 at 773 K. Ti and Zr can be used to achieve positive Seebeck values, e.g. S = +150 μV K -1 for 20% Zr at 773 K. However, the electrical resistivity, ρ 323K = 27-35 mΩ cm, remains too large for these materials to be considered useful p-type materials.

Comparative Transcriptome Analysis of Fetal Skin Reveals Key Genes Related to Hair Follicle Morphogenesis in Cashmere Goats.

PubMed

Gao, Ye; Wang, Xiaolong; Yan, Hailong; Zeng, Jie; Ma, Sen; Niu, Yiyuan; Zhou, Guangxian; Jiang, Yu; Chen, Yulin

2016-01-01

Cashmere goat skin contains two types of hair follicles (HF): primary hair follicles (PHF) and secondary hair follicles (SHF). Although multiple genetic determinants associated with HF formation have been identified, the molecules that determine the independent morphogenesis of HF in cashmere goats remain elusive. The growth and development of SHF directly influence the quantity and quality of cashmere production. Here, we report the transcriptome profiling analysis of nine skin samples from cashmere goats using 60- and 120-day-old embryos (E60 and E120, respectively), as well as newborns (NB), through RNA-sequencing (RNA-seq). HF morphological changes indicated that PHF were initiated at E60, with maturation from E120, while differentiation of SHF was identified at E120 until formation of cashmere occurred after birth (NB). The RNA-sequencing analysis generated over 20.6 million clean reads from each mRNA library. The number of differentially expressed genes (DEGs) in E60 vs. E120, E120 vs. NB, and E60 vs. NB were 1,024, 0 and 1,801, respectively, indicating that no significant differences were found at transcriptomic levels between E120 and NB. Key genes including B4GALT4, TNC, a-integrin, and FGFR1, were up-regulated and expressed in HF initiation from E60 to E120, while regulatory genes such as GPRC5D, PAD3, HOXC13, PRR9, VSIG8, LRRC15, LHX2, MSX-2, and FOXN1 were up-regulated and expressed in HF keratinisation and hair shaft differentiation from E120 and NB to E60. Several genes belonging to the KRT and KRTAP gene families were detected throughout the three HF developmental stages. The transcriptional trajectory analyses of all DEGs indicated that immune privilege, glycosaminoglycan biosynthesis, extracellular matrix receptor interaction, and growth factor receptors all played dominant roles in the epithelial-mesenchymal interface and HF formation. We found that the Wnt, transforming growth factor-beta/bone morphogenetic protein, and Notch family members played vital roles in HF differentiation and maturation. The DEGs we found could be attributed to the generation and development of HF, and thus will be critically important for improving the quantity and quality of fleece production in animals for fibres.

The effect of hydrogen content on ballistic transport behaviors in the Ni-Nb-Zr-H glassy alloys.

PubMed

Fukuhara, Mikio; Umemori, Yoshimasa

2012-01-01

The electronic transport behaviors of (Ni(0.39)Nb(0.25)Zr(0.35))(100-) (x)H(x) (0 ≤ x < 23.5) glassy alloys with subnanostructural icosahedral Zr(5)Nb(5)Ni(3) clusters have been studied as a function of hydrogen content. These alloys show semiconducting, electric current-induced voltage (Coulomb) oscillation and ballistic transport behaviors. Coulomb oscillation and ballistic transport occur at hydrogen contents between 6.7 and 13.5 at% and between 13.5 and 21.2 at%, respectively. These results suggest that the localization effect of hydrogen in the clusters plays an important role in various electron transport phenomena.

The Effect of Hydrogen Content on Ballistic Transport Behaviors in the Ni-Nb-Zr-H Glassy Alloys

PubMed Central

Fukuhara, Mikio; Umemori, Yoshimasa

2012-01-01

The electronic transport behaviors of (Ni0.39Nb0.25Zr0.35)100−xHx (0 ≤ x < 23.5) glassy alloys with subnanostructural icosahedral Zr5Nb5Ni3 clusters have been studied as a function of hydrogen content. These alloys show semiconducting, electric current-induced voltage (Coulomb) oscillation and ballistic transport behaviors. Coulomb oscillation and ballistic transport occur at hydrogen contents between 6.7 and 13.5 at% and between 13.5 and 21.2 at%, respectively. These results suggest that the localization effect of hydrogen in the clusters plays an important role in various electron transport phenomena. PMID:22312246

Effect of Substitution (Ta, Al, Ga) on the Conductivity of Li7La3Zr2O12

DTIC Science & Technology

2012-01-30

xTax012). Conductivity data was not included in their report. Similarly to Ta, Nb substitution for Zr should also lower the Li content of the LLZO and a...high Li ion conductivity (0.8 mS cm−1 at 298 K) cubic garnet sample has been reported with Nb substitution for Zr by Ohta et al. [15]. However, Ta is...substitution for Zr follows this approach and it is desirable for a couple rea- sons. First, Ta is stable relative to Li [13]. Second, Ta substitution

Fluoride barriers in Nb/Pb Josephson junctions

NASA Astrophysics Data System (ADS)

Asano, H.; Tanabe, K.; Michikami, O.; Igarashi, M.; Beasley, M. R.

1985-03-01

Josephson tunnel junctions are fabricated using a new class of artificial barriers, metal fluorides (Al fluoride and Zr fluoride). These fluoride barriers are deposited on the surface of a Nb base electrode, which are previously cleaned using a CF4 cleaning process, and covered by a Pb counterelectrode. The junctions with both Al fluoride and Zr fluoride barriers exhibit good tunneling characteristics and have low specific capacitance. In the case of Zr fluoride, it is observed that reasonable resistances are obtained even at thickness greater than 100 A. This phenomenon might be explained by tunneling via localized states in Zr fluoride.

Neogene volcanism associated with back-arc basin tectonics at the northern Fossa Magna, NE Japan

NASA Astrophysics Data System (ADS)

Okamura, S.; Inaba, M.; Shinjo, R.; Adachi, Y.

2016-12-01

New isotopic and trace element data presented here imply a temporal change in magma sources and thermal conditions beneath the northern Fossa Magna of NE Japan from the Miocene to the Pliocene. Rocks from more sediment melt-rich Early Miocene volcanoes have less radiogenic 176Hf/177Hf and 143Nd/144Nd, high Zr/Hf, and little or no Hf anomaly (Hf/Hf*; ˜1.0). The mantle wedge in the Early Miocene consisted of enriched mantle source. We propose that during the onset of subduction, influx of hot asthenospheric mantle provided sufficient heat to partially melt newly subducting sediment. Geochemical modeling results suggest breakdown of zircon in the slab surface sediments for the Early Miocene lavas in the northern Fossa Magna region. In the Middle Miocene, the injection of hot and depleted asthenospheric material replaced the mantle beneath the northern Fossa Magna region of NE Japan. This caused the isotopic signature of the rocks to change from enriched to depleted. The Middle Miocene lavas characterized by most radiogenic Hf and Nd isotope ratios, have high Zr/Hf, low Lu/Hf, and little or no Hf anomaly. An appropriate working petrogenetic model is that the Middle Miocene lavas were derived from asthenospheric depleted mantle, slightly ( < 1%) contaminated by slab melt accompanied by full dissolution of zircon. All the Late Miocene and Pliocene samples are characterized by distinctly more radiogenic 176Hf/177Hf and 143Nd/144Nd, and more negative Hf anomalies (greater Hf/Hf* variability; ˜0.3). The Pliocene samples are displaced toward lower Hf/Hf* and Zr/Hf, and higher Lu/Hf relative to the Middle Miocene samples, which requires mixing between depleted mantle and a partial melt of subducted metasediment saturated with trace quantity of zircon.

The Effect of 24c-site (A) Cation Substitution on the Tetragonal-Cubic Phase Transition in Li7-xLa3-xAxZr2O12 Garnet-Based Ceramic Electrolyte

DTIC Science & Technology

2012-12-27

Another super-valent substitution scheme involves either Nb (5þ) or Ta (5þ) on the 16a site ( Zr 4þ), that reduces the Li content and/or increases Li...substitution for Zr are as follows [20,22,23]: Ta$ Zr ¼ V0Li (3) Nb $ Zr ¼ V0Li (4) Likewise, super-valent substitution on the 24c (La 3þ) is...Substitution of La with Ce stabilizes the cubic LLZO garnet phase. < CeO2 precipitation at grain boundaries increases grain boundary resistance . < Super

Orthorhombic-tetragonal phase coexistence and enhanced piezo-response at room temperature in Zr, Sn, and Hf modified BaTiO{sub 3}

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

Kalyani, Ajay Kumar; Brajesh, Kumar; Ranjan, Rajeev, E-mail: rajeev@materials.iisc.ernet.in

2014-06-23

The effect of Zr, Hf, and Sn in BaTiO{sub 3} has been investigated at close composition intervals in the dilute concentration limit. Detailed structural analysis by x-ray and neutron powder diffraction revealed that merely 2 mol. % of Zr, Sn, and Hf stabilizes a coexistence of orthorhombic (Amm2) and tetragonal (P4mm) phases at room temperature. As a consequence, all the three systems show substantial enhancement in the longitudinal piezoelectric coefficient (d{sub 33}), with Sn modification exhibiting the highest value ∼425 pC/N.

Electrochemical Characteristics of Cell Cultured Ti-Nb-Zr Alloys After Nano-Crystallized Si-HA Coating.

PubMed

Jeong, Yong-Hoon; Choe, Han-Cheol

2015-01-01

The aim of this study was to investigate the electrochemical characteristics of nano crystallized Si-HA coating on Ti-Nb-Zr alloy after human osteoblast like (HOB) cell attachment. The Ti-Nb-Zr alloy was manufactured with 35 wt.% of Nb and 10 wt.% of Zr by arc melting furnace to appropriate physical properties as biomaterials. The HA and Si-substituted coatings were prepared by electron-beam physical vapor deposition method with 0.5, 0.8 and 1.2 wt.% of Si contents, and nano aging treatment was performed 500 degrees C for 1 h. The characteristics of coating surface were analyzed by field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, respectively. To evaluate of cell attachment on cell cultured surface, the potentiodynamic test was performed on the surface using HOB cells. The results showed that the Si-HA coating surface showed higher tendency of cell attachment than that of single HA coating, corrosion resistance value was increased by dense of cell attachment.

Skin effect suppression for Cu/CoZrNb multilayered inductor

NASA Astrophysics Data System (ADS)

Sato, Noriyuki; Endo, Yasushi; Yamaguchi, Masahiro

2012-04-01

The Cu/Co85Zr3Nb12 multilayer is studied as a conductor of a spiral inductor to suppress the skin effect at the 5 GHz range (matches IEEE 802.11 a standard) using negative-permeability in CoZrNb films beyond the ferromagnetic resonance frequency. The skin effect suppression becomes remarkable when the thickness of Cu in each period of the multilayer, tCu, is less than the skin depth of Cu at the targeting frequency. For the 5 GHz operation, tCu ≤ 750 nm. The resistance of the Cu/CoZrNb multilayered spiral inductor decreases as much as 8.7%, while keeping the same inductance of 1.1 nH as that of a similar air core. Accordingly, Q = 16. Therefore, the proposed method can contribute to realize a high-Q spiral inductor. We also study the potentially applicable frequency of this method. Given a soft magnetic material with Ms = 105 emu/cc and Hk = 5 Oe, the method can be applied at 700 MHz, the lowermost carrier frequency band for the 4th generation cellular phone system.

Fractionation of Zr and Hf during the differentiation of peralkaline magmatic system (Lovozero rare metal deposit, Kola Peninsula)

NASA Astrophysics Data System (ADS)

Kogarko, Liya

2016-04-01

Zirconium and hafnium are valuable strategic metals. We assessed principal features of the distribution of these elements in peralkaline rocks, ores and rock-forming and accessory minerals of Lovozero complex. The accumulation of these elements during the evolution of alkaline magma of Lovozero deposit up to extremely high concentrations in eudialyte ores (5-8% ZrO2 and 1200-1800 ppm Hf) has been established. These ores represent valuable complex raw material not only for Zr and Hf, but for REE as well. We evaluated partition coefficients of these elements in alkaline pyroxenes (aegirines) from porphyry-like agpaitic lujavrites of Lovozero massif which are 0.40 for zirconium and 0.58 for hafnium. We assessed variations of Zr/Hf ratio for all the rocks of Lovozero alkaline massif. The growth of this ratio in the course of the evolution of alkaline magma has been observed from 38 in the earliest magmatic phase, to 44 in the second phase and to 51-53 in the latest manifestation of alkaline magmatsm. On the basis of the obtained data and equations of equilibrium and fractional crystallization the model of the fractionation of zirconium and hafnium during the evolution of Lovozero intrusion has been constructed. We have demonstrated that the source of strongly enriched magmatic systems similar to Lovozero rare metal deposit is short-lived enriched reservoir - metasomatized and carbonatized mantle substrate. We investigated the fractionation of zirconium and hafnium in carbonatized mantle xenoliths from East Antarctica. The elevated Zr/Hf ratios (up to 125) in metasomatized xenoliths by comparison with the chondritic value have been found. The main reactions of carbonate metasomatism lead to the replacement of primary orthopyroxene by clinopyroxene 2Mg2Si2O6 + CaMg(CO3)2 = 2Mg2SiO4 + CaMgSi2O6 + 2CO2 3CaMg(CO3)2 + CaMgSi2O6 = 4CaCO3 + 2Mg2SiO4 + 2CO2 The substantial expansion of the clinopyroxene crystallization field results in increase of Zr/Hf ratio in equilibrium melt due to the higher value of Hf partition coefficient by comparison with Zr. The migration of active carbonate and carbonate-silicate melts equilibrated with the metasomatic wehrlites leads to the increase in Zr/Hf ratio in carbonatized mantle substrate. This work has been financially supported by the grant 15-17-30019 of the Russian Science Foundation.

Electronic and thermodynamic properties of layered Hf2Sfrom first-principles calculations

NASA Astrophysics Data System (ADS)

Nandadasa, Chandani; Yoon, Mina; Kim, Seong-Gon; Erwin, Steve; Kim, Sungho; Kim, Sung Wng; Lee, Kimoon

Theoretically we explored two stable phases of inorganic fullerene-like structure of the layered dihafnium sulfide (Hf2 S) . We investigated structural and electronic properties of the two phases of Hf2 S by using first-principles calculations. Our calculation identifies experimentally observed anti-NbS2 structure of Hf2 S . Our electronic calculation results indicate that the density of states of anti- NbS2 structure of Hf2 S at fermi level is less than that of the other phase of Hf2 S . To study the relative stability of different phases at finite temperature Helmholtz free energies of two phases are obtained using density functional theory and density functional perturbation theory. The free energy of the anti-NbS2 structure of Hf2 S always lies below the free energy of the other phase by confirming the most stable structure of Hf2 S . The phonon dispersion, phonon density of states including partial density of states and total density of states are obtained within density functional perturbation theory. Our calculated zero-pressure phonon dispersion curves confirm that the thermodynamic stability of Hf2 S structures. For further investigation of thermodynamic properties, the temperature dependency of thermal expansion, heat capacities at constant pressure and volume are evaluated within the quasiharmonic approximations (QHA).

Ferroelectric HfZrOx-based MoS2 negative capacitance transistor with ITO capping layers for steep-slope device application

NASA Astrophysics Data System (ADS)

Xu, Jing; Jiang, Shu-Ye; Zhang, Min; Zhu, Hao; Chen, Lin; Sun, Qing-Qing; Zhang, David Wei

2018-03-01

A negative capacitance field-effect transistor (NCFET) built with hafnium-based oxide is one of the most promising candidates for low power-density devices due to the extremely steep subthreshold swing (SS) and high on-state current induced by incorporating the ferroelectric material in the gate stack. Here, we demonstrated a two-dimensional (2D) back-gate NCFET with the integration of ferroelectric HfZrOx in the gate stack and few-layer MoS2 as the channel. Instead of using the conventional TiN capping metal to form ferroelectricity in HfZrOx, the NCFET was fabricated on a thickness-optimized Al2O3/indium tin oxide (ITO)/HfZrOx/ITO/SiO2/Si stack, in which the two ITO layers sandwiching the HfZrOx film acted as the control back gate and ferroelectric gate, respectively. The thickness of each layer in the stack was engineered for distinguishable optical identification of the exfoliated 2D flakes on the surface. The NCFET exhibited small off-state current and steep switching behavior with minimum SS as low as 47 mV/dec. Such a steep-slope transistor is compatible with the standard CMOS fabrication process and is very attractive for 2D logic and sensor applications and future energy-efficient nanoelectronic devices with scaling power supply.

Metastable Structural Phases of Metals in Columns IVB to Vib, and Rows 4 TO 6 OF the Periodic Table

NASA Astrophysics Data System (ADS)

Nnolim, Neme; Tyson, Trevor

2002-03-01

Total energy calculations as a function of strain along the <001> direction have been carried out for the bcc metals V, Nb, Ta, Cr, Mo and W, and the hcp metals Ti, Zr and Hf, all in the block of the periodic table defined by columns IVB to VIB, and rows 4 to 6. Since strain along the <001> direction corresponds to variation of the c lattice constant with respect to the a lattice constant, the total energy per unit cell has being calculated as a function of the c/a ratio. The highly accurate FP-LAPW (Full Potential Linearized Augmented Plane Wave) band structure method in the DFT (Density Functional Theory) formalism has been used for the calculations. In all cases except for the hcp column IVB elements, Zr, Hf and Ti, a metastable state was predicted from the calculations. Electronic properties are computed for all structures and are correlated with electrical and mechanical properties of metastable phases that have been observed experimentally. Properties of metastable phases, which were predicted in this work but which as of yet have not been observed experimentally, have also been predicted. Special attention is paid to the phases of tantalum and calculated transport properties are used to show that the observed high resistivity of the beta phase of tantalum relative to the alpha bcc phase cannot be explained solely by simple tetragonal distortions of the bcc phase.

New production systems at ISOLDE

NASA Astrophysics Data System (ADS)

Hagebø, E.; Hoff, P.; Jonsson, O. C.; Kugler, E.; Omtvedt, J. P.; Ravn, H. L.; Steffensen, K.

1992-08-01

New target systems for the ISOLDE on-line mass separator facility are presented. Targets of carbides, metal/graphite mixtures, foils of refractory metals, molten metals and oxides have been tested. Beams of high intensity of neutron-rich isotopes of a large number of elements are obtained from a uranium carbide target with a hot plasma-discharge ion source. A target of ZrO 2 has been shown to provide high intensity beams of neutron-deficient isotopes of Mn, Cu, Zn, Ga, Ge, As, Se, Br, Kr and Rb, while a SiC target with a hot plasma ion source gives intense beams of radioactive isotopes of a number of light elements. All these systems are rather chemically unselective. Chemically selective performance has been obtained for several systems, i.e.: the production of neutron-deficient Au from ( 3He, pχn) reactions on a Pt/graphite target with a hot plasma ion source; the production of neutron-deficient Lu and LuF + and Hf and HfF 3+ from a Ta-foil target with a hot plasma ion source under CF 4 addition; the production of neutron-deficient Sr as SrF + and Y as YF 2+ form a Nb-foil target with a W surface ionizer under CF 4 addition; the production of neutron-deficient Se as COSe + from a ZrO 2 target with a hot plasma ion source under O 2 addition; and the production of radioactive F from a SiC target with a hot plasma ion source operating in Al vapour.

Petrogenesis and tectonic implications of Late Carboniferous A-type granites and gabbronorites in NW Iran: Geochronological and geochemical constraints

NASA Astrophysics Data System (ADS)

Moghadam, Hadi Shafaii; Li, Xian-Hua; Ling, Xiao-Xiao; Stern, Robert J.; Santos, Jose F.; Meinhold, Guido; Ghorbani, Ghasem; Shahabi, Shirin

2015-01-01

Carboniferous igneous rocks constitute volumetrically minor components of Iranian crust but preserve important information about the magmatic and tectonic history of SW Asia. Ghushchi granites and gabbronorites in NW Iran comprise a bimodal magmatic suite that intruded Ediacaran-Cambrian gneiss and are good representatives of carboniferous igneous activity. Precise SIMS U-Pb zircon ages indicate that the gabbronorites and granites were emplaced synchronously at ~ 320 Ma. Ghushchi granites show A-type magmatic affinities, with typical enrichments in alkalis, Ga, Zr, Nb and Y, depletion in Sr and P and fractionated REE patterns showing strong negative Eu anomalies. The gabbronorites are enriched in LREEs, Nb, Ta and other incompatible trace elements, and are similar in geochemistry to OIB-type rocks. Granites and gabbronorites have similar εNd(t) (+ 1.3 to + 3.4 and - 0.1 to + 4.4, respectively) and zircon εHf(t) (+ 1.7 to + 6.2 and + 0.94 to + 6.5, respectively). The similar variation in bulk rock εNd(t) and zircon εHf(t) values and radiometric ages for the granites and gabbronorites indicate a genetic relationship between mafic and felsic magmas, either a crystal fractionation or silicate liquid immiscibility process; further work is needed to resolve petrogenetic details. The compositional characteristics of the bimodal Ghushchi complex are most consistent with magmatic activity in an extensional tectonic environment. This extension may have occurred during rifting of Cadomian fragments away from northern Gondwana during early phases of Neotethys opening.

Electron Microprobe Analysis of Hf in Zircon: Suggestions for Improved Accuracy of a Difficult Measurement

NASA Astrophysics Data System (ADS)

Fournelle, J.; Hanchar, J. M.

2013-12-01

It is not commonly recognized as such, but the accurate measurement of Hf in zircon is not a trivial analytical issue. This is important to assess because Hf is often used as an internal standard for trace element analyses of zircon by LA-ICPMS. The issues pertaining to accuracy revolve around: (1) whether the Hf Ma or the La line is used; (2) what accelerating voltage is applied if Zr La is also measured, and (3) what standard for Hf is used. Weidenbach, et al.'s (2004) study of the 91500 zircon demonstrated the spread (in accuracy) of possible EPMA values for six EPMA labs, 2 of which used Hf Ma, 3 used Hf La, and one used Hf Lb, and standards ranged from HfO2, a ZrO2-HfO2 compound, Hf metal, and hafnon. Weidenbach, et al., used the ID-TIMS values as the correct value (0.695 wt.% Hf.), for which not one of the EPMA labs came close to that value (3 were low and 3 were high). Those data suggest: (1) that there is a systematic underestimation error of the 0.695 wt% Hf (ID-TIMS Hf) value if Hf Ma is used; most likely an issue with the matrix correction, as the analytical lines and absorption edges of Zr La, Si Ka and Hf Ma are rather tightly packed in the electromagnetic spectrum. Mass absorption coefficients are easily in error (e.g., Donovan's determination of the MAC of Hf by Si Ka of 5061 differs from the typically used Henke value of 5449 (Donovan et al, 2002); and (2) For utilization of the Hf La line, however, the second order Zr Ka line interferes with Hf La if the accelerating voltage is greater than 17.99 keV. If this higher keV is used and differential mode PHA is applied, only a portion of the interference is removed (e.g., removal of escape peaks), causing an overestimation of Hf content. Unfortunately, it is virtually impossible to apply an interference correction in this case, as it is impossible to locate Hf-free Zr probe standard. We have examined many of the combinations used by those six EPMA labs and concluded that the optimal EPMA is done with Hf La with the accelerating voltage under 18 keV (e.g. 17 keV is optimal), and also with synthetic stoichiometric hafnon as the standard. We have developed useful standards that are to be distributed to the community for those researchers working on this problem and can be obtained from the second author at jhanchar@mun.ca. The standards include synthetic stoichiometric undoped zircon and hafnon, and synthetic zircon doped with 2 wt. % Hf. Donovan et al. (2002) Probe for Windows: User's Guide and Reference Wiedenbeck, M., et al. (2004) Further characterisation of the 91500 zircon crystal. Geostandards and Geoanatytical Research, 28: 9-39.

The Mechanical Properties and In Vitro Biocompatibility of PM-Fabricated Ti-28Nb-35.4Zr Alloy for Orthopedic Implant Applications

PubMed Central

Xu, Wei; Li, Ming; Wen, Cuie; Lv, Shaomin; Liu, Chengcheng; Lu, Xin

2018-01-01

A biocompatible Ti-28Nb-35.4Zr alloy used as bone implant was fabricated through the powder metallurgy process. The effects of mechanical milling and sintering temperatures on the microstructure and mechanical properties were investigated systematically, before in vitro biocompatibility of full dense Ti-28Nb-35.4Zr alloy was evaluated by cytotoxicity tests. The results show that the mechanical milling and sintering temperatures have significantly effects on the density and mechanical properties of the alloys. The relative density of the alloy fabricated by the atomized powders at 1500 °C is only 83 ± 1.8%, while the relative density of the alloy fabricated by the ball-milled powders can rapidly reach at 96.4 ± 1.3% at 1500 °C. When the temperature was increased to 1550 °C, the alloy fabricated by ball-milled powders achieve full density (relative density is 98.1 ± 1.2%). The PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C can achieve a wide range of mechanical properties, with a compressive yield strength of 1058 ± 35.1 MPa, elastic modulus of 50.8 ± 3.9 GPa, and hardness of 65.8 ± 1.5 HRA. The in vitro cytotoxicity test suggests that the PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C has no adverse effects on MC3T3-E1 cells with cytotoxicity ranking of 0 grade, which is nearly close to ELI Ti-6Al-4V or CP Ti. These properties and the net-shape manufacturability makes PM-fabricated Ti-28Nb-35.4Zr alloy a low-cost, highly-biocompatible, Ti-based biomedical alloy. PMID:29601517

DFT investigation of electronic structures and magnetic properties of halides family MeHal3 (Me=Ti, Mo,Zr,Nb, Ru, Hal=Cl,Br,I) one dimensional structures

NASA Astrophysics Data System (ADS)

Kuzubov, A. A.; Kovaleva, E. A.; Popova, M. I.; Kholtobina, A. S.; Mikhaleva, N. S.; Visotin, M. A.; Fedorov, A. S.

2017-10-01

Using DFT GGA calculations, electronic structure and magnetic properties of wide family of transition metal trihalides (TMHal3) (Zr, Ti and Nb iodides, Mo, Ru, Ti and Zr bromides and Ti or Zr chlorides) are investigated. These structures consist of transition metal atoms chains surrounded by halides atoms. Chains are connected to each other by weak interactions. All TMHal3 compounds were found to be conductive along chain axis except of MoBr3 which is indirect gap semiconductor. It was shown that NbI3 and MoBr3 have large magnetic moments on metal atoms (1.17 and 1.81 μB, respectively) but other TMHal3 materials have small or zero magnetic moments. For all structures ferromagnetic and anti-ferromagnetic phases have almost the same energies. The causes of these properties are debated.

Ultraviolet photorefraction at 325 nm in doped lithium niobate crystals

NASA Astrophysics Data System (ADS)

Xin, Feifei; Zhang, Guoquan; Bo, Fang; Sun, Haifeng; Kong, Yongfa; Xu, Jingjun; Volk, Tatyana; Rubinina, Natalia M.

2010-02-01

We studied the photorefractive effect of lithium niobate (LiNbO3) doped with Mg, Zn, In, Hf, or codoped with Mg and Fe at an ultraviolet (UV) wavelength down to 325 nm. It is found that the UV photorefraction of LiNbO3 doped with Mg, Zn, In, or Hf was enhanced significantly as compared to that of the nominally pure LiNbO3. Our results show that the property of resistance against photorefraction in highly Mg, Zn, In, or Hf doped LiNbO3 is true only in the visible and near-infrared wavelength range. By contrast, these crystals exhibit excellent photorefractive characteristics at UV wavelength of 325 nm, even better than those at 351 nm. For example, the photorefractive two-wave coupling gain coefficient Γ and the photorefractive recording sensitivity at 325 nm were measured to be ˜38 cm-1 and 37.7 cm/J, respectively, in a LiNbO3 crystal doped with 9 mol % Zn. The photorefractive response time of a Mg:LiNbO3 with a 9 mol % Mg was measured to be 73 ms with a total recording intensity of 614 mW/cm2 at 325 nm. In highly Mg, Zn, In, or Hf doped LiNbO3 crystals, diffusion dominates over photovoltaic effect and electrons are the dominant charge carriers in UV photorefraction at 325 nm. The results are also of interest to the study on the defect structure of LiNbO3 near to the absorption edge.

Microstructure and mechanical properties of the NiNbZrTiAl amorphous alloys with 10 and 25 at.% Nb content.

PubMed

Czeppe, T; Ochin, P; Sypień, A; Major, L

2010-03-01

The results of investigation of two different Ni-based glasses with compositions Ni(58)Nb(10)Zr(13)Ti(12)Al(7) and Ni(58)Nb(25)Zr(8)Ti(6)Al(3) are presented. The structure of the melt spun ribbons was amorphous. The supercooled liquid range decreased and primary crystallization temperature increased with increasing Nb content while the parameter T(g)/T(m) slightly increased. The crystallization process proceeded in a different way. The ribbon containing 10 at.% Nb showed typical primary crystallization of the 50 nm grains of the NiTi(Nb) cubic phase; the ribbon containing 25 at.% of Nb revealed high thermal stability of the amorphous phase, which crystallized only in a small amount in the range of primary crystallization, preserving large fraction of the amorphous phase even high above the end of the crystallization. The tensile load-displacement curves were also different. In both cases, the ribbons revealed quite a large range of the plastic elongation. The ribbon containing 10% Nb showed stress relaxation and was maximally elongated up to 0.6. The ribbon with 25 at.% Nb revealed a hardening effect and the slightly smaller maximal elongation following it. The microstructure of the deformed specimens showed deformation bands parallel to the tensile axis, microcracks formation along shear bands and river-like pattern at the fracture surfaces. In both cases, high resolution electron microscope did not reveal any crystallization after deformation.

Highly conducting divalent Mg{sup 2+} cation solid electrolytes with well-ordered three-dimensional network structure

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

Tamura, Shinji; Yamane, Megumi; Hoshino, Yasunori

2016-03-15

A three-dimensionally well-ordered NASICON-type Mg{sup 2+} cation conductor, (Mg{sub x}Hf{sub 1−x}){sub 4/(4−2x)}Nb(PO{sub 4}){sub 3}, was firstly developed by partial substitution of lower valent Mg{sup 2+} cation onto the Hf{sup 4+} sites in a HfNb(PO{sub 4}){sub 3} solid to realize high Mg{sup 2+} cation conductivity even at moderate temperatures. Due to the formation of well-ordered NASICON-type structure, both the high Mg{sup 2+} cation conductivity below 450 °C and the low activation energy for Mg{sup 2+} cation migration was successfully realized for the (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{sub 4}){sub 3} solid. Pure Mg{sup 2+} cation conduction in the NASICON-type (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{submore » 4}){sub 3} solid was directly and quantitatively demonstrated by means of two kinds of dc electrolysis. - Graphical abstract: Image of the Mg{sup 2+} cation conduction in NASICON-type (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{sub 4}){sub 3} and its Mg{sup 2+} conductivity. - Highlights: • We develop a three-dimensionally well-ordered NASICON-type Mg{sup 2+} cation conductor. • A high magnesium cation conductivity is realized even at moderate temperatures. • Divalent magnesium cation conduction is demonstrated directly and quantitatively.« less

Magnetic and electrical properties of several Mn-based amorphous alloys

NASA Astrophysics Data System (ADS)

Obi, Y.; Morita, H.; Fujimori, H.

1987-03-01

Magnetic and electrical properties of amorphous Mn-Y, Mn-Zr, and Mn-Nb alloys have been investigated. All these alloys have a temperature-dependent susceptibility which is well fitted by a Curie-Weiss law. This implies the existence of localized magnetic moments associated with the Mn atoms. In addition, amorphous Mn-Y alloys exhibit spin-glass characteristics at low temperature. The experimental results of the electrical resistivity show that the temperature coefficient of resistivity (TCR) of both Mn-Y and Mn-Zr are negative, while Mn-Nb has a positive TCR. On the other hand, the resistivity-temperature curves of Mn-Zr and Mn-Nb have nearly the same tendency but are different from that of Mn-Y.

Elevated-Temperature Deformation Properties of a HfC Modified Ti-48Al-2Mn-2Nb Matrix Particulate Composite

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.; Farmer, S. C.; Bors, D. A.; Ray, R.; Lee, D. S.

1994-01-01

Rapid solidification techniques in combination with HIPing have been used to produce Ti-48Al-2Mn-2Nb and a Ti-48Al-2Mn-2Nb+15 wt% HfC composite. While the composite does contain several second phases within the gamma + alpha(sub 2) matrix, none was identified to be HfC. The elevated-temperature properties were determined by constant velocity compression and constant load tensile testing in air between 1000 and 1173 K. Such testing indicated that the elevated temperature strengths of the HfC-modified aluminide was superior to those of the unreinforced matrix with the best 1100 K temperature slow strain rate properties for both materials being achieved after high-temperature annealing prior to testing. Examination of the microstructures after deformation in combination with the measured stress exponents and activation energies suggest that creep resistance of the HfC-modified form is due to solid-solution strengthening from carbon and hafnium rather than the presence of second phases.

Geochemical, modal, and geochronologic data for 1.4 Ga A-type granitoid intrusions of the conterminous United States

USGS Publications Warehouse

du Bray, Edward A.; Holm-Denoma, Christopher S.; San Juan, Carma A.; Lund, Karen; Premo, Wayne R.; DeWitt, Ed

2015-08-10

In addition, Kisvarsanyi (1972) suggests that iron-copper deposits in the St. Francois Mountains of southeastern Missouri are petrogenetically associated with 1.4 Ga A-type granitoids that occur in that region. Similarly, Dall’Agnol and others (2012) summarize important global associations between A-type granitoid rocks and a variety of important ore deposit types, particularly tin, high-field-strength elements (Zr, Hf, Nb, Ta), rare-earth elements, and iron oxide-copper-gold deposits. Consequently, the need to better understand relations between A-type granitoid rocks, tectonic setting, and magma petrogenesis, as well as their genetic associations with important types of ore deposits, suggests that developing a definitive geochemical, modal, and geochronologic database for these rocks in the conterminous United States is of considerable value.

REVIEWS OF TOPICAL PROBLEMS: Order-disorder transformations and phase equilibria in strongly nonstoichiometric compounds

NASA Astrophysics Data System (ADS)

Gusev, Aleksandr I.

2000-01-01

Data on order-disorder phase transformations in strongly nonstoichiometric carbides and nitrides MXy (X=C, N) of Group IV and V transition metals at temperatures below 1300-1400 K are reviewed. The order-parameter functional method as applied to atomic and vacancy ordering in strongly nonstoichiometric MXy compounds and to phase equilibrium calculations for M-X systems is discussed. Phase diagram calculations for the Ti-C, Zr-C, Hf-C, V-C, Nb-C, Ta-C, Ti-N, and Ti-B-C systems (with the inclusion of the ordering of nonstoichiometric carbides and nitrides) and those for pseudobinary carbide M(1)C-M(2)C systems are presented. Heat capacity, electrical resistivity and magnetic susceptibility changes at reversible order-disorder phase transformations in nonstoichiometric carbides are considered.

The characteristics of hot swaged NiAl intermetallic compounds with ternary additions consolidated by HIP techniques

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

Ishiyama, S.; Eto, M.; Mishima, Y.

Stoichiometric and non-stoichiometric NiAl intermetallics with ternary additives, such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or Mo/e, W, Mn, Fe, Cu and B, fabricated with the combination of Hot Isostatic Pressing (HIP) and hot swaging techniques have been investigated. The mechanical properties of hot swaged NiAl with various ternary additives, consolidated by ion beam casting or HIP techniques, have been tested at temperatures ranging from R.T. to 1,000 C. It is found that significant tensile elongation at room temperature can be achieved by hot swaged as-HIP`ed NiAl compounds with Mo or Mo/Re additives, whereas cast and hotmore » swaged compounds with Mo addition resulted in some elongation above 400 C.« less

Oxidation Resistance, Electrical and Thermal Conductivity, and Spectral Emittance of Fully Dense HfB2 and ZrB2 with SiC, TaSi2, and LaB6 Additives

DTIC Science & Technology

2012-01-26

Resistance , Electrical and Thermal Conductivity, and Spectral Emittance of Fully Dense HfB2 and ZrB2 "With SiC, TaSi2, and LaB6 Additives Sb. GRANT NUMBER... RESISTANCE , ELECTRICAL AND THERMAL CONDUCTIVITY, AND SPECTRAL EMITTANCE OF FULLY DENSE HfB2 AND ZrB2 WITH SiC, TaSi2, AND LaB6 ADDITIVES Air Force Office...thickened regions with dry 220 grit SiC sandpaper so that a low- resistance electrical connection could be achieved. A handheld multimeter was used to measure

Carbonate-silicate melt immiscibility, REE mineralising fluids, and the evolution of the Lofdal Intrusive Suite, Namibia

NASA Astrophysics Data System (ADS)

Bodeving, Sarah; Williams-Jones, Anthony E.; Swinden, Scott

2017-01-01

The Lofdal Intrusive Suite, Namibia, consists of calcio-carbonatite and silica-undersaturated alkaline intrusive rocks ranging in composition from phono-tephrite to phonolite (and nepheline syenite). The most primitive of these rocks is the phono-tephrite, which, on the basis of its Y/Ho and Nb/Ta ratios, is interpreted to have formed by partial melting of the mantle. Roughly linear trends in major and trace element contents from phono-tephrite to phonolite and nepheline syenite indicate that the latter two rock types evolved from the phono-tephrite by fractional crystallisation. The nepheline syenite, however, has a lower rare earth element (REE) content than the phonolite. The carbonatite has a primitive mantle-normalised REE profile roughly parallel to that of the silica-undersaturated alkaline igneous rocks, although the absolute REE concentrations are higher. Like the phono-tephrite, it also has a mantle Y/Ho ratio. However, the Nb/Ta and Zr/Hf ratios are significantly higher. Moreover, the carbonatite displays strong negative Ta, Zr and Hf anomalies on spidergrams, whereas the silicate rocks display positive anomalies for these elements. Significantly, this behaviour is predicted by the corresponding carbonatite-silicate melt partition coefficients, as is the behaviour of the REE. Based on these observations, we interpret the carbonatite to represent an immiscible liquid that exsolved from the phono-tephrite or possibly the phonolite melt. The result was a calcio-carbonatite that is enriched in the heavy REE (HREE) relative to most other carbonatites. Fluids released from the corresponding magma are interpreted to have been the source of the REE mineralisation that is currently the target of exploration. 2. The composition of feldspar in nepheline syenite, fenite, calcio-carbonatite and phonolite plotted on the feldspar ternary classification diagram modified after Schairer (1950) in terms of the components albite (Ab), orthoclase (Or) and anorthite (An). Note: ANO = anorthosite, SAN = sanidine, OLI = oligoclase, AND = andesine, LAB = labradorite, BYT = bytownite. 3. Composition of the Lofdal mica plotted on the biotite classification diagram of Rieder et al. (1998). 4. Clinopyroxene composition in nepheline syenite and calcio-carbonatite phenocrysts illustrated on the classification ternary for sodic pyroxenes (after Morimoto; 1989). Quad (Q) represents wollastonite, enstatite and ferrosilite of the Mg-Ca-Fe group of pyroxenes. 5. The range of carbonatite compositions illustrated on the carbonatite classification diagram of Gittins and Harmer (1997). 6. Composition of the Lofdal nepheline syenite on the plutonic Total-Alkali-Silica diagram of Wilson (1989). 7. a. A binary plot showing the concentration of Y versus that of Ho in bulk rock samples of the phono-tephrites, phonolites, nepheline syenites and carbonatites. The trend-line represents the mantle value of approximately 27.7 (Sun and McDonough, 1989). b. A binary plot showing the concentration of Nb versus that of Ta in bulk rock samples of the phono-tephrites, phonolites, nepheline syenites and carbonatites. The trend-line represents the mantle value of approximately 17.4 (Sun and McDonough, 1989). c. A binary plot showing the concentration of Zr versus that of Hf in bulk rock samples of the phono-tephrites, phonolites, nepheline syenites and carbonatites. The trend-line represents the mantle value of approximately 36.2 (Sun and McDonough, 1989). 8. A binary plot showing the concentration of K2O versus Na2O in nepheline syenite and fenite.

The effect of Nb addition on mechanical properties, corrosion behavior, and metal-ion release of ZrAlCuNi bulk metallic glasses in artificial body fluid.

PubMed

Qiu, C L; Liu, L; Sun, M; Zhang, S M

2005-12-15

Bulk metallic glasses (BMGs) of Zr(65 - x)Nb(x)- Cu(17.5)Ni(10)Al(7.5) with Nb = 0, 2, and 5 at % were prepared by copper mold casting. Compression tests reveal that the two BMGs containing Nb exhibited superior strength and plasticity to the base alloy. The corrosion behavior of the alloys obtained was investigated in artificial body fluid by electrochemical measurements. It was found that the addition of Nb significantly enhanced the corrosion resistance of the Zr-based BMG, as indicated by a remarkable increase in corrosion potential and pitting potential. XPS analysis revealed that the passive film formed after anodic polarization was enriched in aluminum oxide and depleted in phosphate ions for the BMGs containing Nb, which accounts for the improvement of corrosion resistance. On the other hand, metal-ion release of different BMGs were determined in PPb (ng/mL) level with inductively coupled plasma mass spectrometry (ICP-MS) after being immersed in artificial body fluid at 37 degrees C for 20 days. It was found that the addition of Nb considerably reduced the ion release of all kinds of metals of the base system. This is probably attributed to the promoting effect of Nb on a rapid formation of highly protective film.

Experimental determination of trace-element partitioning between pargasite and a synthetic hydrous andesitic melt

NASA Astrophysics Data System (ADS)

Brenan, J. M.; Shaw, H. F.; Ryerson, F. J.; Phinney, D. L.

1995-10-01

In order to more fully establish a basis for quantifying the role of amphibole in trace-element fractionation processes, we have measured pargasite/silicate melt partitioning of a variety of trace elements (Rb, Ba, Nb, Ta, Hf, Zr, Ce, Nd, Sm, Yb), including the first published values for U, Th and Pb. Experiments conducted at 1000°C and 1.5 GPa yielded large crystals free of compositional zoning. Partition coefficients were found to be constant at total concentrations ranging from ˜ 1 to > 100 ppm, indicating Henry's Law is oparative over this interval. Comparison of partition coefficients measured in this study with previous determinations yields good agreement for similar compositions at comparable pressure and temperature. The compatibility of U, Th and Pb in amphibole decreases in the order Pb > Th > U. Partial melting or fractional crystallization of amphibole-bearing assemblages will therefore result in the generation of excesses in 238U activity relative to 230Th, similar in magnitude to that produced by clinopyroxene. The compatibility of Pb in amphibole relative to U or Th indicates that melt generation in the presence of residual amphibole will result in the long-term enrichment in Pb relative to U or Th in the residue. This process is therefore incapable of producing the depletion in Pb relative to U or Th inferred from the Pb isotopic composition of MORB and OIB. Comparison of partition coefficients measured in this study with previous values for clinopyroxene allows some distinction to be made between expected trace-element fractionations produced during dry (cpx present) and wet (cpx + amphibole present) melting. Rb, Ba, Nb and Ta are dramatically less compatible in clinopyroxene than in amphibole, whereas Th, U, Hf and Zr have similar compatibilities in both phases. Interelement fractionations, such as DNb/DBa are also different for clinopyroxene and amphibole. Changes in certain ratios, such as Ba/Nb, Ba/Th, and Nb/Th within comagmatic suites may therefore offer a means to discern the loss of amphibole from the melting assemblage. Elastic strain theory is applied to the partitioning data after the approaches of Beattie and Blundy and Wood and is used to predict amphibole/melt partition coefficients at conditions of P, T and composition other than those employed in this study. Given values of DCa, DTi and DK from previous partitioning studies, this approach yields amphibole/melt trace-element partition coefficients that reproduce measured values from the literature to within 40-45%. This degree of reproducibility is considered reasonable given that model parameters are derived from partitioning relations involving iron- and potassium-free amphibole.

Lattice Thermal Conductivity of Ultra High Temperature Ceramics (UHTC) ZrB2 and HfB2 from Atomistic Simulations

NASA Technical Reports Server (NTRS)

Lawson, John W.; Daw, Murray S.; Bauschlicher, Charles W.

2012-01-01

Ultra high temperature ceramics (UHTC) including ZrB2 and HfB2 have a number of properties that make them attractive for applications in extreme environments. One such property is their high thermal conductivity. Computational modeling of these materials will facilitate understanding of fundamental mechanisms, elucidate structure-property relationships, and ultimately accelerate the materials design cycle. Progress in computational modeling of UHTCs however has been limited in part due to the absence of suitable interatomic potentials. Recently, we developed Tersoff style parameterizations of such potentials for both ZrB2 and HfB2 appropriate for atomistic simulations. As an application, Green-Kubo molecular dynamics simulations were performed to evaluate the lattice thermal conductivity for single crystals of ZrB2 and HfB2. The atomic mass difference in these binary compounds leads to oscillations in the time correlation function of the heat current, in contrast to the more typical monotonic decay seen in monoatomic materials such as Silicon, for example. Results at room temperature and at elevated temperatures will be reported.

Lattice Thermal Conductivity from Atomistic Simulations: ZrB2 and HfB2

NASA Technical Reports Server (NTRS)

Lawson, John W.; Daw, Murray S.; Bauschlicher, Charles W.

2012-01-01

Ultra high temperature ceramics (UHTC) including ZrB2 and HfB2 have a number of properties that make them attractive for applications in extreme environments. One such property is their high thermal conductivity. Computational modeling of these materials will facilitate understanding of fundamental mechanisms, elucidate structure-property relationships, and ultimately accelerate the materials design cycle. Progress in computational modeling of UHTCs however has been limited in part due to the absence of suitable interatomic potentials. Recently, we developed Tersoff style parameterizations of such potentials for both ZrB2 and HfB2 appropriate for atomistic simulations. As an application, Green-Kubo molecular dynamics simulations were performed to evaluate the lattice thermal conductivity for single crystals of ZrB2 and HfB2. The atomic mass difference in these binary compounds leads to oscillations in the time correlation function of the heat current, in contrast to the more typical monotonic decay seen in monoatomic materials such as Silicon, for example. Results at room temperature and at elevated temperatures will be reported.

The mechanical, optoelectronic and thermoelectric properties of NiYSn (Y = Zr and Hf) alloys

NASA Astrophysics Data System (ADS)

Hamioud, Farida; Mubarak, A. A.

2017-09-01

First-principle calculations are performed using DFT as implemented in Wien2k code to compute the mechanical, electronic, optical and thermoelectric properties of NiYSn (Y = Zr and Hf) alloys. The computed lattice constants, bulk modulus and cohesive energy of these alloys at 0 K and 0 GPa are performed. NiZrSn and NiHfSn are found to be anisotropic and elastically stable. Furthermore, both alloys are confirmed to be thermodynamically stable by the calculated values of the standard enthalpy of formation. The Young’s and shear moduli values show that NiZrSn seems to be stiffer than NiHfSn. The optical properties are performed using the dielectric function. Some beneficial optoelectronic applications are found as exposed in the optical spectra. Moreover, the alloys are classified as good insulators for solar heating. The thermoelectric properties as a function of temperature are computed utilizing BoltzTrap code. The major charge carriers are found to be electrons and the alloys are classified as p-type doping alloys.

Calcium hydride synthesis of Ti-Nb-based alloy powders

NASA Astrophysics Data System (ADS)

Kasimtsev, A. V.; Shuitsev, A. V.; Yudin, S. N.; Levinskii, Yu. V.; Sviridova, T. A.; Alpatov, A. V.; Novosvetlova, E. E.

2017-09-01

The metallothermic (calcium hydride) synthesis of Ti-Nb alloy powders alloyed with tantalum and zirconium is experimentally studied under various conditions. Chemical, X-ray diffraction, and metallographic analyses of the synthesized products show that initial oxides are completely reduced and a homogeneous β-Ti-based alloy powder forms under the optimum synthesis conditions at a temperature of 1200°C. At a lower synthesis temperature, the end products have a high oxygen content. The experimental results are used to plot the thermokinetic dependences o formation of a bcc solid solution at various times of isothermal holding of Ti-22Nb-6Ta and Ti-22Nb-6Zr (at %) alloys. The physicochemical and technological properties of the Ti-22Nb-6Ta and Ti-22Nb-6Zr alloy powders synthesized by calcium hydride reduction under the optimum conditions are determined.

Development of AlN and TiB2 Composites with Nb2O5, Y2O3 and ZrO2 as Sintering Aids

PubMed Central

González, José C.; Rodríguez, Miguel Á.; Figueroa, Ignacio A.; Villafuerte-Castrejón, María-Elena; Díaz, Gerardo C.

2017-01-01

The synthesis of AlN and TiB2 by spark plasma sintering (SPS) and the effect of Nb2O5, Y2O3 and ZrO2 additions on the mechanical properties and densification of the produced composites is reported and discussed. After the SPS process, dense AlN and TiB2 composites with Nb2O5, Y2O3 and ZrO2 were successfully prepared. X-ray diffraction analysis showed that in the AlN composites, the addition of Nb2O5 gives rise to Nb4N3 during sintering. The compound Y3Al5O12 (YAG) was observed as precipitate in the sample with Y2O3. X-ray diffraction analysis of the TiB2 composites showed TiB2 as a single phase in these materials. The maximum Vickers and toughness values were 14.19 ± 1.43 GPa and 27.52 ± 1.75 GPa for the AlN and TiB2 composites, respectively. PMID:28772681

Enhancement of High Temperature Strength of 2219 Alloys Through Small Additions of Nb and Zr and a Novel Heat Treatment

NASA Astrophysics Data System (ADS)

Mondol, S.; Makineni, S. K.; Kumar, S.; Chattopadhyay, K.

2018-07-01

This paper presents a detailed investigation on the effect of small amount of Nb and Zr additions to 2219 Al alloy coupled with a novel three-stage heat treatment process. The main aim of the work is to increase the high temperature strength of 2219 alloy by introducing thermally stable L12 type ordered precipitates in the matrix as well as by reducing the coarsening of metastable strengthening θ″ and θ' precipitates. To achieve this, small amounts of Nb and Zr are added to 2219 alloy melt and retained in solid solution by suction casting in a water-cooled copper mould having a cooling rate of 102 to 103 K/s. The suction cast alloy is directly aged at 673 K (400 °C) to form L12 type ordered coherent Al3Zr precipitates. Subsequently, the alloy is solution treated at 808 K (535 °C) for 30 minutes to get supersaturation of Cu in the matrix without significantly affecting the Al3Zr precipitates. Finally, the alloy is aged at 473 K (200 °C), which results in the precipitation of θ″ and θ'. Microstructural characterization reveals that θ″ and θ' are heterogeneously precipitated on pre-existing uniformly distributed Al3Zr precipitates, which leads to a higher number density of these precipitates. This results in a significant increase in strength at room temperature as well as at 473 K (200 °C) as compared to the 2219 alloy. Furthermore, the alloy remains thermally stable after prolonged exposure at 473 K (200 °C), which is attributed to the elastic strain energy minimization by the conjoint Al3Zr/ θ' or Al3Zr/ θ″ precipitates, and the high Zr and Nb solute-vacancy binding energy, retarding the growth and coarsening of θ″ and θ' precipitates.

Enhancement of High Temperature Strength of 2219 Alloys Through Small Additions of Nb and Zr and a Novel Heat Treatment

NASA Astrophysics Data System (ADS)

Mondol, S.; Makineni, S. K.; Kumar, S.; Chattopadhyay, K.

2018-05-01

This paper presents a detailed investigation on the effect of small amount of Nb and Zr additions to 2219 Al alloy coupled with a novel three-stage heat treatment process. The main aim of the work is to increase the high temperature strength of 2219 alloy by introducing thermally stable L12 type ordered precipitates in the matrix as well as by reducing the coarsening of metastable strengthening θ″ and θ' precipitates. To achieve this, small amounts of Nb and Zr are added to 2219 alloy melt and retained in solid solution by suction casting in a water-cooled copper mould having a cooling rate of 102 to 103 K/s. The suction cast alloy is directly aged at 673 K (400 °C) to form L12 type ordered coherent Al3Zr precipitates. Subsequently, the alloy is solution treated at 808 K (535 °C) for 30 minutes to get supersaturation of Cu in the matrix without significantly affecting the Al3Zr precipitates. Finally, the alloy is aged at 473 K (200 °C), which results in the precipitation of θ″ and θ'. Microstructural characterization reveals that θ″ and θ' are heterogeneously precipitated on pre-existing uniformly distributed Al3Zr precipitates, which leads to a higher number density of these precipitates. This results in a significant increase in strength at room temperature as well as at 473 K (200 °C) as compared to the 2219 alloy. Furthermore, the alloy remains thermally stable after prolonged exposure at 473 K (200 °C), which is attributed to the elastic strain energy minimization by the conjoint Al3Zr/θ' or Al3Zr/θ″ precipitates, and the high Zr and Nb solute-vacancy binding energy, retarding the growth and coarsening of θ″ and θ' precipitates.

First-principles study of lattice thermal conductivity in ZrTe5 and HfTe5

NASA Astrophysics Data System (ADS)

Wang, Cong; Wang, Haifeng; Chen, Y. B.; Yao, Shu-Hua; Zhou, Jian

2018-05-01

Recently, the layered transition-metal pentatellurides ZrTe5 and HfTe5 have attracted increasing attention because of their interesting topological electronic properties. Nevertheless, some of their other good physical properties seem to be ignored now. Actually, both ZrTe5 and HfTe5 have high electric conductivities (>105 Ω-1 m-1) and Seebeck coefficients (> 100 μV/K) at room temperature, thus making them promising thermoelectric materials. However, the disadvantage is that the thermal conductivities of the two materials are relatively high according to the few available experiments; meanwhile, the detailed mechanism of the intrinsic thermal conductivity has not been studied yet. Based on the density functional theory and the Boltzmann transport theory, we present here the theoretical study of the intrinsic lattice thermal conductivities of ZrTe5 and HfTe5, which are found to be in the range of 5-8 W/mṡK at room temperature and well consistent with the experimental results. We also find that the thermal conductivities of the two materials are anisotropic, which are mainly caused by their anisotropic crystal structures. Based on the detailed analysis, we proposed that the thermal conductivities of the two materials could possibly be reduced by different kinds of structural engineering at the atomic and mesoscopic scales, such as alloying, doping, nano-structuring, and polycrystalline structuring, which could make ZrTe5 and HfTe5 good thermoelectric materials for room temperature thermoelectric applications.

H-Phase Precipitation and Martensitic Transformation in Ni-rich Ni-Ti-Hf and Ni-Ti-Zr High-Temperature Shape Memory Alloys

NASA Astrophysics Data System (ADS)

Evirgen, A.; Pons, J.; Karaman, I.; Santamarta, R.; Noebe, R. D.

2018-03-01

The distributions of H-phase precipitates in Ni50.3Ti29.7Hf20 and Ni50.3Ti29.7Zr20 alloys formed by aging treatments at 500 and 550 °C or slow furnace cooling and their effects on the thermal martensitic transformation have been investigated by TEM and calorimetry. The comparative study clearly reveals faster precipitate-coarsening kinetics in the NiTiZr alloy than in NiTiHf. For precipitates of a similar size of 10-20 nm in both alloys, the martensite plates in Ni50.3Ti29.7Zr20 have larger widths and span a higher number of precipitates compared with the Ni50.3Ti29.7Hf20 alloy. However, for large H-phase particles with hundreds of nm in length, no significant differences in the martensitic microstructures of both alloy systems have been observed. The martensitic transformation temperatures of Ni50.3Ti29.7Hf20 are 80-90 °C higher than those of Ni50.3Ti29.7Zr20 in the precipitate-free state and in the presence of large particles of hundreds on nm in length, but this difference is reduced to only 10-20 °C in samples with small H-phase precipitates. The changes in the transformation temperatures are consistent with the differences in the precipitate distributions between the two alloy systems observed by TEM.

Novel Ti-Ta-Hf-Zr alloys with promising mechanical properties for prospective stent applications

NASA Astrophysics Data System (ADS)

Lin, Jixing; Ozan, Sertan; Li, Yuncang; Ping, Dehai; Tong, Xian; Li, Guangyu; Wen, Cuie

2016-11-01

Titanium alloys are receiving increasing research interest for the development of metallic stent materials due to their excellent biocompatibility, corrosion resistance, non-magnetism and radiopacity. In this study, a new series of Ti-Ta-Hf-Zr (TTHZ) alloys including Ti-37Ta-26Hf-13Zr, Ti-40Ta-22Hf-11.7Zr and Ti-45Ta-18.4Hf-10Zr (wt.%) were designed using the d-electron theory combined with electron to atom ratio (e/a) and molybdenum equivalence (Moeq) approaches. The microstructure of the TTHZ alloys were investigated using optical microscopy, XRD, SEM and TEM and the mechanical properties were tested using a Vickers micro-indenter, compression and tensile testing machines. The cytocompatibility of the alloys was assessed using osteoblast-like cells in vitro. The as-cast TTHZ alloys consisted of primarily β and ω nanoparticles and their tensile strength, yield strength, Young’s modulus and elastic admissible strain were measured as being between 1000.7-1172.8 MPa, 1000.7-1132.2 MPa, 71.7-79.1 GPa and 1.32-1.58%, respectively. The compressive yield strength of the as-cast alloys ranged from 1137.0 to 1158.0 MPa. The TTHZ alloys exhibited excellent cytocompatibility as indicated by their high cell viability ratios, which were close to that of CP-Ti. The TTHZ alloys can be anticipated to be promising metallic stent materials by virtue of the unique combination of extraordinarily high elastic admissible strain, high mechanical strength and excellent biocompatibility.

Superelasticity, corrosion resistance and biocompatibility of the Ti-19Zr-10Nb-1Fe alloy.

PubMed

Xue, Pengfei; Li, Yan; Li, Kangming; Zhang, Deyuan; Zhou, Chungen

2015-05-01

Microstructure, mechanical properties, superelasticity and biocompatibility of a Ti-19Zr-10Nb-1Fe alloy are investigated. X-ray diffraction spectroscopy and transmission electron microscopy observations show that the as-cast Ti-19Zr-10Nb-1Fe alloy is composed of α' and β phases, but only the β phase exists in the as-rolled and as-quenched alloys. The tensile stress-strain tests indicate that the as-quenched alloy exhibits a good combination of mechanical properties with a large elongation of 25%, a low Young's modulus of 59 GPa and a high ultimate tensile stress of 723 MPa. Superelastic recovery behavior is found in the as-quenched alloy during tensile tests, and the corresponding maximum of superelastic strain is 4.7% at the pre-strain of 6%. A superelastic recovery of 4% with high stability is achieved after 10 cyclic loading-unloading training processes. Potentiodynamic polarization and ion release measurements indicate that the as-quenched alloy shows a lower corrosion rate in Hank's solution and a much less ion release rate in 0.9% NaCl solution than those of the NiTi alloys. Cell culture results indicate that the osteoblasts' adhesion and proliferation are similar on both the Ti-19Zr-10Nb-1Fe and NiTi alloys. A better hemocompatibility is confirmed for the as-quenched Ti-19Zr-10Nb-1Fe alloy, attributed to more stable platelet adhesion and small activation degree, and a much lower hemolysis rate compared with the NiTi alloy. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigating the Structural, Thermal, and Electronic Properties of the Zircon-Type ZrSiO4, ZrGeO4 and HfSiO4 Compounds

NASA Astrophysics Data System (ADS)

Chiker, Fafa; Boukabrine, Fatiha; Khachai, H.; Khenata, R.; Mathieu, C.; Bin Omran, S.; Syrotyuk, S. V.; Ahmed, W. K.; Murtaza, G.

2016-11-01

In the present study, the structural, thermal, and electronic properties of some important orthosilicate dielectrics, such as the ZrSiO4, ZrGeO4, and HfSiO4 compounds, have been investigated theoretically with the use of first-principle calculations. We attribute the application of the modified Becke-Johnson exchange potential, which is basically an improvement over the local density approximation and the Perdew-Burke-Ernzerhof exchange-correlation functional, for a better description of the band gaps of the compounds. This resulted in a good agreement with our estimated values in comparison with the reported experimental data, specifically for the ZrSiO4, and HfSiO4 compounds. Conversely, for the ZrGeO4 compound, the calculated electronic band structure shows a direct band gap at the Γ point with the value of 5.79 eV. Furthermore, our evaluated thermal properties that are calculated by using the quasi-harmonic Debye model indicated that the volume variation with temperature is higher in the ZrGeO4 compound as compared to both the ZrSiO4 and HfSiO4 compounds, which is ascribed to the difference between the electron shells of the Si and Ge atoms. Therefore, these results also indicate that while the entropy ( S) and enthalpy ( U) parameters increase monotonically, the free energy ( G), in contrast, decreases monotonically with increasing temperature, respectively. Moreover, the pressure and temperature dependencies of the Debye temperature Θ, thermal expansion coefficient, and heat capacities C V were also predicted in our study.

First-principles study of adsorption and diffusion of oxygen on surfaces of TiN, ZrN and HfN

NASA Astrophysics Data System (ADS)

Guo, Fangyu; Wang, Jianchuan; Du, Yong; Wang, Jiong; Shang, Shun-Li; Li, Songlin; Chen, Li

2018-09-01

Using first-principles calculations based on density functional theory, we systematically study the adsorption and diffusion behaviors of single oxygen (O) atom on the (0 0 1) surfaces of TiN, ZrN and HfN nitride coatings. The top of N site (top(N)) is the most energetic favorable site for O atom and followed by the hollow site for all the three nitrides. O atom tends to diffuse on the (0 0 1) surfaces of the nitrides from the top of transition metal top(TM) sites to a neighboring top(TM) sites by avoiding N sites. The adsorption of O on ZrN and HfN is more stable than that on TiN. Our findings could explain the experimental phenomenon that the oxide thickness of TiN is smaller than that of ZrN under the same oxidation conditions.

Effective Enrichment and Mass Spectrometry Analysis of Phosphopeptides Using Mesoporous Metal Oxide Nanomaterials

PubMed Central

Nelson, Cory A.; Szczech, Jeannine R.; Dooley, Chad J.; Xu, Qingge; Lawrence, Matthew J.; Zhu, Haoyue; Jin, Song; Ge, Ying

2010-01-01

Mass spectrometry (MS)-based phosphoproteomics remains challenging due to the low abundance of phosphoproteins and substoichiometric phosphorylation. This demands better methods to effectively enrich phosphoproteins/peptides prior to MS analysis. We have previously communicated the first use of mesoporous zirconium oxide (ZrO2) nanomaterials for effective phosphopeptide enrichment. Here we present the full report including the synthesis, characterization, and application of mesoporous titanium dioxide (TiO2), ZrO2, and hafnium oxide (HfO2) in phosphopeptide enrichment and MS analysis. Mesoporous ZrO2 and HfO2 are demonstrated to be superior to TiO2 for phosphopeptide enrichment from a complex mixture with high specificity (>99%), which could almost be considered as “a purification”, mainly because of the extremely large active surface area of mesoporous nanomaterials. A single enrichment and Fourier transform MS analysis of phosphopeptides digested from a complex mixture containing 7% of α-casein identified 21 out of 22 phosphorylation sites for α-casein. Moreover, the mesoporous ZrO2 and HfO2 can be reused after a simple solution regeneration procedure with comparable enrichment performance to that of fresh materials. Mesoporous ZrO2 and HfO2 nanomaterials hold great promise for applications in MS-based phosphoproteomics. PMID:20704311

Zircon U-Pb ages, geochemistry, and Nd-Hf isotopes of the TTG gneisses from the Jiaobei terrane: Implications for Neoarchean crustal evolution in the North China Craton

NASA Astrophysics Data System (ADS)

Shan, Houxiang; Zhai, Mingguo; Wang, Fang; Zhou, Yanyan; Santosh, M.; Zhu, Xiyan; Zhang, Huafeng; Wang, Wei

2015-02-01

The Precambrian basement in the Jiaobei terrane is largely composed of Tonalite-Trondhjemite-Granodiorite (TTG) suite of rocks and offers important insights into the crustal evolution history of the North China Craton (NCC). The LA-ICP-MS zircon U-Pb age data presented in this study show that the magmatic protoliths of the TTG gneisses formed during 2508-2547 Ma and recorded the Paleoproterozoic metamorphism (∼1905 Ma). The rocks are enriched in LILE (Rb, Ba and Sr) and depleted in HFSE (Nb, Ta, Zr and Hf). They are characterized by high Sr contents (406-2906 ppm), Sr/Y ratios (31.3-355) and subchondritic Nb/Ta ratios (18.5-68.9). The TTGs show relatively high ΣREE contents (72.0-266 ppm) with strongly enriched LREE ((La/Yb)N = 11.5-121) and positive or negligible negative Eu anomalies (Eu/Eu∗ = 0.84-1.89). These geochemical features suggest that the magma source might have been rutile-bearing amphibole eclogite. Their high Mg# numbers (42-56) and high Cr (153-285 ppm) and Ni contents (22.2-74.5 ppm) indicate interaction with the mantle wedge during magma ascent. The whole rock εNd (t) values (+2.6 to +3.8) and most of the magmatic zircon εHf (t) values (+1.3 to +7.6) suggest juvenile to evolved isotopic signatures. All these lines of evidence suggest that the TTG rocks in this study formed through partial melting of subducted oceanic slab in a continental arc environment. The drill holes in the Jiaobei terrane are dominated by ∼2.5 Ga TTG gneisses, suggesting that the TTG magma at ∼2.5 Ga is more widely distributed deep underground than that of ∼2.7-2.9 Ga, at least within the approachable depth range of our research. Some zircon grains from Jiaobei TTGs give high εHf (t) values plotting above the curve of 0.75 ∗ εHf of DM, and their TCDM ages are very close to the time of the zircon crystallization. However, the majority of the εHf (t) values fall below the curve of 0.75 ∗ εHf of DM and their TCDM ages are concentrated between ∼2.7-2.9 Ga. Therefore, combining with other related studies, we propose that the ∼2.5-2.6 Ga magmatism in the NCC probably represents a coherent event of crustal growth and major reworking (remelting).

Low-Temperature Reactivities of Ultra-High Temperature Ceramics (Hf-X System)

DTIC Science & Technology

2005-12-01

as interacting fillers with the preceramic polymer formulations. In situ formation of the SiC phase was also evaluated as a practical approach in...led to a renewal of activities to fabricate MB2/ SiC composites as the materials of choice, because of their high thermal and oxidation resistance...HfB2/ SiC composite microstructures (and also HfC, ZrB2, and ZrC composites ) under pressureless conditions. These can be employed in reactive and

Application of carbide cutting tools with nano-structured multilayer composite coatings for turning austenitic steels, type 16Cr-10NI

NASA Astrophysics Data System (ADS)

Vereschaka, Alexey; Migranov, Mars; Oganyan, Gaik; Sotova, Catherine S.; Batako, Andre

2018-03-01

This paper addresses the challenges of increasing the efficiency of the machining of austenitic stainless steels AISI 321 and S31600 by application of cutting tools with multilayer composite nano-structured coatings. The main mechanical properties and internal structures of the coatings under study (hardness, adhesion strength in the "coating-substrate" system) were investigated, and their chemical compositions were analyzed. The conducted research of tool life and nature of wear of carbide tools with the investigated coatings during turning of the above mentioned steels showed that the application of those coatings increases the tool life by up to 2.5 times. In addition, the use of a cutting tool with coatings allows machining at higher cutting speeds. It was also found that the use of a tool with multilayer composite nano-structured coating (Zr,Nb)N-(Zr,Al,Nb)N ensures better results compared with not only monolithic coating TiN, but also with nano-structured coatings Ti-TiN-(Ti,Al)N and (Zr,Nb)N-(Cr,Zr,Nb,Al)N. The mechanism of failure of the coatings under study was also investigated.

Biocompatible Materials Based on Self-Assembling Peptides on Ti25Nb10Zr Alloy: Molecular Structure and Organization Investigated by Synchrotron Radiation Induced Techniques.

PubMed

Secchi, Valeria; Franchi, Stefano; Santi, Marta; Vladescu, Alina; Braic, Mariana; Skála, Tomáš; Nováková, Jaroslava; Dettin, Monica; Zamuner, Annj; Iucci, Giovanna; Battocchio, Chiara

2018-03-07

In this work, we applied advanced Synchrotron Radiation (SR) induced techniques to the study of the chemisorption of the Self Assembling Peptide EAbuK16, i.e., H-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-NH₂ that is able to spontaneously aggregate in anti-parallel β-sheet conformation, onto annealed Ti25Nb10Zr alloy surfaces. This synthetic amphiphilic oligopeptide is a good candidate to mimic extracellular matrix for bone prosthesis, since its β-sheets stack onto each other in a multilayer oriented nanostructure with internal pores of 5-200 nm size. To prepare the biomimetic material, Ti25Nb10Zr discs were treated with aqueous solutions of EAbuK16 at different pH values. Here we present the results achieved by performing SR-induced X-ray Photoelectron Spectroscopy (SR-XPS), angle-dependent Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, FESEM and AFM imaging on Ti25Nb10Zr discs after incubation with self-assembling peptide solution at five different pH values, selected deliberately to investigate the best conditions for peptide immobilization.

Role of Hf on Phase Formation in Ti45Zr(38-x)Hf(x)Ni17 Liquids and Solids

NASA Technical Reports Server (NTRS)

Wessels, V.; Sahu, K. K.; Gangopadhyay, A. K.; Huett, V. T.; Canepari, S.; Goldman, A. I.; Hyers, R. W.; Kramer, M. J.; Rogers, J. R.; Kelton, K. F.;

Fatigue behaviour of boron free and boron containing heat treated Ti-13Zr-13Nb alloy for biomedical applications

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

Majumdar, P., E-mail: m.pallab@gmail.com; Singh, S.B.; Chakraborty, M.

2010-12-15

Fatigue behaviour of heat treated Ti-13Zr-13Nb (TZN) and Ti-13Zr-13Nb-0.5B (TZNB) alloys for biomedical implants has been investigated by rotating bending test. It was found that fatigue strength of TZN and TZNB alloys is comparable with that of conventionally used biomedical titanium alloys. Addition of boron to TZN alloy deteriorates fatigue strength. - Research Highlights: {yields}The microstructure of the aged TZN consists of {alpha} phase in {beta} matrix. {yields}Addition of boron to TZN leads to the formation of dispersed acicular TiB. {yields}Presence of TiB deteriorates the fatigue strength of TZN alloy. {yields}Fatigue strength of aged TZN/TZNB alloys is comparable with biomedicalmore » Ti-alloys.« less

Pressure-induced positive electrical resistivity coefficient in Ni-Nb-Zr-H glassy alloy

NASA Astrophysics Data System (ADS)

Fukuhara, M.; Gangli, C.; Matsubayashi, K.; Uwatoko, Y.

2012-06-01

Measurements under hydrostatic pressure of the electrical resistivity of (Ni0.36Nb0.24Zr0.40)100-xHx (x = 9.8, 11.5, and 14) glassy alloys have been made in the range of 0-8 GPa and 0.5-300 K. The resistivity of the (Ni0.36Nb0.24Zr0.40)86H14 alloy changed its sign from negative to positive under application of 2-8 GPa in the temperature range of 300-22 K, coming from electron-phonon interaction in the cluster structure under pressure, accompanied by deformation of the clusters. In temperature region below 22 K, the resistivity showed negative thermal coefficient resistance by Debye-Waller factor contribution, and superconductivity was observed at 1.5 K.

ac impedance analysis of a Ni-Nb-Zr-H glassy alloy with femtofarad capacitance tunnels

NASA Astrophysics Data System (ADS)

Fukuhara, M.; Seto, M.; Inoue, A.

2010-01-01

A Nyquist diagram of a (Ni0.36Nb0.24Zr0.40)90H10 glassy alloy shows a semitrue circle, indicating that it is a conducting material with a total capacitance of 17.8 μF. The Bode plots showing the dependencies of its real and imaginary impedances, and phase on frequency suggest a simpler equivalent circuit having a resistor in parallel with a capacitor. Dividing the total capacitance (17.8 μF) by the capacitance of a single tunnel (0.9 fF), we deduced that this material has a high number of dielectric tunnels, which can be regarded as regular prisms separated from the electric-conducting distorted icosahedral Zr5Ni5Nb3 clusters by an average of 0.225 nm.

Heart failure risk among patients with rheumatoid arthritis starting a TNF antagonist.

PubMed

Solomon, Daniel H; Rassen, Jeremy A; Kuriya, Bindee; Chen, Lang; Harrold, Leslie R; Graham, David J; Lewis, James D; Lii, Joyce; Liu, Liyan; Griffin, Marie R; Curtis, J R

2013-11-01

While heart failure (HF) is associated with elevations in tumor necrosis factor (TNF)α, several trials of TNF antagonists showed no benefit and possibly worsening of disease in those with known severe HF. We studied the risk of new or recurrent HF among a group of patients receiving these agents to treat rheumatoid arthritis (RA). We used data from four different US healthcare programmes. Subjects with RA receiving methotrexate were eligible to enter the study cohort if they added or switched to a TNF antagonist or another non-biological disease modifying antirheumatic drug (nbDMARD). These groups were compared in Cox regression models stratified by propensity score decile and adjusted for oral glucocorticoid dosage, prior HF hospitalisations, and the use of loop diuretics. We compared 8656 new users of a nbDMARD with 11 587 new users of a TNF antagonist with similar baseline covariates. The HR for the TNF antagonists compared with nbDMARD was 0.85 (95% CI 0.63 to 1.14). The HR was also not elevated in subjects with a history of HF. But, it was elevated prior to 2002 (HR 2.17, 95% CI 0.45 to 10.50, test for interaction p=0.036). Oral glucocorticoids were associated with a dose-related gradient of HF risk: compared with no use, 1≤5 mg HR 1.30 (95% CI 0.91 to 1.85), ≥5 mg HR 1.54 (95% CI 1.09 to 2.19). TNF antagonists were not associated with a risk of HF hospital admissions compared with nbDMARDs in this RA population.

Geochemical constraints on the petrogenesis of the pyroclastic rocks in Abakaliki basin (Lower Benue Rift), Southeastern Nigeria

NASA Astrophysics Data System (ADS)

Chukwu, Anthony; Obiora, Smart C.

2018-05-01

The pyroclastic rocks in the Cretaceous Abakaliki basin occur mostly as oval-shaped bodies, consisting of lithic/lava and vitric fragments. They are commonly characterized by parallel and cross laminations, as well contain xenoliths of shale, mudstone and siltstones from the older Asu River Group of Albian age. The rocks are basic to ultrabasic in composition, comprising altered alkali basalts, altered tuffs, minor lapillistones and agglomerates. The mineral compositions are characterized mainly by laths of calcic plagioclase, pyroxene (altered), altered olivines and opaques. Calcite, zeolite and quartz represent the secondary mineral constituents. Geochemically, two groups of volcaniclastic rocks, are distinguished: alkaline and tholeiitic rocks, both represented by fresh and altered rock samples. The older alkali basalts occur within the core of the Abakaliki anticlinorium while the younger tholeiites occur towards the periphery. Though most of the rocks are moderate to highly altered [Loss on ignition (LOI, 3.43-22.07 wt. %)], the use of immobile trace element such as Nb, Zr, Y, Hf, Ti, Ta and REEs reflect asthenospheric mantle source compositions. The rocks are enriched in incompatible elements and REEs (∑REE = 87.98-281.0 ppm for alkaline and 69.45-287.99 ppm for tholeiites). The ratios of La/Ybn are higher in the alkaline rocks ranging from 7.69 to 31.55 compared to the tholeiitic rocks which range from 4.4 to 16.89 and indicating the presence of garnet-bearing lherzolite in the source mantle. The spidergrams and REEs patterns along with Zr/Nb, Ba/Nb, Rb/Nb ratios suggest that the rocks were generated by a mantle plume from partial melting of mixed enriched mantle sources (HIMU, EMI and EMII) similar to the rocks of the south Atlantic Ocean such as St. Helena (alkaline rocks) and Ascension rocks (tholeiitic rocks). The rocks were formed in a within-plate setting of the intra-continental rift type similar to other igneous rocks in the Benue Rift and are not related to any subduction event as previously suggested.

Efficient UV-emitting X-ray phosphors: octahedral Zr(PO 4) 6 luminescence centers in potassium hafnium-zirconium phosphates K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3

NASA Astrophysics Data System (ADS)

Torardi, C. C.; Miao, C. R.; Li, J.

2003-02-01

Potassium hafnium-zirconium phosphates, K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3, are broad-band UV-emitting phosphors. At room temperature, they have emission peak maxima at approximately 322 and 305 nm, respectively, under 30 kV peak molybdenum X-ray excitation. Both phosphors demonstrate luminescence efficiencies that make them up to ˜60% as bright as commercially available CaWO 4 Hi-Plus. The solid-state and flux synthesis conditions, and X-ray excited UV luminescence of these two phosphors are discussed. Even though the two compounds have different atomic structures, they contain zirconium in the same active luminescence environment as that found in highly efficient UV-emitting BaHf 1- xZr x(PO 4) 2. All the three materials have hafnium and zirconium in octahedral coordination via oxygen-atom corner sharing with six separate PO 4 tetrahedra. This octahedral Zr(PO 4) 6 moiety appears to be an important structural element for efficient X-ray excited luminescence, as are the edge-sharing octahedral TaO 6 chains for tantalate emission.

Production of nuclear grade zirconium: A review

NASA Astrophysics Data System (ADS)

Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

2015-11-01

Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium as a fuel cladding material. This paper provides an overview of the processes for nuclear grade zirconium production with emphasis on the methods of Zr-Hf separation. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The known pyrometallurgical Zr-Hf separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt-metal equilibrium. In the present paper, the available Zr-Hf separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

Prediction study of structural, elastic and electronic properties of FeMP (M = Ti, Zr, Hf) compounds

NASA Astrophysics Data System (ADS)

Tanto, A.; Chihi, T.; Ghebouli, M. A.; Reffas, M.; Fatmi, M.; Ghebouli, B.

2018-06-01

First principles calculations are applied in the study of FeMP (M = Ti, Zr, Hf) compounds. We investigate the structural, elastic, mechanical and electronic properties by combining first-principles calculations with the CASTEP approach. For ideal polycrystalline FeMP (M = Ti, Zr, Hf) the shear modulus, Young's modulus, Poisson's ratio, elastic anisotropy indexes, Pugh's criterion, elastic wave velocities and Debye temperature are also calculated from the single crystal elastic constants. The shear anisotropic factors and anisotropy are obtained from the single crystal elastic constants. The Debye temperature is calculated from the average elastic wave velocity obtained from shear and bulk modulus as well as the integration of elastic wave velocities in different directions of the single crystal.

Development and Processing of Nickel Aluminide-Carbide Alloys

NASA Technical Reports Server (NTRS)

Newport, Timothy Scott

1996-01-01

With the upper temperature limit of the Ni-based superalloys attained, a new class of materials is required. Intermetallics appear as likely candidates because of their attractive physical properties. With a relatively low density, high thermal conductivity, excellent oxidation resistance, high melting point, and simple crystal structure, nickel aluminide (NiAl) appears to be a potential candidate. However, NiAl is limited in structural applications due to its low room temperature fracture toughness and poor elevated temperature strength. One approach to improving these properties has been through the application of eutectic composites. Researchers have shown that containerless directional solidification of NiAl-based eutectic alloys can provide improvement in both the creep strength and fracture toughness. Although these systems have shown improvements in the mechanical properties, the presence of refractory metals increases the density significantly in some alloys. Lower density systems, such as the carbides, nitrides, and borides, may provide NiAl-based eutectic structure. With little or no information available on these systems, experimental investigation is required. The objective of this research was to locate and develop NiAl-carbide eutectic alloys. Exploratory arc-melts were performed in NiAl-refractory metal-C systems. Refractory metal systems investigated included Co, Cr, Fe, Hf, Mo, Nb, Ta, Ti, W, and Zr. Systems containing carbides with excellent stability (i.e.,HfC, NbC, TaC, TiC, and ZrC) produced large blocky cubic carbides in an NiAl matrix. The carbides appeared to have formed in the liquid state and were randomly distributed throughout the polycrystalline NiAl. The Co, Cr, Fe, Mo, and W systems contained NiAl dendrites with a two-phase interdendritic microconstituent present. Of these systems, the NiAl-Mo-C system had the most promising microstructure for in-situ composites. Three processing techniques were used to evaluate the NiAl-Mo-C system: arc-melting, slow cooling, and containerless directional solidification. Arc-melting provided a wide range of compositions in an economical and simple fashion. The slow cooled ingots provided larger ingots and slower cooling rates than arc-melting. Directional solidification was used to produce in-situ composites consisting of NiAl reinforced with molybdenum carbides.

Th-REE- and Nb-Ta-accessory minerals in post-collisional Ediacaran felsic rocks from the Katerina Ring Complex (S. Sinai, Egypt): An assessment for the fractionation of Y/Nb, Th/Nb, La/Nb and Ce/Pb in highly evolved A-type granites

NASA Astrophysics Data System (ADS)

Moreno, J. A.; Molina, J. F.; Bea, F.; Abu Anbar, M.; Montero, P.

2016-08-01

The relationships of Y/Nb, Th/Nb, La/Nb and Ce/Pb ratios in A-type felsic rocks from the Ediacaran Katerina Ring Complex, northernmost Arabian-Nubian Shield (ANS; S. Sinai, Egypt), are investigated in this work to understand their behavior during generation of highly evolved granitic magmas and to explore the nature of magma sources. Textural and compositional relationships of cognate Th-REE- and Nb-Ta-accessory minerals in Katerina felsic rocks show that chevkinite-group minerals (CGM), monazite, thorite, allanite and xenotime formed from residual liquids in quartz syenite porphyries, quartz monzonites and peralkaline granites, whereas in aluminous granites, allanite and monazite crystallized early, and thorite and columbite formed from residual liquids. Relationships of Y/Nb, Th/Nb, La/Nb and Ce/Pb ratios with Zr/Hf ratios in the aluminous granites and with Be abundances in the peralkaline granites suggest a decrease in La/Nb and Ce/Pb ratios in the former, and in Y/Nb and La/Nb ratios in the latter with crystallization progress. This contrasts with absence of systematic variations of Th/Nb and Ce/Pb ratios in the peralkaline compositions and of Y/Nb ratio in the aluminous ones. In this latter, Th/Nb ratio can present a significant decrease only in highly evolved compositions. An analysis of Y/Nb, Th/Nb, La/Nb and Ce/Pb relationships in worldwide OIB and subduction-related magmatic suites reveals that A-type felsic rocks with (Th/Nb)N < 1.3, (La/Nb)N < 1.3, and (Ce/Pb)N > 1 may have A1-type affinity, and those with (Th/Nb)N > 2, (La/Nb)N > 2, and (Ce/Pb)N < 1 tend to present A2-type affinity. The crystal fractionation of Th-LREE- and Nb-Ta-accessory minerals and mixing of components derived from the two granite groups may cause deviations from these compositional limits that can be evaluated using constraints imposed by Th/Nb-La/Nb, Ce/Pb-Th/Nb and Ce/Pb-La/Nb relationships in OIB and subduction-related magmatic suites. Three mantle sources might have been involved in the Ediacaran alkaline magmatism from northernmost ANS that are chemically similar to those of (1) OIB suites, (2) subduction-related magmatic suites, and (3) carbonatite-metasomatized peridotites. In addition, compositions characterized by (Y/Nb)N > 0.18, (Th/Nb)N > 2, (La/Nb)N > 2, (Ce/Pb)N < 1, and crustal-like Nb/Ta ratios may point to a significant contribution of crustal sources.

Electronic and optical response of zirconium sulphoselenides: Compton spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Kumar, Kishor; Bhatt, Samir; Jani, A. R.; Ahuja, B. L.

2015-12-01

We present the first-ever experimental Compton profiles (CPs) of ZrSSe2 and ZrS1.5Se1.5 using 100 mCi 241Am Compton spectrometer. To analyze the experimental momentum densities, we have computed for the first-time the CPs, energy bands and density of states using linear combination of atomic orbitals (LCAO) method. To model the exchange and correlation effects within LCAO approach, we have considered Hartree-Fock (HF), density functional theory (DFT) with revised functional of Perdew-Becke-Ernzerhof (PBEsol) and hybridization of HF and DFT. Going beyond computation of electronic properties using LCAO method, we have also derived electronic and optical properties using the modified Becke-Johnson (mBJ) potential within full potential linearized augmented plane wave (FP-LAPW) method. There is notable decrease in the energy band gap on replacing S by Se atoms in ZrSSe2 to obtain ZrS1.5Se1.5 composition, which is mainly attributed to readjustment of Zr-4d, S-3p and Se-4p states. It is seen that the CPs based on hybridization of HF and DFT show a better agreement with the experimental profiles than those based on individual HF and DFT-GGA-PBEsol schemes. The optical properties computed using FP-LAPW-mBJ method unambiguously depict feasibility of using both the sulphoselenides in photovoltaics and also utility of ZrS1.5Se1.5 in the field of non-linear optics.

Correlation between the oxide impedance and corrosion behavior of Zr-Nb-Sn-Fe-Cu alloys

NASA Astrophysics Data System (ADS)

Park, Sang-Yoon; Lee, Myung-Ho; Jeong, Yong-Hwan; Jung, Youn-Ho

2004-12-01

The correlation between the oxide impedance and corrosion behavior of two series of Zr-Nb-Sn-Fe-Cu alloys was evaluated. Corrosion tests were performed in a 70 ppm LiOH aqueous solution at 360°C for 300 days. The results of the corrosion tests revealed that the corrosion behavior of the alloys depended on the Nb and Sn content. The impedance characteristics for the pre- and post-transition oxide layers formed on the surface of the alloys were investigated in sulfuric acid at room temperature. From the results, a pertinent equivalent circuit model was preferably established, explaining the properties of double oxide layers. The impedance of the oxide layers correlated with the corrosion behavior; better corrosion resistance always showed higher electric resistance for the inner layers. It is thus concluded that a pertinent equivalent circuit model would be useful for evaluating the long-term corrosion behavior of Zr-Nb-Sn-Fe-Cu alloys.

In-situ trace element and Sr isotopic compositions of mantle xenoliths constrain two-stage metasomatism beneath the northern North China Craton

NASA Astrophysics Data System (ADS)

Wu, Dan; Liu, Yongsheng; Chen, Chunfei; Xu, Rong; Ducea, Mihai N.; Hu, Zhaochu; Zong, Keqing

2017-09-01

Subduction and collision are the key processes triggering geochemical refertilization of the lithospheric mantle beneath cratons. However, the way that the subducted plate influences the cratonic lithospheric mantle remains unclear. Here, in-situ major and trace-element and Sr isotopic compositions of peridotite and pyroxenite xenoliths carried by the Dongbahao Cenozoic basalts, located close to the northern margin of North China Craton (NCC), were examined to investigate the effects of the subducted Paleo-Asian oceanic plate on the lithospheric mantle of the NCC. Based on petrographic and geochemical features, peridotites were subdivided into two types recording two-stage metasomatism. Clinopyroxene (Cpx) in both types of peridotites show chemical zoning. In those peridotites we refer to as Type 1 peridotites, Cpx exhibit uniform convex-upward rare earth element (REE) patterns but core-rim variations in 87Sr/86Sr ratios (0.7065-0.7082 in the cores and 0.7043-0.7059 in the spongy rims), and have high (La/Yb)N ratios (> 1.12) (N means normalized to chondrite), relatively low Ti/Eu ratios (< 3756) and negative high field strength element (HFSE) (Nb, Ta, Zr, Hf and Ti) anomalies in the cores, indicating early-stage metasomatism by carbonatitic melts derived from the subducted sedimentary carbonate rocks. Cpx in the Type 2 peridotites have highly variable REE patterns (from light rare earth element (LREE)-depleted to LREE-enriched) and feature zoned Sr isotopic compositions contrasting to those in Type 1, i.e., increasing 87Sr/86Sr ratios from the cores (0.7020-0.7031) to the spongy rims (0.7035-0.7041). Accompanying variations of 87Sr/86Sr ratios, Cpx in both types of peridotites display increasing Nb/La ratios from the cores to the spongy rims. In addition, Cpx in the Type 2 peridotites show remarkably increased (La/Yb)N, Ca/Al, Sm/Hf and Zr/Hf ratios but decreased Ti/Eu and Ti/Nb ratios from the cores to the spongy rims. These features imply a later-stage metasomatism by CO2-rich silicate melts derived from carbonated eclogites. Pyroxenites were also classified into two types. Both types of pyroxenites show higher Ni content in Cpx and orthopyroxene than peridotites at the same Mg# (= 100 ∗ Mg/(Mg + Fe), atomic number) level. Their Cpx show high Ti/Eu, Ti/Sr ratios and similar 87Sr/86Sr ratios (0.7039-0.7055) to the Cpx spongy rims in peridotites, suggesting that pyroxenites originated from silicate melt-peridotite reactions in the later-stage metasomatism. These observations collectively indicate that the lithospheric mantle beneath the northern NCC presents evidence for two distinct mantle metasomatic events. We propose that both were caused by the subduction of the Paleo-Asian oceanic plate, which could have contributed significantly to the transformation of the lithospheric mantle beneath the northern NCC.

Atomic layer deposition of hafnium oxide: A detailed reaction mechanism from first principles

NASA Astrophysics Data System (ADS)

Widjaja, Yuniarto; Musgrave, Charles B.

2002-08-01

Atomic layer deposition (ALD) of hafnium oxide (HfO2) using HfCl4 and H2O as precursors is studied using density functional theory. The mechanism consists of two deposition half-reactions: (1) HfCl4 with Hf-OH sites, and (2) H2O with Hf-Cl sites. Both half-reactions exhibit stable intermediates with energies lower than those of the final products. We show that increasing the temperature reduces the stability of the complex. However, increasing temperature also increases the dissociation free-energy barrier, which in turn results in increased desorption of adsorbed precursors. Both half-reactions are qualitatively similar to the corresponding reactions of ZrO2 ALD using ZrCl4 and H2O.

HFSE systematics of rutile-bearing eclogites: New insights into subduction zone processes and implications for the earth’s HFSE budget

NASA Astrophysics Data System (ADS)

Schmidt, Alexander; Weyer, Stefan; John, Timm; Brey, Gerhard P.

2009-01-01

The depleted mantle and the continental crust are generally thought to balance the budget of refractory and lithophile elements of the Bulk Silicate Earth (BSE), resulting in complementary trace element patterns. However, the two high field strength elements (HFSE) niobium and tantalum appear to contradict this mass balance. All reservoirs of the silicate Earth exhibit subchondritic Nb/Ta ratios, possibly as a result of Nb depletion. In this study a series of nineteen orogenic MORB-type eclogites from different localities was analyzed to determine their HFSE concentrations and to contribute to the question of whether subducted oceanic crust could form a hidden reservoir to account for the mass imbalance of Nb/Ta between BSE and the chondritic reservoir. Concentrations of HFSE were analyzed with isotope dilution (ID) techniques. Additionally, LA-ICPMS analyses of clinopyroxene, garnet and rutile have been performed. Rutile is by far the major host for Nb and Ta in all analyzed eclogites. However, many rutiles revealed zoning in Nb/Ta ratios, with cores being higher than rims. Accordingly, in situ analyses of rutiles have to be evaluated carefully and rutile cores do not necessarily reflect a bulk rock Nb and Ta composition, although over 90% of these elements reside in rutile. The HFSE concentration data in bulk rocks show that the orogenic eclogites have subchondritic Nb/Ta ratios and near chondritic Zr/Hf ratios. The investigated eclogites show neither enrichment of Nb compared to similarly incompatible elements (e.g. La), nor fractionation of Nb/Ta ratios relative to MOR-basalts, the likely precursor of these rocks. This indicates that during the conversion of the oceanic crust to eclogites in most cases, (1) HFSE and REE have similar mobility on average, possibly because both element groups remain in the down going slab, and (2) no significant fractionation of Nb/Ta occurs in subducted oceanic crust. With an average Nb/Ta ratio of 14.2 ± 1.4 (2s.e.), the investigated eclogites cannot balance the differences between BSE and chondrite. Additionally, as their average Nb/Ta is indistinguishable from the Nb/Ta of MORB, they are also an unlikely candidate to balance the potentially small differences in Nb/Ta between the continental crust and the mantle.

Investigation of static properties of medical alloys Ti-(20-30)Nb-(10-13)Ta-5Zr

NASA Astrophysics Data System (ADS)

Sergienko, K. V.; Sevost’yanov, M. A.; Konushkin, S. V.; Nasakina, E. O.; Baikin, A. S.; Shatova, L. A.; Kolmakov, A. G.

2018-04-01

In the work, static properties of TiNbTaZr titanium alloy were carried out. The search for a NiTi alloy replacement is necessary for medical products to eliminate the negative effects of nickel on the body. Conclusions are drawn about the adequacy of the mechanical properties of the test alloy for use in stent implants.

Hydrogenation behavior of Ti-implanted Zr-1Nb alloy with TiN films deposited using filtered vacuum arc and magnetron sputtering

NASA Astrophysics Data System (ADS)

Kashkarov, E. B.; Nikitenkov, N. N.; Sutygina, A. N.; Bezmaternykh, A. O.; Kudiiarov, V. N.; Syrtanov, M. S.; Pryamushko, T. S.

2018-02-01

More than 60 years of operation of water-cooled reactors have shown that local or general critical hydrogen concentration is one of the basic limiting criteria of zirconium-based fuel element claddings. During the coolant radiolysis, released hydrogen penetrates and accumulates in zirconium alloys. Hydrogenation of zirconium alloys leads to degradation of their mechanical properties, hydride cracking and stress corrosion cracking. In this research the effect of titanium nitride (TiN) deposition on hydrogenation behavior of Ti-implanted Zr-1Nb alloy was described. Ti-implanted interlayer was fabricated by plasma immersion ion implantation (PIII) at the pulsed bias voltage of 1500 V to improve the adhesion of TiN and reduce hydrogen penetration into Zr-1Nb alloy. We conducted the comparative analysis on hydrogenation behavior of the Ti-implanted alloy with sputtered and evaporated TiN films by reactive dc magnetron sputtering (dcMS) and filtered cathodic vacuum arc deposition (FVAD), respectively. The crystalline structure and surface morphology were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The elemental distribution was analyzed using glow-discharge optical emission spectroscopy (GD-OES). Hydrogenation was performed from gas atmosphere at 350 °C and 2 atm hydrogen pressure. The results revealed that TiN films as well as Ti implantation significantly reduce hydrogen absorption rate of Zr-1Nb alloy. The best performance to reduce the rate of hydrogen absorption is Ti-implanted layer with evaporated TiN film. Morphology of the films impacted hydrogen permeation through TiN films: the denser film the lower hydrogen permeation. The Ti-implanted interface plays an important role of hydrogen accumulation layer for trapping the penetrated hydrogen. No deterioration of adhesive properties of TiN films on Zr-1Nb alloy with Ti-implanted interface occurs under high-temperature hydrogen exposure. Thus, the fabrication of Ti-implanted layer with dense TiN films can be an effective way to protect Zr-1Nb alloy from hydrogen embrittlement.

New Intermetallic Ternary Phosphide Chalcogenide AP2-xXx (A = Zr, Hf; X = S, Se) Superconductors with PbFCl-Type Crystal Structure

NASA Astrophysics Data System (ADS)

Kitô, Hijiri; Yanagi, Yousuke; Ishida, Shigeyuki; Oka, Kunihiko; Gotoh, Yoshito; Fujihisa, Hiroshi; Yoshida, Yoshiyuki; Iyo, Akira; Eisaki, Hiroshi

2014-07-01

We have synthesized a series of intermetallic ternary phosphide chalcogenide superconductors, AP2-xXx (A = Zr, Hf; X = S, Se), using the high-pressure synthesis technique. These materials have a PbFCl-type crystal structure (space group P4/nmm) when x is greater than 0.3. The superconducting transition temperature Tc changes systematically with x, yielding dome-like phase diagrams. The maximum Tc is achieved at approximately x = 0.7, at which point the Tc is 6.3 K for ZrP2-xSex (x = 0.75), 5.5 K for HfP2-xSex (x = 0.7), 5.0 K for ZrP2-xSx (x = 0.675), and 4.6 K for Hfp2-xSx (x = 0.5). They are typical type-II superconductors and the upper and lower critical fields are estimated to be 2.92 T at 0 K and 0.021 T at 2 K for ZrP2-xSex (x = 0.75), respectively.

The peculiar geochemical signatures of São Miguel (Azores) lavas: Metasomatised or recycled mantle sources?

NASA Astrophysics Data System (ADS)

Beier, Christoph; Stracke, Andreas; Haase, Karsten M.

2007-07-01

The island of São Miguel, Azores consists of four large volcanic systems that exhibit a large systematic intra-island Sr-Nd-Pb-Hf isotope and trace element variability. The westernmost Sete Cidades volcano has moderately enriched Sr-Nd-Pb-Hf isotope ratios. In contrast, lavas from the easternmost Nordeste volcano have unusually high Sr and Pb and low Nd and Hf isotope ratios suggesting a long-term evolution with high Rb/Sr, U/Pb, Th/Pb, Th/U and low Sm/Nd and Lu/Hf parent-daughter ratios. They have trace element concentrations similar to those of the HIMU islands, with the exception of notably higher alkali element (Cs, Rb, K, Ba) and Th concentrations. The time-integrated parent-daughter element evolution of both the Sete Cidades and Nordeste source matches the incompatibility sequence commonly observed during mantle melting and consequently suggests that the mantle source enrichment is caused by a basaltic melt, either as a metasomatic agent or as recycled oceanic crust. Our calculations show that a metasomatic model involving a small degree basaltic melt is able to explain the isotopic enrichment but, invariably, produces far too enriched trace element signatures. We therefore favour a simple recycling model. The trace element and isotopic signatures of the Sete Cidades lavas are consistent with the presence of ancient recycled oceanic crust that has experienced some Pb loss during sub-arc alteration. The coherent correlation of the parent-daughter ratios (e.g. Rb/Sr, Th/U, U/Pb) and incompatible element ratios (e.g. Nb/Zr, Ba/Rb, La/Nb) with the isotope ratios in lavas from the entire island suggest that the Sete Cidades and Nordeste source share a similar genetic origin. The more enriched trace element and isotopic variations of Nordeste can be reproduced by recycled oceanic crust in the Nordeste source that contains small amounts of evolved lavas (˜ 1-2%), possibly from a subducted seamount. The rare occurrence of enriched source signatures comparable to Nordeste may be taken as circumstantial evidence that stirring processes in the Earth's mantle are not able to homogenise material within the size of seamounts over timescales of mantle recycling.

Thermal Conductivity and Water Vapor Stability of Ceramic HfO2-Based Coating Materials

NASA Technical Reports Server (NTRS)

Zhu, Dong-Ming; Fox, Dennis S.; Bansal, Narottam P.; Miller, Robert A.

2004-01-01

HfO2-Y2O3 and La2Zr2O7 are candidate thermal/environmental barrier coating materials for gas turbine ceramic matrix composite (CMC) combustor liner applications because of their relatively low thermal conductivity and high temperature capability. In this paper, thermal conductivity and high temperature phase stability of plasma-sprayed coatings and/or hot-pressed HfO2-5mol%Y2O3, HfO2-15mol%Y2O3 and La2Zr2O7 were evaluated at temperatures up to 1700 C using a steady-state laser heat-flux technique. Sintering behavior of the plasma-sprayed coatings was determined by monitoring the thermal conductivity increases during a 20-hour test period at various temperatures. Durability and failure mechanisms of the HfO2-Y2O3 and La2Zr2O7 coatings on mullite/SiC Hexoloy or CMC substrates were investigated at 1650 C under thermal gradient cyclic conditions. Coating design and testing issues for the 1650 C thermal/environmental barrier coating applications will also be discussed.

Corrosion Protection of Copper Using Al2O3, TiO2, ZnO, HfO2, and ZrO2 Atomic Layer Deposition.

PubMed

Daubert, James S; Hill, Grant T; Gotsch, Hannah N; Gremaud, Antoine P; Ovental, Jennifer S; Williams, Philip S; Oldham, Christopher J; Parsons, Gregory N

2017-02-01

Atomic layer deposition (ALD) is a viable means to add corrosion protection to copper metal. Ultrathin films of Al 2 O 3 , TiO 2 , ZnO, HfO 2 , and ZrO 2 were deposited on copper metal using ALD, and their corrosion protection properties were measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). Analysis of ∼50 nm thick films of each metal oxide demonstrated low electrochemical porosity and provided enhanced corrosion protection from aqueous NaCl solution. The surface pretreatment and roughness was found to affect the extent of the corrosion protection. Films of Al 2 O 3 or HfO 2 provided the highest level of initial corrosion protection, but films of HfO 2 exhibited the best coating quality after extended exposure. This is the first reported instance of using ultrathin films of HfO 2 or ZrO 2 produced with ALD for corrosion protection, and both are promising materials for corrosion protection.

Novel Ti-Ta-Hf-Zr alloys with promising mechanical properties for prospective stent applications

PubMed Central

Lin, Jixing; Ozan, Sertan; Li, Yuncang; Ping, Dehai; Tong, Xian; Li, Guangyu; Wen, Cuie

2016-01-01

Titanium alloys are receiving increasing research interest for the development of metallic stent materials due to their excellent biocompatibility, corrosion resistance, non-magnetism and radiopacity. In this study, a new series of Ti-Ta-Hf-Zr (TTHZ) alloys including Ti-37Ta-26Hf-13Zr, Ti-40Ta-22Hf-11.7Zr and Ti-45Ta-18.4Hf-10Zr (wt.%) were designed using the d-electron theory combined with electron to atom ratio (e/a) and molybdenum equivalence (Moeq) approaches. The microstructure of the TTHZ alloys were investigated using optical microscopy, XRD, SEM and TEM and the mechanical properties were tested using a Vickers micro-indenter, compression and tensile testing machines. The cytocompatibility of the alloys was assessed using osteoblast-like cells in vitro. The as-cast TTHZ alloys consisted of primarily β and ω nanoparticles and their tensile strength, yield strength, Young’s modulus and elastic admissible strain were measured as being between 1000.7–1172.8 MPa, 1000.7–1132.2 MPa, 71.7–79.1 GPa and 1.32–1.58%, respectively. The compressive yield strength of the as-cast alloys ranged from 1137.0 to 1158.0 MPa. The TTHZ alloys exhibited excellent cytocompatibility as indicated by their high cell viability ratios, which were close to that of CP-Ti. The TTHZ alloys can be anticipated to be promising metallic stent materials by virtue of the unique combination of extraordinarily high elastic admissible strain, high mechanical strength and excellent biocompatibility. PMID:27897215

Effect of calcium pyrophosphate on microstructural evolution and in vitro biocompatibility of Ti-35Nb-7Zr composite by spark plasma sintering.

PubMed

Zhang, L; Tan, J; He, Z Y; Jiang, Y H

2018-09-01

β-type Ti-35Nb-7Zr alloy has attracted considerable attentions as a bone implant material. The alloy, however, has poor bioactivity, which difficult to form a strong osseointegration between the bone tissues. Combining Ti alloy with a bioactive and biodegradable ceramic has been of interest to researchers. But the large difference in physicochemical property of high-melting metal and ceramic elements would bring the manufacturing restriction. In this work, Ti-35Nb-7Zr-CPP composites were fabricated with mechanical alloy of Ti, Nb, Zr and Nano calcium pyrophosphate (CPP) powders mixture followed by spark plasma sintering (SPS) routes. The effect of CPP ceramic on microstructural evolution and in vitro biocompatibility were investigated. As the addition of CPP (10-30 wt%), ceramic elements spreading towards the matrix, the generated metal-ceramic bioactive phases CaTiO 3 are observed well consolidated with β-Ti matrix. With the CPP increasing, Ca and P atoms rapidly migrated to the β-Ti matrix to form granulated Ti 5 P 3 , which leads to the increasing porosity (10%-18%) in the composites. The results demonstrated that the favorable cell viability (the cell proliferation rates were higher than 100%) and growth inside the pores of the composites arise from the rough micro-porous surface and the release of bioactive metal-ceramic phase ions into the biological environment. The enhanced bioactivity and microstructural evolution behaviors of the Ti-35Nb-7Zr-CPP composites may provide a strategy for designing and fabricating multifunctional implants. Copyright © 2018 Elsevier B.V. All rights reserved.

Proton-irradiation induced defects in modified 310S steels characterized with positron annihilation spectroscopy and transmission electron microscopy

NASA Astrophysics Data System (ADS)

Zhang, Weiping; Shen, Zhenyu; Tang, Rui; Jin, Suoxue; Song, Yaoxiang; Long, Yunxiang; Wei, Yaxia; Zhou, Xiong; Chen, Cheng; Guo, Liping

2018-07-01

An effective method to improve the irradiation resistance of austenitic stainless steels is adding oversized solutes into steels. In this work, the irradiation resistances of two type of modified 310S steels, in one of which Zr was added and in another Nb, Ta, and W were added, were investigated by proton irradiations at 563 K. Irradiation induced vacancy-type defects was characterized with positron annihilation spectroscopy (PAS), while dislocation loops and bubbles whose size are greater than 1 nm are characterized with transmission electron microscopy (TEM). It is found that the relative S parameter ΔS/S extracted from PAS is more effective than S parameter in evaluating the quantity of vacancy-type defects. It was revealed from ΔS/S that more vacancy-type defects produced in (Nb, Ta, W)-added steels than that in Zr-added steels, and this trend became more obvious with the dose increasing. S-W curves reveal that proton irradiation induced two kinds of vacancy-type defects, i.e. vacancy clusters and proton-vacancy clusters. TEM observation shows that the density of small bubbles induced by proton in (Nb, Ta, W)-added steels is much higher than that in Zr-added steels. Both 1/3 <1 1 1> and 1/2 <1 1 0> dislocation loops were observed with TEM in all of the specimens. The mean size and number density of dislocation loops in (Nb, Ta, W)-added steels are slightly larger than that in Zr-added steels, and increased with increasing irradiation dose. Both PAS and TEM observations shows that irradiation damage in Zr-added steels is less serious than that (Nb, Ta, W)-added steels, and the possible mechanisms are discussed through the enhancement of point defect recombination by oversized solute atoms.

Bone bonding bioactivity of Ti metal and Ti-Zr-Nb-Ta alloys with Ca ions incorporated on their surfaces by simple chemical and heat treatments.

PubMed

Fukuda, A; Takemoto, M; Saito, T; Fujibayashi, S; Neo, M; Yamaguchi, S; Kizuki, T; Matsushita, T; Niinomi, M; Kokubo, T; Nakamura, T

2011-03-01

Ti15Zr4Nb4Ta and Ti29Nb13Ta4.6Zr, which do not contain the potentially cytotoxic elements V and Al, represent a new generation of alloys with improved corrosion resistance, mechanical properties, and cytocompatibility. Recently it has become possible for the apatite forming ability of these alloys to be ascertained by treatment with alkali, CaCl2, heat, and water (ACaHW). In order to confirm the actual in vivo bioactivity of commercially pure titanium (cp-Ti) and these alloys after subjecting them to ACaHW treatment at different temperatures, the bone bonding strength of implants made from these materials was evaluated. The failure load between implant and bone was measured for treated and untreated plates at 4, 8, 16, and 26 weeks after implantation in rabbit tibia. The untreated implants showed almost no bonding, whereas all treated implants showed successful bonding by 4 weeks, and the failure load subsequently increased with time. This suggests that a simple and economical ACaHW treatment could successfully be used to impart bone bonding bioactivity to Ti metal and Ti-Zr-Nb-Ta alloys in vivo. In particular, implants heat treated at 700 °C exhibited significantly greater bone bonding strength, as well as augmented in vitro apatite formation, in comparison with those treated at 600 °C. Thus, with this improved bioactive treatment process these advantageous Ti-Zr-Nb-Ta alloys can serve as useful candidates for orthopedic devices. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Diffusion Barrier Selection from Refractory Metals (Zr, Mo and Nb) via Interdiffusion Investigation for U-Mo RERTR Fuel Alloy

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

K. Huang; C. Kammerer; D. D. Keiser, Jr.

2014-04-01

U-Mo alloys are being developed as low enrichment monolithic fuel under the Reduced Enrichment for Research and Test Reactor (RERTR) Program. Diffusional interactions between the U-Mo fuel alloy and Al-alloy cladding within the monolithic fuel plate construct necessitate incorporation of a barrier layer. Fundamentally, a diffusion barrier candidate must have good thermal conductivity, high melting point, minimal metallurgical interaction, and good irradiation performance. Refractory metals, Zr, Mo, and Nb are considered based on their physical properties, and the diffusion behavior must be carefully examined first with U-Mo fuel alloy. Solid-to-solid U-10wt.%Mo vs. Mo, Zr, or Nb diffusion couples were assembledmore » and annealed at 600, 700, 800, 900 and 1000 degrees C for various times. The interdiffusion microstructures and chemical composition were examined via scanning electron microscopy and electron probe microanalysis, respectively. For all three systems, the growth rate of interdiffusion zone were calculated at 1000, 900 and 800 degrees C under the assumption of parabolic growth, and calculated for lower temperature of 700, 600 and 500 degrees C according to Arrhenius relationship. The growth rate was determined to be about 10 3 times slower for Zr, 10 5 times slower for Mo and 10 6 times slower for Nb, than the growth rates reported for the interaction between the U-Mo fuel alloy and pure Al or Al-Si cladding alloys. Zr, however was selected as the barrier metal due to a concern for thermo- mechanical behavior of UMo/Nb interface observed from diffusion couples, and for ductile-to-brittle transition of Mo near room temperature.« less

Distribution of chemical elements in soils and stream sediments in the area of abandoned Sb-As-Tl Allchar mine, Republic of Macedonia.

PubMed

Bačeva, Katerina; Stafilov, Trajče; Šajn, Robert; Tănăselia, Claudiu; Makreski, Petre

2014-08-01

The aim of this study was to investigate the distribution of some toxic elements in topsoil and subsoil, focusing on the identification of natural and anthropogenic element sources in the small region of rare As-Sb-Tl mineralization outcrop and abandoned mine Allchar known for the highest natural concentration of Tl in soil worldwide. The samples of soil and sediments after total digestion were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Factor analysis (FA) was used to identify and characterize element associations. Six associations of elements were determined by the method of multivariate statistics: Rb-Ta-K-Nb-Ga-Sn-Ba-Bi-Li-Be-(La-Eu)-Hf-Zr-Zn-In-Pd-Ag-Pt-Mg; Tl-As-Sb-Hg; Te-S-Ag-Pt-Al-Sc-(Gd-Lu)-Y; Fe-Cu-V-Ge-Co-In; Pd-Zr-Hf-W-Be and Ni-Mn-Co-Cr-Mg. The purpose of the assessment was to determine the nature and extent of potential contamination as well as to broadly assess possible impacts to human health and the environment. The results from the analysis of the collected samples in the vicinity of the mine revealed that As and Tl elements have the highest median values. Higher median values for Sb are obviously as a result of the past mining activities and as a result of area surface phenomena in the past. Copyright © 2014 Elsevier Inc. All rights reserved.

Interfacial Energy Transfer during Gamma Radiolysis of Water on the Surface of ZrO2 and Some Other Oxides

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

Petrik, Nikolay G.; Alexandrov, Alexandr B.; Vall, Andrey I.

Effect of oxide interface on 60Co gamma radiolysis of water molecules was studied. Based on the molecular hydrogen yield when compared with that from the radiolysis of pure gas-phase water, all tested oxides can be classified into three groups: (i) inhibitors - MnO2, Co3O4, CuO and Fe2O3; (ii) oxides with H2 yields, which are similar to or slightly greater than radiolysis of pure gas-phase water - MgO, CaO, SrO, BaO, ZnO, CdO, Cu2O, NiO, Cr2O3, Al2O3, CeO2, SiO2, TiO2, Nb2O5 and WO3; (iii) promoters - Ga2O3, Y2O3, La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Yb2O3, Er2O3, HfO2, and ZrO2. H2O radiolysis enhancementmore » for ZrO2 and other promoters is result of effective energy transfer at the oxide/water interface, presumably due to migration of excitons to the surface and their resonant coupling with the H2O adsorption complex. Plot''effective H2 yield vs. band-gap (Eg) energy'' shows a maximum near 5 eV.« less

Thermal Conductivity and Stability of HfO2-Y2O3 and La2Zr2O7 Evaluated for 1650 Deg C Thermal/Environmental Barrier Coating Applications

NASA Technical Reports Server (NTRS)

Zhu, Dong-Ming; Bansal, Narottam P.; Miller, Robert A.

2003-01-01

HfO2-Y2O3 and La2Zr2O7 are candidate thermal and environmental barrier coating (T/EBC) materials for gas turbine ceramic matrix composite (CMC) combustor applications because of their relatively low thermal conductivity and high temperature capability. In this paper, thermal conductivity and high temperature stability of hot-pressed and plasma sprayed specimens with representative partially-stabilized and fully-cubic HfO2-Y2O3 compositions and La2Zr2O7 were evaluated at temperatures up to 1700 C using a steady-state laser heat-flux technique. Sintering behavior of the plasmasprayed coatings was determined by monitoring the thermal conductivity increases during a 20-hour test period at various temperatures. Durability and failure mechanisms of the HfO2-Y2O3 and La2Zr2O7 coatings on mullite/SiC hexoloy or SiC/SiC CMC substrates were investigated at 1650 C under thermal gradient cyclic conditions. Coating design and testing issues for the 1650 C thermal/environmental barrier coating applications are also discussed.

Oxidation behavior of FeAl+Hf,Zr,B

NASA Technical Reports Server (NTRS)

Smialek, James L.; Doychak, Joseph

1988-01-01

The oxidation behavior of Fe-40Al-1Hf, Fe-40Al-1Hf-0.4B, and Fe-40Al-0.1Zr-0.4B (at. percent) alloys was characterized after 900, 1000, and 100 C exposures. Isothermal tests revealed parabolic kinetics after a period of transitional theta-alumina scale growth. The parabolic growth rates for the subsequent alpha-alumina scales were about five times higher than those for NiAl+0.1Zr alloys. The isothermally grown scales showed a propensity toward massive scale spallation due to both extensive rumpling from growth stresses and to an inner layer of HfO2. Cyclic oxidation for 200 1-hr cycles produced little degradation at 900 or 1000 C, but caused significant spallation at 1100 C in the form of small segments of the outer scale. The major difference in the cyclic oxidation of the three FeAl alloys was increased initial spallation for FeAl+Zr,B. Although these FeAl alloys showed many similarities to NiAl alloys, they were generally less oxidation resistant. It is believed that this resulted from nonoptimal levels of dopants and larger thermal expansion mismatch stresses.

Zr and Hf diffusion in rutile

NASA Astrophysics Data System (ADS)

Cherniak, D. J.; Manchester, J.; Watson, E. B.

2007-09-01

Chemical diffusion of Zr and Hf under anhydrous conditions has been measured in synthetic and natural rutile. The sources of diffusant used were hafnon or zircon powders or a hafnon-rutile mixture. Experiments were run in crimped Pt capsules in air, or in sealed silica glass capsules with solid buffers (to buffer at NNO or QFM). Rutherford Backscattering Spectrometry (RBS) was used to measure Zr and Hf diffusion profiles. From these measurements, the following Arrhenius relations were obtained: For Zr diffusion parallel to c, over the temperature range 750-1100 °C DZr¦c = 9.8 × 10 - 15 exp(- 170 ± 30 kJ mol - 1 /RT) m 2 s - 1 For Hf diffusion parallel to c, over the temperature range 800-1000 °C DHf¦c = 9.1 × 10 - 15 exp(- 169 ± 36 kJ mol - 1 /RT) m 2 s - 1 For Hf diffusion normal to c, over the temperature range 750-1050 °C DHf⊥c = 2.5 × 10 - 12 exp(- 227 ± 62 kJ mol - 1 /RT) m 2 s - 1 . Diffusivities for experiments buffered at QFM and NNO are similar to those run in air. Diffusivities in synthetic and natural rutile are likewise similar, indicating that these findings can be applied directly in determining Zr diffusivities in rutile in natural systems. These data indicate that rutile should be moderately retentive of Zr chemical signatures, with Zr diffusivities within an order of magnitude of those for Pb in rutile over most geologic conditions. When applied in evaluation of the relative robustness of the recently developed Zr-in-rutile geothermometer [T. Zack, R. Moraes, A. Kronz, Temperature dependence of Zr in rutile: empirical calibration of a rutile thermometer, Contributions to Mineralogy and Petrology 148 (2004) 471-488., E.B. Watson, D.A. Wark, J.B. Thomas, Crystallization thermometers for zircon and rutile, Contributions to Mineralogy and Petrology 151 (2006) 413-433.], these findings suggest that Zr concentrations in rutile will be somewhat more likely to be affected by later thermal disturbance than the geothermometer based on Zr concentrations in titanite [L. Hayden, E.B.Watson, D.A. Wark, A thermobarometer for sphene, Abstract, 16th V.M. Goldschmidt Conference (2006).], and much less resistant to diffusional alteration subsequent to crystallization than the Ti-in-zircon geothermometer [E.B. Watson, D.A. Wark, J.B. Thomas, Crystallization thermometers for zircon and rutile, Contributions to Mineralogy and Petrology 151 (2006) 413-433., E.B.Watson, T.M.Harrison, Zircon thermometer reveals minimum melting conditions on earliest Earth, Science 308 (2005) 841-844.].

The Effect of 24c-Site (A) Cation Substitution on the Tetragonal-Cubic Phase Transition in Li7-xLa3-xAxZr2O12 Garnet-Based Ceramic Electrolyte

DTIC Science & Technology

2013-01-01

with Al [16,20]. In KrogereVink notation, the relationships for Ta and Nb substitution for Zr are as follows [20,22,23]: Ta$ Zr ¼ V0Li (3) Nb ...garnet phase. < CeO2 precipitation at grain boundaries increases grain boundary resistance . < Super-valent cation substitution likely stabilizes the...Introduction Li-ion batteries have played a vital role in the development of current generation mobile devices, microelectronics and electric vehicles [1]. Due

Synthesis and characterisation of ionic liquids based on 1-butyl-3-methylimidazolium chloride and MCl(4), M = Hf and Zr.

PubMed

Campbell, Paul S; Santini, Catherine C; Bouchu, Denis; Fenet, Bernard; Rycerz, Leszek; Chauvin, Yves; Gaune-Escard, Marcelle; Bessada, Catherine; Rollet, Anne-Laure

2010-02-07

Dialkylimidazolium chlorometallate molten salts resulting from the combination of zirconium or hafnium tetrachloride and 1-butyl-3-methylimidazolium chloride, [C(1)C(4)Im][Cl], have been prepared with a molar fraction of MCl(4), R = n(MCl4)/n(MCl4) + n([C1C4IM][Cl]) equal to 0, 0.1, 0.2, 0.33, 0.5, 0.67. The structure and composition were studied by Differential Scanning Calorimetry (DSC), (35)Cl (263 to 333 K), (1)H and (13)C solid state and solution NMR spectroscopy, and electrospray ionisation (ESI) mass spectrometry. The primary anions of the MCl(4)-based ILs were [MCl(5)], [MCl(6)] and [M(2)Cl(9)], whose relative abundances varied with R. For R = 0.33, pure solid [C(1)C(4)Im](2)[MCl(6)], for both M = Zr and Hf are formed (m.p. = 366 and 385 K, respectively). For R = 0.67 pure ionic liquids [C(1)C(4)Im][M(2)Cl(9)] for both M = Zr and Hf are formed (T(g) = 224 and 220 K, respectively). The thermal dissociation has been attempted of [C(1)C(4)Im](2)[HfCl(6)], and [C(1)C(4)Im](2)[ZrCl(6)] monitored by (35)Cl and (91)Zr solid NMR (high temperature up to 551 K).

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

High performance p-type half-Heusler thermoelectric materials

NASA Astrophysics Data System (ADS)

Yu, Junjie; Xia, Kaiyang; Zhao, Xinbing; Zhu, Tiejun

2018-03-01

Half-Heusler compounds, which possess robust mechanical strength, good high temperature thermal stability and multifaceted physical properties, have been verified as a class of promising thermoelectric materials. During the last two decades, great progress has been made in half-Heusler thermoelectrics. In this review, we summarize some representative work of p-type half-Heusler materials, the thermoelectric performance of which has been remarkably enhanced in recent years. We introduce the features of the crystal and electronic structures of half-Heusler compounds, and successful strategies for optimizing electrical and thermal transport in the p-type RFeSb (R  =  V, Nb, Ta) and MCoSb (M  =  Ti, Zr, Hf) based systems, including band engineering, the formation of solid solutions and hierarchical phonon scattering. The outlook for future research directions of half-Heusler thermoelectrics is also presented.

For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

2002-01-01

A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

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

Palmieri, M.D.; Fritz, J.S.

Metal ions are determined by adding N-methylfurohydroxamic acid to an aqueous sample and then separating the metal chelates by direct injection onto a liquid chromatographic column. Separations on a C/sub 8/ silica column and a polystyrene-divinylbenzene column are compared, with better separations seen on the polymeric column. The complexes formed at low pH values are cationic and are separated by an ion pairing mechanism. Retention times and selectivity of the metal complexes can be varied by changing the pH. Several metal ions can be separated and quantified; separation conditions, linear calibration curve ranges, and detection limits are presented for Zr(IV),more » Hf(IV), Fe(III), Nb(V), Al(III), and Sb(III). Interferences due to the presence of other ions in solution are investigated. Finally, an antiperspirant sample is analyzed for zirconium by high-performance liquid chromatography.« less

Spin-Orbit Torque from a Magnetic Heterostructure of High-Entropy Alloy

NASA Astrophysics Data System (ADS)

Chen, Tian-Yue; Chuang, Tsao-Chi; Huang, Ssu-Yen; Yen, Hung-Wei; Pai, Chi-Feng

2017-10-01

High-entropy alloy (HEA) is a family of metallic materials with nearly equal partitions of five or more metals, which might possess mechanical and transport properties that are different from conventional binary or tertiary alloys. In this work, we demonstrate current-induced spin-orbit torque (SOT) magnetization switching in a Ta-Nb-Hf-Zr-Ti HEA-based magnetic heterostructure with perpendicular magnetic anisotropy. The maximum dampinglike SOT efficiency from this particular HEA-based magnetic heterostructure is further determined to be |ζDLHEA | ≈0.033 by hysteresis-loop-shift measurements, while that for the Ta control sample is |ζDLTa | ≈0.04 . Our results indicate that HEA-based magnetic heterostructures can serve as an alternative group of potential candidates for SOT device applications due to the possibility of tuning buffer-layer properties with more than two constituent elements.

Alumina forming iron base superalloy

DOEpatents

Yamamoto, Yukinori; Muralidharan, Govindarajan; Brady, Michael P.

2014-08-26

An austenitic stainless steel alloy, consists essentially of, in weight percent 2.5 to 4 Al; 25 to 35 Ni; 12 to 19 Cr; at least 1, up to 4 total of at least one element selected from the group consisting of Nb and Ta; 0.5 to 3 Ti; less than 0.5 V; 0.1 to 1 of at least on element selected from the group consisting of Zr and Hf; 0.03 to 0.2 C; 0.005 to 0.1 B; and base Fe. The weight percent Fe is greater than the weight percent Ni. The alloy forms an external continuous scale including alumina, and contains coherent precipitates of .gamma.'-Ni.sub.3Al, and a stable essentially single phase FCC austenitic matrix microstructure. The austenitic matrix is essentially delta-ferrite-free and essentially BCC-phase-free.

Chemical evidence for differentiation, evaporation and recondensation from silicate clasts in Gujba

NASA Astrophysics Data System (ADS)

Oulton, Jonathan; Humayun, Munir; Fedkin, Alexei; Grossman, Lawrence

2016-03-01

The silicate and metal clasts in CB chondrites have been inferred to form as condensates from an impact-generated vapor plume between a metal-rich body and a silicate body. A detailed study of the condensation of impact-generated vapor plumes showed that the range of CB silicate clast compositions could not be successfully explained without invoking a chemically differentiated target. Here, we report the most comprehensive elemental study yet performed on CB silicates with 32 silicate clasts from nine slices of Gujba analyzed by laser ablation inductively coupled plasma mass spectrometry for 53 elements. Like in other studies of CBs, the silicate clasts are either barred olivine (BO) or cryptocrystalline (CC) in texture. In major elements, the Gujba silicate clasts ranged from chondritic to refractory enriched. Refractory element abundances ranged from 2 to 10 × CI, with notable anomalies in Ba, Ce, Eu, and U abundances. The two most refractory-enriched BO clasts exhibited negative Ce anomalies and were depleted in U relative to Th, characteristic of volatilization residues, while other BO clasts and the CC clasts exhibited positive Ce anomalies with excess U (1-3 × CI), and Ba (1-6 × CI) anomalies indicating re-condensation of ultra-refractory element depleted vapor. The Rare Earth Elements (REE) also exhibit light REE (LREE) enrichment or depletion in several clasts with a range of (La/Sm)CI of 0.9-1.8. This variation in the LREE is essentially impossible to accomplish by processes involving vapor-liquid or vapor-solid exchange of REE, and appears to have been inherited from a differentiated target. The most distinctive evidence for inherited chemical differentiation is observed in highly refractory element (Sc, Zr, Nb, Hf, Ta, Th) systematics. The Gujba clasts exhibit fractionations in Nb/Ta that correlate positively with Zr/Hf and span the range known from lunar and Martian basalts, and exceed the range in Zr/Hf variation known from eucrites. Variations of highly incompatible refractory elements (e.g., Th) against less incompatible elements (e.g., Zr, Sr, Sc) are not chondritic, but exhibit distinctly higher Th abundances requiring a differentiated crust to be admixed with depleted mantle in ratios that are biased to higher crust/mantle ratios than in a chondritic body. The possibility that these variations are due to admixture of refractory inclusion-debris into normal chondritic matter is raised but cannot be definitively tested because existing ;bulk; analyses of CAIs carry artifacts of unrepresentative sampling. The inferences drawn from the compositions of Gujba silicate clasts, here, complement what has been inferred from the compositions of metallic clasts, but provide surprisingly detailed insight into the structure of the target. Evidence that metal and silicate in CB chondrites both formed from impact-generated vapor plumes, taken together with recent work on metallic nodules in E chondrites, and on ordinary chondrites, indicates that chondrule formation occurs by this mechanism quite widely. However, the nature of the impact on the CB body is quite different than the popular conceptions of impact of partially or wholly molten chondritic bodies and the younger (5 Ma) age of CB chondrules is consistent with origin in a disk with more evolved targets and impactors gravitationally perturbed by nascent planets.

Senary refractory high-entropy alloy HfNbTaTiVZr

DOE PAGES

Gao, Michael C.; Zhang, B.; Yang, S.; ...

2015-09-03

Discovery of new single-phase high-entropy alloys (HEAs) is important to understand HEA formation mechanisms. The present study reports computational design and experimental validation of a senary HEA, HfNbTaTiVZr, in a body-centered cubic structure. The phase diagrams and thermodynamic properties of this senary system were modeled using the CALPHAD method. Its atomic structure and diffusion constants were studied using ab initio molecular dynamics simulations. Here, the microstructure of the as-cast HfNbTaTiVZr alloy was studied using X-ray diffraction and scanning electron microscopy, and the microsegregation in the as-cast state was found to qualitatively agree with the solidification predictions from CALPHAD. Supported bymore » both simulation and experimental results, the HEA formation rules are discussed.« less

METHOD OF MAKING ALLOYS OF SECOND RARE EARTH SERIES METALS

DOEpatents

Baker, R.D.; Hayward, B.R.

1963-01-01

>This invention relates to a process for alloying the second rare earth series metals with Mo, Nb, or Zr. A halide of the rare earth metal is mixed with about 1 to 20 at.% of an oxide of Mo, Nb, or Zr. Iodine and an alkali or alkaline earth metal are added, and the resulting mixture is heated in an inert atmosphere to 350 deg C. (AEC)

Micro-abrasion-corrosion behaviour of a biomedical Ti-25Nb-3Mo-3Zr-2Sn alloy in simulated physiological fluid.

PubMed

Wang, Zhenguo; Li, Yan; Huang, Weijiu; Chen, Xiaoli; He, Haoran

2016-10-01

The micro-abrasion-corrosion behaviour of the biomedical Ti-25Nb-3Mo-3Zr-2Sn alloy in Hank׳s solution with protein has been investigated using electrochemical measurements, tribological tests and scanning electron microscope (SEM) observations. The potentiodynamic polarization tests showed that the corrosion potential (Ecorr) exhibits the maximum value at the abrasive concentration of 0.05gcm(-3) despite of the load level. The tribological results indicated that the total material loss of the Ti-25Nb-3Mo-3Zr-2Sn alloy during micro-abrasion increased with the increasing abrasive concentration at a certain applied load. When the abrasive concentration is no more than 0.15gcm(-3), the total material loss increases with increasing load, while the total material loss exhibits the maximum value at a moderate load in case of higher abrasive concentration levels. This was ascribed to the three-body or two-body micro-abrasion-corrosion at different abrasive concentration levels. The wastage map, abrasion mode map and synergy map associated with the applied load and the abrasive concentration were constructed to evaluate the micro-abrasion-corrosion behaviour of the Ti-25Nb-3Mo-3Zr-2Sn alloy in potential biomedical applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of thermomechanical processing on tensile and long-time creep behavior of Nb-1 percent Zr-0.1 percent C sheet

NASA Technical Reports Server (NTRS)

Titran, Robert H.; Uz, Mehmet

1994-01-01

Effects of thermomechanical processing on the mechanical properties of Nb-1 wt. percent Zr-0.1 wt. percent C, a candidate alloy for use in advanced space power systems, were investigated. Sheet bars were cold rolled into 1-mm thick sheets following single, double, or triple extrusion operations at 1900 K. All the creep and tensile specimens were given a two-step heat treatment 1 hr at 1755 K + 2 hr 1475 K prior to testing. Tensile properties were determined at 300 as well as at 1350 K. Microhardness measurements were made on cold rolled, heat treated, and crept samples. Creep tests were carried out at 1350 K and 34.5 MPa for times of about 10,000 to 19,000 hr. The results show that the number of extrusions had some effects on both the microhardness and tensile properties. However, the long-time creep behavior of the samples were comparable, and all were found to have adequate properties to meet the design requirements of advanced power systems regardless of thermomechanical history. The results are discussed in correlation with processing and microstructure, and further compared to the results obtained from the testing of Nb-1 wt. percent Zr and Nb-1 wt. percent Zr-0.06 wt. percent C alloys.

Biocompatible Materials Based on Self-Assembling Peptides on Ti25Nb10Zr Alloy: Molecular Structure and Organization Investigated by Synchrotron Radiation Induced Techniques

PubMed Central

Franchi, Stefano; Braic, Mariana; Skála, Tomáš; Nováková, Jaroslava; Zamuner, Annj

2018-01-01

In this work, we applied advanced Synchrotron Radiation (SR) induced techniques to the study of the chemisorption of the Self Assembling Peptide EAbuK16, i.e., H-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-NH2 that is able to spontaneously aggregate in anti-parallel β-sheet conformation, onto annealed Ti25Nb10Zr alloy surfaces. This synthetic amphiphilic oligopeptide is a good candidate to mimic extracellular matrix for bone prosthesis, since its β-sheets stack onto each other in a multilayer oriented nanostructure with internal pores of 5–200 nm size. To prepare the biomimetic material, Ti25Nb10Zr discs were treated with aqueous solutions of EAbuK16 at different pH values. Here we present the results achieved by performing SR-induced X-ray Photoelectron Spectroscopy (SR-XPS), angle-dependent Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, FESEM and AFM imaging on Ti25Nb10Zr discs after incubation with self-assembling peptide solution at five different pH values, selected deliberately to investigate the best conditions for peptide immobilization. PMID:29518968

Structural Analysis, Electrochemical Behavior, and Biocompatibility of Novel Quaternary Titanium Alloy with near β Structure

NASA Astrophysics Data System (ADS)

Popa, Monica; Calderon Moreno, Jose Maria; Vasilescu, Cora; Drob, Silviu Iulian; Neacsu, Elena Ionela; Coer, Andrej; Hmeljak, Julija; Zerjav, Gregor; Milošev, Ingrid

2014-06-01

This article analyses the microstructure, electrochemical behavior, and biocompatibility of a novel Ti-20Nb-10Zr-5Ta alloy with low Young's modulus (59 GPa) much closer to that of bone, between 10 and 30 GPa, than Ti and other Ti alloys used as implant biomaterial. XRD and SEM measurements revealed a near β crystalline microstructure containing β phase matrix and secondary α phase, with a typical grain size of around 200 μm. The corrosion behavior in neutral Ringer solution evidenced: self-passivation behavior characterizing a very resistant passive film; an easy passivation as a result of favorable influence of the alloying elements Nb, Zr, and Ta that participate with their passive oxides to the formation of the alloy passive film; low corrosion and ion release rates corresponding with very low toxicity. In MEM solution, the novel alloy demonstrated very high corrosion resistance and no susceptibility to localized corrosion. Biocompatibility was evaluated on in vitro human osteoblast-like and human immortalized pulmonary fibroblast cell (Wi-38) lines and the new Ti-20Nb-10Zr-5Ta alloy exhibited no cytotoxicity. The new Ti-20Nb-10Zr5Ta alloy is a promising material for implants due to combined properties of low elastic modulus, very low corrosion rate, and good biocompatibility.

Physical and chemical characteristics of baddeleyite (monoclinic zirconia) in natural environments: an overview and case study

NASA Astrophysics Data System (ADS)

Lumpkin, G. R.

1999-08-01

This report provides an overview of the natural occurrence, physical characteristics, and chemical composition of the mineral baddeleyite, ideally ZrO 2. A survey of the literature shows that baddeleyite is widespread in nature as a trace mineral, but has a rather limited composition of 87-99 wt% ZrO 2 with most of the remainder comprised of FeO, TiO 2 and HfO 2. Natural baddeleyite is invariably monoclinic due to the low concentrations of large cations such as Ca and Y. Although the concentrations of Th and U are low (generally <1500 ppm U and <100 ppm Th), the cumulative alpha-decay dose reaches 0.1-1.1 × 10 16 mg -1 for samples with ages of 1-2 × 10 9 yr. The available data also suggest that baddeleyite is highly durable in aqueous fluids. For nuclear waste form applications, both the radiation damage effects and durability of baddeleyite need to be examined in further detail. A case study of baddeleyite from the Jacupiranga carbonatite complex of southern Brazil provides some additional information on the crystal chemistry, durability and radiation damage effects of the mineral. This work shows that baddeleyite can incorporate up to 4.1 wt% Nb 2O 5 and 1.2 wt% Ta 2O 5. Incorporation of Nb 5+ and Ta 5+ is partially compensated by the incorporation of up to 0.4 wt% MgO and 0.3 wt% FeO in a charge balanced substitution of the form 3Zr↔2(Nb, Ta) + (Mg, Fe). Similar substitution mechanisms may enable the incorporation of Np 5+ in the ZrO 2 phases of fuel and waste matrices. The mineral is highly resistant to hydrothermal alteration which affected associated uranpyrochlore crystals. Many of the baddeleyite crystals are partially enclosed within the uranpyrochlore grains which contain 19-26 wt% UO 2 and 0.3-3.5 wt% ThO 2. These baddeleyite crystals received maximum alpha-particle doses of 3-4.5 × 10 16 mg -1 within 10 μm of the uranpyrochlore grain boundary, but the intense irradiation has not affected either the structural integrity or the aqueous durability of the mineral.

Petrogenesis of the Late Jurassic peraluminous biotite granites and muscovite-bearing granites in SE China: geochronological, elemental and Sr-Nd-O-Hf isotopic constraints

NASA Astrophysics Data System (ADS)

Jiang, Yao-Hui; Zhu, Shu-Qi

2017-12-01

Biotite granites and muscovite-bearing granites are dominant rock types of the widespread granites in SE China. However, their petrogenesis has been enigmatic. A combined study of zircon U-Pb dating and Lu-Hf isotopes, whole-rock element geochemistry and Sr-Nd-O isotopes was performed for three late Mesozoic granitic plutons (Xinfengjie, Jiangbei and Dabu) in central Jiangxi province, SE China. All the plutons are composed of biotite granites and muscovite-bearing granites that have been poorly investigated previously. The new data not only allow us to assess their sources and magma evolution processes, but also helps us to better understand the genetic link to the large-scale polymetallic mineralization in SE China. LA-ICP-MS zircon U-Pb dating shows that three plutons were emplaced in the Late Jurassic (159-148 Ma) and that the muscovite-bearing granites are almost contemporaneous with the biotite granites. The biotite granites have SiO2 contents of 70.3-74.4 wt% and are weakly to strongly peraluminous with ASI from 1.00 to 1.26, and show a general decrease in ASI with increasing SiO2. They have relatively high zircon saturation temperatures ( T Zr = 707-817 °C, most > 745 °C) and show a general decrease in T Zr with increasing SiO2. They have high initial 87Sr/86Sr ratios (0.7136 to 0.7166) and high δ18O values (9.1-12.8‰, most > 9.5‰) and clearly negative ɛ Nd (T) (- 9.5 to - 11.8) and ɛ Hf (T) (in situ zircon) (- 13.1 to - 13.5). The muscovite-bearing granites have high SiO2 contents (74.7-78.2 wt%). They are also weakly to strongly peraluminous with ASI of 1.04-1.18 but show a general increase in ASI with increasing SiO2. They have relatively low T Zr (671-764 °C, most < 745 °C) and also show a general decrease in T Zr with increasing SiO2. The muscovite-bearing granites have high Rb (up to 810 ppm) and high (K2O + Na2O)/CaO (up to 270), Rb/Sr (up to 42) and Rb/Ba (up to 30) as well as low K/Rb (< 150, down to 50), Zr/Hf (< 24, down to 11) and Nb/Ta (< 6, down to 2). They show similar Nd-O-Hf isotopic compositions to the biotite granites with ɛ Nd (T) of - 8.7 to - 12.0, δ18O of 8.7-13.0‰ (most > 9.5‰) and ɛ Hf (T) (in situ zircon) of - 11.3 to - 13.1. Geochemical data suggest the origin of the biotite granites and muscovite-bearing granites as follows: Partial melting of Precambrian metasedimentary rocks (mainly two-mica schist) in the lower crust at temperatures of ca. 820 °C generated the melts of the less felsic biotite granites. Such primary crustal melts underwent biotite-dominant fractionation crystallization, forming the felsic biotite granites. Progressive plagioclase-dominant fractionation crystallization from the evolved biotite granites produced the more felsic muscovite-bearing granites. Thus, the biotite granites belong to the S-type whereas the muscovite-bearing granites are highly fractionated S-type granites. We further suggest that during the formation of the muscovite-bearing granites the fractional crystallization was accompanied by fluid fractionation and most likely the addition of internally derived mineralizing fluids. That is why the large-scale polymetallic mineralization is closely related to the muscovite-bearing granites rather than biotite granites in SE China. This is important to further understand the source and origin of biotite granites and muscovite-bearing granites in SE China even worldwide.

Subduction-related cryptic metasomatism in fore-arc to nascent fore-arc Neoproterozoic mantle peridotites beneath the Eastern Desert of Egypt: mineral chemical and geochemical evidences

NASA Astrophysics Data System (ADS)

Hamdy, Mohamed; Salam Abu El-Ela, Abdel; Hassan, Adel; Kill, Youngwoo; Gamal El Dien, Hamed

2013-04-01

Mantle spinel peridotites beneath the Arabian Nubian Shield (ANS) in the Eastern Desert (ED) of Egypt were formed in arc stage in different tectonic setting. Thus they might subject to exchange with the crustal material derived from recycling subducting oceanic lithosphere. This caused metasomatism enriching the rocks in incompatible elements and forming non-residual minerals. Herein, we present mineral chemical and geochemical data of four ophiolitic mantle slice serpentinized peridotites (W. Mubarak, G. El-Maiyit, W. Um El Saneyat and W. Atalla) widely distributed in the ED. These rocks are highly serpentinized, except some samples from W. Mubarak and Um El-Saneyat, which contain primary olivine (Fo# = 90-92 mol %) and orthopyroxene (En# = 86-92 mol %) relics. They have harzburgite composition. Based on the Cr# and Mg# of the unaltered spinel cores, all rocks formed in oceanic mantle wedge in the fore-arc setting, except those from W. Atalla formed in nascent fore-arc. This implies that the polarity of the subduction during the arc stage was from the west to the east. These rocks are restites formed after partial melting between 16.58 in W. Atalla to 24 % in G-El Maiyit. Melt extraction occurred under oxidizing conditions in peridotites from W. Mubarak and W. Atalla and under reducing conditions in peridotites from G. El-Maiyit and Um El-Saneyat. Cryptic metasomatism in the studied mantle slice peridotites is evident. This includes enrichment in incompatible elements in minerals and whole rocks if compared with the primitive mantle (PM) composition and the trend of the depletion in melt. In opx the Mg# doesn't correlate with TiO2, CaO, MnO, NiO and Cr2O3concentrations. In addition, in serpentinites from W. Mubarak and W. Atalla, the TiO2spinel is positively correlated with the TiO2 whole-rock, proposing enrichment by the infiltration of Ti-rich melts, while in G. El- Maiyit and Um El-Saneyat serpentinites they are negatively correlated pointing to the reaction with the Ti-rich melts. All rocks are enriched LREE, FMEs and HFSEs. This took place mostly by different agents. As the H2O-rich liquid, which seems to have been produced from the subducting oceanic slab percolating peridotites, gradually loses trace elements, the HFSEs are fractionated from LILEs and REEs. This could explain the high ratios of (Nb/La)N and (Nb/Ba)N of some of the studied rocks. All the studied serpentinized mantle slices have subchonddritic to near chondritic ratios of Nb/Ta (< 13.8) and Zr/ Hf (< 36.09). It is suggested that Nb did not fractionate from Ta and Zr from Hf. There are might be silicate melts enriched the peridotites in Ta rather than Nb causing a much great decrease in the Nb/Ta especially serpentinites from W. Mubarak. This melt/fluid might have been derived from recycled subducted oceanic crust or from hot asthenosphere. Concentrations of U in all the studied samples (except for W. Mubarak serpentinites) are positively correlated with LILEs, Pb and Mo, indicating that the studied serpentinites were enriched in these elements from the same fluids, most probably derived from subducted oceanic lithosphere. Positive anomalies of Li (in W. Mubarak and G. El-Maiyit serpentinites), U (except for W. Mubarak serpentinites), Mo and Pb are characteristics of hydrothermally altered ocean-floor peridotites. High Sr/Nd ratios may be typical of the hydrous metasomatism caused by hydrous melt/fluid.

Intrusive rocks of the Wadi Hamad Area, North Eastern Desert, Egypt: Change of magma composition with maturity of Neoproterozoic continental island arc and the role of collisional plutonism in the differentiation of arc crust

NASA Astrophysics Data System (ADS)

Basta, Fawzy F.; Maurice, Ayman E.; Bakhit, Bottros R.; Azer, Mokhles K.; El-Sobky, Atef F.

2017-09-01

The igneous rocks of the Wadi Hamad area are exposed in the northernmost segment of the Arabian-Nubian Shield (ANS). These rocks represent part of crustal section of Neoproterozoic continental island arc which is intruded by late to post-collisional alkali feldspar granites. The subduction-related intrusives comprise earlier gabbro-diorites and later granodiorites-granites. Subduction setting of these intrusives is indicated by medium- to high-K calc-alkaline affinity, Ta-Nb troughs on the spider diagrams and pyroxene and biotite compositions similar to those crystallized from arc magmas. The collisional alkali feldspar granites have high-K highly fractionated calc-alkaline nature and their spider diagrams almost devoid of Ta-Nb troughs. The earlier subduction gabbro-diorites have lower alkalis, LREE, Nb, Zr and Hf values compared with the later subduction granodiorites-granites, which display more LILE-enriched spider diagrams with shallower Ta-Nb troughs, reflecting variation of magma composition with arc evolution. The later subduction granitoids were generated by lower degree of partial melting of mantle wedge and contain higher arc crustal component compared with the earlier subduction gabbro-diorites. The highly silicic alkali feldspar granites represent extensively evolved melts derived from partial melting of intermediate arc crustal sources during the collisional stage. Re-melting of arc crustal sources during the collisional stage results in geochemical differentiation of the continental arc crust and the silicic collisional plutonism drives the composition of its upper part towards that of mature continental crust.

Synthesis, integration, and characterization of metal oxide films as alternative gate dielectric materials

NASA Astrophysics Data System (ADS)

Lin, You-Sheng

ZrO2 and HfO2 were investigated in this study to replace SiO2 as the potential gate dielectric materials in metal-oxide-semiconductor field effect transistors. ZrO2 and HfO2 films were deposited on p-type Si (100) wafers by an atomic layer chemical vapor deposition (ALCVD) process using zirconium (IV) t-butoxide and hafnium (IV) t-butoxide as the metal precursors, respectively. Oxygen was used alternatively with these metal alkoxide precursors into the reactor with purging and evacuation in between. The as-deposited ZrO2 and HfO2 films were stoichiometric and uniform based on X-ray photoemission spectroscopy and ellipsometry measurements. X-ray diffraction analysis indicated that the deposited films were amorphous, however, the high-resolution transmission electron microscopy showed an interfacial layer formation on the silicon substrate. Time-of-flight secondary ion mass spectrometry and medium energy ion scattering analysis showed significant intermixing between metal oxides and Si, indicating the formation of metal silicates, which were confirmed by their chemical etching resistance in HF solutions. The thermal stability of ZrO2 and HfO2 thin films on silicon was examined by monitoring their decomposition temperatures in ultra-high vacuum, using in-situ synchrotron radiation ultra-violet photoemission spectroscopy. The as-deposited ZrO2 and HfO2 thin films were thermally stable up to 880°C and 950°C in vacuum, respectively. The highest achieveable dielectric constants of as-deposited ZrO 2 and HfO2 were 21 and 24, respectively, which were slightly lower than the reported dielectric constants of bulk ZrO2 and HfO 2. These slight reductions in dielectric constants were attributed to the formation of the interfacial metal silicate layers. Very small hysteresis and interface state density were observed for both metal oxide films. Their leakage currents were a few orders of magnitude lower than that of SiO 2 at the same equivalent oxide thickness. NMOSFETs were also fabricated with the as-deposited metal oxide films, and reasonable ID-V D and IG-VG results were obtained. The electron mobilities were high from devices built using a plasma etching process to pattern the metal oxide films. However, they can be degraded if an HF wet etching process was used due to the large contact resistences. Upon oxygen annealing, the formation of SiOx at the interface improved the thermal stability of the as-deposited metal oxide films, however, lower overall dielectric constant and higher leakage current were observed. Upon ammonia annealing, the formation of SiOxNy improved not only the thermal stability but also reduced the leakage current. However, the overall dielectric constant of the film was still reduced due to the formation of the additional interfacial layer.

Electrochemical characterization of pulsed layer deposited hydroxyapatite-zirconia layers on Ti-21Nb-15Ta-6Zr alloy for biomedical application

NASA Astrophysics Data System (ADS)

Izquierdo, Javier; Bolat, Georgiana; Cimpoesu, Nicanor; Trinca, Lucia Carmen; Mareci, Daniel; Souto, Ricardo Manuel

2016-11-01

A new titanium base Ti-21Nb-15Ta-6Zr alloy covered with hydroxyapatite-zirconia (HA-ZrO2) by pulsed laser deposition (PLD) technique was characterized regarding its corrosion resistance in simulated physiological Ringer's solution at 37 °C. For the sake of comparison, Ti-6Al-4V standard implant alloy, with and without hydroxyapatite-zirconia coating, was also characterized. Multiscale electrochemical analysis using both conventional averaging electrochemical techniques, namely electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization, and spatially-resolved microelectrochemical techniques (scanning electrochemical microscopy, SECM) were used to investigate the electrochemical behaviour of the materials. In addition, scanning electron microscopy evidenced that no relevant surface morphology changes occurred on the materials upon immersion in the simulated physiological solution, despite variations in their electrochemical behaviour. Although uncoated metals appear to show better performances during conventional corrosion tests, the response is still quite similar for the HA-ZrO2 coated materials while providing superior resistance towards electron transfer due to the formation of a more dense film on the surface, thus effectively behaving as a passive material. It is believed corrosion of the HA-ZrO2 coated Ti-21Nb-15Ta-6Zr alloy will have negligible effect upon biochemical and cellular events at the bone-implant interface and could facilitate osseointegration.

A STUDY OF THE STABILITY OF ZIRCONIUM AND HAFNIUM TETRAHALIDES ON HITTING A HOT SURFACE IN VACUUM (in Russian)

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

Tsirel'nikov, V.I.; Komissarova, L.N.; Spitsyn, V.I.

1962-09-01

The decomposition coefficients of the chlorides, bromides, and iodides of Zr and Hf were determined as a function of the temperature of a hot surface. The tetrahalides were carefully purified in an inert atmosphere of argon. The halide compound in a quartz ampoule was heated by a removable heater. The vapors passed through a capillary opening and struck a tungsten foil 0.5 mm thick and 12 to 15 mm wide. The Mo foil was heated electrically to control the surface temperature which was measured by an optical pyrometer. The tetrahalide decomposed according to the following reaction: Me(Hal)/sub 4/ yields Memore » + 2(Hal)/sub 2/. The lower halides dissociated completely to metal and free halides, since the temperature was >600 deg C. The Mo backing was dissolved in nitric acid, and the unsupported metal deposit of Zr or Hf was weighed, The decomposition coefficient was calcuweight of metal evaporated. Zrl/sub 4/ decomposed completely (100%) at 1500 deg C, while only 96% of the HfI/sub 4/ was decomposed at this temperature. The ZrBr/sub 4/ and HfBr/sub 4/ were decomposed by 68 and 61% respectively. The ZrCl/sub 4/ and HfCl/sub 4/ were stable at l500 deg C (5% of the ZrCl/sub 4/ was decomposed at l500 deg C). In all cases, the hafnium halide was more stable than the zirconium halide, especially in the case of the iodides. The decomposition was directly proportional to the temperature of the molybdenum target. (TTT)« less

High strength Sn-Mo-Nb-Zr alloy tubes and method of making same

DOEpatents

Cheadle, Brian A.

1977-01-01

Tubes for use in nuclear reactors fabricated from a quaternary alloy comprising 2.5-4.0 wt% Sn, 0.5-1.5 wt% Mo, 0.5-1.5 wt% Nb, balance essentially Zr. The tubes are fabricated by a process of hot extrusion, heat treatment, cold working to size and age hardening, so as to produce a microstructure comprising elongated .alpha. grains with an acicular transformed .beta. grain boundary phase.

Effects of shot-peening and atmospheric-pressure plasma on aesthetic improvement of Ti-Nb-Ta-Zr alloy for dental applications

NASA Astrophysics Data System (ADS)

Miura-Fujiwara, Eri; Suzuki, Yuu; Ito, Michiko; Yamada, Motoko; Matsutake, Sinpei; Takashima, Seigo; Sato, Hisashi; Watanabe, Yoshimi

2018-01-01

Ti and Ti alloys are widely used for biomedical applications such as artificial joints and dental devices because of their good mechanical properties and biochemical compatibility. However, dental devices made of Ti and Ti alloys do not have the same color as teeth, so they are inferior to ceramics and polymers in terms of aesthetic properties. In a previous study, Ti-29Nb-13Ta-4.6Zr was coated with a white Ti oxide layer by heat treatment to improve its aesthetic properties. Shot-peening is a severe plastic deformation process and can introduce a large shear strain on the peened surface. In this study, the effects of shot-peening and atmospheric-pressure plasma on Ti-29Nb-13Ta-4.6Zr were investigated to form a white layer on the surface for dental applications.

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

Ahn, Sol; Thornburg, Nicholas E.; Li, Zhanyong

In this study by developing structurally well-defined, supported oxide catalysts remains a significant challenge. Here, we report the grafting of Nb(V) oxide sites onto the nodes of the Zr-based metal organic framework (MOF) NU-1000 as a stable, well-defined catalyst support. Nb(V) oxide was deposited with loadings up to 1.6 mmol/g via two post-synthetic methods: atomic layer deposition in a MOF (AIM), and solution-phase grafting in a MOF (SIM). Difference envelope density (DED) measurements indicated that the two synthetic methods resulted in different local structures of the Nb(V) ions within NU-1000. Despite their high Nb(V) loadings, which were equivalent to >60%more » surface coverage, nearly all Nb(V) sites of the MOF-supported catalysts were active sites for alkene epoxidation, as confirmed by phenylphosphonic acid titration. The MOF-supported catalysts were more selective than the control Nb-ZrO 2 catalyst for cyclohexene epoxidation with aqueous H 2O 2, and were far more active on a gravimetric basis.« less

Stable metal–organic framework-supported niobium catalysts

DOE PAGES

Ahn, Sol; Thornburg, Nicholas E.; Li, Zhanyong; ...

2016-10-31

In this study by developing structurally well-defined, supported oxide catalysts remains a significant challenge. Here, we report the grafting of Nb(V) oxide sites onto the nodes of the Zr-based metal organic framework (MOF) NU-1000 as a stable, well-defined catalyst support. Nb(V) oxide was deposited with loadings up to 1.6 mmol/g via two post-synthetic methods: atomic layer deposition in a MOF (AIM), and solution-phase grafting in a MOF (SIM). Difference envelope density (DED) measurements indicated that the two synthetic methods resulted in different local structures of the Nb(V) ions within NU-1000. Despite their high Nb(V) loadings, which were equivalent to >60%more » surface coverage, nearly all Nb(V) sites of the MOF-supported catalysts were active sites for alkene epoxidation, as confirmed by phenylphosphonic acid titration. The MOF-supported catalysts were more selective than the control Nb-ZrO 2 catalyst for cyclohexene epoxidation with aqueous H 2O 2, and were far more active on a gravimetric basis.« less

Ferroelectricity-induced resistive switching in Pb(Zr0.52Ti0.48)O3/Pr0.7Ca0.3MnO3/Nb-doped SrTiO3 epitaxial heterostructure

NASA Astrophysics Data System (ADS)

Md. Sadaf, Sharif; Mostafa Bourim, El; Liu, Xinjun; Hasan Choudhury, Sakeb; Kim, Dong-Wook; Hwang, Hyunsang

2012-03-01

We investigated the effect of a ferroelectric Pb(Zr0.52Ti0.48)O3 (PZT) thin film on the generation of resistive switching in a stacked Pr0.7Ca0.3MnO3 (PCMO)/Nb-doped SrTiO3 (Nb:STO) heterostructure forming a p-n junction. To promote the ferroelectric effect, the thin PZT active layer was deposited on an epitaxially grown p-type PCMO film on a lattice-matched n-type Nb:STO single crystal. It was concluded that the observed resistive switching behavior in the all-perovskite Pt/PZT/PCMO/Nb:STO heterostructure was related to the modulation of PCMO/Nb:STO p-n junction's depletion width, which was caused either by the PZT ferroelectric polarization field effect, the electrochemical drift of oxygen ions under an electric field, or both simultaneously.

Effect of Instant Cooked Giant Embryonic Rice on Body Fat Weight and Plasma Lipid Profile in High Fat-Fed Mice

PubMed Central

Chung, Soo Im; Kim, Tae Hyeong; Rico, Catherine W.; Kang, Mi Young

2014-01-01

The comparative effects of instant cooked rice made from giant embryo mutant or ordinary normal rice on body weight and lipid profile in high fat-fed mice were investigated. The animals were given experimental diets for seven weeks: normal control (NC), high fat (HF), and HF supplemented with instant normal white (HF-NW), normal brown (HF-NB), giant embryonic white (HF-GW), or giant embryonic brown (HF-GB) rice. The HF group showed markedly higher body weight, body fat, plasma and hepatic triglyceride and cholesterol concentrations, and atherogenic index relative to NC group. However, instant rice supplementation counteracted this high fat-induced hyperlipidemia through regulation of lipogenesis and adipokine production. The GB rice exhibited greater hypolipidemic and body fat-lowering effects than the GW or NB rice. These findings illustrate that the giant embryo mutant may be useful as functional biomaterial for the development of instant rice with strong preventive action against high fat diet-induced hyperlipidemia and obesity. PMID:24932656

Deformation Mechanisms in Tube Billets from Zr-1%Nb Alloy under Radial Forging

NASA Astrophysics Data System (ADS)

Perlovich, Yuriy; Isaenkova, Margarita; Fesenko, Vladimir; Krymskaya, Olga; Zavodchikov, Alexander

2011-05-01

Features of the deformation process by cold radial forging of tube billets from Zr-1%Nb alloy were reconstructed on the basis of X-ray data concerning their structure and texture. The cold radial forging intensifies grain fragmentation in the bulk of billet and increases significantly the latent hardening of potentially active slip systems, so that operation only of the single slip system becomes possible. As a result, in radially-forged billets unusual deformation and recrystallization textures arise. These textures differ from usual textures of α-Zr by the mutual inversion of crystallographic axes, aligned along the axis of tube.

Phase transition temperature in the Zr-rich corner of Zr-Nb-Sn-Fe alloys

NASA Astrophysics Data System (ADS)

Canay, M.; Danón, C. A.; Arias, D.

2000-08-01

The influence of small composition changes on the phase transformation temperature of Zr-1Nb-1Sn-0.2(0.7)Fe alloys was studied in the present work, by electrical resistivity measurements and metallographic techniques. For the alloy with 0.2 at.% Fe we have determined Tα↔α+β=741°C and Tα+β↔β=973°C, and for the 0.7 at.% Fe the transformation temperatures were T α↔α+β=712°C and T α+β↔β=961°C. We have verified that the addition of Sn stabilized the β phase.

Delta Niobium or Delta VICE?

NASA Astrophysics Data System (ADS)

Hofmann, A. W.

2006-12-01

Delta Niobium or Delta VICE? Niobium is one of a few chemical elements that can be used to discriminate between melts derived from upwelling mantle, represented by MORBs and OIBs, and those derived from subduction and continental crust environments. The Nb/U ratio was introduced because these two elements appear to partition nearly identically in upwelling environments, but very differently (from one another) in subduction and continental environments (Hofmann et al., 1986). Fitton et al. (1997, 2003) have taken a radically different approach, using log(Nb/Y)-log(Zr/Y) correlations that appear to discriminate between MORB and OIB (or plume) environments. MORB correlations are parallel to, and at lower Nb/Y ratios than, Iceland basalt correlations. This is expressed by a discrimination parameter defined as Delta Nb = 1.74 + log(Nb/Y) - 1.92 log(Zr/Y). N-MORB have negative Delta-Nb values, whereas Iceland and other OIBs have positive values. Fitton et al. interpret this in terms of a niobium deficiency in MORB that is balanced by a Nb excess in OIBs. This interpretation conflicts with evidence based on Nb/U ratios (Hofmann et al., 1986), that MORB and OIB are parts of a common reservoir, which is different from, and complementary to, the continental crust. Both parts of this MORB-OIB reservoir are characterized by higher-than-primitive Nb/U and Nb/Th ratios, whereas continental crust has dramatically lower Nb/U and Nb/Th ratios. The use of VICE/MICE (very-incompatible- element to moderately-incompatible-element) ratios, such as Nb/Y, obscures this. The significance of the VICE/MICE plot becomes clear if one replaces Nb by other VICEs in the log(Nb/Y)-log(Zr/Y) plot. This shows that any of these VICEs yield similar topologies as Nb/Y. Thus for a given Zr/Y ratio, depleted MORB have consistently lower Ba/Y, Th/Y, and La/Y ratios than do Iceland basalts, even the most incompatible-element- depleted Iceland picrites. This is caused by a less extreme depletion of Icelandic picrites (and tholeiites) in VICEs relative to Y, causing their spidergram patterns to be flatter than those of depleted MORB, which "drop off" more steeply. The important point is that there is no special Nb effect. The difference between Iceland-style and MORB-style depletion might therefore be called "Delta VICE" rather than "Delta Niobium." This assessment of Nb geochemistry is confirmed by new compilations for several MORB and OIB suites, which shows that in some of these suites, Nb and Th yield the most uniform ratios, whereas Nb/U is more uniform in others (including Iceland). Similarly, Ta is similar to Nb in some suites, whereas it is slightly more compatible than Nb in others. These slight regional differences are of minor consequence in the present context. The cause of the greater depletion in VICEs relative to MICEs in N-MORB compared with the most depleted Icelandic is most likely related to the roles of garnet and clinopyroxene during source depletion processes.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Nanostructured microtubes based on TiO2 doped by Zr and Hf oxides with the anatase structure

NASA Astrophysics Data System (ADS)

Zheleznov, VV; Voit, EI; Sushkov, YV; Sarin, SA; Kuryavyi, VG; Opra, DP; Gnedenkov, SV; Sinebryukhov, SL; Sokolov, AA

2016-01-01

The nanostructured microtubes based on TiO2 have been prepared on the carbon fiber template using the sol-gel method. The microtubes consist of nanoparticles of metal oxides: TiO2/ZrO2 and TiO2/HfO2. The dependence of microtubes morphology and nanoparticles structure on the synthesis conditions has been studied using the methods of SEM, SAXS, and Raman spectroscopy. It has been demonstrated that at the stoichiometric ratio of up to 0.04 for Zr/Ti and up to 0.06 for Hf/Ti microtubes consist of uniform nanoparticles with the anatase structure. Along with further increase of the dopants content in the microtubes composition, nanoparticles acquire the core-shell structure. It has been suggested that nanoparticles have a core composed of the solid solutions Ti1-xZrxO2 or Ti1-xHfxO2 and a shell consisting of zirconium or hafnium titanate. The fabricated Zr- and Hf-doped TiO2 materials were investigated in view of their possible use as anode materials for Li-ion batteries. Charge- discharge measurements showed that the doped samples manifested significantly higher reversibility in comparison with the undoped TiO2. The method opens new prospects in synthesis of nanostructured materials for Li-ion batteries application.

Fabrication and Characterization of Nanoporous Niobia, and Nanotubular Tantala, Titania and Zirconia via Anodization

PubMed Central

Minagar, Sepideh; Berndt, Christopher C.; Wen, Cuie

2015-01-01

Valve metals such as titanium (Ti), zirconium (Zr), niobium (Nb) and tantalum (Ta) that confer a stable oxide layer on their surfaces are commonly used as implant materials or alloying elements for titanium-based implants, due to their exceptional high corrosion resistance and excellent biocompatibility. The aim of this study was to investigate the bioactivity of the nanostructures of tantala (Ta2O5), niobia (Nb2O5), zirconia (ZrO2) and titania (TiO2) in accordance to their roughness and wettability. Therefore, four kinds of metal oxide nanoporous and nanotubular Ta2O5, Nb2O5, ZrO2 and TiO2 were fabricated via anodization. The nanosize distribution, morphology and the physical and chemical properties of the nanolayers and their surface energies and bioactivities were investigated using SEM-EDS, X-ray diffraction (XRD) analysis and 3D profilometer. It was found that the nanoporous Ta2O5 exhibited an irregular porous structure, high roughness and high surface energy as compared to bare tantalum metal; and exhibited the most superior bioactivity after annealing among the four kinds of nanoporous structures. The nanoporous Nb2O5 showed a uniform porous structure and low roughness, but no bioactivity before annealing. Overall, the nanoporous and nanotubular layers of Ta2O5, Nb2O5, ZrO2 and TiO2 demonstrated promising potential for enhanced bioactivity to improve their biomedical application alone or to improve the usage in other biocompatible metal implants. PMID:25837724

Electrochemical Behavior of Biomedical Titanium Alloys Coated with Diamond Carbon in Hanks' Solution

NASA Astrophysics Data System (ADS)

Gnanavel, S.; Ponnusamy, S.; Mohan, L.; Radhika, R.; Muthamizhchelvan, C.; Ramasubramanian, K.

2018-03-01

Biomedical implants in the knee and hip are frequent failures because of corrosion and stress on the joints. To solve this important problem, metal implants can be coated with diamond carbon, and this coating plays a critical role in providing an increased resistance to implants toward corrosion. In this study, we have employed diamond carbon coating over Ti-6Al-4V and Ti-13Nb-13Zr alloys using hot filament chemical vapor deposition method which is well-established coating process that significantly improves the resistance toward corrosion, wears and hardness. The diamond carbon-coated Ti-13Nb-13Zr alloy showed an increased microhardness in the range of 850 HV. Electrochemical impedance spectroscopy and polarization studies in SBF solution (simulated body fluid solution) were carried out to understand the in vitro behavior of uncoated as well as coated titanium alloys. The experimental results showed that the corrosion resistance of Ti-13Nb-13Zr alloy is relatively higher when compared with diamond carbon-coated Ti-6Al-4V alloys due to the presence of β phase in the Ti-13Nb-13Zr alloy. Electrochemical impedance results showed that the diamond carbon-coated alloys behave as an ideal capacitor in the body fluid solution. Moreover, the stability in mechanical properties during the corrosion process was maintained for diamond carbon-coated titanium alloys.

Comparison of metal release from various metallic biomaterials in vitro.

PubMed

Okazaki, Yoshimitsu; Gotoh, Emiko

2005-01-01

To investigate the metal release of each base and alloying elements in vitro, SUS316L stainless steel, Co-Cr-Mo casting alloy, commercially pure Ti grade 2, and Ti-6Al-4V, V-free Ti-6Al-7Nb and Ti-15Zr-4Nb-4Ta alloys were immersed in various solutions, namely, alpha-medium, PBS(-), calf serum, 0.9% NaCl, artificial saliva, 1.2 mass% L-cysteine, 1 mass% lactic acid and 0.01 mass% HCl for 7d. The difference in the quantity of Co released from the Co-Cr-Mo casting alloy was relatively small in all the solutions. The quantities of Ti released into alpha-medium, PBS(-), calf serum, 0.9% NaCl and artificial saliva were much lower than those released into 1.2% L-cysteine, 1% lactic acid and 0.01% HCl. The quantity of Fe released from SUS316L stainless steel decreased linearly with increasing pH. On the other hand, the quantity of Ti released from Ti materials increased with decreasing pH, and it markedly attenuated at pHs of approximately 4 and higher. The quantity of Ni released from stainless steel gradually decreased with increasing pH. The quantities of Al released from the Ti-6Al-4V and Ti-6Al-7Nb alloys gradually decreased with increasing pH. A small V release was observed in calf serum, PBS(-), artificial saliva, 1% lactic acid, 1.2% l-cysteine and 0.01% HCl. The quantity of Ti released from the Ti-15Zr-4Nb-4Ta alloy was smaller than those released from the Ti-6Al-4V and Ti-6Al-7Nb alloys in all the solutions. In particular, it was approximately 30% or smaller in 1% lactic acid, 1.2% L-cysteine and 0.01% HCl. The quantity of (Zr + Nb + Ta) released was also considerably lower than that of (Al + Nb) or (Al + V) released. Therefore, the Ti-15Zr-4Nb-4Ta alloy with its low metal release in vitro is considered advantageous for long-term implants. Copyright 2004 Elsevier Ltd.

A chilled margin of komatiite and Mg-rich basaltic andesite in the western Bushveld Complex, South Africa

NASA Astrophysics Data System (ADS)

Maier, W. D.; Barnes, S.-J.; Karykowski, B. T.

2016-06-01

A chill sequence at the base of the Lower Zone of the western Bushveld Complex at Union Section, South Africa, contains aphanitic Mg-rich basaltic andesite and spinifex-textured komatiite. The basaltic andesite has an average composition of 15.2 % MgO, 52.8 % SiO2, 1205 ppm Cr, and 361 ppm Ni, whereas the komatiite has 18.7 % MgO, 1515 ppm Cr, and 410 ppm Ni. Both rock types have very low concentrations of immobile incompatible elements (0.14-0.72 ppm Nb, 7-31 ppm Zr, 0.34-0.69 ppm Th, 0.23-0.27 wt% TiO2), but high PGE contents (19-23 ppb Pt, 15-16 ppb Pd) and Pt/Pd ratios (Pt/Pd 1.4). Strontium and S isotopes show enriched signatures relative to most other Lower Zone rocks. The rocks could represent a ~20 % partial melt of subcontinental lithospheric mantle. This would match the PGE content of the rocks. However, this model is inconsistent with the high SiO2, Fe, and Na2O contents and, in particular, the low K2O, Zr, Hf, Nb, Ta, Th, LREE, Rb, and Ba contents of the rocks. Alternatively, the chills could represent a komatiitic magma derived from the asthenosphere that underwent assimilation of the quartzitic floor accompanied by crystallization of olivine and chromite. This model is consistent with the lithophile elements and the elevated Sr and S isotopic signatures of the rocks. However, in order to account for the high Pt and Pd contents of the magma, the mantle must have been twice as rich in PGE as the current estimate for PUM, possibly due to a component of incompletely equilibrated late veneer.

Band Structures and Transport Properties of High-Performance Half-Heusler Thermoelectric Materials by First Principles.

PubMed

Fang, Teng; Zhao, Xinbing; Zhu, Tiejun

2018-05-19

Half-Heusler (HH) compounds, with a valence electron count of 8 or 18, have gained popularity as promising high-temperature thermoelectric (TE) materials due to their excellent electrical properties, robust mechanical capabilities, and good high-temperature thermal stability. With the help of first-principles calculations, great progress has been made in half-Heusler thermoelectric materials. In this review, we summarize some representative theoretical work on band structures and transport properties of HH compounds. We introduce how basic band-structure calculations are used to investigate the atomic disorder in n-type M NiSb ( M = Ti, Zr, Hf) compounds and guide the band engineering to enhance TE performance in p-type Fe R Sb ( R = V, Nb) based systems. The calculations on electrical transport properties, especially the scattering time, and lattice thermal conductivities are also demonstrated. The outlook for future research directions of first-principles calculations on HH TE materials is also discussed.

Robust zero resistance in a superconducting high-entropy alloy at pressures up to 190 GPa

NASA Astrophysics Data System (ADS)

Guo, Jing; Wang, Honghong; von Rohr, Fabian; Wang, Zhe; Cai, Shu; Zhou, Yazhou; Yang, Ke; Li, Aiguo; Jiang, Sheng; Wu, Qi; Cava, Robert J.; Sun, Liling

2017-12-01

We report the observation of extraordinarily robust zero-resistance superconductivity in the pressurized (TaNb)0.67(HfZrTi)0.33 high-entropy alloy--a material with a body-centered-cubic crystal structure made from five randomly distributed transition-metal elements. The transition to superconductivity (TC) increases from an initial temperature of 7.7 K at ambient pressure to 10 K at ˜60 GPa, and then slowly decreases to 9 K by 190.6 GPa, a pressure that falls within that of the outer core of the earth. We infer that the continuous existence of the zero-resistance superconductivity from 1 atm up to such a high pressure requires a special combination of electronic and mechanical characteristics. This high-entropy alloy superconductor thus may have a bright future for applications under extreme conditions, and also poses a challenge for understanding the underlying quantum physics.

Nanoamorphous carbon-based photonic crystal infrared emitters

DOEpatents

Norwood, Robert A [Tucson, AZ; Skotheim, Terje [Tucson, AZ

2011-12-13

Provided is a tunable radiation emitting structure comprising: a nanoamorphous carbon structure having a plurality of relief features provided in a periodic spatial configuration, wherein the relief features are separated from each other by adjacent recessed features, and wherein the nanoamorphous carbon comprises a total of from 0 to 60 atomic percent of one or more dopants of the dopant group consisting of: transition metals, lanthanoids, electro-conductive carbides, silicides and nitrides. In one embodiment, a dopant is selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La and other lanthanides, Hf, Ta, W, Rh, Os, Ir, Pt, Au, and Hg. In one embodiment, a dopant is selected from the group consisting of: electro-conductive carbides (like Mo.sub.2C), silicides (like MoSi.sub.2) and nitrides (like TiN).

Band Structures and Transport Properties of High-Performance Half-Heusler Thermoelectric Materials by First Principles

PubMed Central

Fang, Teng; Zhao, Xinbing

2018-01-01

Half-Heusler (HH) compounds, with a valence electron count of 8 or 18, have gained popularity as promising high-temperature thermoelectric (TE) materials due to their excellent electrical properties, robust mechanical capabilities, and good high-temperature thermal stability. With the help of first-principles calculations, great progress has been made in half-Heusler thermoelectric materials. In this review, we summarize some representative theoretical work on band structures and transport properties of HH compounds. We introduce how basic band-structure calculations are used to investigate the atomic disorder in n-type MNiSb (M = Ti, Zr, Hf) compounds and guide the band engineering to enhance TE performance in p-type FeRSb (R = V, Nb) based systems. The calculations on electrical transport properties, especially the scattering time, and lattice thermal conductivities are also demonstrated. The outlook for future research directions of first-principles calculations on HH TE materials is also discussed. PMID:29783759

Robust zero resistance in a superconducting high-entropy alloy at pressures up to 190 GPa

PubMed Central

Guo, Jing; Wang, Honghong; von Rohr, Fabian; Wang, Zhe; Cai, Shu; Zhou, Yazhou; Yang, Ke; Li, Aiguo; Jiang, Sheng; Wu, Qi; Cava, Robert J.; Sun, Liling

2017-01-01

We report the observation of extraordinarily robust zero-resistance superconductivity in the pressurized (TaNb)0.67(HfZrTi)0.33 high-entropy alloy––a material with a body-centered-cubic crystal structure made from five randomly distributed transition-metal elements. The transition to superconductivity (TC) increases from an initial temperature of 7.7 K at ambient pressure to 10 K at ∼60 GPa, and then slowly decreases to 9 K by 190.6 GPa, a pressure that falls within that of the outer core of the earth. We infer that the continuous existence of the zero-resistance superconductivity from 1 atm up to such a high pressure requires a special combination of electronic and mechanical characteristics. This high-entropy alloy superconductor thus may have a bright future for applications under extreme conditions, and also poses a challenge for understanding the underlying quantum physics. PMID:29183981

Band gap tuning in transition metal oxides by site-specific substitution

DOEpatents

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

Producing carbon-based boundary films from catalytically active lubricant additives

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

Erdemir, Ali; Mane, Anil U.; Elam, Jeffrey W.

A lubricant composition includes an oil including a plurality of long-chain hydrocarbon molecules. A quantity of a catalytically active metal-organic additive is mixed with the oil. The metal-organic additive is formulated to fragment the long-chain hydrocarbon molecules of the oil into at least one of dimers and trimers under the influence of at least one of a mechanical loading and a thermal loading. In some embodiments, the metal-organic additive includes a compound of formula II: ##STR00001## where: X is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf,more » Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg or Cn, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are alkyl or alkyl halide.« less

First-principles study of transition-metal nitrides as diffusion barriers against Al

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

Mei, Zhi-Gang; Yacout, Abdellatif M.; Kim, Yeon Soo

2016-04-01

Using density-functional theory based first-principles calculations we provided a comparative study of the diffusion barrier properties of TiN, ZrN, and HfN against Al for U-Mo dispersion fuel applications. We firstly examined the thermodynamic stability of these transition-metal nitrides with Al. The calculated heats of reaction show that both TiN and ZrN are thermodynamically unstable diffusion barrier materials, which might be decomposed by Al at relatively high temperatures. As a comparison, HfN is a stable diffusion barrier material for Al. To evaluate the kinetic stability of these nitride systems against Al diffusion, we investigated the diffusion mechanisms of Al in TiN,more » ZrN and HfN using atomic scale simulations. The effect of non-stoichiometry on the defect formation and Al migration was systematically studied. (C) 2015 ELSEVIER B.V. All rights reserved« less

Strengthening Mechanisms, Creep and Fatigue Processes in Dispersion Hardened Niobium Alloy

DTIC Science & Technology

1992-04-01

studies of Nb and Nb-l%Zr were completed. Cyclic hardening is observed and there is a microplastic plateau in Nb. The Nb- l%Lr is stronger in cyclic...strain rate intergranular cracking occurred and a microplastic plateau was observed in the cyclic stress - strain curve for cp Nb. At the slow strain...rate, no definitely intergranular cracks were detected and a microplastic plateau was not observed for cp Nb. The results of these experiments can be

Petrology and trace element geochemistry of the Honolulu volcanics, Oahu: implications for the oceanic mantle below Hawaii.

USGS Publications Warehouse

Clague, D.A.; Frey, F.A.

1982-01-01

These volcanic rocks are the products of small-volume, late-stage vents along rifts cutting the older massive Koolan tholeiitic shield on Oahu. Most of the lavas and tuffs have the geochemical features expected of near-primary magmas derived from a peridotite source with olivine Fo87-89, e.g. 100 Mg/(Mg + Fe2+) > 65, Ni > 250 p.p.m. and the presence of ultramafic mantle xenoliths at 18 of the 37 vents. Thus the geochemistry of the alkali olivine basalt, basanite, nephelinite and nepheline melilitite lavas and tuffs of these Honolulu volcanic rocks has been used to deduce the composition of their mantle source and the conditions under which they were generated by partial melting in the mantle. New major- and trace-element analyses for 31 samples are tabulated and indicate derivation by partial melting of a garnet (<10%) lherzolite source which was isotopically homogeneous and compositionally uniform for most major and trace elements, though apparently heterogeneous in TiO2, Zr, Hf, Nb and Ta (due perhaps to the low inferred degrees of melting which failed to exhaust the source in minor residual phases). In comparison with estimates of a primordial mantle composition and the mantle source of MORB, the garnet peridotite source of these Honolulu volcanics was increasingly enriched in the sequence heavy REE, Y, Tb, Ti, Sm, Zr and Hf, for which a multi-stage history is required. This composition differs from the source of the previously erupted tholeiitic shield, nor is it represented in the upper-mantle xenoliths in the lavas and tuff of the unit.-R.A.H.

Local environments and transport properties of heavily doped strontium barium niobates Sr0.5Ba0.5Nb2O6

NASA Astrophysics Data System (ADS)

Ottini, Riccardo; Tealdi, Cristina; Tomasi, Corrado; Tredici, Ilenia G.; Soffientini, Alessandro; Burriel, Ramón; Palacios, Elías; Castro, Miguel; Anselmi-Tamburini, Umberto; Ghigna, Paolo; Spinolo, Giorgio

2018-02-01

Undoped as well as K-doped (40%), Y-doped (40%), Zr-doped (10%), and Mo-doped (12.5%) strontium barium niobate Sr0.5Ba0.5Nb2O6 (SBN50) materials have been investigated to explore the effect of heavy doping on the structural and functional properties (thermo-power, thermal and electrical conductivities) both in the as prepared (oxidized) and reduced states. For all materials, the EXAFS spectra at the Nb - K edge can be consistently analyzed with the same model of six shells around the Nb sites. Doping mostly gives a simple size effect on the structural parameters, but doping on the Nb sites weakens the Nb-O bond regardless of dopant size and charge. Shell sizes and Debye-Waller factors are almost unaffected by temperature and oxidation state, and the disorder is of static nature. The functional effects of heavy doping do not agree with a simple model of hole or electron injection by aliovalent substitutions on a large band gap semiconductor. With respect to the undoped samples, doping with Mo depresses the thermal conductivity by 30%, Y doping enhances the electrical conductivity by an order of magnitude, while Zr doping increases the Seebeck coefficient by a factor of 2-3. Globally, the ZT efficiency factor of the K-, Y-, and Zr-doped samples is enhanced at least by one order of magnitude with respect to the undoped or Mo-doped materials.

Intermetallic Growth and Interfacial Properties of the Grain Refiners in Al Alloys.

PubMed

Li, Chunmei; Cheng, Nanpu; Chen, Zhiqian; Xie, Zhongjing; Hui, Liangliang

2018-04-20

Al₃TM(TM = Ti, Zr, Hf, Sc) particles acting as effective grain refiners for Al alloys have been receiving extensive attention these days. In order to judge their nucleation behaviors, first-principles calculations are used to investigate their intermetallic and interfacial properties. Based on energy analysis, Al₃Zr and Al₃Sc are more suitable for use as grain refiners than the other two intermetallic compounds. Interfacial properties show that Al/Al₃TM(TM = Ti, Zr, Hf, Sc) interfaces in I-ter interfacial mode exhibit better interface wetting effects due to larger Griffith rupture work and a smaller interface energy. Among these, Al/Al₃Sc achieves the lowest interfacial energy, which shows that Sc atoms should get priority for occupying interfacial sites. Additionally, Sc-doped Al/Al₃(Zr, Sc) interfacial properties show that Sc can effectively improve the Al/Al₃(Zr, Sc) binding strength with the Al matrix. By combining the characteristics of interfaces with the properties of intermetallics, the core-shell structure with Al₃Zr-core or Al₃Zr(Sc1-1)-core encircled with an Sc-rich shell forms.

Glory of piezoelectric perovskites.

PubMed

Uchino, Kenji

2015-08-01

This article reviews the history of piezoelectric perovskites and forecasts future development trends, including Uchino's discoveries such as the Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 electrostrictor, Pb(Zn 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal, (Pb, La)(Zr, Ti)O 3 photostriction, and Pb(Zr, Ti)O 3 -Terfenol magnetoelectric composites. We discuss five key trends in the development of piezomaterials: performance to reliability, hard to soft, macro to nano, homo to hetero, and single to multi-functional.

Electrical resistance oscillations during plastic deformation in A Ti-Al-Nb-Zr alloy at 4·2 K

NASA Astrophysics Data System (ADS)

Nikiforenko, V. N.; Lavrentev, F. F.

1986-10-01

The serrated plastic flow in titanium alloy containing 5% Al, 2·5% Zr and 2% Nb has been investigated by measuring its electrical resistance and applying selective chemical etching. The electrical resistance was found to oscillate under active deformation at 4·2 K. Analysis of the possible causes seems to indicate a dominant role of break by dislocation pile-ups through obstacles, viz second phase precipitates and grain boundaries.

Iron-based alloys with corrosion resistance to oxygen-sulfur mixed gases

DOEpatents

Natesan, K.

1992-11-17

An iron-based alloy with improved performance with exposure to oxygen-sulfur mixed gases with the alloy containing about 9--30 wt. % Cr and a small amount of Nb and/or Zr implanted on the surface of the alloy to diffuse a depth into the surface portion, with the alloy exhibiting corrosion resistance to the corrosive gases without bulk addition of Nb and/or Zr and without heat treatment at temperatures of 1000--1100 C. 7 figs.

Iron-based alloys with corrosion resistance to oxygen-sulfur mixed gases

DOEpatents

Natesan, Krishnamurti

1992-01-01

An iron-based alloy with improved performance with exposure to oxygen-sulfur mixed gases with the alloy containing about 9-30 wt. % Cr and a small amount of Nb and/or Zr implanted on the surface of the alloy to diffuse a depth into the surface portion, with the alloy exhibiting corrosion resistance to the corrosive gases without bulk addition of Nb and/or Zr and without heat treatment at temperatures of 1000.degree.-1100.degree. C.

Cu-Cr-Nb-Zr Alloy for Rocket Engines and Other High-Heat- Flux Applications

NASA Technical Reports Server (NTRS)

Ellis, David L.

2013-01-01

Rocket-engine main combustion chamber liners are used to contain the burning of fuel and oxidizer and provide a stream of high-velocity gas for propulsion. The liners in engines such as the Space Shuttle Main Engine are regeneratively cooled by flowing fuel, e.g., cryogenic hydrogen, through cooling channels in the back side of the liner. The heat gained by the liner from the flame and compression of the gas in the throat section is transferred to the fuel by the liner. As a result, the liner must either have a very high thermal conductivity or a very high operating temperature. In addition to the large heat flux (>10 MW/sq m), the liners experience a very large thermal gradient, typically more than 500 C over 1 mm. The gradient produces thermally induced stresses and strains that cause low cycle fatigue (LCF). Typically, a liner will experience a strain differential in excess of 1% between the cooling channel and the hot wall. Each time the engine is fired, the liner undergoes an LCF cycle. The number of cycles can be as few as one for an expendable booster engine, to as many as several thousand for a reusable launch vehicle or reaction control system. Finally, the liners undergo creep and a form of mechanical degradation called thermal ratcheting that results in the bowing out of the cooling channel into the combustion chamber, and eventual failure of the liner. GRCop-84, a Cu-Cr-Nb alloy, is generally recognized as the best liner material available at the time of this reporting. The alloy consists of 14% Cr2Nb precipitates in a pure copper matrix. Through experimental work, it has been established that the Zr will not participate in the formation of Laves phase precipitates with Cr and Nb, but will instead react with Cu to form the desired Cu-Zr compounds. It is believed that significant improvements in the mechanical properties of GRCop-84 will be realized by adding Zr. The innovation is a Cu-Cr-Nb-Zr alloy covering the composition range of 0.8 to 8.1 weight percent Cr, 0.7 to 7.2 weight percent Nb, 0.1 to 1.5 weight percent Zr, and balance Cu. The alloy combines two known strengthening mechanisms - dispersion strengthening by Cr2Nb precipitates (GRCop-84), and precipitation strengthening by CuxZr (AMZIRC) - to produce a synergistic increase in the capabilities of the alloy with the goal of achieving properties greater than either of the methods could achieve alone. The anticipated advantages of the alloy are higher strength at temperatures up to 700 C, improved creep strength, and significantly higher LCF lives relative to GRCop-84. The thermal expansion, thermal conductivity, and processing of the alloy are anticipated to remain largely unchanged relative to GRCop-84.

Features of structure formation in the low modulus quasi-single crystal from Zr-25%Nb alloy at cold rolling

NASA Astrophysics Data System (ADS)

Isaenkova, M.; Perlovich, Yu.; Fesenko, V.; Babich, Y.; Zaripova, M.; Krapivka, N.

2018-05-01

The paper presents the results of investigation of the regularities of the structure and texture formation during rolling of single crystals of Zr-25%Nb alloy differing in their initial orientations relative to the external principal directions in the rolled plate: normal (ND) and rolling directions (RD). The features of rolled single crystals with initial orientations of planes {001}, {011} or {111} parallel to the rolling plane and different crystallographic directions along RD are considered. A comparison of the peculiarities of plastic deformation in a polycrystalline alloy of the same composition is made. For the samples studied, a decrease in the lattice parameter of the β-phase has been recorded, the minimum of the parameter being observed for different degrees of deformation, varying from 20 to 50%. Observed decrease in the unit cell parameter can be connected with the precipitation of the α(α')-Zr phase from the deformed nonequilibrium β-phase of the Zr-25%Nb alloy, i.e. change in the composition of the solid solution. Distributions of the increase in the dimensions of the deformed single crystal along RD and the transverse direction (TD) with its deformation up to 30% in thickness, which indicate the anisotropy of the plasticity of single crystals during their rolling, are constructed on stereographic projection. It is shown, that the deformation of single crystals occurs practically without increasing of their dimensions in the <110> direction with a total thickness deformation of up to 30%. Direction <110> is characterized by maximum hardening (microhardness) with indentation along it, which causes low plasticity of deformed and annealed foils from Zr-25%Nb alloy at the stretching along and across RD, that is connected with the features of their crystallographic texture.

Lattice Thermal Conductivity of Ultra High Temperature Ceramics ZrB2 and HfB2 from Atomistic Simulations

NASA Technical Reports Server (NTRS)

Lawson, John W.; Murray, Daw S.; Bauschlicher, Charles W., Jr.

2011-01-01

Atomistic Green-Kubo simulations are performed to evaluate the lattice thermal conductivity for single crystals of the ultra high temperature ceramics ZrB2 and HfB2 for a range of temperatures. Recently developed interatomic potentials are used for these simulations. Heat current correlation functions show rapid oscillations which can be identified with mixed metal-Boron optical phonon modes. Agreement with available experimental data is good.

Kinetics of Glass Transition and Crystallization of a Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 Bulk Metallic Glass with High Mixing Entropy

NASA Astrophysics Data System (ADS)

Gong, Pan; Wang, Sibo; Li, Fangwei; Wang, Xinyun

2018-04-01

The kinetics of glass transition and crystallization of a novel Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 bulk metallic glass (BMG) with high mixing entropy have been studied by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The continuous DSC curves show five stages of crystallization at lower heating rates (≤ 20 K/min). The activation energies of glass transition were determined by Moynihan and Kissinger methods, while the activation energies of crystallization were calculated utilizing Kissinger, Ozawa, and Boswell models. The crystalline phases corresponding to each crystallization step have been found out. The kinetic fragility of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG has also been evaluated. Based on the isothermal DSC curves, the Avrami exponent, evaluated from the Johnson-Mehl-Avrami equation, has been analyzed in detail. The current study reveals that the crystallization behavior of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG exhibits characteristics of both the high entropy BMGs and traditional BMGs with a single principal element, leading to its high glass-forming ability.

Buffer architecture for biaxially textured structures and method of fabricating same

DOEpatents

Norton, David P.; Park, Chan; Goyal, Amit

2004-04-06

The invention relates to an article with an improved buffer layer architecture comprising a substrate having a metal surface, and an epitaxial buffer layer on the surface of the substrate. The epitaxial buffer layer comprises at least one of the group consisting of ZrO.sub.2, HfO.sub.2, and compounds having at least one of Ca and a rare earth element stabilizing cubic phases of ZrO.sub.2 and/or HfO.sub.2. The article can also include a superconducting layer deposited on the epitaxial buffer layer. The article can also include an epitaxial capping layer between the epitaxial buffer layer and the superconducting layer. A method for preparing an epitaxial article comprises providing a substrate with a metal surface, depositing on the metal surface an epitaxial buffer layer comprising at least one material selected from the group consisting of ZrO.sub.2, HfO.sub.2, and compounds having at least one of Ca and a rare earth element stabilizing cubic phases of at least one of ZrO.sub.2 and HfO.sub.2. The epitaxial layer depositing step occurs in a vacuum with a background pressure of no more than 1.times.10.sup.-5 Torr. The method can further comprise depositing a superconducting layer on the epitaxial layer, and depositing an epitaxial capping layer between the epitaxial buffer layer and the superconducting layer.

Effect of Laser Powder Bed Fusion Parameters on the Microstructure and Texture Development in Superelastic Ti-18Zr-14Nb Alloy

NASA Astrophysics Data System (ADS)

Kreitcberg, A.; Brailovski, V.; Sheremetyev, V.; Prokoshkin, S.

2017-12-01

The effect of different laser powder bed fusion (L-PBF) parameters on the phase composition, microstructure, and crystallographic texture of Ti-18Zr-14Nb alloy was studied. Two levels of laser power, scanning speed, and hatching space were used, while the layer thickness was kept constant. The resulting volume energy density was ranged from 20 to 60 J/mm3, and the build rate, from 12 to 36 cm3/h. The manufactured coupons were analyzed by X-ray diffractometry, transmission, and scanning electron microscopy. It was found that the greater influence observed on the microstructure and texture development was caused by the value of laser power, while the lowest, by that of hatching space. Based on the results obtained, the processing optimization strategy aimed at improving the density, superelastic, and fatigue properties of the L-PBF manufactured Ti-18Zr-14Nb alloy was proposed.

Determination of diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb pressure tube material using hot vacuum extraction-quadrupole mass spectrometry

NASA Astrophysics Data System (ADS)

Shrivastava, Komal Chandra; Kulkarni, A. S.; Ramanjaneyulu, P. S.; Sunil, Saurav; Saxena, M. K.; Singh, R. N.; Tomar, B. S.; Ramakumar, K. L.

2015-06-01

The diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb alloy were measured in the temperature range 523 to 673 K, employing hot vacuum extraction-quadrupole mass spectrometry (HVE-QMS). One end of the Zr-2.5%Nb alloy specimens was charged electrolytically with the desired hydrogen isotope. After annealing at different temperatures for a predetermined time, the specimens were cut into thin slices, which were analyzed for their H2/D2 content using the HVE-QMS technique. The depth profile data were fitted into the equation representing the solution of Fick's second law of diffusion. The activation energy of hydrogen/deuterium diffusion was obtained from the Arrhenius relation between the diffusion coefficient and temperature. The temperature dependent diffusion coefficient can be represented as DH = 1.41 × 10-7 exp(-36,000/RT) and DD = 6.16 × 10-8 exp(-35,262/RT) for hydrogen and deuterium, respectively.

Characterization of the microstructure of Nb-1wt.%Zr-0.1wt.%C tubes as affected by thermomechanical processing

NASA Technical Reports Server (NTRS)

Uz, Mehmet; Titran, Robert H.

1993-01-01

Microstructure of Nb-1Zr-0.1C tubes were characterized as affected by extrusion temperature of the tube shell and its thermomechanical processing to tubing. Two tube shells of about 40-mm outside diameter (OD) and 25-mm inside diameter (ID) were extruded 8:1 from a vacuum arc-melted ingot at 1900 and 1550 K. Two different OD tubes of approximately 0.36-mm wall thickness were fabricated from each tube shell by a series of 26 cold drawing operations with two in process anneals. The microstructure of tube shells and the tubing before and after a 2-step heat treatment were characterized. Residue extracted chemically from each sample was also analyzed to identify the precipitates. The results concerning the effect of the initial extrusion temperature and subsequent processing on the microstructure of the tubes are presented together with a review of results from similar work on Nb-1Zr-0.1C sheet stock.

Optimization of stress relief heat treatment of PHWR pressure tubes (Zr 2.5Nb alloy)

NASA Astrophysics Data System (ADS)

Choudhuri, Gargi; Srivastava, D.; Gurumurthy, K. R.; Shah, B. K.

2008-12-01

The micro-structure of cold worked Zr-2.5%Nb pressure tube material consists of elongated grains of α-zirconium enclosed by a thin film of β-zirconium phase. This β-Zr phase is unstable and on heating, progressively decomposes to α-Zr phase and β-phase enriched with Nb and ultimately form β Nb. Meta-stable ω-phase precipitates as an intermediate step during decomposition depending on the heat treatment schedule, β→α+β→α+ω+β→α+β→α+β Morphological changes occur in the β-zirconium phase during the decomposition. The continuous ligaments of β Zr phase turn into a discontinuous array of particles followed by globulization of the β-phase. The morphological changes impose a significant effect on the creep rate and on the delayed hydride cracking velocity due to reduction in the hydrogen diffusion coefficient in α Zr. If the continuity of β-phase is disrupted by heat treatment, the effective diffusion coefficient decreases with a concomitant reduction in DHC velocity. The pressure tubes for the Indian PHWRs are made by a process of hot extrusion followed by cold pilgering in two stages and an intermediate annealing. Autoclaving at 400 °C for 36 h ensures stress relieving of the finished tubes. In the present studies, autoclaving duration at 400 °C was varied from 24 h to 96 h at 12 h-steps and the micro-structural changes in the β-phase were observed by TEM. Dislocation density, hardness and the micro-structural features such as thickness of β-phase, inter-particle spacing and volume fraction of the phases were measured at each stage. Autoclaving for a longer duration was found to change the morphology of β-phase and increase the inter-particle spacing. Progressive changes in the aspect ratio of the β-phase and their size and distribution are documented and reported. These micro-structural modifications are expected to decrease DHC velocity during reactor operation.

Element mobilization and redistribution under extreme tropical weathering of basalts from the Hainan Island, South China

NASA Astrophysics Data System (ADS)

Jiang, Ke; Qi, Hua-Wen; Hu, Rui-Zhong

2018-06-01

Chemical weathering of rocks has substantial influence on the global geochemical cycle. In this paper, the geochemical profile of a well-developed basalt weathering profile (>15 m thick, including soil, saprolite, semi-weathered rock and fresh basalt) on the Island of Hainan (South China) was presented. The soil and saprolite samples from this profile are characterized by high Al2O3 and Fe2O3 concentrations (up to 32.3% and 28.5%, respectively). The mineral assemblage is dominated by kaolinite, Fe-oxides/-hydroxides and gibbsite (or boehmite), indicating extensive desilicate and ferrallitic weathering. The acidic and organic-rich environment in the soil horizon may have promoted elemental remobilization and leaching. The strongest SiO2 depletion and Al2O3 enrichment at about 2.4 m deep indicate that the main kaolinite hydrolysis and gibbsite formation occurred near the soil-saprolite interface. The mild Sr reconcentration at about 3.9 m and 7.1 m deep may be attributed to secondary carbonate precipitation. Mn-oxides/-hydroxides precipitated at 6.1 m deep, accompanied by the strongest enrichment of Ba and Co. Uranium is mildly enriched in the middle part (about 7.1 m and 9.1 m deep) of the weathering profile, and the enrichment may have been caused by the decomposition of uranyl carbonates or the accumulation of zircon. Immobile element (i.e., Zr, Hf, Nb, Ta, Th and Ti) distributions at different depths are mainly controlled by secondary Fe-oxides/-hydroxides, and follow the stability sequence of Nb ≈ Ta ≈ Th > Zr ≈ Hf > Ti. The limited thickness (∼15 cm) of the semi-weathered basalt horizon at the rock-regolith interface (15.28 m deep) suggests that plagioclase and pyroxene are readily altered to kaolinite, smectite and Fe-oxides under tropical climate. The marked enrichment of transitional metals (such as Cu, Zn, Ni, and Sc) along the rock-regolith interface may have associated mainly with increasing pH values, as well as the dissolution of primary apatite and formation of secondary phosphates. Our findings highlight the importance of secondary phosphates in the redistribution of transition metals, and in the possible Mg, Cu, and Ni isotopic fractionation under extreme weathering of basalt in tropic climate.

Petrogenesis of the mafic microgranular enclaves (MMEs) and their host granodiorites from the Zijinshan intrusion along the Middle-Lower Yangtze River Valley: Implications for geodynamic setting and mineralization

NASA Astrophysics Data System (ADS)

Liu, Peng; Mao, Jingwen; Yao, Wei; Wang, Xiaoxia; Jia, Lihui; Yang, Hanwen

2017-09-01

The Zijinshan intrusion is located to the south of the Tongling ore cluster of the Middle-Lower Yangtze River Valley metallogenic belt (YRB) and even south to the Yangxing-Changzhou Fault (YCF), which separates the YRB and the Jiangnan Massif. It is an I-type high-K calc-alkaline granodiorite with abundant MMEs. Zircon LA-MC-ICP-MS U-Pb ages of 144.0 ± 1.0 Ma and 142.5 ± 1.0 Ma for the host granodiorite and MMEs indicate coeval formation. Biotites from the host granodiorites and MMEs have similar composition, with low FeOt/(FeOt + MgO) values of 0.60-0.65 and 0.60-0.65, and high MgO contents of 10.51-11.70 wt.% and 10.89-12.37 wt.%, respectively. All the biotite samples are between the NNO and the MH buffers. The host granodiorites are metaluminous (A/CNK = 0.94-0.95), enriched in Cs, Rb, U and Pb, depleted in Ba, Sr, Nb, Zr, P, and Ti, with moderate negative Eu anomalies of 0.80-0.87, (87Sr/86Sr)i of 0.70874 to 0.70887, εNd(t) of - 5.63 to - 5.36 and εHf(t) of - 8.68 to - 2.76. The MMEs have lower SiO2 and higher K2O, and they are also enriched in Cs, Rb, U, Ta and Pb, and depleted in Ba, Sr, Nb, Zr, P and Ti, with (87Sr/86Sr)i of 0.70889 to 0.70927, εNd(t) of - 5.52 to - 5.20 and εHf(t) of - 6.46 to - 3.59. All these characteristics demonstrate that partial melting of both the lower crust and an enriched lithospheric mantle metasomatized by subducted slab fluid and their subsequent mixing led to the origin of the I-type granodiorite magmas of the Zijinshan intrusion, which took place in the geodynamic context of the subduction of the Izanagi plate. Combined with the field investigations, we suggest that the Zijinshan intrusion has potential for porphyry Cu-Au mineralization and the Cu-Au metallogenic belt of the YRB may have extended to the south of the YCF.

The Effect of Element Substitution on Ti-in-Zircon Geothermometry in Volcanic Zircons from Mount Pinatubo, Philippines

NASA Astrophysics Data System (ADS)

Lee, S. L.; Hattori, K.

2017-12-01

Despite the extensive application of the Ti-in-zircon geothermometer, its accuracy in natural systems remains uncertain. In order to investigate the parameters contributing to Ti in zircon, we examined zircons from dacitic eruption products of Mount Pinatubo, Philippines, from the Pliocene (>2.5-2.7 Ma), 35000BP and 1991AD. All samples are unaltered and quenched from magmas at 790-825°C (Fe-Ti-oxide thermometry). Furthermore, the magma conditions of 1991 samples are well characterized: 780°C (cummingtonite rims on hornblende, Fe-Ti-oxide thermometry), 2 kbar pressure, 5.5-6.5 wt.% H2O and fO2 of NNO+1.6. Calculated zircon saturation temperatures are 760, 744 and 738°C (oldest to youngest). Zircon Ti concentrations are low (2.0-8.8 ppm), show positive covariation with U (35.6-639 ppm), Th (18.7-696 ppm), ∑REE (237-1310 ppm) and Y (247-1770 ppm), and negative covariation with Hf (7610-12000 ppm). The Ti-in-zircon geothermometer by Ferry and Watson (2007) yields mean temperatures of 690, 666 and 663°C (oldest to youngest), using TiO2 activity=0.6, SiO2 activity=1 and -40°C pressure correction. Therefore, temperatures calculated using this method are underestimated by >100°C. We suggest that elements in the Zr site impact the substitution of Ti in the Si site of zircon. Ti shows a positive covariation with Zr/Hf (37.0-57.3, r2=0.551). The ionic radius of Hf4+ is smaller than Zr4+, whereas cations like U4+, Th4+, REE3+ and Y3+ are larger. The departure from the ideal crystal configuration is evaluated using the parameter Zr/(Hf-x), whereby x=U4+, Th4+, ∑REE and Y3+. Ti contents are more strongly correlated with the parameter than Zr/Hf (r2=0.559, 0.565, 0.608, 0.616; respectively). This suggests that large cations replacing Zr strain the lattice, reducing the amount of Ti incorporated into zircon. This further suggests that ZrSiO4 activity is less than 1 in natural rocks, resulting in the systematic underestimation of Ti-in-zircon temperatures.

Materials properties of hafnium and zirconium silicates: Metal interdiffusion and dopant penetration studies

NASA Astrophysics Data System (ADS)

Quevedo Lopez, Manuel Angel

Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050°C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixO y are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford Backscattering Spectroscopy (RBS), Heavy Ion RBS (HI-RBS), X-ray Photoelectron Spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM), and Time of Flight and Dynamic Secondary Ion Mass Spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling of the dopant profiles in the Si substrate. In this disseration is reported that Hf silicate films are more stable than Zr silicate films, from the metal interdiffusion point of view. On the other hand, dopant (B, As, and P) penetration is observed for HfSixO y films. However, the addition of nitrogen to the Hf - Si - O systems improves the dopant penetration properties of the resulting HfSi xOyNz films.

Kinetic and mechanistic aspects of propene oligomerization with ionic organozirconium and -hafnium compounds: Crystal structures of [Cp* {sub 2}MMe(THT)]{sup +}[BPh{sub 4}]{sup {minus}} (M=Zr, Hf)

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

Eshuis, J.J.W.; Tan, Y.Y.; Meetsma, A.

1992-01-01

In N,N-dimethylaniline the ionic complexes [Cp{sup *}{sub 2}MMe(THT)]{sup +}[BPh{sub 4}]{sup {minus}}(M=Zr,Hf) oligomerize propene to low molecular weight oligomers. At room temperature for M = Zr a rather broad molecular weight distribution is obtained (C{sub 6} to C{sub 24}), whereas for M = Hf only one dimer (4-methyl-1-pentene) and one trimer (4,6-dimethyl-1-heptene) are formed. With an increase in temperature the product composition shifts to lower molecular weights, but the specific formation of head-to-tail oligomers is retained. The oligomers are formed by {beta}-Me transfer from the growing oligopropene alkyl chain to the metal center. The molecular weight distributions of the oligomers producedmore » at temperature between 5 and 45 {degrees}C are satisfactorily described by the Flory-Schulz theory. This allows the calculation of ratios of rate coefficients for propagation (k{sub p}) and termination (k{sub t}). Inactivation of the catalysts is caused by two different mechanisms. At room temperature allylic C-H activation of monomer and isobutene (formed by a minor {beta}-H transfer termination) gives inactive (meth) allyl compounds, [Cp{sup *} {sub 2}M({eta}{sup 3}-C{sub 3}H{sub 5})]{sup +} and [Cp{sup *}{sub 2}M({eta}{sup 3}-C{sub 4}H{sub 7})]{sup +} (M = Zr, Hf). At elevated temperatures (>45 {degrees}C) catalytically inactive zwitterionic complexes Cp{sup *}{sub M}{sup +}-m-C{sub 6}H{sub 4}-BPh{sub 3}{sup {minus}}(M = Zr, Hf) are formed through aromatic C-H activation. Reactivation of the inactive (meth)allyl complexes can be achieved by addition of hydrogen to the oligomerization mixtures. 38 refs., 4 figs., 7 tabs.« less

Accumulation degree and source apportionment of trace metals in smaller than 63 μm road dust from the areas with different land uses: A case study of Xi'an, China.

PubMed

Shi, Dongqi; Lu, Xinwei

2018-09-15

Finer urban dusts have more serious environmental detriment and health risk than coarser urban dusts. The trace metals Pb, Cu, Zn, Cr, Co, Ba, Mn, Ni, V, Y, Rb, Ga, Hf, and Zr were analyzed using X-ray fluorescence spectrometry in smaller than 63 μm road dust collected from the areas with different land use types and human activities in Xi'an city. The purposes of this study were to reveal the impact of human activities on the environment through element enrichment factor, and to determine the sources of trace metals measured by multivariate statistical analysis and multiple liner regression of absolute principal component scores. The results indicated that the smaller than 63 μm road dust in Xi'an, in comparison to the element background value of local soil, had higher Cu, Pb, Zn, Cr, Y, Hf and Zr concentrations. Trace metals had different variations in the dusts, while the anthropogenic trace metals had no significant difference in the four areas owing to the wide existing of human activities. The accumulation level of Pb was the highest, followed by Cr, Cu and Zn, and then was Hf and Zr, while the other trace metals were deficient or deficient to minimal enrichment in the finer road dust. Source analysis results indicated that Co, Ga, Mn, Ni, V, Rb and Y mainly originated from natural source, which accounted about 57%-87% for these metals' concentration. Ba, Cr, Pb, Cu and Zn primarily derived from traffic source, which contributed approximately 59%-79% to these metals' content. Hf and Zr were mainly from construction source, which contributed 74.6% to Hf concentration and 78.2% to Zr concentration. The study indicated that traffic and construction activities had a predominant influence on local environment. Copyright © 2018 Elsevier B.V. All rights reserved.

Interference-free determination of sub ng kg-1 levels of long-lived 93Zr in the presence of high concentrations (μg kg-1) of 93Mo and 93Nb using ICP-MS/MS.

PubMed

Petrov, Panayot; Russell, Ben; Douglas, David N; Goenaga-Infante, Heidi

2018-01-01

Long-lived high abundance radionuclides are of increasing interest with regard to decommissioning of nuclear sites and longer term nuclear waste storage and disposal. In many cases, no routine technique is available for their measurement in nuclear waste and low-level (ng kg -1 ) environmental samples. Recent advances in ICP-MS technology offer attractive features for the selective and sensitive determination of a wide range of long-lived radionuclides. In this work, inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS)-based methodology, suitable for accurate routine determinations of 93 Zr at very low (ng kg -1 ) levels in the presence of high levels (μg kg -1 ) of the isobaric interferents 93 Nb and 93 Mo (often present in nuclear waste samples), is reported for the first time. Additionally, a novel and systematic strategy for method development based on the use of non-radioactive isotopes is proposed. It relies on gas-phase chemical reactions for different molecular ion formation to achieve isobaric interference removal. Using cell gas mixtures of NH 3 /He/H 2 or H 2 /O 2 , and suitable mass shifts, the signal from the 93 Nb and 93 Mo isobaric interferences on 93 Zr were suppressed by up to 5 orders of magnitude. The achieved limit of detection for 93 Zr was 1.3 × 10 -5  Bq g -1 (equivalent to 0.14 ng kg -1 ). The sample analysis time is 2 min, which represents a significant improvement in terms of sample throughput, compared to liquid scintillation counting methods. The method described here can be used for routine measurements of 93 Zr at environmentally relevant levels. It can also be combined with radiometric techniques for use towards the standardisation of 93 Zr measurements. Graphical abstract Interference-free determination of 93 Zr in the presence of high concentrations of isobaric 93 Mo and 93 Nb by ICP-MS/MS.

Preparation, glass forming ability, crystallization and deformation of (zirconium, hafnium)-copper-nickel-aluminum-titanium-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Gu, Xiaofeng

Multicomponent Zr-based bulk metallic glasses are the most promising metallic glass forming systems. They exhibit great glass forming ability and fascinating mechanical properties, and thus are considered as potential structural materials. One potential application is that they could be replacements of the depleted uranium for making kinetic energy armor-piercing projectiles, but the density of existing Zr-based alloys is too low for this application. Based on the chemical and crystallographic similarities between Zr and Hf, we have developed two series of bulk metallic glasses with compositions of (HfxZr1-x) 52.5Cu17.9Ni14.6Al10Ti5 and (HfxZr1-x) 57Cu20Ni8Al10Ti5 ( x = 0--1) by gradually replacing Zr by Hf. Remarkably increased density and improved mechanical properties have been achieved in these alloys. In these glasses, Hf and Zr play an interchangeable role in determining the short range order. Although the glass forming ability decreases continuously with Hf addition, most of these alloys remain bulk glass-forming. Recently, nanocomposites produced from bulk metallic glasses have attracted wide attention due to improved mechanical properties. However, their crystalline microstructure (the grain size and the crystalline volume fraction) has to be optimized. We have investigated crystallization of (Zr, Hf)-based bulk metallic glasses, including the composition dependence of crystallization paths and crystallization mechanisms. Our results indicate that the formation of high number density nanocomposites from bulk metallic glasses can be attributed to easy nucleation and slowing-down growth processes, while the multistage crystallization behavior makes it more convenient to control the microstructure evolution. Metallic glasses are known to exhibit unique plastic deformation behavior. At low temperature and high stress, plastic flow is localized in narrow shear bands. Macroscopic investigations of shear bands (e.g., chemical etching) suggest that the internal structure of shear bands is different from that of undeformed surroundings, but the direct structural characterization of shear bands down to the atomic level has been lacking. In this work, we have used transmission electron microscopy to explore the structural and chemical changes inside the shear bands. Nanometer-scale defects (void-like and high density regions) have been identified as a result of plastic deformation. It is these defects that distinguish shear bands from undeformed regions. Processes occurring in an active shear band and after stress removal are analogous to a thermally activated relaxation except that the relaxation time is much shorter in the former case.

Negative thermal expansion materials related to cubic zirconium tungstate

NASA Astrophysics Data System (ADS)

Lind, Cora

2001-12-01

A non-hydrolytic sol-gel method for the preparation of ZrW2O 8 was developed. A new trigonal polymorph was discovered, which is structurally related to trigonal ZrMO2O8 and MnRe2O 8 as evidenced by powder x-ray diffraction and EXAFS studies. Seeding of the starting mixtures with cubic ZrW2O8 promoted crystallization of the cubic phase instead of trigonal material. Dehydration of ZrW2O7(OH)2·2H 2O gave cubic ZrW2O8 at 650°C, and a modification of this route led to the discovery of the new NTE materials cubic ZrMo 2O8 and HfMo2O8. These compounds crystallize in the same temperature range as the more stable trigonal AMo2O 8 polymorphs. To facilitate preparation of phase pure cubic molybdates, the influence of precursor chemistry on the crystallization behavior was investigated. The synthesis was extended to the solid solution system ZrxHf 1-xMoyW2-yO8 (0 ≤ x ≤ 1, 0 ≤ y ≤ 2). All compounds showed negative thermal expansion between 77 and 573 K. High-pressure in situ diffraction experiments were conducted on several AM2O8 polymorphs. With the exception of monoclinic ZrMo2O8, all materials underwent at least one pressure induced phase transition. Quasi-hydrostatic experiments on cubic AMo 2O8 led to a reversible transition to a new high-pressure structure, while low-pressure amorphization was observed under non-hydrostatic conditions. Isothermal kinetic studies of the cubic to trigonal transformation for ZrMo2O8 were carried out on four samples. Apparent activation energies of 170--290 kJ/mol were obtained using an Avrami model in combination with an Arrhenius analysis. This corresponds to 5% conversion levels after one year at temperatures between 220 and 315°C. Ex situ studies showed that the conversion at lower temperatures was considerably slower than what would be expected from extrapolation of the kinetic data. Drop solution calorimetry was carried out on several polymorphs of ZrMo 2O8, HfMo2O8 and ZrW2O 8. Only monoclinic ZrMo2O8 was enthalpically stabilized with respect to the binary oxides. For all other polymorphs, the differences in enthalpies of formation from the binary oxides for each AM2O 8 system (A = Zr, Hf; M = Mo, W) were small. Attempts to synthesize new materials MIIRe2O 8 (M = Mg, Zn, Mn, Co) with the cubic ZrW2O8 structure from a hydrate precursor were not successful.

Characterization of deformation mechanisms in zirconium alloys: effect of temperature and irradiation

NASA Astrophysics Data System (ADS)

Long, Fei

Zirconium alloys have been widely used in the CANDU (CANada Deuterium Uranium) reactor as core structural materials. Alloy such as Zircaloy-2 has been used for calandria tubes; fuel cladding; the pressure tube is manufactured from alloy Zr-2.5Nb. During in-reactor service, these alloys are exposed to a high flux of fast neutron at elevated temperatures. It is important to understand the effect of temperature and irradiation on the deformation mechanism of zirconium alloys. Aiming to provide experimental guidance for future modeling predictions on the properties of zirconium alloys this thesis describes the result of an investigation of the change of slip and twinning modes in Zircaloy-2 and Zr-2.5Nb as a function of temperature and irradiation. The aim is to provide scientific fundamentals and experimental evidences for future industry modeling in processing technique design, and in-reactor property change prediction of zirconium components. In situ neutron diffraction mechanical tests carried out on alloy Zircaloy-2 at three temperatures: 100¢ªC, 300¢ªC, and 500¢ªC, and described in Chapter 3. The evolution of the lattice strain of individual grain families in the loading and Poisson's directions during deformation, which probes the operation of slip and twinning modes at different stress levels, are described. By using the same type of in situ neutron diffraction technique, tests on Zr-2.5Nb pressure tube material samples, in either the fast-neutron irradiated or un-irradiated condition, are reported in Chapter 4. In Chapter 5, the measurement of dislocation density by means of line profile analysis of neutron diffraction patterns, as well as TEM observations of the dislocation microstructural evolution, is described. In Chapter 6 a hot-rolled Zr-2.5Nb with a larger grain size compared with the pressure tubing was used to study the development of dislocation microstructures with increasing plastic strain. In Chapter 7, in situ loading of heavy ion irradiated hot-rolled Zr-2.5Nb alloy is described, providing evidence for the interaction between moving dislocations and irradiation induced loops. Chapter 8 gives the effect on the dislocation structure of different levels of compressive strains along two directions in the hot-rolled Zr-2.5Nb alloy. By using high resolution neutron diffraction and TEM observations, the evolution of type and dislocation densities, as well as changes of dislocation microstructure with plastic strain were characterized.

AMS of 93Zr: Passive absorber versus gas-filled magnet

NASA Astrophysics Data System (ADS)

Hain, Karin; Deneva, Boyana; Faestermann, Thomas; Fimiani, Leticia; Gómez-Guzmán, José Manuel; Koll, Dominik; Korschinek, Gunther; Ludwig, Peter; Sergeyeva, Victoria; Thiollay, Nicolas

2018-05-01

Two different isobar separation techniques were tested for the detection of the long-lived fission product 93Zr (T1/2 = 1.64 · 106 a) using Accelerator Mass Spectrometry (AMS), i.e. a passive absorber and a gas-filled magnet, respectively. Both techniques were used in combination with a Time-of-Flight path for the identification of the stable neighboring isotopes 92Zr and 94Zr. The passive absorber was represented by a stack of silicon nitride foils for high flexibility regarding the thickness for optimal isobar separation. Ion beams with a large variety of energies, between 80 and 180 MeV, were provided for this experiment by the tandem accelerator at the Maier-Leibnitz Laboratory in Garching, Germany. With these beams, the stopping powers of 93Zr and 93Nb as a function of energy were determined experimentally and compared to the results obtained with the simulation program SRIM. Considerable discrepancies regarding the energy dependence of the two stopping power curves relative to each other were found. The lowest detection limit for 93Zr achieved with the passive absorber setup was 93Zr/Zr = 1 · 10-10. In comparison, by optimizing the gas-filled magnet set-up, 93Nb was suppressed by around six orders of magnitude and a detection limit of 93Zr/Zr = 5 · 10-11 was obtained. To our knowledge, these results represent the lowest detection limit achieved for 93Zr until now.

Enhanced thermoelectric properties of n-type NbCoSn half-Heusler by improving phase purity

DOE PAGES

He, Ran; Huang, Lihong; Wang, Yumei; ...

2016-06-01

In this paper, we report the thermoelectric properties of NbCoSn-based n-type half-Heuslers (HHs) that were obtained through arc melting, ball milling, and hot pressing process. With 10% Sb substitution at the Sn site, we obtained enhanced n-type properties with a maximum power factor reaching ~35 μW cm -1 K -2 and figure of merit (ZT) value ~0.6 in NbCoSn 0.9Sb 0.1. The ZT is doubled compared to the previous report. In addition, the specific power cost ($ W -1) is decreased by ~68% comparing to HfNiSn-based n-type HH because of the elimination of Hf.

Development of a High Chromium Ni-Base Filler Metal Resistant to Ductility Dip Cracking and Solidification Cracking

NASA Astrophysics Data System (ADS)

Hope, Adam T.

Many nuclear reactor components previously constructed with Ni-based alloys containing 20 wt% Cr have been found to be susceptible to stress corrosion cracking. The nuclear power industry now uses high chromium (˜30wt%) Ni-based filler metals to mitigate stress corrosion cracking. Current alloys are plagued with weldability issues, either solidification cracking or ductility dip cracking (DDC). Solidification cracking is related to solidification temperature range and the DDC is related to the fraction eutectic present in the microstructure. It was determined that an optimal alloy should have a solidification temperature range less than 150°C and at least 2% volume fraction eutectic. Due to the nature of the Nb rich eutectic that forms, it is difficult to avoid both cracking types simultaneously. Through computational modeling, alternative eutectic forming elements, Hf and Ta, have been identified as replacements for Nb in such alloys. Compositions have been optimized through a combination of computational and experimental techniques combined with a design of experiment methodology. Small buttons were melted using commercially pure materials in a copper hearth to obtain the desired compositions. These buttons were then subjected to a gas tungsten arc spot weld. A type C thermocouple was used to acquire the cooling history during the solidification process. The cooling curves were processed using Single Sensor Differential Thermal Analysis to determine the solidification temperature range, and indicator of solidification cracking susceptibility. Metallography was performed to determine the fraction eutectic present, an indicator of DDC resistance. The optimal level of Hf to resist cracking was found to be 0.25 wt%. The optimal level of Ta was found to be 4 wt%. gamma/MC type eutectics were found to form first in all Nb, Ta, and Hf-bearing compositions. Depending on Fe and Cr content, gamma/Laves eutectic was sometimes found in Nb and Ta-bearing compositions, while Hf-bearing compositions had gamma/Ni7Hf2 as the final eutectic to solidify. This study found that the extra Cr in the current generation alloys promotes the gamma/Laves phase eutectic, which expands the solidification temperature range and promotes solidification cracking. Both Ta-bearing and Hf-bearing eutectics were found to solidify at higher temperatures than Nb-bearing eutectics, leading to narrower solidification temperature ranges. Weldability testing on the optimized Ta-bearing compositions revealed good resistance to both DDC and solidification cracking. Unexpectedly, the optimized Hf-bearing compositions were quite susceptible to solidification cracking. This led to an investigation on the possible wetting effect of eutectics on solidification cracking susceptibly, and a theory on how wetting affects the solidification crack susceptibility and the volume fraction of eutectic needed for crack healing has been proposed. Alloys with eutectics that easily wet the grain boundaries have increased solidification crack susceptibility at low volume fraction eutectics, but as the fraction eutectic is increased, experience crack healing at relatively lower fraction eutectics than alloys with eutectics that don't wet as easily. Hf rich eutectics were found to wet grain boundaries significantly more than Nb rich eutectics. Additions of Mo were also found to increase the wetting of eutectics in Nb-bearing alloys.

Development of binary and ternary titanium alloys for dental implants.

PubMed

Cordeiro, Jairo M; Beline, Thamara; Ribeiro, Ana Lúcia R; Rangel, Elidiane C; da Cruz, Nilson C; Landers, Richard; Faverani, Leonardo P; Vaz, Luís Geraldo; Fais, Laiza M G; Vicente, Fabio B; Grandini, Carlos R; Mathew, Mathew T; Sukotjo, Cortino; Barão, Valentim A R

2017-11-01

The aim of this study was to develop binary and ternary titanium (Ti) alloys containing zirconium (Zr) and niobium (Nb) and to characterize them in terms of microstructural, mechanical, chemical, electrochemical, and biological properties. The experimental alloys - (in wt%) Ti-5Zr, Ti-10Zr, Ti-35Nb-5Zr, and Ti-35Nb-10Zr - were fabricated from pure metals. Commercially pure titanium (cpTi) and Ti-6Al-4V were used as controls. Microstructural analysis was performed by means of X-ray diffraction and scanning electron microscopy. Vickers microhardness, elastic modulus, dispersive energy spectroscopy, X-ray excited photoelectron spectroscopy, atomic force microscopy, surface roughness, and surface free energy were evaluated. The electrochemical behavior analysis was conducted in a body fluid solution (pH 7.4). The albumin adsorption was measured by the bicinchoninic acid method. Data were evaluated through one-way ANOVA and the Tukey test (α=0.05). The alloying elements proved to modify the alloy microstructure and to enhance the mechanical properties, improving the hardness and decreasing the elastic modulus of the binary and ternary alloys, respectively. Ti-Zr alloys displayed greater electrochemical stability relative to that of controls, presenting higher polarization resistance and lower capacitance. The experimental alloys were not detrimental to albumin adsorption. The experimental alloys are suitable options for dental implant manufacturing, particularly the binary system, which showed a better combination of mechanical and electrochemical properties without the presence of toxic elements. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Ferroelectricity in Ruddlesden-Popper Chalcogenide Perovskites for Photovoltaic Application: The Role of Tolerance Factor.

PubMed

Zhang, Yajun; Shimada, Takahiro; Kitamura, Takayuki; Wang, Jie

2017-12-07

Chalcogenide perovskites with optimal band gap and desirable light absorption are promising for photovoltaic devices, whereas the absence of ferroelectricity limits their potential in applications. On the basis of first-principles calculations, we reveal the underlying mechanism of the paraelectric nature of Ba 3 Zr 2 S 7 observed in experiments and demonstrate a general rule for the appearance of ferroelectricity in chalcogenide perovskites with Ruddlesden-Popper (RP) A 3 B 2 X 7 structures. Group theoretical analysis shows that the tolerance factor is the primary factor that dominates the ferroelectricity. Both Ba 3 Zr 2 S 7 and Ba 3 Hf 2 S 7 with large tolerance factor are paraelectric because of the suppression of in-phase rotation that is indispensable to hybrid improper ferroelectricity. In contrast, Ca 3 Zr 2 S 7 , Ca 3 Hf 2 S 7 , Ca 3 Zr 2 Se 7 , and Ca 3 Hf 2 S 7 with small tolerance factor exhibit in-phase rotation and can be stable in the ferroelectric Cmc2 1 ground state with nontrivial polarization. These findings not only provide useful guidance to engineering ferroelectricity in RP chalcogenide perovskites but also suggest potential ferroelectric semiconductors for photovoltaic applications.

Origin and evolution of the Ilmeny-Vishnevogorsky carbonatites (Urals, Russia): insights from trace-element compositions, and Rb-Sr, Sm-Nd, U-Pb, Lu-Hf isotope data

NASA Astrophysics Data System (ADS)

Nedosekova, I. L.; Belousova, E. A.; Sharygin, V. V.; Belyatsky, B. V.; Bayanova, T. B.

2013-02-01

The carbonatites of the Ilmeny-Vishnevogorsky Alkaline Complex (IVAC) are specific in geological and geochemical aspects and differ by some characteristics from classic carbonatites of the zoned alkaline-ultramafic complexes. Geological, geochemical and isotopic data and comparison with relevant experimental systems show that the IVAC carbonatites are genetically related to miaskites, and seem to be formed as a result of separation of carbonatite liquid from a miaskitic magma. Appreciable role of a carbonate fluid is established at the later stages of carbonatite formation. The trace element contents in the IVAC carbonatites are similar to carbonatites of the ultramafic-alkaline complexes. The characteristic signatures of the IVAC carbonatites are a high Sr content, a slight depletion in Ba, Nb, Та, Ti, Zr, and Hf, and enrichment in HREE in comparison with carbonatites of ultramafic-alkaline complexes. This testifies a specific nature of the IVAC carbonatites related to the fractionation of a miaskitic magma and to further Late Paleozoic metamorphism. Isotope data suggest a mantle source for IVAC carbonatites and indicate that moderately depleted mantle and enriched EMI-type components participated in magma generation. The lower crust could have been involved in the generation of the IVAC magma.

Uranium nitride fuel fabrication for SP-100 reactors

NASA Technical Reports Server (NTRS)

Mason, Richard E.; Chidester, Kenneth M.; Hoth, Carl W.; Matthews, Bruce R.

1987-01-01

Fuel pins of uranium mononitride clad in Nb-1 percent Zr were fabricated for irradiation tests in EBR-II. Laboratory scale process parameters to synthesize UN powders and fabricate UN pellets were developed. Uranium mononitride was prepared by converting UO2 to UN. Fuel pellets were prepared by communition of UN briquettes, uniaxial pressing, and high temperature sintering. Techniques for machining, cleaning, and welding Nb-1 percent Zr cladding components were developed. End caps were electron beam welded to the tubing. Helium back-fill holes were sealed with a laser weld.

First-principles phase stability at high temperatures and pressure in Nb 90Zr 10 alloy

DOE PAGES

Landa, A.; Soderlind, P.

2016-08-18

The phase stability of Nb 90Zr 10 alloy at high temperatures and compression is explored by means of first-principles electronic-structure calculations. Utilizing the self-consistent ab initio lattice dynamics (SCAILD) approach in conjunction with density-functional theory, we show that pressure-induced mechanical instability of the body-centered cubic phase, which results in formation of a rhombohedral phase at around 50 GPa, will prevail significant heating. As a result, the body-centered cubic structure will recover before melting at ~1800 K.

Glory of piezoelectric perovskites

PubMed Central

Uchino, Kenji

2015-01-01

This article reviews the history of piezoelectric perovskites and forecasts future development trends, including Uchino’s discoveries such as the Pb(Mg1/3Nb2/3)O3–PbTiO3 electrostrictor, Pb(Zn1/3Nb2/3)O3–PbTiO3 single crystal, (Pb, La)(Zr, Ti)O3 photostriction, and Pb(Zr, Ti)O3–Terfenol magnetoelectric composites. We discuss five key trends in the development of piezomaterials: performance to reliability, hard to soft, macro to nano, homo to hetero, and single to multi-functional. PMID:27877827

Uranium nitride fuel fabrication for SP-100 reactors

NASA Astrophysics Data System (ADS)

Mason, Richard E.; Chidester, Kenneth M.; Hoth, Carl W.; Matthews, Bruce R.

Fuel pins of uranium mononitride clad in Nb-1 percent Zr were fabricated for irradiation tests in EBR-II. Laboratory scale process parameters to synthesize UN powders and fabricate UN pellets were developed. Uranium mononitride was prepared by converting UO2 to UN. Fuel pellets were prepared by communition of UN briquettes, uniaxial pressing, and high temperature sintering. Techniques for machining, cleaning, and welding Nb-1 percent Zr cladding components were developed. End caps were electron beam welded to the tubing. Helium back-fill holes were sealed with a laser weld.

Zircon U-Pb age, Hf isotope and geochemistry of Carboniferous intrusions from the Langshan area, Inner Mongolia: Petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Liu, Min; Zhang, Da; Xiong, Guangqiang; Zhao, Hongtao; Di, Yongjun; Wang, Zhong; Zhou, Zhiguang

2016-04-01

Late Paleozoic was a critical period for the tectonic evolution of the northern margin of the Alxa-North China craton, but the evolutionary history is not well constrained. The Carboniferous intrusions in the Langshan area in the western part of the northern margin of the Alxa-North China craton are mainly composed of tonalite, quartz diorite, olivine gabbro and pyroxene peridotite. Zircon LA-ICP-MS U-Pb dating indicates that the Langshan Carboniferous intrusions were emplaced at ca. 338-324 Ma. The quartz diorites are characterized by high amounts of compatible trace elements (Cr, Ni and V) and high Mg# values, which may suggest a significant mantle source. The positive Pb and negative Nb-Ta-Ti anomalies, the variable εHf(t) (-6.9 to 2.0) values and the old Hf model ages (1218-1783 Ma) imply some involvement of ancient continental materials in its petrogenesis. The tonalite has relatively high Sr/Y ratios, low Mg#, Yb and Y contents, features of adakite-like rocks, negative εHf(t) values (-9.8 to -0.1) and older Hf model ages (1344-1953 Ma), which suggest significant involvement of ancient crust materials and mantle-derived basaltic component in its petrogenesis. The high Mg# values, high Cr and Ni contents, and low Zr and Hf contents of the mafic-ultramafic rocks show evidence of a mantle source, and the relatively low zircon εHf(t) values (-5.9 to 3.2) might point to an enriched mantle. The trace element characteristics indicate the influence of subducted sediments and slab-derived fluids. In the tectonic discrimination diagrams, all the rocks plot in subduction-related environment, such as volcanic arc and continental arc. Considering the regional geology, we suggest that the Carboniferous intrusions in the Langshan area were likely emplaced during the late stage of the southward subduction of the Paleo-Asian Ocean plate, which formed a continental arc along the northern margin of the Alxa-North China craton.

Intermetallic Growth and Interfacial Properties of the Grain Refiners in Al Alloys

PubMed Central

Li, Chunmei; Cheng, Nanpu; Chen, Zhiqian; Xie, Zhongjing; Hui, Liangliang

2018-01-01

Al3TM(TM = Ti, Zr, Hf, Sc) particles acting as effective grain refiners for Al alloys have been receiving extensive attention these days. In order to judge their nucleation behaviors, first-principles calculations are used to investigate their intermetallic and interfacial properties. Based on energy analysis, Al3Zr and Al3Sc are more suitable for use as grain refiners than the other two intermetallic compounds. Interfacial properties show that Al/Al3TM(TM = Ti, Zr, Hf, Sc) interfaces in I-ter interfacial mode exhibit better interface wetting effects due to larger Griffith rupture work and a smaller interface energy. Among these, Al/Al3Sc achieves the lowest interfacial energy, which shows that Sc atoms should get priority for occupying interfacial sites. Additionally, Sc-doped Al/Al3(Zr, Sc) interfacial properties show that Sc can effectively improve the Al/Al3(Zr, Sc) binding strength with the Al matrix. By combining the characteristics of interfaces with the properties of intermetallics, the core-shell structure with Al3Zr-core or Al3Zr(Sc1-1)-core encircled with an Sc-rich shell forms. PMID:29677155

The transition from granite to banded aplite-pegmatite sheet complexes: An example from Megiliggar Rocks, Tregonning topaz granite, Cornwall

NASA Astrophysics Data System (ADS)

Breiter, K.; Ďurišová, J.; Hrstka, T.; Korbelová, Z.; Vašinová Galiová, M.; Müller, A.; Simons, B.; Shail, R. K.; Williamson, B. J.; Davies, J. A.

2018-03-01

The genetic relationship between a granite pluton and adjacent complex of rare-metal pegmatite-aplite-banded sheets (Megiliggar Sheet Complex - MSC) has been studied at the border of the Tregonning topaz granite at Megiliggar Rocks, Cornwall, SW England. Similarities in whole-rock chemical and mineralogical compositions, together with a gradual change in textures away from the granite margin, provide strong evidence for a genetic link between the Tregonning Granite and MSC. The sheets are likely to represent apophyses of residual melt which escaped from the largely crystallized roof of the granite pluton. The escaping melt was peraluminous, had a composition near the F, B, Li slightly enriched granite minimum, and, in comparison with other Cornish granites, was enriched in F, Li, Rb, Cs, Sn, W, Nb, Ta, and U, and depleted in Fe, Mg, Ca, Sr, Th, Zr, and REE. With increasing distance from the Tregonning Granite, the silicate melt crystallized as homogeneous leucogranite sheets and banded complex sheets (i.e. combinations of bands with granitic, aplitic and pegmatitic textures), then layered aplite-pegmatites; this sequence becoming progressively more depleted in the fluxing and volatile elements F, Li, Rb, and Cs, but showing no change in Zr/Hf ratios. The fixed Zr/Hf ratio is interpreted as indicating a direct genetic link (parental melt) between all rock types, however the melt progressively lost fluxing and volatile elements with distance from the granite pluton, probably due to wall-rock reaction or fluid exsolution and migration via fractures. Differentiation of the primary melt into Na-Li-F-rich and separate K-B-rich domains was the dominant chemical process responsible for the textural and mineral diversity of the MSC. On a large (cliff-section) scale, the proximal Na-Li-F-rich leucogranite passes through complex sheets into K-B-rich aplite-pegmatites, whilst at a smaller (<1 m) scale, the K-B-rich bands are interspersed (largely overlain) by Na-Li-F-rich segregations. The grain size differences between the aplite and pegmatite could be related to pressure fluctuations and/or undercooling.

Synthesis, characterization and biological study on Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide and bis(3-hydroxyimino)butan-2-ylidene)-oxalohydrazide.

PubMed

El-Asmy, A A; El-Gammal, O A; Radwan, H A

2010-09-01

Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide (H(2)L(1)) and oxalyl bis(diacetylmonoxime hydrazone) [its IUPAC name is oxalyl bis(3-hydroxyimino)butan-2-ylidene)oxalohydrazide] (H(4)L(2)) have been synthesized and characterized by partial elemental analysis, spectral (IR; electronic), thermal and magnetic measurements. [Cr(L(1))(H(2)O)(3)(Cl)].H(2)O, [ZrO(HL(1))(2)].C(2)H(5)OH, [UO(2)(L(1))(H(2)O)(2)] [ZrO(H(3)L(2))(Cl)](2).2H(2)O, [HfO(H(3)L(2))(Cl)](2).2H(2)O and [UO(2)(H(2)L(2))].2H(2)O have been suggested. H(2)L(1) behaves as a monobasic or dibasic bidentate ligand while H(4)L(2) acts as a tetrabasic octadentate with the two metal centers. The molecular modeling of the two ligands have been drawn and their molecular parameters were calculated. Examination of the DNA degradation of H(2)L(1) and H(4)L(2) as well as their complexes revealed that direct contact of [ZrO(H(3)L(2))(Cl)](2).2H(2)O or [HfO(H(3)L(2))(Cl)](2).2H(2)O degrading the DNA of Eukaryotic subject. The ligands and their metal complexes were tested against Gram's positive Bacillus thuringiensis (BT) and Gram's negative (Escherichia coli) bacteria. All compounds have small inhibitory effects. Copyright 2010 Elsevier B.V. All rights reserved.

INTERMEDIATE STAGES OF REACTIONS FORMING CARBIDES OF TITANIUM, ZIRCONIUM, VANADIUM, NIOBIUM, AND TANTALIUM

DTIC Science & Technology

Tensimetric examination was made of the formation of the carbides TiC , ZrC, VC, NbC and TaC in a vacuum. During x-ray and chemical analysis of...for obtaining TiC , and ZrC through the stage of intermediate oxides Ti2O3, Ti3O5, TiO and Zr2O3, ZrO, respectively and also for the reaction of

Pressure-dependence of the phase transitions and thermal expansion in zirconium and hafnium pyrovanadate

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

Gallington, Leighanne C.; Hester, Brett R.; Kaplan, Benjamin S.

Low or negative thermal expansion (NTE) has been previously observed in members of the ZrP{sub 2}O{sub 7} family at temperatures higher than their order-disorder phase transitions. The thermoelastic properties and phase behavior of the low temperature superstructure and high temperature negative thermal expansion phases of ZrV{sub 2}O{sub 7} and HfV{sub 2}O{sub 7} were explored via in situ variable temperature/pressure powder x-ray diffraction measurements. The phase transition temperatures of ZrV{sub 2}O{sub 7} and HfV{sub 2}O{sub 7} exhibited a very strong dependence on pressure (∼700 K GPa), with moderate compression suppressing the formation of their NTE phases below 513 K. Compression alsomore » reduced the magnitude of the coefficients of thermal expansion in both the positive and negative thermal expansion phases. Additionally, the high temperature NTE phase of ZrV{sub 2}O{sub 7} was found to be twice as stiff as the low temperature positive thermal expansion superstructure (24 and 12 GPa respectively). - Graphical abstract: The temperature at which ZrV{sub 2}O{sub 7} transforms to a phase displaying negative thermal expansion is strongly pressure dependent. The high temperature form of ZrV{sub 2}O{sub 7} is elastically stiffer than the low temperature form. - Highlights: • The order-disorder phase transition temperatures in ZrV{sub 2}O{sub 7} and HfV{sub 2}O{sub 7} are strongly pressure dependent (∼700 K.GPa). • The high temperature (disordered) phase of ZrV{sub 2}O{sub 7} is much stiffer than the ambient temperature (ordered) phase. • Compression reduces the magnitude of the negative thermal expansion in the high temperature phase of ZrV{sub 2}O{sub 7}.« less

Shear bond strength between an indirect composite layering material and feldspathic porcelain-coated zirconia ceramics.

PubMed

Fushiki, Ryosuke; Komine, Futoshi; Blatz, Markus B; Koizuka, Mai; Taguchi, Kohei; Matsumura, Hideo

2012-10-01

This study aims to evaluate the effect of both feldspathic porcelain coating of zirconia frameworks and priming agents on shear bond strength between an indirect composite material and zirconia frameworks. A total of 462 airborne-particle-abraded zirconia disks were divided into three groups: untreated disks (ZR-AB), airborne-particle-abraded zirconia disks coated with feldspathic porcelain, (ZR-PO-AB), and hydrofluoric acid-etched zirconia disks coated with feldspathic porcelain (ZR-PO-HF). Indirect composite (Estenia C&B) was bonded to zirconia specimens with no (CON) or one of four priming agents--Clearfil Photo Bond (CPB), Clearfil Photo Bond with Clearfil Porcelain Bond Activator (CPB + activator), Estenia Opaque primer, or Porcelain Liner M Liquid B (PLB)--with or without an opaque material (Estenia C&B Opaque). All specimens were tested for shear bond strength before and after 20,000 thermocycles. The Steel-Dwass test and Mann-Whitney U test were used to compare shear bond strength. In ZR-AB specimens, the initial bond strength of the CPB and CPB + Activator groups was significantly higher as compared with the other three groups (P < 0.05), whereas the PLB and CPB + Activator groups had the highest pre- and post-thermocycling bond strengths in ZR-PO-AB and ZR-PO-HF specimens. Among CON disks without opaque material, bond strength was significantly lower in ZR-AB specimens than in ZR-PO-AB and ZR-PO-HF specimens (P < 0.05). Feldspathic porcelain coating of a Katana zirconia framework enhanced the bond strength of Estenia C&B indirect composite to zirconia independent of surface treatment. The use of a silane coupling agent and opaque material yields durable bond strength between the indirect composite and feldspathic-porcelain-coated zirconia. The results of the present study suggest that feldspathic porcelain coating of zirconia frameworks is an effective method to obtain clinically acceptable bond strengths of a layering indirect composite material to a zirconia framework.

Double and Triple Si-H-M Bridge Bonds: Matrix Infrared Spectra and Theoretical Calculations for Reaction Products of Silane with Ti, Zr, and Hf Atoms.

PubMed

Xu, Bing; Shi, Peipei; Huang, Tengfei; Wang, Xuefeng; Andrews, Lester

2017-05-25

Infrared spectra of matrix isolated dibridged Si(μ-H) 2 MH 2 and tribridged Si(μ-H) 3 MH molecules (M = Zr and Hf) were observed following the laser-ablated metal atom reactions with SiH 4 during condensation in excess argon and neon, but only the latter species was observed with titanium. Assignments of the major vibrational modes, which included terminal MH, MH 2 and hydrogen bridge Si-H-M stretching modes, were confirmed by the appropriate SiD 4 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). The Si-H-M hydrogen bridge bond is calculated as weak covalent interaction and compared with the C-H···M agostic interaction in terms of electron localization function (ELF) analysis and noncovalent interaction index (NCI) calculations. Furthermore, the different products of Ti, Zr, and Hf reactions with SiH 4 are discussed in detail.

Spectroscopic characterization of zirconium(IV) and hafniumf(IV) gallate phthalocyanines in monolithic silica gels obtained by sol gel method

NASA Astrophysics Data System (ADS)

Gerasymchuk, Y. S.; Chernii, V. Ya.; Tomachynski, L. A.; Legendziewicz, J.; Radzki, St.

2005-07-01

The Zr(IV) and Hf(IV) phthalocyanines, with gallate as axial ligand coordinated to the central metal atom of phthalocyanine, were incorporated in silica gels during sol-gel process with using tetraethyl orthosilicate (TEOS) as precursor. The obtained mixed inorganic-organic composites were transparent and homogeneous. The absorption and emission properties of these materials in comparison with the spectra of the Zr(IV) and Hf(IV) phthalocyanines in various solvents were investigated. The spectra were correlated with various stage of the sol-gel process. It was established that in the gels concurrence of the monomer and dimer form is different in sol, alco-, hydro- and xerogels. The intensive 700-725 nm fluorescence emission upon relatively long-wavelength excitation and unusually large (about 45 nm) Stokes shift in the Q region, suggest that Zr(IV) and Hf(IV) phthalocyanines could be considered as photosensitizers in the PDT method (photodynamic therapy).

Unusual and Tunable Negative Linear Compressibility in the Metal-Organic Framework MFM-133(M) (M = Zr, Hf).

PubMed

Yan, Yong; O'Connor, Alice E; Kanthasamy, Gopikkaa; Atkinson, George; Allan, David R; Blake, Alexander J; Schröder, Martin

2018-03-21

High-pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB 4- [H 4 TCHB = 3,3',5,5'-tetrakis(4-carboxyphenyl)-2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl] and {M 6 (μ 3 -OH) 8 (OH) 8 (COO) 8 } clusters confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional wine-rack NLC mechanism leading to distortion of the octahedral cage toward a more elongated polyhedron under static compression. Despite the isomorphous nature of these two structures, MFM-133(Hf) shows a higher degree of NLC than the Zr(IV) analogue. Thus, for the first time, we demonstrate here that the NLC property can be effectively tuned in a framework material by simply varying the inorganic component of the frameworks without changing the network topology and structure.

Shear bond, wettability and AFM evaluations on CO2 laser-irradiated CAD/CAM ceramic surfaces.

PubMed

El Gamal, Ahmed; Medioni, Etienne; Rocca, Jean Paul; Fornaini, Carlo; Muhammad, Omid H; Brulat-Bouchard, Nathalie

2017-05-01

The purpose of this study is to determine the CO 2 laser irradiation in comparison with sandblasting (Sb), hydrofluoric acid (Hf) and silane coupling agent (Si) on shear bond strength (SBS), roughness (Rg) and wettability (Wt) of resin cement to CAD/CAM ceramics. Sixty (CAD/CAM) ceramic discs were prepared and distributed into six different groups: group A, control lithium disilicate (Li); group B, control zirconia (Zr); group C, Li: CO 2 /HF/Si; group D, Li: HF/Si; group E, Zr: CO 2 /Sb/Si; group F, Zr: Sb/Si. Result showed significant difference between irradiated and non-irradiated in terms of shear bond strength for zirconia ceramics (p value = 0.014). Moreover, partial surface wettability for irradiated and non-irradiated ceramics. Irradiated surface demonstrated more rough surface in lithium disilicate than zirconia ceramics. CO 2 irradiation could increase shear bond strength, surface roughness and wettability for both CAD/CAM ceramics.

Electronic structure and energetics of the tetragonal distortion for TiH2, ZrH2 and HfH2: a first principles study

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

Quijano, Ramiro; DeCoss, Romeo; Singh, David J

2009-01-01

The electronic structure and energetics of the tetragonal distortion for the fluorite-type dihydrides TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} are studied by means of highly accurate first-principles total-energy calculations. For HfH{sub 2}, in addition to the calculations using the scalar relativistic (SR) approximation, calculations including the spin-orbit coupling have also been performed. The results show that TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} in the cubic phase are unstable against tetragonal strain. For the three systems, the total energy shows two minima as a function of the c/a ratio with the lowest-energy minimum at c/a < 1 in agreementmore » with the experimental observations. The band structure of TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} (SR) around the Fermi level shows two common features along the two major symmetry directions of the Brillouin zone, {Lambda}?L and {Lambda}?K, a nearly flat doubly degenerate band, and a van Hove singularity, respectively. In cubic HfH{sub 2} the spin-orbit coupling lifts the degeneracy of the partially filled bands in the {Lambda}?L path, while the van Hove singularity in the {Lambda}?K path remains unchanged. The density of states of the three systems in the cubic phase shows a sharp peak at the Fermi level. We found that the tetragonal distortion produces a strong reduction in the density of states at the Fermi level resulting mainly from the splitting of the doubly-degenerate bands in the {Lambda}?L direction and the shift of the van Hove singularity to above the Fermi level. The validity of the Jahn-Teller model in explaining the tetragonal distortion in this group of dihydrides is discussed.« less

Physical characterization of a new composition of oxidized zirconium-2.5 wt% niobium produced using a two step process for biomedical applications

NASA Astrophysics Data System (ADS)

Pawar, V.; Weaver, C.; Jani, S.

2011-05-01

Zirconium and particularly Zr-2.5 wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate. In this study, we demonstrate a two step process that forms a thicker DHZ and thus increased depth of hardening than that can be obtained using a one step oxidation process. The first step is thermal oxidation in air and the second step is a heat treatment in vacuum. The second step drives oxygen from the oxide formed in the first step deeper into the substrate to form a thicker DHZ. During the process only a portion of the oxide is dissolved. This new composition (DHOxZr) has approximately 4-6 μm oxide similar to that of OxZr. The nano-hardness of the oxide is similar but the DHZ is approximately 10 times thicker. The stoichiometry of the oxide is similar and a secondary phase rich in oxygen is present through the entire thickness. Due to the increased depth of hardening, the critical load required for the onset of oxide cracking is approximately 1.6 times more than that of the oxide of OxZr. This new composition has a potential to be used as a bearing surface in applications where greater depth of hardening is required.

Across-arc geochemical variations in the Southern Volcanic Zone, Chile (34.5-38.0°S): Constraints on mantle wedge and slab input compositions

NASA Astrophysics Data System (ADS)

Jacques, G.; Hoernle, K.; Gill, J.; Hauff, F.; Wehrmann, H.; Garbe-Schönberg, D.; van den Bogaard, P.; Bindeman, I.; Lara, L. E.

2013-12-01

Crustal assimilation (e.g. Hildreth and Moorbath, 1988) and/or subduction erosion (e.g. Stern, 1991; Kay et al., 2005) are believed to control the geochemical variations along the northern portion of the Chilean Southern Volcanic Zone. In order to evaluate these hypotheses, we present a comprehensive geochemical data set (major and trace elements and O-Sr-Nd-Hf-Pb isotopes) from Holocene primarily olivine-bearing volcanic rocks across the arc between 34.5°S and 38.0°S, including volcanic front centers from Tinguiririca to Callaqui, the rear arc centers of Infernillo Volcanic Field, Laguna del Maule and Copahue, and extending 300 km into the backarc. We also present an equivalent data set for Chile trench sediments outboard of this profile. The volcanic arc (including volcanic front and rear arc) samples primarily range from basalt to andesite/trachyandesite, whereas the backarc rocks are low-silica alkali basalts and trachybasalts. All samples show some characteristic subduction zone trace element enrichments and depletions, but the backarc samples show the least. Backarc basalts have higher Ce/Pb, Nb/U, Nb/Zr, and Ta/Hf, and lower Ba/Nb and Ba/La, consistent with less of a slab-derived component in the backarc and, consequently, lower degrees of mantle melting. The mantle-like δ18O in olivine and plagioclase phenocrysts (volcanic arc = 4.9-5.6‰ and backarc = 5.0-5.4‰) and lack of correlation between δ18O and indices of differentiation and other isotope ratios, argue against significant crustal assimilation. Volcanic arc and backarc samples almost completely overlap in Sr and Nd isotopic composition. High precision (double-spike) Pb isotope ratios are tightly correlated, precluding significant assimilation of older sialic crust but indicating mixing between a South Atlantic Mid Ocean-Ridge Basalt (MORB) source and a slab component derived from subducted sediments and altered oceanic crust. Hf-Nd isotope ratios define separate linear arrays for the volcanic arc and backarc, neither of which trend toward subducting sediment, possibly reflecting a primarily asthenospheric mantle array for the volcanic arc and involvement of enriched Proterozoic lithospheric mantle in the backarc. We propose a quantitative mixing model between a mixed-source, slab-derived melt and a heterogeneous mantle beneath the volcanic arc. The model is consistent with local geodynamic parameters, assuming water-saturated conditions within the slab.

Sc–Zr–Nb–Rh–Pd and Sc–Zr–Nb–Ta–Rh–Pd High-Entropy Alloy Superconductors on a CsCl-Type Lattice

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

Stolze, Karoline; Tao, Jing; von Rohr, Fabian O.

We have synthesized previously unreported High-Entropy Alloys (HEAs) in the pentanary (ScZrNb) 1-x[RhPd] x and hexanary (ScZrNbTa) 1-x[RhPd] x systems. The materials have CsCl-type structures and mixed site occupancies. Both HEAs are type-II superconductors with strongly varying critical temperatures (T cs) depending on the valence electron count (VEC); the T cs increase monotonically with decreasing VEC within each series, and do not follow the trends seen for either crystalline or amorphous transition metal superconductors. The (ScZrNb) 0.65[RhPd] 0.35 HEA with the highest T c, ~9.3 K, also exhibits the largest µ 0H c2(0) = 10.7 T. The pentanary and hexanarymore » HEAs have higher superconducting transition tempera-tures than their simple binary intermetallic relatives with the CsCl-type structure and a surprisingly ductile mechanical behavior. The presence of niobium, even at the 20% level, has a positive impact on the T c. Nevertheless, niobium-free (ScZr) 0.50[RhPd] 0.50, as mother-compound of both superconducting HEAs found here, is itself superconducting, proving that superconductivity is an intrinsic feature of the bulk material.« less

Sc–Zr–Nb–Rh–Pd and Sc–Zr–Nb–Ta–Rh–Pd High-Entropy Alloy Superconductors on a CsCl-Type Lattice

DOE PAGES

Stolze, Karoline; Tao, Jing; von Rohr, Fabian O.; ...

2018-01-17

We have synthesized previously unreported High-Entropy Alloys (HEAs) in the pentanary (ScZrNb) 1-x[RhPd] x and hexanary (ScZrNbTa) 1-x[RhPd] x systems. The materials have CsCl-type structures and mixed site occupancies. Both HEAs are type-II superconductors with strongly varying critical temperatures (T cs) depending on the valence electron count (VEC); the T cs increase monotonically with decreasing VEC within each series, and do not follow the trends seen for either crystalline or amorphous transition metal superconductors. The (ScZrNb) 0.65[RhPd] 0.35 HEA with the highest T c, ~9.3 K, also exhibits the largest µ 0H c2(0) = 10.7 T. The pentanary and hexanarymore » HEAs have higher superconducting transition tempera-tures than their simple binary intermetallic relatives with the CsCl-type structure and a surprisingly ductile mechanical behavior. The presence of niobium, even at the 20% level, has a positive impact on the T c. Nevertheless, niobium-free (ScZr) 0.50[RhPd] 0.50, as mother-compound of both superconducting HEAs found here, is itself superconducting, proving that superconductivity is an intrinsic feature of the bulk material.« less

Search for thermoelectrics with high figure of merit in half-Heusler compounds with multinary substitution

NASA Astrophysics Data System (ADS)

Choudhary, Mukesh K.; Ravindran, P.

2018-04-01

In order to improve the thermoelectric performance of TiCoSb we have substituted 50% of Ti equally with Zr and Hf at Ti site and Sb with Sn and Se equally at Sb site. The electronic structure of Ti0.5Zr0.25Hf0.25CoSn0.5Se0.5 is investigated using the full potential linearized augmented plane wave method and the thermoelectric transport properties are calculated on the basis of semi-classical Boltzmann transport theory. Our band structure calculations show that Ti0.5Zr0.25Hf0.25CoSn0.5Se0.5 has semiconducting behavior with indirect band gap value of 0.98 eV which follow the empirical rule of 18 valence-electron content to bring semiconductivity in half Heusler compounds, indicating that one can have semiconducting behavior in multinary phase of half Heusler compounds if they full fill the 18 VEC rule and this open-up the possibility of designing thermoelectrics with high figure of merit in half Heusler compounds. We show that at high temperature of around 700K Ti0.5Zr0.25Hf0.25CoSn0.5Se0.5 has high thermoelectric figure of merit of ZT = 1.05 which is higher than that of TiCoSb (˜ 0.95) suggesting that by going from ternary to multinary phase system one can enhance the thermoelectric figure of merit at higher temperatures.

Energy efficient microwave synthesis of mesoporous Ce 0.5M 0.5O 2 (Ti, Zr, Hf) nanoparticles for low temperature CO oxidation in an ionic liquid – a comparative study

DOE PAGES

Alammar, Tarek; Chow, Ying -Kit; Mudring, Anja -Verena

2014-11-19

Ce 0.5M 0.5O 2 (M = Ti, Zr, Hf) nanoparticles have been successfully synthesized by microwave irradiation in the ionic liquid [C 4mim][Tf 2N] (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide). The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and N 2–adsorption measurements. XRD and Raman spectroscopy analyses confirmed the formation of solid solutions with cubic fluorite structure. The catalytic activities of the Ce 0.5M 0.5O 2 (M = Ti, Zr, Hf) nanoparticles were investigated in the low-temperature oxidation of CO. Ce 0.5Zr 0.5O 2 nanospheresmore » exhibit the best performance (100% conversion at 350 °C), followed by Ce 0.5Hf 0.5O 2 (55% conversion at 360 °C) and Ce 0.5Ti 0.5O 2 (11% conversion at 350 °C). Heating the as-prepared Ce 0.5Zr 0.5O 2 to 600 °C for extended time leads to a decrease in surface area and, as expected decreased catalytic activity. Depending on the ionic liquid the obtained Ce 0.5Zr 0.5O 2 exhibits different morphologies, varying from nano-spheres in [C 4mim][Tf 2N] and [P 66614][Tf 2N] (P 66614 = trishexyltetradecylphosphonium) to sheet-like assemblies in [C 3mimOH][Tf 2N] (C 3mimOH = 1-(3-hydroxypropyl)-3-methylimidazolium). As a result, the microwave synthesis superiority to other heating methods like sonochemical synthesis and conventional heating was proven by comparative experiments where the catalytic activity of Ce 0.5Zr 0.5O 2 obtained by alternate methods such as conventional heating was found to be poorer than that of the microwave-synthesised material.« less

Study of a ;hot; particle with a matrix of U-bearing metallic Zr: Clue to supercriticality during the Chernobyl nuclear accident

NASA Astrophysics Data System (ADS)

Pöml, P.; Burakov, B.

2017-05-01

This paper is dedicated to the 30th anniversary of the severe nuclear accident that occurred at the Chernobyl NPP on 26 April 1986. A detailed study on a Chernobyl "hot" particle collected from contaminated soil was performed. Optical and electron microscopy, as well as quantitative x-ray microbeam analysis methods were used to determine the properties of the sample. The results show that the particle (≈ 240 x 165 μm) consists of a metallic Zr matrix containing 2-3 wt. % U and bearing veins of an U,Nb admixture. The metallic Zr matrix contains two phases with different amounts of O with the atomic proportions (U,Zr,Nb)0.73O0.27 and (U,Zr,Nb)0.61O0.39. The results confirm the interaction between UO2 fuel and zircaloy cladding in the reactor core. To explain the process of formation of the particle, its properties are compared to laboratory experiments. Because of the metallic nature of the particle it is concluded that it must have formed during a very high temperature (> 2400∘C) process that lasted for only a very short time (few microseconds or less); otherwise the particle should have been oxidised. Such a rapid very high temperature process indicates that at least part of the reactor core could have been supercritical prior to an explosion as it was previously suggested in the literature.

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

NASA Astrophysics Data System (ADS)

Gómez, Luis A.; Menezes, Leonardo de S.; de Araújo, Cid B.; Gonçalves, Rogeria R.; Ribeiro, Sidney J. L.; Messaddeq, Younes

2010-06-01

Frequency upconversion (UC) luminescence in nanocrystalline zirconia (ZrO2) and hafnia (HfO2) doped with Er3+ and Yb3+ was studied under continuous-wave excitation at 980 nm. Samples of ZrO2:Er3+, ZrO2:Er3+/Yb3+, and HfO2:Er3+/Yb3+ were prepared by the sol-gel technique and characterized using x-ray diffraction and electron microscopy. A study of the infrared-to-green and infrared-to-red UC processes was performed including the analysis of the spectral and the temporal behavior. The mechanisms contributing to the UC luminescence were identified as excited state absorption and energy transfer among rare-earth ions.

Irradiation testing of high density uranium alloy dispersion fuels

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

Hayes, S.L.; Trybus, C.L.; Meyer, M.K.

1997-10-01

Two irradiation test vehicles have been designed, fabricated, and inserted into the Advanced Test Reactor in Idaho. Irradiation of these experiments began in August 1997. These irradiation tests were designed to obtain irradiation performance information on a variety of potential new, high-density dispersion fuels. Each of the two irradiation vehicles contains 32 microplates. Each microplate is aluminum clad, having an aluminum matrix phase and containing one of the following compositions as the fuel phase: U-10Mo, U-8Mo, U-6Mo, U-4Mo, U-9Nb-3Zr, U-6Nb-4Zr, U-5Nb-3Zr, U-6Mo-1Pt, U-6Mo-0.6Ru, U-10Mo-0.05Sn, U{sub 2}Mo, or U{sub 3}Si{sub 2}. These experiments will be discharged at peak fuel burnups ofmore » 40% and 80%. Of particular interest is the fission gas retention/swelling characteristics of these new fuel alloys. This paper presents the design of the irradiation vehicles and the irradiation conditions.« less

[Radioactive nuclides in the marine environment--distribution and behaviour of 95Zr, 95Nb originated from fallout].

PubMed

Yamato, A; Miyagawa, N; Miyanaga, N

1984-07-01

To investigate behaviour of 95Zr, 95Nb in the marine environment, various samples have been collected and measured by means of Ge(Li) gamma-ray spectrometry and/or radiochemical analysis during a period from 1974 to 1982 at coastal area of Tokai-mura, Ibaraki prefecture. Concentration of the nuclides in seaweeds increased remarkably after atmospheric nuclear detonation by P.R. of China, and the activity ratio between the nuclides changed by time was not fit well by the transient decay equation. Concentration variation in sea water was smaller than that in sea weeds, and the minimum change in sea sediment. Increase of concentration in these environmental samples was observed in chronological order of sea water, sea weeds then sediment after detonations, suggesting that the uptake of the nuclides by these sea weeds from sea water is faster than that via root. Observed concentration factors on the nuclides by sea weeds were calculated from the observed concentrations in sea water and sea weeds. Maximum values on 95Zr and 95Nb were 2110, 2150, respectively for Ecklonia cava and Eisenia bicyclis.

Effect of Zr, Nb and Ti addition on injection molded 316L stainless steel for bio-applications: Mechanical, electrochemical and biocompatibility properties.

PubMed

Gulsoy, H Ozkan; Pazarlioglu, Serdar; Gulsoy, Nagihan; Gundede, Busra; Mutlu, Ozal

2015-11-01

The research investigated the effect of Zr, Nb and Ti additions on mechanical, electrochemical properties and biocompatibility of injection molded 316L stainless steel. Addition of elemental powder is promoted to get high performance of sintered 316L stainless steels. The amount of additive powder plays a role in determining the sintered microstructure and all properties. In this study, 316L stainless steel powders used with the elemental Zr, Nb and Ti powders. A feedstock containing 62.5 wt% powders loading was molded at different injection molded temperature. The binders were completely removed from molded components by solvent and thermal debinding at different temperatures. The debinded samples were sintered at 1350°C for 60 min. Mechanical, electrochemical property and biocompatibility of the sintered samples were performed mechanical, electrochemical, SBF immersion tests and cell culture experiments. Results of study showed that sintered 316L and 316L with additives samples exhibited high corrosion properties and biocompatibility in a physiological environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Advanced TEM characterization of oxide nanoparticles in ODS Fe–12Cr–5Al alloys

DOE PAGES

Unocic, Kinga A; Hoelzer, David T; Pint, Bruce A

2016-01-01

For oxide nanoparticles present in three oxide-dispersion-strengthened (ODS) Fe–12Cr–5Al alloys containing additions of (1) Y 2O 3 (125Y), (2) Y 2O 3 + ZrO 2 (125YZ), and (3) Y 2O 3 + HfO 2 (125YH), were investigated using transmission and scanning transmission electron microscopy. Furthermore, in all three alloys nano-sized (<3.5 nm) oxide particles distributed uniformly throughout the microstructure were characterized using advanced electron microscopy techniques. In the 125Y alloy, mainly Al 2O 3 and yttrium–aluminum garnet (YAG) phases (Y 3Al 5O 12) were present, while in the 125YZ alloy, additional Zr(C,N) precipitates were identified. The 125YH alloy had themore » most complex precipitation sequence whereby in addition to the YAG and Al 2O 3 phases, Hf(C,N), Y 2Hf 2O 7, and HfO 2 precipitates were also found. The presence of HfO 2 was mainly due to the incomplete incorporation of HfO 2 powder during mechanical alloying of the 125YH alloy. The alloy having the highest total number density of the oxides, the smallest grain size, and the highest Vickers hardness was the 125YZ alloy indicating, that Y 2O 3 + ZrO 2 additions had the strongest effect on grain size and tensile properties. Finally, high-temperature mechanical testing will be addressed in the near future, while irradiation studies are underway to investigate the irradiation resistance of these new ODS FeCrAl alloys.« less

VizieR Online Data Catalog: Atomic mass excesses (Schatz+, 2017)

NASA Astrophysics Data System (ADS)

Schatz, H.; Ong, W.-J.

2018-03-01

X-ray burst model predictions of light curves and the final composition of the nuclear ashes are affected by uncertain nuclear masses. However, not all of these masses are determined experimentally with sufficient accuracy. Here we identify the remaining nuclear mass uncertainties in X-ray burst models using a one-zone model that takes into account the changes in temperature and density evolution caused by changes in the nuclear physics. Two types of bursts are investigated-a typical mixed H/He burst with a limited rapid proton capture process (rp-process) and an extreme mixed H/He burst with an extended rp-process. When allowing for a 3σ variation, only three remaining nuclear mass uncertainties affect the light-curve predictions of a typical H/He burst (27P, 61Ga, and 65As), and only three additional masses affect the composition strongly (80Zr, 81Zr, and 82Nb). A larger number of mass uncertainties remain to be addressed for the extreme H/He burst, with the most important being 58Zn, 61Ga, 62Ge, 65As, 66Se, 78Y, 79Y, 79Zr, 80Zr, 81Zr, 82Zr, 82Nb, 83Nb, 86Tc, 91Rh, 95Ag, 98Cd, 99In, 100In, and 101In. The smallest mass uncertainty that still impacts composition significantly when varied by 3σ is 85Mo with 16keV uncertainty. For one of the identified masses, 27P, we use the isobaric mass multiplet equation to improve the mass uncertainty, obtaining an atomic mass excess of -716(7)keV. The results provide a roadmap for future experiments at advanced rare isotope beam facilities, where all the identified nuclides are expected to be within reach for precision mass measurements. (1 data file).

Carbon K-edge X-ray absorption spectroscopy and time-dependent density functional theory examination of metal-carbon bonding in metallocene dichlorides.

PubMed

Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J

2013-10-02

Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.

Plasma electrolytic oxidation treatment mode influence on corrosion properties of coatings obtained on Zr-1Nb alloy in silicate-phosphate electrolyte

NASA Astrophysics Data System (ADS)

Farrakhov, R. G.; Mukaeva, V. R.; Fatkullin, A. R.; Gorbatkov, M. V.; Tarasov, P. V.; Lazarev, D. M.; Babu, N. Ramesh; Parfenov, E. V.

2018-01-01

This research is aimed at improvement of corrosion properties for Zr-1Nb alloy via plasma electrolytic oxidation (PEO). The coatings obtained in DC, pulsed unipolar and pulsed bipolar modes were assessed using SEM, XRD, PDP and EIS techniques. It was shown that pulsed unipolar mode provides the PEO coatings having promising combination of the coating thickness, surface roughness, porosity, corrosion potential and current density, and charge transfer resistance, all contributing to corrosion protection of the zirconium alloy for advanced fuel cladding applications.

Production and properties of high strength Ni free Zr-based BMGs

NASA Astrophysics Data System (ADS)

Iqbal, M.; Wang, W. H.

2014-06-01

Bulk metallic glasses (BMGs) are well known for very attractive physical, mechanical and thermal properties. Zr-based BMGs are used as structural materials in sports goods, electronics, jewelry, medical and aerospace applications. Ni free Zr48Cu36Al8M8 (M = Nb, Ti and Ta) BMGs are successfully synthesized by Cu mold casting technique. Differential scanning calorimetery (DSC) results show that the Zr48Cu36Al8Nb8 BMG have good thermal stability, wide supercooled liquid region of 80 K and contain the double stage crystallization. The alloy has fracture strength of 1.953 GPa. Shear angle was measured to be in the range of 43.5±5° for the alloy studied. Vicker's hardness of the BMGs was found to be over 500 Hv for the as cast alloy which enhanced about 11 % more by annealing up to 600 °C/20 min. Intersected shear bands were observed. The observed promising mechanical and thermal properties showed that BMG studied can be used for industrial applications.

Thickness and Nb-doping effects on ferro- and piezoelectric properties of highly a-axis-oriented Nb-doped Pb(Zr0.3Ti0.7)O3 films

NASA Astrophysics Data System (ADS)

Zhu, Zhi-Xiang; Ruangchalermwong, C.; Li, Jing-Feng

2008-09-01

Tetragonal Nb-doped Pb(Zr0.3Ti0.7)O3 (PNZT) films with a lead oxide seeding layer were deposited on the Pt(111)/Ti/SiO2/Si(100) substrates by sol-gel processing. The as-grown PNZT films with thicknesses ranging from about 0.08 to 0.78 μm show highly a-axis preferential orientation, and their ferroelectric and piezoelectric properties improved with increasing film thickness. Due to the combined effects of Nb doping and a-axis texturing as well as reduced substrate constraint, a high d33 constant up to 196 pm/V was obtained for PNZT film at 0.78 μm in addition to a large remnant polarization of 69 μC/cm2. This well a-axis-oriented PNZT films on platinized Si with a high piezoresponse are suitable for the fabrication of microelectromechanical devices.

Half-Heusler Alloys as Promising Thermoelectric Materials

NASA Astrophysics Data System (ADS)

Page, Alexander A.

This thesis describes Ph.D. research on the half-Heusler class of thermoelectric materials. Half-Heusler alloys are a versatile class of materials that have been studied for use in photovoltaics, phase change memory, and thermoelectric power generation. With respect to thermoelectric power generation, new approaches were recently developed in order to improve the thermoelectric figure of merit, ZT, of half-Heusler alloys. Two of the strategies discussed in this work are adding excess Ni within MNiSn (M = Ti, Zr, or Hf) compounds to form full-Heusler nanostructures and using isoelectronic substitution of Ti, Zr, and Hf in MNiSn compounds to create microscale grain boundaries. This work uses computational simulations based on density functional theory, combined with the cluster expansion method, to predict the stable phases of pseudo-binary and pseudo-ternary composition systems. Statistical mechanics methods were used to calculate temperature-composition phase diagrams that relate the equilibrium phases. It is shown that full-Heusler nanostructures are predicted to remain stable even at high temperatures, and the microscale grain boundaries observed in (Ti,Zr,Hf)NiSn materials are found to be thermodynamically unstable at equilibrium. A new strategy of combining MNiSn materials with ZrNiPb has also recently emerged, and theoretical and experimental work show that a solid solution of the two materials is stable.

Densification and Thermal Properties of Zirconium Diboride Based Ceramics

DTIC Science & Technology

2012-01-01

pulse on the front face and the radiant energy going to an infrared detector on the back face of the specimen...changes going across a row of the periodic table (e.g., Zr, Nb, Mo…) because of the filling of bonding and anti-bonding states in the hybrid orbitals...the relatively small amounts of ZrC (i.e., ə wt%) likely to go into solid solution with the ZrB2, based on the Zr-B-C phase diagram.6 (2

The intrinsic disorder related alloy scattering in ZrNiSn half-Heusler thermoelectric materials

PubMed Central

Xie, Hanhui; Wang, Heng; Fu, Chenguang; Liu, Yintu; Snyder, G. Jeffrey; Zhao, Xinbing; Zhu, Tiejun

2014-01-01

The intrinsic structural disorder dramatically affects the thermal and electronic transport in semiconductors. Although normally considered an ordered compound, the half-Heusler ZrNiSn displays many transport characteristics of a disordered alloy. Similar to the (Zr,Hf)NiSn based solid solutions, the unsubstituted ZrNiSn compound also exhibits charge transport dominated by alloy scattering, as demonstrated in this work. The unexpected charge transport, even in ZrNiSn which is normally considered fully ordered, can be explained by the Ni partially filling interstitial sites in this half-Heusler system. The influence of the disordering and defects in crystal structure on the electron transport process has also been quantitatively analyzed in ZrNiSn1-xSbx with carrier concentration nH ranging from 5.0×1019 to 2.3×1021 cm−3 by changing Sb dopant content. The optimized carrier concentration nH ≈ 3–4×1020 cm−2 results in ZT ≈ 0.8 at 875K. This work suggests that MNiSn (M = Hf, Zr, Ti) and perhaps most other half-Heusler thermoelectric materials should be considered highly disordered especially when trying to understand the electronic and phonon structure and transport features. PMID:25363573

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

MC Carbide Characterization in High Refractory Content Powder-Processed Ni-Based Superalloys

NASA Astrophysics Data System (ADS)

Antonov, Stoichko; Chen, Wei; Huo, Jiajie; Feng, Qiang; Isheim, Dieter; Seidman, David N.; Sun, Eugene; Tin, Sammy

2018-04-01

Carbide precipitates in Ni-based superalloys are considered to be desirable phases that can contribute to improving high-temperature properties as well as aid in microstructural refinement of the material; however, they can also serve as crack initiation sites during fatigue. To date, most of the knowledge pertaining to carbide formation has originated from assessments of cast and wrought Ni-based superalloys. As powder-processed Ni-based superalloys are becoming increasingly widespread, understanding the different mechanisms by which they form becomes increasingly important. Detailed characterization of MC carbides present in two experimental high Nb-content powder-processed Ni-based superalloys revealed that Hf additions affect the resultant carbide morphologies. This morphology difference was attributed to a higher magnitude of elastic strain energy along the interface associated with Hf being soluble in the MC carbide lattice. The composition of the MC carbides was studied through atom probe tomography and consisted of a complex carbonitride core, which was rich in Nb and with slight Hf segregation, surrounded by an Nb carbide shell. The characterization results of the segregation behavior of Hf in the MC carbides and the subsequent influence on their morphology were compared to density functional theory calculations and found to be in good agreement, suggesting that computational modeling can successfully be used to tailor carbide features.

MC Carbide Characterization in High Refractory Content Powder-Processed Ni-Based Superalloys

NASA Astrophysics Data System (ADS)

Antonov, Stoichko; Chen, Wei; Huo, Jiajie; Feng, Qiang; Isheim, Dieter; Seidman, David N.; Sun, Eugene; Tin, Sammy

2018-06-01

Carbide precipitates in Ni-based superalloys are considered to be desirable phases that can contribute to improving high-temperature properties as well as aid in microstructural refinement of the material; however, they can also serve as crack initiation sites during fatigue. To date, most of the knowledge pertaining to carbide formation has originated from assessments of cast and wrought Ni-based superalloys. As powder-processed Ni-based superalloys are becoming increasingly widespread, understanding the different mechanisms by which they form becomes increasingly important. Detailed characterization of MC carbides present in two experimental high Nb-content powder-processed Ni-based superalloys revealed that Hf additions affect the resultant carbide morphologies. This morphology difference was attributed to a higher magnitude of elastic strain energy along the interface associated with Hf being soluble in the MC carbide lattice. The composition of the MC carbides was studied through atom probe tomography and consisted of a complex carbonitride core, which was rich in Nb and with slight Hf segregation, surrounded by an Nb carbide shell. The characterization results of the segregation behavior of Hf in the MC carbides and the subsequent influence on their morphology were compared to density functional theory calculations and found to be in good agreement, suggesting that computational modeling can successfully be used to tailor carbide features.

On the Alloying and Properties of Tetragonal Nb₅Si₃ in Nb-Silicide Based Alloys.

PubMed

Tsakiropoulos, Panos

2018-01-04

The alloying of Nb₅Si₃ modifies its properties. Actual compositions of (Nb,TM)₅X₃ silicides in developmental alloys, where X = Al + B + Ge + Si + Sn and TM is a transition and/or refractory metal, were used to calculate the composition weighted differences in electronegativity (Δχ) and an average valence electron concentration (VEC) and the solubility range of X to study the alloying and properties of the silicide. The calculations gave 4.11 < VEC < 4.45, 0.103 < Δχ < 0.415 and 33.6 < X < 41.6 at.%. In the silicide in Nb-24Ti-18Si-5Al-5Cr alloys with single addition of 5 at.% B, Ge, Hf, Mo, Sn and Ta, the solubility range of X decreased compared with the unalloyed Nb₅Si₃ or exceeded 40.5 at.% when B was with Hf or Mo or Sn and the Δχ decreased with increasing X. The Ge concentration increased with increasing Ti and the Hf concentration increased and decreased with increasing Ti or Nb respectively. The B and Sn concentrations respectively decreased and increased with increasing Ti and also depended on other additions in the silicide. The concentration of Sn was related to VEC and the concentrations of B and Ge were related to Δχ. The alloying of Nb₅Si₃ was demonstrated in Δχ versus VEC maps. Effects of alloying on the coefficient of thermal expansion (CTE) anisotropy, Young's modulus, hardness and creep data were discussed. Compared with the hardness of binary Nb₅Si₃ (1360 HV), the hardness increased in silicides with Ge and dropped below 1360 HV when Al, B and Sn were present without Ge. The Al effect on hardness depended on other elements substituting Si. Sn reduced the hardness. Ti or Hf reduced the hardness more than Cr in Nb₅Si₃ without Ge. The (Nb,Hf)₅(Si,Al)₃ had the lowest hardness. VEC differentiated the effects of additions on the hardness of Nb₅Si₃ alloyed with Ge. Deterioration of the creep of alloyed Nb₅Si₃ was accompanied by decrease of VEC and increase or decrease of Δχ depending on alloying addition(s).

Implications of Eocene-age Philippine Sea and forearc basalts for initiation and early history of the Izu-Bonin-Mariana arc

NASA Astrophysics Data System (ADS)

Yogodzinski, Gene M.; Bizimis, Michael; Hickey-Vargas, Rosemary; McCarthy, Anders; Hocking, Benjamin D.; Savov, Ivan P.; Ishizuka, Osamu; Arculus, Richard

2018-05-01

Whole-rock isotope ratio (Hf, Nd, Pb, Sr) and trace element data for basement rocks at ocean drilling Sites U1438, 1201 and 447 immediately west of the KPR (Kyushu-Palau Ridge) are compared to those of FAB (forearc basalts) previously interpreted to be the initial products of IBM subduction volcanism. West-of-KPR basement basalts (drill sites U1438, 1201, 447) and FAB occupy the same Hf-Nd and Pb-Pb isotopic space and share distinctive source characteristics with εHf mostly > 16.5 and up to εHf = 19.8, which is more radiogenic than most Indian mid-ocean ridge basalts (MORB). Lead isotopic ratios are depleted, with 206Pb/204Pb = 17.8-18.8 accompanying relatively high 208Pb/204Pb, indicating an Indian-MORB source unlike that of West Philippine Basin plume basalts. Some Sr isotopes show affects of seawater alteration, but samples with 87Sr/86Sr < 0.7034 and εNd > 8.0 appear to preserve magmatic compositions and also indicate a common source for west-of-KPR basement and FAB. Trace element ratios resistant to seawater alteration (La/Yb, Lu/Hf, Zr/Nb, Sm/Nd) in west-of-KPR basement are generally more depleted than normal MORB and so also appear similar to FAB. At Site U1438, only andesite sills intruding sedimentary rocks overlying the basement have subduction-influenced geochemical characteristics (εNd ∼ 6.6, εHf ∼ 13.8, La/Yb > 2.5, Nd/Hf ∼ 9). The key characteristic that unites drill site basement rocks west of KPR and FAB is the nature of their source, which is more depleted in lithophile trace elements than average MORB but with Hf, Nd, and Pb isotope ratios that are common in MORB. The lithophile element-depleted nature of FAB has been linked to initiation of IBM subduction in the Eocene, but Sm-Nd model ages and errorchron relationships in Site U1438 basement indicate that the depleted character of the rocks is a regional characteristic that was produced well prior to the time of subduction initiation and persists today in the source of modern IBM arc volcanic rocks with Sm/Nd > 0.34 and εNd ∼ 9.0.

The influence of HF treatment on corrosion resistance and in vitro biocompatibility of Mg-Zn-Zr alloy

NASA Astrophysics Data System (ADS)

Ye, Xin-Yu; Chen, Min-Fang; You, Chen; Liu, De-Bao

2010-06-01

The samples made of a Mg-2.5wt.%Zn-0.5wt.%Zr alloy were immersed in the 20% hydrofluoric acid (HF) solution at room temperature for different time, with the aim of improving the properties of magnesium (Mg) alloy in applications as biomaterials. The corrosion resistance and in vitro biocompatibility of untreated and fluoride-coated samples were investigated. The results show that the optimum process is to immerse Mg alloys in the 20% HF solution for 6 h. After the immersion, a dense magnesium fluoride (MgF2) coating of 0.5 μm was synthesized on the surface of Mg-Zn-Zr alloy. Polarization tests recorded a reduction in the corrosion current density from 2.10 to 0.05 μA/cm2 due to the MgF2 protective coating. Immersion tests in the simulated body fluid (SBF) also reveal a much milder corrosion on the fluoride-coated samples, and its corrosion rate was calculated to be 0.05 mm/yr. Hemolysis test suggests that the conversion coated Mg alloy has no obvious hemolysis reaction. The hemolysis ratio (HR) of the samples decreases from 11.34% to 1.86% with the HF treatment, which meets the requirements of biomaterials (HR < 5%). The coculture of 3T3 fibroblasts with Mg alloy results in the adhesion and proliferation of cells on the surface of fluoride-coated samples. All the results show that the MgF2 conversion coating would markedly improve the corrosion resistance and in vitro biocompatibility of Mg-Zn-Zr alloy.

A source-depleted Early Jurassic granitic pluton from South China: Implication to the Mesozoic juvenile accretion of the South China crust

NASA Astrophysics Data System (ADS)

Zhou, Zuo-Min; Ma, Chang-Qian; Wang, Lian-Xun; Chen, Shu-Guang; Xie, Cai-Fu; Li, Yong; Liu, Wei

2018-02-01

Source-depleted granites were rarely reported in South China. Hereby we identified such a granitic pluton, the Tiandong pluton, at Northeastern Guangdong province in Southeastern (SE) China. Whole-rock Sr-Nd and zircon Hf isotopes of the Tiandong granites both revealed obviously depleted source signatures, with initial isotopic values of initial 87Sr/86Sr = 0.7032-0.7040, εNd(t) = 1.1-1.5, and εHf(t) = 6-13, respectively. Zircon U-Pb dating implied the granite was intruded in Early Jurassic (188 Ma). The dominant minerals of the Tiandong granite consist of K-feldspar, plagioclase, quartz and biotite, with accessory mineral assemblage of apatite + zircon + magnetite. Based on the mineralogy and the depleted isotopic signature, the granites chemically show I-type affinity such as low Zr + Nb + Ce + Y (131.6 to 212.2), 104 × Ga/Al (2.12-2.27), A/CNK values < 1.1 (0.97-1.03), corundum molecule < 1 (0-0.55) and extremely low P2O5 contents (0.05 wt%). The one-stage and two-stage depleted mantle Nd model ages (TDM = 0.89 to 0.84 Ga, T2DM = 0.88 to 0.85 Ga) are consistent. TDM(Hf) values of 0.31-0.63 Ga are also indistinguishable from T2DM(Hf) values of 0.35-0.75 Ga. The Nd and Hf isotopic compositions confirm that the Tiandong granites are juvenile crustal accretion but decoupled Nd-Hf isotopic systems. The juvenile crust is likely to originate from a mixed source of the primary asthenospheric mantle and the subordinate EMII. Combined with early studies of adjacent rocks, we propose that the early Jurassic ( 200-175 Ma) magmatism as evidenced by the Tiandong granites might be driven by upwelling of asthenosphere and subsequent underplating of mafic melts in an intra-plate extensional setting as a response to far-field stress during early stage subduction of the paleo-pacific plate.

High temperature dielectrics and defect characteristic of (Nb, Mn, Zr) modified 0.4(Ba0.8Ca0.2)TiO3 - 0.6Bi(Mg0.5Ti0.5)O3 ceramics

NASA Astrophysics Data System (ADS)

Ren, Shaokai; Chen, Zhi; Yan, Tianxiang; Han, Feifei; Kuang, Xiaojun; Fang, Liang; Liu, Laijun

2018-07-01

Transition elements Nb, Mn and Zr were selected to substitute Ti of 0.4(Ba0.8Ca0.2)TiO3 -0.6Bi(Mg0.5Ti0.5)O3 (BCT-BMT) ceramic in order to extend its operation temperature and decrease its dielectric loss for the application of high-temperature capacitors. Nb and Mn play an opposite role on the defect compensation, decreasing and increasing the concentration of oxygen vacancies, respectively. The temperature of the maximum relative permittivity, Tm, decreases from 140 °C to 90 °C for the Nb and Zr modified BCT-BMT ceramics. The permittivity (εr) peak of the former exhibits a broad and stable relative permittivity ∼600 (±5% variation) from 50 °C to 520 °C with the dielectric loss ≤0.02 from 60 °C to 440 °C (1 kHz). The modified Curie-Weiss law indicates that the doping elements result in an enhancement of diffuse phase transition. Activation energies of relaxation frequency and conduction of the samples were characterized by the impedance spectroscopy. A clear relationship between the magnitude of activation energy and the concentration of oxygen vacancies was revealed.

Very large phase shift of microwave signals in a 6 nm Hf x Zr1-x O2 ferroelectric at ±3 V

NASA Astrophysics Data System (ADS)

Dragoman, Mircea; Modreanu, Mircea; Povey, Ian M.; Iordanescu, Sergiu; Aldrigo, Martino; Romanitan, Cosmin; Vasilache, Dan; Dinescu, Adrian; Dragoman, Daniela

2017-09-01

In this letter, we report for the first time very large phase shifts of microwaves in the 1-10 GHz range, in a 1 mm long gold coplanar interdigitated structure deposited over a 6 nm Hf x Zr1-x O2 ferroelectric grown directly on a high resistivity silicon substrate. The phase shift is larger than 60° at 1 GHz and 13° at 10 GHz at maximum applied DC voltages of ±3 V, which can be supplied by a simple commercial battery. In this way, we demonstrate experimentally that the new ferroelectrics based on HfO2 could play an important role in the future development of wireless communication systems for very low power applications.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, O.H.; Curtis, P.G.

1992-03-31

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof. 1 figure.

Organic solvent soluble oxide supported hydrogenation catalyst precursors

DOEpatents

Edlund, David J.; Finke, Richard G.; Saxton, Robert J.

1992-01-01

The present invention discloses two polyoxoanion supported metal complexes found to be useful in olefin hydrogenation. The complexes are novel compositions of matter which are soluble in organic solvents. In particular, the compositions of matter comprise A.sub.x [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.15 M'.sub.3 O.sub.62 ].sup.x- and A.sub.y [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.9 M'.sub.3 O.sub.40 ].sup.y- where L is a ligand preferably chosen from 1,5-cyclooctadiene (COD), ethylene, cyclooctene, norbornadiene and other olefinic ligands; n=1 or 2 depending upon the number of double bonds present in the ligand L; X is a "hetero" atom chosen from B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M is either W or Mo; M' is preferably Nb or V but Ti, Zr, Ta, Hf are also useful; and A is a countercation preferably selected from tetrabutyl ammonium and alkali metal ions.

Magnetic field annealing for improved creep resistance

DOEpatents

Brady, Michael P.; Ludtka, Gail M.; Ludtka, Gerard M.; Muralidharan, Govindarajan; Nicholson, Don M.; Rios, Orlando; Yamamoto, Yukinori

2015-12-22

The method provides heat-resistant chromia- or alumina-forming Fe-, Fe(Ni), Ni(Fe), or Ni-based alloys having improved creep resistance. A precursor is provided containing preselected constituents of a chromia- or alumina-forming Fe-, Fe(Ni), Ni(Fe), or Ni-based alloy, at least one of the constituents for forming a nanoscale precipitate MaXb where M is Cr, Nb, Ti, V, Zr, or Hf, individually and in combination, and X is C, N, O, B, individually and in combination, a=1 to 23 and b=1 to 6. The precursor is annealed at a temperature of 1000-1500.degree. C. for 1-48 h in the presence of a magnetic field of at least 5 Tesla to enhance supersaturation of the M.sub.aX.sub.b constituents in the annealed precursor. This forms nanoscale M.sub.aX.sub.b precipitates for improved creep resistance when the alloy is used at service temperatures of 500-1000.degree. C. Alloys having improved creep resistance are also disclosed.

Electrical conductivity and Hf 4+ ion substitution range in NaSICON system

NASA Astrophysics Data System (ADS)

Essoumhi, A.; Favotto, C.; Mansori, M.; Ouzaouit, K.; Satre, P.

2007-03-01

In this paper, we present the synthesis and characterizations of NaSICON-type ionic conducting ceramics of the general formula Na 1+ xM 1.775Si x-0.9P 3.9- xO 12 with 1.8 ≤ x ≤ 2.2 and M = Zr or Hf. The effect of the total substitution of zirconium by hafnium on electric properties has been studied. The various compositions were prepared by using the sol-gel method and the synthesized precursors were characterized by coupled DTA-TG. The oxides obtained after pyrolysis of the precursors were identified by X-ray diffraction. A sintering study by thermodilatometry permits to select the best thermal cycle adapted to our ceramics. Furthermore, the electric conductivity of the sintered ceramic samples was characterized by complex impedance spectroscopy. These results show that ceramics containing Zr synthesized by soft method, present a higher total conductivity than those obtained in literature (to be around 10 -4 S cm -1). The total substitution of Zr by Hf still improves this conductivity for some compositions.

Electrochemical Corrosion and In Vitro Bioactivity of Nano-Grained Biomedical Ti-20Nb-13Zr Alloy in a Simulated Body Fluid

PubMed Central

Kumar, Madhan; Drew, Robin; Al-Aqeeli, Nasser

2017-01-01

The bioactivity and the corrosion protection for a novel nano-grained Ti-20Nb-13Zr at % alloy were examined in a simulated body fluid (SBF). The effect of the SPS’s temperature on the corrosion performance was investigated. The phases and microstructural details of the developed alloy were analyzed by XRD (X-ray Diffraction), SEM (Scanning Electron Microscopy), and TEM (Transmission Electron Microscope). The electrochemical study was investigated using linear potentiodynamic polarization and electrochemical impedance spectroscopy in a SBF, and the bioactivity was examined by immersing the developed alloy in a SBF for 3, 7, and 14 days. The morphology of the depositions after immersion was examined using SEM. Alloy surface analysis after immersion in the SBF was characterized by XPS (X-ray Photoelectron Spectroscopy). The results of the bioactivity test in SBF revealed the growth of a hydroxyapatite layer on the surface of the alloy. The analysis of XPS showed the formation of protective oxides of TiO2, Ti2O3, ZrO2, Nb2O5, and a Ca3(PO4)2 compound (precursor of hydroxyapatite) deposited on the alloy surface, indicating that the presented alloy can stimulate bone formation. The corrosion resistance increased by increasing the sintering temperature and the highest corrosion resistance was obtained at 1200 °C. The improved corrosion protection was found to be related to the alloy densification. The bioactivity and the corrosion resistance of the developed nanostructured alloy in a SBF renders the nanostructured Ti-20Nb-13Zr alloy a promising candidate as an implant material. PMID:29280956

Wear measurement using radioactive tracer technique based on proton, deuteron and α-particle induced nuclear reactions on molybdenum

NASA Astrophysics Data System (ADS)

Ditrói, F.; Tárkányi, F.; Takács, S.

2012-11-01

Excitation functions of light ion induced nuclear reactions on natural molybdenum have been studied in the frame of a systematic investigation of charged particle induced nuclear reactions on metals for various applications. Excitation functions of 93,94g,94m,95g,95m,96,99mTc, 90,93m,99Mo, 90,91m,92m,95m,95g,96Nb and 88,89Zr were measured up to 50 MeV deuteron energy Tárkányi et al., 2012 [1], 93m,93g,94m,94g,95m,95g,96g,99mTc, 90,93m,99Mo, 90,92m,95m,95g,96Nb and 88,89Zr were measured up to 40 MeV proton energy Tárkányi et al., 2012 [2] and 93m,93g,94m,94g,95m,95g,96g,99mTc, 93m,99Mo, 90Nb, 94,95,97,103Ru and 88Zr were measured up to 40 MeV alpha energy Ditrói et al., 2012 [3] by using the stacked foil technique and activation method. The results for 3He induced reactions on natural Mo were taken from the literature Comparetto and Qaim, 1980 [4]. According to their half-lives, from the above listed radionuclides the 95m,96Tc, 91m,92m,95m,95gNb, 99Mo, 103,97Ru and 88Zr are suitable candidates for wear measurement by using thin layer activation (TLA) method. The goal of this work was to determine the necessary nuclear data for TLA of the above radionuclides and to prove their applicability for wear measurements.

Creep Strength of Nb-1Zr for SP-100 Applications

NASA Astrophysics Data System (ADS)

Horak, James A.; Egner, Larry K.

1994-07-01

Power systems that are used to provide electrical power in space are designed to optimize conversion of thermal energy to electrical energy and to minimize the mass and volume that must be launched. Only refractory metals and their alloys have sufficient long-term strength for several years of uninterrupted operation at the required temperatures of 1200 K and above. The high power densities and temperatures at which these reactors must operate require the use of liquid-metal coolants. The alloy Nb-1 wt % Zr (Nb-lZr), which exhibits excellent corrosion resistance to alkali liquid-metals at high temperatures, is being considered for the fuel cladding, reactor structural, and heat-transport systems for the SP-100 reactor system. Useful lifetime of this system is limited by creep deformation in the reactor core. Nb-lZr sheet procured to American Society for Testing and Materials (ASTM) specifications for reactor grade and commercial grade has been processed by several different cold work and annealing treatments to attempt to produce the grain structure (size, shape, and distribution of sizes) that provides the maximum creep strength of this alloy at temperatures from 1250 to 1450 K. The effects of grain size, differences in oxygen concentrations, tungsten concentrations, and electron beam and gas tungsten arc weldments on creep strength were studied. Grain size has a large effect on creep strength at 1450 K but only material with a very large grain size (150 μm) exhibits significantly higher creep strength at 1350 K. Differences in oxygen or tungsten concentrations did not affect creep strength, and the creep strengths of weldments were equal to, or greater than, those for base metal.

In vitro bio-functional performances of the novel superelastic beta-type Ti-23Nb-0.7Ta-2Zr-0.5N alloy.

PubMed

Ion, Raluca; Gordin, Doina-Margareta; Mitran, Valentina; Osiceanu, Petre; Dinescu, Sorina; Gloriant, Thierry; Cimpean, Anisoara

2014-02-01

The materials used for internal fracture fixations and joint replacements are mainly made of metals which still face problems ranging from higher rigidity than that of natural bone to leaching cytotoxic metallic ions. Beta (β)-type titanium alloys with low elastic modulus made from non-toxic and non-allergenic elements are desirable to reduce stress shielding effect and enhance bone remodeling. In this work, a new β-type Ti-23Nb-0.7Ta-2Zr-0.5N alloy with a Young's modulus of approximately 50 GPa was designed and characterized. The behavior of MC3T3-E1 pre-osteoblasts on the new alloy, including adhesion, proliferation and differentiation, was evaluated by examining the cytoskeleton, focal adhesion formation, metabolic activity and extracellular matrix mineralization. Results indicated that the pre-osteoblast cells exhibited a similar degree of attachment and growth on Ti-23Nb-0.7Ta-2Zr-0.5N and Ti-6Al-4V. However, the novel alloy proved to be significantly more efficient in sustaining mineralized matrix deposition upon osteogenic induction of the cells than Ti-6Al-4V control. Further, the analysis of RAW 264.7 macrophages cytokine gene and protein expression indicated no significant inflammatory response. Collectively, these findings suggest that the Ti-23Nb-0.7Ta-2Zr-0.5N alloy, which has an increased mechanical biocompatibility with bone, allows a better osteogenic differentiation of osteoblast precursor cells than Ti-6Al-4V and holds great potential for future clinical prosthetic applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Fabrication of nano ZrO2 dispersed novel W79Ni10Ti5Nb5 alloy by mechanical alloying and pressureless sintering

NASA Astrophysics Data System (ADS)

Sahoo, R. R.; Patra, A.; Karak, S. K.

2017-02-01

A high energy planetary ball-mill was employed to synthesize tungsten (W) based alloy with nominal composition of W79Ni10Ti5Nb5(ZrO2)1 (in wt. %) for 20 h with chrome steel as grinding media, toluene as process control agent (PCA) along with compaction at 500 MPa pressure for 5 mins and sintering at 1500°C for 2 h using Ar atmosphere. X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS), elemental mapping and Transmission electron microscopy (TEM) was used to study the phase formation, microstructure of both milled powder and consolidated alloy. The crystallite size of W in W79Ni10Ti5Nb5(ZrO2)1 powder was 37 nm, 14.7 nm at 10 h and 20 h of milling respectively and lattice strain enhances to 0.54% at 20 h of milling. The crystallite size reduction is more at 10 h of milling and the rate drop beyond 10 to 20 h of milling. The intense improvement in dislocation density was evident upto 10 h of milling and the rate decreases between 10 to 20 h of milling. Increase in the lattice parameter of tungsten in W79Ni10Ti5Nb5(ZrO2)1 alloy upto 0.09% was observed at 10 h of milling owing to severe stress assisted deformation followed by contraction upto 0.07% at 20 h of milling due to formation of solid solution. The large spherical particles at 0 h of milling transformed to elongated shape at 10 h of milling and finer morphology at 20 h of milling. The average particle size reduced from 100 µm to 4.5 µm with the progress of milling from 0 to 20 h. Formation of fine polycrystallites of W was revealed by bright field TEM analysis and the observed crystallite size from TEM study was well supported by the evaluated crystallite size from XRD. XRD pattern and SEM micrograph of sintered alloy revealed the formation of NbNi, Ni3Ti intermetallic phases. Densification of 91.5% was attained in the 20 h milled and sintered alloy. Mechanical behaviour of the sintered product was evaluated by hardness and wear study. W79Ni10Ti5Nb5(ZrO2)1 alloy showed increase in hardness with decreasing load. The wear rate increases with increasing load due to higher abrasion effect at higher load.

The importance of mantle wedge heterogeneity to subduction zone magmatism and the origin of EM1

NASA Astrophysics Data System (ADS)

Turner, Stephen J.; Langmuir, Charles H.; Dungan, Michael A.; Escrig, Stephane

2017-08-01

The composition of the convecting asthenospheric mantle that feeds the mantle wedge can be investigated via rear-arc lavas that have minimal slab influence. This "ambient mantle wedge" composition (the composition of the wedge prior to the addition of a slab component) varies substantially both worldwide and within individual arcs. 143Nd/144Nd measurements of rear-arc samples that have minimal slab influence are similar to 143Nd/144Nd in the stratovolcanoes of the adjacent volcanic fronts, suggesting that 143Nd/144Nd of arc-front volcanics are largely inherited from the ambient mantle composition. 143Nd/144Nd correlates with ratios such as Th/U, Zr/Nb, and La/Sm, indicating that these ratios also are strongly influenced by ambient wedge heterogeneity. The same phenomenon is observed among individual volcanoes from the Chilean Southern Volcanic Zone (SVZ), where along-strike variability of the volcanic front tracks that of rear-arc monogenetic volcanics. Depleted mantle wedges are more strongly influenced by slab-derived components than are enriched wedges. This leads to surprising trace element correlations in the global dataset, such as between Pb/Nb and Zr/Nb, which are not explicable by variable compositions or fluxes of slab components. Depleted ambient mantle is present beneath arcs with back-arc spreading; relatively enriched mantle is present adjacent to continents. Ambient mantle wedge heterogeneity both globally and regionally forms isotope mixing trajectories for Sr, Nd and Hf between depleted mantle and EM1-type enriched compositions as represented by Gough Island basalts. Making use of this relationship permits a quantitative match with the SVZ data. It has been suggested that EM1-type mantle reservoirs are the result of recycled lower continental crust, though such models do not account for certain trace element ratios such as Ce/Pb and Nb/U or the surprisingly homogeneous trace element compositions of EM1 volcanics. A model in which the EM1 end-member found in continental arcs is produced by low-degree melt-metasomatism of the sub-continental lithospheric mantle may be more plausible. The 143Nd/144Nd maximum along the SVZ may be a consequence of either rifting and collision of two ancient lithospheric domains or a slab tear. The correspondence of mantle wedge variations with EM1 suggests a potential role for metasomatized sub-continental lithosphere in creating EM1 sources globally.

Pressure-dependence of the phase transitions and thermal expansion in zirconium and hafnium pyrovanadate

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

Gallington, Leighanne C.; Hester, Brett R.; Kaplan, Benjamin S.

Low or negative thermal expansion (NTE) has been previously observed in members of the ZrP 2O 7 family at temperatures higher than their order-disorder phase transitions. The thermoelastic properties and phase behavior of the low temperature superstructure and high temperature negative thermal expansion phases of ZrV 2O 7 and HfV 2O 7 were explored via in situ variable temperature/pressure powder x-ray diffraction measurements. The phase transition temperatures of ZrV 2O 7 and HfV 2O 7 exhibited a very strong dependence on pressure (~700 K GPa), with moderate compression suppressing the formation of their NTE phases below 513 K. Compression alsomore » reduced the magnitude of the coefficients of thermal expansion in both the positive and negative thermal expansion phases. Additionally, the high temperature NTE phase of ZrV 2O 7 was found to be twice as stiff as the low temperature positive thermal expansion superstructure (24 and 12 GPa respectively).« less

Laser Cladding of Ni, Nb, and Mg Alloys for Improved Environmental Resistance at High Temperature

DTIC Science & Technology

1989-01-01

v*LASER CLADDING OF NI , Nb AND Mg ALLOYS < FOR 7IMPR-OVED ENVIIONM ENTAL I RESISTANCE AT HIGH TEMPERATURE Final Report for Research Conducted through...resistance at high temperature. Major emphasis has been on Ni -Cr-Al-Hf system. Microstructural evolution and oxidation properties of Ni and Nb alloys ...metastable crystalline and amorphous structure on a) the high temperature oxidation properties of laser clad Ni and Nb alloys , and b) the corrosion

Tunneling STM/STS and break-junction spectroscopy of the layered nitro-chloride superconductors MNCl (M = Ti, Hf, Zr)

NASA Astrophysics Data System (ADS)

Ekino, Toshikazu; Sugimoto, Akira; Gabovich, Alexander M.; Zheng, Zhanfeng; Zhang, Shuai; Yamanaka, Shoji

2014-05-01

The layered superconductors β-MNCl with the critical temperatures Tc = 14 K (M = Zr) - 25 K (M = Hf) were investigated by means of scanning-tunneling microscopy/spectroscopy and break-junction tunneling spectroscopy. The STM/STS was used to investigate the surface electronic structures in nanometer length scale, while the BJTS was employed to precisely determine the gap characteristics. Both techniques consistently clarified the unusually large size of the superconducting gap. Wide gap distributions with large-scale maximum gap values were also revealed in α-KyTiNCl with a different crystal structure.

Characterization of flux-grown Trace-element-doped titanite using the high-mass-resolution ion microprobe (SHRIMP-RG)

USGS Publications Warehouse

Mazdab, F.K.

2009-01-01

Crystals of titanite can be readily grown under ambient pressure from a mixture of CaO, TiO2 and SiO2 in the presence of molten sodium tetraborate. The crystals produced are euhedral and prismatic, lustrous and transparent, and up to 5 mm in length. Titanite obtained by this method contains approximately 4300 ppm Na and 220 ppm B contributed from the flux. In addition to dopant-free material, titanite containing trace alkali and alkaline earth metals (K, Sr, Ba), transition metals (Sc, Cr, Ni, Y, Zr, Nb, Hf and Ta), rare-earth elements (REE), actinides (Th, U) and p-block elements (F, S, Cl, Ge, Sn and Pb) have been prepared using the same procedure. Back-scattered electron (BSE) imaging accompanied by ion-microprobe (SHRIMP-RG) analysis confirms significant incorporation of selected trace-elements at structural sites. Regardless of some zonation, the large size of the crystals and broad regions of chemical homogeneity make these crystals useful as experimental starting material, and as matrix-matched trace-element standards for a variety of microbeam analytical techniques where amorphous titanite glass, heterogeneous natural titanite or a non-titanite standard may be less than satisfactory. Trace-element-doped synthetic crystals can also provide a convenient proxy for a better understanding of trace-element incorporation in natural titanite. Comparisons with igneous, authigenic and high-temperature metasomatic titanite are examined. The use of high-mass-resolution SIMS also demonstrates the analytical challenges inherent to any in situ mass-spectrometry-based analysis of titanite, owing to the production of difficult-to-resolve molecular interferences. These interferences are dominated by Ca-Ca, Ca-Ti and Ti-Ti dimers that are significant in the mass range of 80-100, affecting all isotopes of Sr and Zr, as well as 89Y and 93Nb. Methods do exist for the evaluation of interferences by these dimers and of polyatomic interferences on the LREE.

Geochemistry and mineralogy of sediments from the Ventersdorp and Transvaal Supergroups, South Africa: Cratonic evolution during the early Proterozoic

NASA Astrophysics Data System (ADS)

Wronkiewicz, David J.; Condie, Kent C.

1990-02-01

Approximately 100 pelite and 12 quartzite samples from the Ventersdorp (~2.7 Ga) and Transvaal Supergroups (~2.6-2.1 Ga) have been analyzed to monitor the early Proterozoic evolution of the Kaapvaal Craton, southern Africa. From oldest to youngest, pelites were sampled from the Ventersdorp-Bothaville (BOT), Transvaal-Selati (SEL), Black Reef (BR), Timeball Hill (TH), Strubenkop (STR), and Silverton (SIL) Formations. Paleocurrent measurements in Transvaal quartzites indicate sources lying predominantly to the north and east. Relative to the BOT-SEL-BR, pelites from the TH-STR-SIL are enriched in heavy-REE, LILE, Zr, Hf, Nb, and Ta, depleted in K 2O, MgO, Ni, and Cr, and have lower Cr/Zr, Sc/Th, K 2O/Na 2O, and K/ Rb ratios. Compared to SEL-BR, BOT-TH-STR-SIL pelites have higher light-REE contents and La/Yb ratios, and lower Eu/Eu∗ ratios (0.61-0.66). Relative to NASC (North American Shale Composite), THSTR-SIL pelites are enriched in light-REE, Th, U, Ta, Nb, Sc, Cs, have higher La/Yb ratios, and are depleted in K 2O and MgO. BOT-SEL-BR pelites are enriched in K 2O, MgO, Cr, and Ni, have higher K 2O/Na 2O, Sc/Th, and Eu/Eu∗ ratios, and are depleted in Th, U, heavy-REE, and High Field Strength Elements (HFSE) relative to NASC. Compositions of TH-STR-SIL pelites suggest a provenance similar to average Phanerozoic uppercontinental crust. This source is more evolved than that of BOT-SEL-BR pelites, indicating a transformation from primitive (mafic-rich) to evolved (felsic-rich) upper-crust at 2.2 Ga. This transition follows earlier primitive to evolved trends in Moodies-Pongola (3.3-3.0 Ga) and Witwatersrand (~2.8 Ga) successions. These data suggest that several cycles of changing upper-continental crust occurred in the Kaapvaal craton between 3.3-2.1 Ga.

Effect of Ar9+ irradiation on Zr-1Nb-1Sn-0.1Fe alloy characterized by Grazing Incidence X-ray diffraction technique

NASA Astrophysics Data System (ADS)

Dutta, Argha; Das, Kalipada; Gayathri, N.; Menon, Ranjini; Nabhiraj, P. Y.; Mukherjee, Paramita

2018-03-01

The microstructural parameters such as domain size and microstrain have been estimated from Grazing Incidence X-ray Diffraction (GIXRD) data for Ar9+ irradiated Zr-1Nb-1Sn-0.1Fe sample as a function of dpa (dose). Detail studies using X-ray Diffraction Line Profile Analysis (XRDLPA) from GIXRD data has been carried out to characterize the microstructural parameters like domain size and microstrain. The reorientation of the grains due to effect of irradiation at high dpa (dose) has been qualitatively assessed by the texture parameter P(hkl).

TEM analysis of irradiation-induced interaction layers in coated UMo/X/Al trilayer systems (X= Ti, Nb, Zr, and Mo)

NASA Astrophysics Data System (ADS)

Chiang, H.-Y.; Wiss, T.; Park, S.-H.; Dieste-Blanco, O.; Petry, W.

2018-02-01

Uranium-molybdenum (UMo) alloy powder embedded in an Al matrix is considered as a promising candidate for fuel conversion of research reactors. A modified system with a diffusion barrier X as coating, UMo/X/Al trilayer (X = Ti, Zr, Nb, and Mo), has been investigated to suppress interdiffusion between UMo and the Al matrix. The trilayer systems were tested by swift heavy ion irradiation, the thereby created interaction zone has been analyzed by scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDX). Detailed structural characterization are presented and compared to earlier μ-XRD analysis.

Formation of an amorphous phase and its crystallization in the immiscible Nb-Zr system by mechanical alloying

NASA Astrophysics Data System (ADS)

Al-Aqeeli, N.; Suryanarayana, C.; Hussein, M. A.

2013-10-01

Mechanical alloying of binary Nb-Zr powder mixtures was carried out to evaluate the formation of metastable phases in this immiscible system. The milled powders were characterized for their constitution and structure by X-ray diffraction and transmission electron microscopy methods. It was shown that an amorphous phase had formed on milling the binary powder mixture for about 10 h and that it had crystallized on subsequent milling up to 50-70 h, referred to as mechanical crystallization. Thermodynamic and structural arguments have been presented to explain the formation of the amorphous phase and its subsequent crystallization.

Transitions of the type 2s-2p in oxygenlike Y, Zr, and Nb

NASA Technical Reports Server (NTRS)

Behring, W. E.; Brown, C. M.; Feldman, U.; Seely, J. F.; Reader, J.

1986-01-01

Transitions of the type 2s-2p in the oxygenlike ions Y XXXII, Zr XXXIII, and Nb XXXIV were identified in spectra recorded at the University of Rochester's Omega laser facility. Solid targets were spherically irradiated by 24 beams of frequency-tripled (351-nm) Nd-glass laser radiation. The spectra were photographed with a 3-m grazing-incidence spectrograph. The identified transitions of the oxygenlike ions are in the range 30 to 73 A. The wavelengths for the magnetic-dipole transitions within the 2s2p4 ground configurations of these ions are predicted from the experimental energy levels.

Measurements of the electrical resistance and the hydrogen depth distribution for Ni 60Nb 20Zr 20 amorphous alloy before and after hydrogen charging

NASA Astrophysics Data System (ADS)

Nakano, Sumiaki; Ohtsu, Naofumi; Nagata, Shinji; Yamaura, Shin-ichi; Uchinashi, Sakae; Kimura, Hisamichi; Shikama, Tatsuo; Inoue, Akihisa

2005-02-01

A Ni 60Nb 20Zr 20 amorphous alloy was prepared by the single-roller melt-spinning technique. The change in the electrical resistance of the alloy after electrochemical hydrogen charging in 6 N KOH solution was investigated. The change in the hydrogen depth distribution in the alloy was also investigated by elastic recoil detection. As a result, we found that the electrical resistance of the alloy increases with increasing the hydrogen content in the alloy and that a large number of hydrogen atoms are remained in the surface area of the hydrogen-charged alloy.

Deformation mechanism study of a hot rolled Zr-2.5Nb alloy by transmission electron microscopy. II. In situ transmission electron microscopy study of deformation mechanism change of a Zr-2.5Nb alloy upon heavy ion irradiation

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

Long, Fei; Daymond, Mark R., E-mail: mark.daymond@queensu.ca; Yao, Zhongwen

2015-03-14

The effect of heavy-ion irradiation on deformation mechanisms of a Zr-2.5Nb alloy was investigated by using the in situ transmission electron microscopy deformation technique. The gliding behavior of prismatic 〈a〉 dislocations has been dynamically observed before and after irradiation at room temperature and 300 °C. Irradiation induced loops were shown to strongly pin the gliding dislocations. Unpinning occurred while loops were incorporated into or eliminated by 〈a〉 dislocations. In the irradiated sample, loop depleted areas with a boundary parallel to the basal plane trace were found by post-mortem observation after room temperature deformation, supporting the possibility of basal channel formation inmore » bulk neutron irradiated samples. Strong activity of pyramidal slip was also observed at both temperatures, which might be another important mechanism to induce plastic instability in irradiated zirconium alloys. Finally, (011{sup ¯}1)〈01{sup ¯}12〉 twinning was identified in the irradiated sample deformed at 300 °C.« less

Deformation mechanism study of a hot rolled Zr-2.5Nb alloy by transmission electron microscopy. II. In situ transmission electron microscopy study of deformation mechanism change of a Zr-2.5Nb alloy upon heavy ion irradiation.

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

Long, Fei; Daymond, Mark R.; Yao, Zhongwen

2015-03-14

The effect of heavy-ion irradiation on deformation mechanisms of a Zr-2.5Nb alloy was investigated by using the in situ transmission electron microscopy deformation technique. The gliding behavior of prismatic < a > dislocations has been dynamically observed before and after irradiation at room temperature and 300 degrees C. Irradiation induced loops were shown to strongly pin the gliding dislocations. Unpinning occurred while loops were incorporated into or eliminated by < a > dislocations. In the irradiated sample, loop depleted areas with a boundary parallel to the basal plane trace were found by post-mortem observation after room temperature deformation, supporting themore » possibility of basal channel formation in bulk neutron irradiated samples. Strong activity of pyramidal slip was also observed at both temperatures, which might be another important mechanism to induce plastic instability in irradiated zirconium alloys. Finally, {01 (1) over bar1}< 0 (1) over bar 12 > twinning was identified in the irradiated sample deformed at 300 degrees C.« less

Biomimetic Hydroxyapatite Growth on Functionalized Surfaces of Ti-6Al-4V and Ti-Zr-Nb Alloys

NASA Astrophysics Data System (ADS)

Pylypchuk, Ie V.; Petranovskaya, A. L.; Gorbyk, P. P.; Korduban, A. M.; Markovsky, P. E.; Ivasishin, O. M.

2015-08-01

A biomimetic approach for coating titanium-containing alloys with hydroxyapatite (HA) is reported in the article. Two types of Ti-containing alloys were chosen as an object for coating: Ti-6Al-4V (recommended for orthopedic application) and a novel highly biocompatible Ti-Zr-Nb alloy, with good mechanical compatibility due to a modulus that is more close to that of human bones (E ≈ 50 GPa instead of 110 GPa in Ti-6Al-4V). Coating process was carried out in a 10×-concentrated simulated body fluid (SBF)—synthetic analog of human body plasma. The effect of oxidized and carboxylated alloy surface on formation of biomimetic hydroxyapatite has been studied. By XRD, we found influence of thermal conditions on HA crystal formation and size. SEM images and Fourier transform infrared confirmed that hydroxyapatite with different morphology, crystallinity, and Ca/P ratio formed on metallic surfaces. X-ray photoelectron spectroscopy showed that in the Ti-6AL-4V sample the observed Ca/P ratio reach 0.97, whereas in the Ti-Zr-Nb sample the observed Ca/P ratio reach 1.15.

A comparison of the fatigue behavior of cast Ti-7.5Mo with c.p. titanium, Ti-6Al-4V and Ti-13Nb-13Zr alloys.

PubMed

Lin, Chia-Wei; Ju, Chien-Ping; Chern Lin, Jiin-Huey

2005-06-01

The purpose of the present study is to compare the high-cycle fatigue behavior of newly developed Ti-7.5Mo alloy with that of c.p. Ti, Ti-13Nb-13Zr and Ti-6Al-4V alloys in their as-cast state. Experimental results indicate that Ti-6Al-4V and c.p. Ti have higher stress-controlled fatigue resistance but lower strain-controlled fatigue resistance than Ti-7.5Mo and Ti-13Nb-13Zr. Among four materials Ti-7.5Mo demonstrates the best strain-controlled fatigue performance. The fracture surfaces of the present materials are comprised of three morphologically distinct zones: crack initiation zone, crack propagation zone, and the final-stage overload zone. The fatigue cracks almost always initiate from casting-induced surface/subsurface pores. A river pattern is observed in the propagation zone. In the overload zone dimples are typically observed. Three factors most significantly affecting the fatigue performance of the present materials are the presence of the casting-induced surface/subsurface pores; the location of the pores; and the inherent mechanical properties of the materials.

Dynamic recrystallization behavior of a biomedical Ti-13Nb-13Zr alloy.

PubMed

Bobbili, Ravindranadh; Madhu, V

2016-06-01

The dynamic recrystallization (DRX) behavior of a biomedical titanium Ti-13Nb-13Zr alloy has been investigated using the high temperature compression tests under wide range of strain rates (0.001-1/s) and temperatures 900-1050°C. A constitutive equation represented as a function of temperature, strain rate and true strain is developed and the hot deformation apparent activation energy is calculated about 534kJ/mol. By considering the exponential relationship between work-hardening rate (θ) and stress, a new mathematical model was proposed for predicting flow stress up to the critical strain during hot deformation. The mathematical model for predicting flow stress up to the critical strain exhibits better consistency and accuracy. The DRX kinetic equation of Ti-13Nb-13Zr alloy is described as XDRX=1-exp[-0.32(Ɛ-ƐcƐ(*))(2.3)] . The DRX kinetic model was validated by microstructure observation. It was also found that the process of DRX was promoted by decreasing strain rate and increasing deformation temperature. Eventually, the continuous dynamic recrystallization (CDRX) was identified to be the DRX mechanism using transmission electron microscope (TEM). Copyright © 2015 Elsevier Ltd. All rights reserved.

The formation of the Late Cretaceous Xishan Sn-W deposit, South China: Geochronological and geochemical perspectives

NASA Astrophysics Data System (ADS)

Zhang, Lipeng; Zhang, Rongqing; Hu, Yongbin; Liang, Jinlong; Ouyang, Zhixia; He, Junjie; Chen, Yuxiao; Guo, Jia; Sun, Weidong

2017-10-01

The Xishan Sn-W deposit is spatially related to K-feldspar granites in the Yangchun basin, western Guangdong Province, South China. LA-ICP-MS zircon U-Pb dating for the Xishan pluton defines an emplacement age of 79 Ma (78.1 ± 0.9 Ma; 79.0 ± 1.2 Ma; 79.3 ± 0.8 Ma), consistent with the mineralization age of the Xishan Sn-W deposit constrained by molybdenite Re-Os isochron age (79.4 ± 4.5 Ma) and LA-ICP-MS cassiterite U-Pb ages (78.1 ± 0.9 Ma and 79.0 ± 1.2 Ma) for the cassiterite-quartz vein. These indicate a close genetic relationship between the granite and Sn-W mineralization. The Xishan K-feldspar granites have geochemical characteristics of A-type granites, e.g., high total alkali (Na2O + K2O = 7.88-10.07 wt.%), high Ga/Al ratios (10000*Ga/Al > 2.6) and high Zr + Nb + Ce + Y concentrations (> 350 ppm). They are further classified as A2-type granites. The whole-rock isotopic compositions of K-feldspar granites (initial 87Sr/86Sr = 0.705256-0.706181; εNd(t) = - 5.4 to - 4.8) and zircon εHf(t) values (- 7.8 to 2.0) suggest a mixed magma source. The low zircon Ce4 +/Ce3 + ratios (12-88) of K-feldspar granites suggest low oxygen fugacities, which is key for enrichment of tin in primary magmas. The K-feldspar granites have experienced strong differentiation as indicated by their high Rb/Sr and K/Rb ratios, and low Nb/Ta and Zr/Hf ratios, which play an important role in ore-forming element transportation and concentration. A-type granite characteristics of the Xishan pluton show that it formed in an extensional environment. The high F and low Cl characteristics of the K-feldspar granite are most probably attributed to slab rollback. In the Late Cretaceous, the Xishan Sn-W deposit was located near the interaction of the circum-Pacific and the Tethys tectonic realms. Late Cretaceous Sn-W deposits, including the Xishan deposit, form an EW-trending belt from Guangdong to Yunnan Province in South China. This belt is in accordance with the direction of the Neo-Tethys slab rollback in the Late Cretaceous. In addition, the NS-trending extension has been recognized in the Late Cretaceous in South China. We propose that the Xishan Sn-W deposit should be attributed to the Neo-Tethys slab rollback in the Late Cretaceous.

SUPERNOVA NEUTRINO NUCLEOSYNTHESIS OF THE RADIOACTIVE {sup 92}Nb OBSERVED IN PRIMITIVE METEORITES

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

Hayakawa, T.; Chiba, S.; Iwamoto, N.

2013-12-10

The isotope {sup 92}Nb decays to {sup 92}Zr with a half-life of 3.47 × 10{sup 7} yr. Although this isotope does not exist in the current solar system, initial abundance ratios for {sup 92}Nb/{sup 93}Nb at the time of solar system formation have been measured in primitive meteorites. The astrophysical origin of this material, however, has remained unknown. In this Letter, we present new calculations which demonstrate a novel origin for {sup 92}Nb via neutrino-induced reactions in core-collapse supernovae (ν-process). Our calculated result shows that the observed ratio of {sup 92}Nb/{sup 93}Nb ∼ 10{sup –5} can be explained by the ν-process.

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

Vexler, M. I., E-mail: shulekin@mail.ioffe.ru; Grekhov, I. V.

The features of electron tunneling from or into the silicon valence band in a metal–insulator–semiconductor system with the HfO{sub 2}(ZrO{sub 2})/SiO{sub 2} double-layer insulator are theoretically analyzed for different modes. It is demonstrated that the valence-band current plays a less important role in structures with HfO{sub 2}(ZrO{sub 2})/SiO{sub 2} than in structures containing only silicon dioxide. In the case of a very wide-gap high-K oxide ZrO{sub 2}, nonmonotonic behavior related to tunneling through the upper barrier is predicted for the valence-band–metal current component. The use of an insulator stack can offer certain advantages for some devices, including diodes, bipolar tunnel-emittermore » transistors, and resonant-tunneling diodes, along with the traditional use of high-K insulators in a field-effect transistor.« less

Hydrogen calibration of GD-spectrometer using Zr-1Nb alloy

NASA Astrophysics Data System (ADS)

Mikhaylov, Andrey A.; Priamushko, Tatiana S.; Babikhina, Maria N.; Kudiiarov, Victor N.; Heller, Rene; Laptev, Roman S.; Lider, Andrey M.

2018-02-01

To study the hydrogen distribution in Zr-1Nb alloy (Э110 alloy) GD-OES was applied in this work. Qualitative analysis needs the standard samples with hydrogen. However, the standard samples with high concentrations of hydrogen in the zirconium alloy which would meet the requirements of the shape, size are absent. In this work method of Zr + H calibration samples production was performed at the first time. Automated Complex Gas Reaction Controller was used for samples hydrogenation. To calculate the parameters of post-hydrogenation incubation of the samples in an inert gas atmosphere the diffusion equations were used. Absolute hydrogen concentrations in the samples were determined by melting in the inert gas atmosphere using RHEN602 analyzer (LECO Company). Hydrogen distribution was studied using nuclear reaction analysis (HZDR, Dresden, Germany). RF GD-OES was used for calibration. The depth of the craters was measured with the help of a Hommel-Etamic profilometer by Jenoptik, Germany.

The excretion of biotrace elements using the multitracer technique in tumour-bearing mice.

PubMed

Wang, X; Tian, J; Yin, X M; Zhang, X; Wang, Q Z

2000-12-01

A radioactive multitracer solution obtained from the nuclear reaction of selenium with 25 MeV/nucleon 40Ar ions was used for investigation of trace element excretion into the faeces and urine of cancerous mice. The excretion rates of 22 elements (Na, K, Rb, Mg, Ca, Sr, Ga, As, Sc, V, Cr, Mn, Co, Fe, Y, Zr, Mo, Nb, Tc, Ru, Ag and In) were simultaneously measured under strictly identical experimental conditions, in order to clarify the excretion behavior of these elements in cancerous mice. The faecal and urinary excretion rates of Mg, Sr, Ga, As, Sc, V, Cr, Mn, Co, Fe, Y, Zr, Nb, Ru and Mo in cancerous mice, showed the in highest value at 0-8 hours. The accumulative excretion of Ca, Mo, Y and Zr was decreased and Na, Fe, Mn and Co increased in tumour-bearing mice, when compared to normal mice.

Vibrational micro-energy harvesters utilizing Nb-doped Pb(Zr,Ti)O3 films on stainless steel substrates

NASA Astrophysics Data System (ADS)

Van Minh, L.; Sano, T.; Fujii, T.; Kuwano, H.

2016-11-01

This work presents the micromachined energy harvesters using Nb-doped Pb(Zr,Ti)O3 (PNZT) films grown directly on the stainless steel substrates (SUS430). Piezoelectric materials on metallic substrates have been attracted to practical and robust energy harvesters. Nb-doped PZT films with (001)-preferred orientation grown on SUS substrates provided excellent properties for energy harvesting - high piezoelectric coefficient (e 31 = -10.6 C/m2) and low dielectric permittivity (ɛr = 373). The PNZT-based micro-energy harvester comprising a cantilever of 1.7 mm× 5 mm × 0.05 mm and a proof mass of 3 mm× 5 mm × 47 mm achieved the normalized power density (NPD) of 2.87 mW.g-2.cm-3. It is the highest performance among the published SUS-based energy harvesters, being closer to the best Si- based energy harvesters.

Microstructure and Interfacial Shear Strength in W/(Zr55Cu30Al10Ni5)100- x Nb x Composites

NASA Astrophysics Data System (ADS)

Mahmoodan, M.; Gholamipour, R.; Mirdamadi, Sh.; Nategh, S.

2017-11-01

In the present study, (Zr55Cu30Al10Ni5)100- x Nb( x=0,1,2,3) bulk metallic glass matrix/tungsten wire composites were fabricated by a gas pressure infiltration process at temperature 950 °C for 5 min. Microstructural studies and mechanical behaviors of the materials have been investigated by scanning electron microscopy, transmission electron microscopy and pullout tests. The mechanical results showed that the interface shear strength in the composite sample with X = 2 increased more than twice compared to the composite sample with X = 0. Based on the microstructural results, the addition of two atomic percent Nb in the matrix composite causes an increase in the diffusion band thickness during the melt infiltration and change in the interface fracture mode as a result of pullout test.

Electrical and structural properties of group-4 transition-metal nitride (TiN, ZrN, and HfN) contacts on Ge

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

Yamamoto, Keisuke; Nakashima, Hiroshi, E-mail: nakasima@astec.kyushu-u.ac.jp; Noguchi, Ryutaro

2015-09-21

Electrical and structural properties were investigated for group-4 transition-metal nitride contacts on Ge (TiN/Ge, ZrN/Ge, and HfN/Ge), which were prepared by direct sputter depositions using nitride targets. These contacts could alleviate the intrinsic Fermi-level pinning (FLP) position toward the conduction band edge. It was revealed that this phenomenon is induced by an amorphous interlayer (a-IL) containing nitrogen atoms at the nitride/Ge interfaces. The strength of FLP alleviation positively depended on the thickness of a-IL. TiN/Ge and ZrN/Ge contacts with ∼2 nm-thick a-ILs showed strong FLP alleviations with hole barrier heights (Φ{sub BP}) in the range of 0.52–56 eV, and a HfN/Ge contactmore » with an ∼1 nm-thick a-IL showed a weaker one with a Φ{sub BP} of 0.39 eV. However, TaN/Ge contact without a-IL did not show such FLP alleviation. Based on the results of depth distributions for respective elements, we discussed the formation kinetics of a-ILs at TiN/Ge and ZrN/Ge interfaces. Finally, we proposed an interfacial dipole model to explain the FLP alleviation.« less

Effect of dopants on the soft magnetic properties and high frequency characteristics of FeCoBM (M = Ti, Nb, Hf, and Ta) thin films.

PubMed

Hsieh, C C; Lin, T H; Chang, H W; Chang, C W; Chang, W C; Yang, C C

2011-03-01

Effect of dopants on the soft magnetic properties and high frequency characteristics of FeCoBM thin films (M = Ti, Nb, Hf, and Ta) have been studied. For (Fe0.55Co0.45)(100-x)B(x) (x = 5-15) thin films, with the increase of B content, the resistivity was increased because B could decrease the crystallinity of the films. The (Fe0.55Co0.45)90B10 thin film showed the optimum properties, where 4piM(s) = 16.1 kG, H(ce) = 64.2 Oe, H(ch) = 13.5 Oe, H(k) = 310 Oe and p = 338 microomega-cm. To reduce the coercivity of the film, the elements M, including Ti, Nb, Hf, and Ta, were selected to substitute for B in the FeCoB films. It was found that (Fe0.55Co0.45)90B6Ti2Nb2 thin film after annealing at a temperature of 200 degrees C for 30 min showed the optimal properties, where 4piM(s) = 15.8 kG, H(ce) = 4.8 Oe, H(ch) = 3.6 Oe, H(k) = 224 Oe and p = 290 microomega-cm. The theoretically calculated ferromagnetic resonance frequency of the developed films can be higher than 5 GHz.

Electronic structure and glass forming ability in early and late transition metal alloys

NASA Astrophysics Data System (ADS)

Babić, E.; Ristić, R.; Figueroa, I. A.; Pajić, D.; Skoko, Ž.; Zadro, K.

2018-03-01

A correlation between the change in magnetic susceptibility (Δχexp) upon crystallisation of Cu-Zr and Hf metallic glasses (MG) with their glass forming ability (GFA) observed recently, is found to apply to Cu-Ti and Zr-Ni alloys, too. In particular, small Δχexp, which reflects similar electronic structures, ES, of glassy and corresponding crystalline alloys, corresponds to high GFA. Here, we studied Δχexp for five Cu-Ti and four Cu-Zr and Ni-Zr MGs. The fully crystalline final state of all alloys was verified from X-ray diffraction patterns. The variation of GFA with composition in Cu-Ti, Cu-Zr and Cu-Hf MGs was established from the variation of the corresponding critical casting thickness, dc. Due to the absence of data for dc in Ni-Zr MGs their GFA was described using empirical criteria, such as the reduced glass transition temperature. A very good correlation between Δχexp and dc (and/or other criteria for GFA) was observed for all alloys studied. The correlation between the ES and GFA showed up best for Cu-Zr and NiZr2 alloys where direct data for the change in ES (ΔES) upon crystallisation are available. The applicability of the Δχexp (ΔES) criterion for high GFA (which provides a simple way to select the compositions with high GFA) to other metal-metal MGs (including ternary and multicomponent bulk MGs) is briefly discussed.

Fulvene to cyclopentadienyl conversion with homoleptic complexes of zirconium and hafnium

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

Rogers, J.S.; Lachicotte, R.J.; Bazan, G.C.

1999-09-27

The reaction of 6,6-dimethylfulvene with M(CH{sub 2}Ph){sub 4} (M = Zr, Hf) in benzene gives [{eta}{sup 5}-C{sub 5}H{sub 4}(CMe{sub 2}CH{sub 2}Ph)]M(CH{sub 2}Ph){sub 3} (1, M = Zr; 2, M = Hf) without any observable byproducts. A similar reaction for M = Ti is not observed. The single-crystal X-ray study of 1 shows a three-legged piano-stool geometry with an {eta}{sup 2}-bound benzyl ligand. A second equivalent of 6,6-dimethylfulvene does not react with either 1 or 2. The bulkier 6,6-diphenyfulvene only reacts cleanly with the more Lewis acidic Hf(CH{sub 2}Ph){sub 4} to give [{eta}{sup 5}-C{sub 5}H{sub 4}(CPh{sub 2}CH{sub 2}Ph)]Hf(CH{sub 2}Ph){sub 3} (3).more » Using the tetraamido complexes M(NMe{sub 2}Ph){sub 4} and 6,6-dimethylfulvene, one obtains dimethylamine and [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]M(NMe{sub 2}){sub 3} (4 for M = Zr) in good yield. These products are formally derived from the deprotonation of a fulvene methyl group and subsequent coordination of the resulting 2-propenylcyclopentadienyl fragment. Reaction of 4 and 6,6-dimethylfulvene affords the bent metallocene [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]{sub 2}Zr(NMe{sub 2}){sub 2} (5). Excess 8,8-dimethylbenzofulvene and M(NMe{sub 2}){sub 4} provides exclusively the product with only one coordinated indene.« less

Contribution of slab melting to magmatism at the active rifts zone in the middle of the Izu-Bonin arc

NASA Astrophysics Data System (ADS)

Hirai, Y.; Okamura, S.; Sakamoto, I.; Shinjo, R.; Wada, K.; Yoshida, T.

2016-12-01

The active rifts zone lies just behind the Quaternary volcanic front in the middle of the Izu-Bonin arc. Volcanism at the active rifts zone has been active since ca. 2 Ma, and late Quaternary basaltic lavas (< 0.1 Ma) and hydrothermal activity occur along the central axis of the rifts (Taylor, 1992; Ishizuka et al., 2003). In this paper we present new Sr, Nd, and Hf isotope and trace element data for the basalts erupted in the active rifts zone, including the Aogashima, Myojin and Sumisu rifts. Two geochemical groups can be identified within the active rift basalts: High-Zr basalts (HZB) and Low-Zr basalts (LZB). In the case of the Sumisu rift, the HZB exhibits higher in K2O, Na2O, Y, Zr and Ni, and also has higher Ce/Yb and Zr/Y, lower Ba/Th than the LZB. Depletion of Zr-Hf in the N-MORB spidergram characterizes the LZB from the Aogashima, Myojin and Sumisu rifts. The 176Hf/177Hf ratios are slightly lower in the HZB than in the LZB, decoupling of 176Hf/177Hf ratios and 143Nd/144Nd ratios. Estimated primary magma compositions suggest that primary magma segregation for the HZB occurred at depths less than 70 km ( 2 GPa), whereas the LZB more than 70 km (2 3 GPa). ODP Leg126 site 788, 790, and 791 reached the basaltic basement of the Sumisu rift (Gill et al., 1992). The geochemical data and stratigraphic relations of the basement indicate that the HZB is younger than the LZB. Geochemical modelling demonstrates that slab-derived melt mixed with mantle wedge produces the observed isotopic and trace elemental characteristics. The LZB volcanism at the early stage of the back-arc rifting is best explained by a partial melting of subducted slab saturated with trace quantities of zircon under low-temperature conditions in the mantle wedge. On the other hand, the HZB requires a partial melt of subducted slab accompanied by full dissolution of zircon under high-temperature conditions in the mantle wedge, which could have been caused by hot asthenospheric injection during the syn stage of the back-arc rifting. referencesGill et al. (1992) Proc. ODP, Sci. Result, 126, 383-403. Ishizuka et al. (2003) Geol. Soc. Spec. Publ., 219, 187-205. Taylor (1992) Proc. ODP, Sci. Result, 126, 627-651.

A-site- and/or B-site-modified PbZrTiO3 materials and (Pb, Sr, Ca, Ba, Mg) (Zr, Ti, Nb, Ta)O3 films having utility in ferroelectric random access memories and high performance thin film microactuators

NASA Technical Reports Server (NTRS)

Bilodeau, Steven (Inventor); Baum, Thomas H. (Inventor); Roeder, Jeffrey F. (Inventor); Chen, Ing-Shin (Inventor)

2001-01-01

A modified PbZrTiO.sub.3 perovskite crystal material thin film, wherein the PbZrTiO.sub.3 perovskite crystal material includes crystal lattice A-sites and B-sites at least one of which is modified by the presence of a substituent selected from the group consisting of (i) A-site substituents consisting of Sr, Ca, Ba and Mg, and (ii) B-site substituents selected from the group consisting of Nb and Ta. The perovskite crystal thin film material may be formed by liquid delivery MOCVD from metalorganic precursors of the metal components of the thin film, to form PZT and PSZT, and other piezoelectric and ferroelectric thin film materials. The thin films of the invention have utility in non-volatile ferroelectric memory devices (NV-FeRAMs), and in microelectromechanical systems (MEMS) as sensor and/or actuator elements, e.g., high speed digital system actuators requiring low input power levels.

Activation Cross-Sections for 14.2 MeV Neutrons on Molybdenum

NASA Astrophysics Data System (ADS)

Srinivasa Rao, C. V.; Lakshmana Das, N.; Thirumala Rao, B. V.; Rama Rao, J.

1981-12-01

Using the activation method, the cross-section for the following reactions on molybdenum were measured employing the mixed powder technique and Ge(Li) gamma-ray spectroscopy: 94Mo(n, 2n)93mMo, 3.5 ± 0.5 mbarn; 92Mo(n, 2n)91mMo, 19 ± 3 mbarn; 92Mo(n, 2n)91m+gMo, 226 ± 11 mbarn; 100Mo(n, p)100m2Nb, 9 ± 1 mbarn; 98Mo(n, p)98Nb, 10 ± 1 mbarn; 97Mo(n, p)97mNb, 5 ± 1 mbarn; 96Mo(n, p)96Nb, 12 ± 2 mbarn; 92Mo(n, α)89mZr, 2.1 ± 0.5 mbarn; and 92Mo(n, α)89m+gZr 24 ± 6 mbarn; the neutron energy was 14.2 ± 0.2 MeV. The experimental cross-sections were compared with the predictions of evaporation model and of different versions of pre-equilibrium model. The master equation approach appears to give satisfactory results.

Geochemical characterization of the largest upland lake of the Brazilian Amazonia: Impact of provenance and processes

NASA Astrophysics Data System (ADS)

Sahoo, Prafulla Kumar; Guimarães, José Tasso Felix; Souza-Filho, Pedro Walfir Martins; da Silva, Marcio Sousa; Nascimento, Wilson, Júnior; Powell, Mike A.; Reis, Luiza Santos; Pessenda, Luiz Carlos Ruiz; Rodrigues, Tarcísio Magevski; da Silva, Delmo Fonseca; Costa, Vladimir Eliodoro

2017-12-01

Lake Três Irmãs (LTI), the largest upland lake in the Brazilian Amazonia, located in Serra dos Carajás, was characterized using multi-elemental and isotope geochemistry (δ13C and δ15N) to understand the significance of organic and inorganic sources, weathering and sedimentary processes on the distribution of elements in lake bottom (surficial) sediments. Carbon and nitrogen isotopes from sedimentary organic matter suggest C3 terrestrial plants (forests > canga vegetation), macrophytes and freshwater DOC as the main sources. Sediments are depleted in most of the major oxides (except Fe2O3 and P2O5) when compared to upper continental crust (UCC) and their spatial distribution is highly influenced by catchment lithology. Principal Component Analysis revealed that most of the trace elements (Ba, Sr, Rb, Sc, Th, U, Zr, Hf, Nb, Y, V, Cr, Ga, Co, Ni) and REEs are closely correlated with Al and Ti (PC1; Group-1), so their redistribution is less influenced by post-depositional process. This is due to their relative immobility and being hosted by Al-bearing minerals during laterization. High Chemical Index of Alteration (CIA), Mafic Index of Alteration (MIA) and Index of Laterization (IOL) values indicate intense chemical weathering at source areas, but the weathering transformation was better quantified by IOL. A-CN-K plot along with elemental ratios (Al/K, Ti/K, Ti/Zr, La/Al, Cr/Th, Co/Th, La/Sm, La/Gd, Zr/Y, and Eu/Eu*) as well as chondrite-normalized REE patterns show that the detritic sediments are mainly sourced from ferruginous laterites and soils in the catchment, which may have characteristics similar to mafic rocks.

Crustal evolution at mantle depths constrained from Pamir xenoliths

NASA Astrophysics Data System (ADS)

Kooijman, E.; Hacker, B. R.; Smit, M. A.; Kylander-Clark, A. R.; Ratschbacher, L.

2012-12-01

Lower crustal xenoliths erupted in the Pamir at ~11 Ma provide an exclusive opportunity to study the evolution of crust at mantle depths during a continent-continent collision. To investigate, and constrain the timing of, the petrologic processes that occurred during burial to the peak conditions (2.5-2.8 GPa, 1000-1100 °C; [1]), we performed chemical- and isotope analyses of accessory minerals in 10 xenoliths, ranging from eclogites to grt-ky-qtz granulites. In situ laser ablation split-stream ICPMS yielded 1) U-Pb ages, Ti concentrations and REE in zircon, 2) U/Th-Pb ages and REE in monazite, and 3) U-Pb ages and trace elements in rutile. In addition, garnet, and biotite and K-feldspar were dated using Lu-Hf and 40Ar/39Ar geochronology, respectively. Zircon and monazite U-(Th-)Pb ages are 101.9±1.8, 53.7±1.0, 39.1±0.8, 21.7±0.4, 18.2±0.5, 16.9±0.8, 15.1±0.3 (2σ) and 12.5-11.1 Ma; most samples showed several or all of these populations. The 53.7 Ma and older ages are xenocrystic or detrital. For younger ages, zircon and monazite in individual samples recorded different ages-although zircon in one rock and monazite in another can be the same age. The 39.1 Ma zircon and monazite mostly occur as inclusions in minerals of the garnet-bearing assemblage that represents the early, low-P stages of burial. Garnet Lu-Hf ages of 37.8±0.3 Ma support garnet growth at this time. Spinifex-like textures containing 21.7-11.1 Ma zircon and monazite record short-lived partial melting events during burial. Aligned kyanite near these patches indicates associated deformation. Zircons yielding ≤12.5 Ma exhibit increased Eu/Eu* and markedly decreased HREE concentrations, interpreted to record feldspar breakdown and omphacite growth during increasing pressure. Rutile U-Pb cooling ages are 10.8±0.3 Ma in all samples. This agrees with the weighted mean 40Ar/39Ar age of eight biotite, K-feldspar and whole rock separates of 11.00+0.16/-0.09 Ma. Rutile in eclogites provides Zr/Hf and Nb/Ta trends that indicate clinopyroxene fractionation. This is consistent with the occurrence of rutile in omphacite-rich parts of the rocks and supports their HP petrogenesis. In the felsic granulites rutile is associated with the amphibolite-facies garnet-bearing assemblage and its Nb/Ta and Zr/Hf primarily reflect fractionation by rutile. Zirconium-in-rutile temperatures are 800-835 °C for the felsic granulites and 860-895 °C for the eclogites. Titanium-in-zircon temperatures increase from ~735 °C (0.7-1.0 GPa) at 39.1 Ma to ~900 °C (>2.5 GPa) at 11.5 Ma; a further, abrupt increase toward 1000 °C at 11.1 Ma marks melting at the onset of eruption. The analytical uncertainty on the Miocene ages is small compared to the 28-Myr burial record, enabling precise dating of individual reaction and deformation events. These events are at least an order of magnitude shorter than the duration of burial, and evidently occurred in pulses recorded by the (re)crystallization of zircon or monazite. Reference: [1] Hacker et al. (2005) J Petrol 46 (8): 1661-1687.

Dependence of X-Ray Burst Models on Nuclear Masses

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

Schatz, H.; Ong, W.-J.

X-ray burst model predictions of light curves and the final composition of the nuclear ashes are affected by uncertain nuclear masses. However, not all of these masses are determined experimentally with sufficient accuracy. Here we identify the remaining nuclear mass uncertainties in X-ray burst models using a one-zone model that takes into account the changes in temperature and density evolution caused by changes in the nuclear physics. Two types of bursts are investigated—a typical mixed H/He burst with a limited rapid proton capture process (rp-process) and an extreme mixed H/He burst with an extended rp-process. When allowing for a 3more » σ variation, only three remaining nuclear mass uncertainties affect the light-curve predictions of a typical H/He burst ({sup 27}P, {sup 61}Ga, and {sup 65}As), and only three additional masses affect the composition strongly ({sup 80}Zr, {sup 81}Zr, and {sup 82}Nb). A larger number of mass uncertainties remain to be addressed for the extreme H/He burst, with the most important being {sup 58}Zn, {sup 61}Ga, {sup 62}Ge, {sup 65}As, {sup 66}Se, {sup 78}Y, {sup 79}Y, {sup 79}Zr, {sup 80}Zr, {sup 81}Zr, {sup 82}Zr, {sup 82}Nb, {sup 83}Nb, {sup 86}Tc, {sup 91}Rh, {sup 95}Ag, {sup 98}Cd, {sup 99}In, {sup 100}In, and {sup 101}In. The smallest mass uncertainty that still impacts composition significantly when varied by 3 σ is {sup 85}Mo with 16 keV uncertainty. For one of the identified masses, {sup 27}P, we use the isobaric mass multiplet equation to improve the mass uncertainty, obtaining an atomic mass excess of −716(7) keV. The results provide a roadmap for future experiments at advanced rare isotope beam facilities, where all the identified nuclides are expected to be within reach for precision mass measurements.« less

Growth of Pb(Ti,Zr)O 3 thin films by metal-organic molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Avrutin, V.; Liu, H. Y.; Izyumskaya, N.; Xiao, B.; Özgür, Ü.; Morkoç, H.

2009-02-01

Single-crystal Pb(Zr xTi 1-x)O 3 thin films have been grown on (0 0 1) SrTiO 3 and SrTiO 3:Nb substrates by molecular beam epitaxy using metal-organic source of Zr and two different sources of reactive oxygen—RF plasma and hydrogen-peroxide sources. The same growth modes and comparable structural properties were observed for the films grown with both oxygen sources, while the plasma source allowed higher growth rates. The films with x up to 0.4 were single phase, while attempts to increase x beyond gave rise to the ZrO 2 second phase. The effects of growth conditions on growth modes, Zr incorporation, and phase composition of the Pb(Zr xTi 1-x)O 3 films are discussed. Electrical and ferroelectric properties of the Pb(Zr xTi 1-x)O 3 films of ~100 nm in thickness grown on SrTiO 3:Nb were studied using current-voltage, capacitance-voltage, and polarization-field measurements. The single-phase films show low leakage currents and large breakdown fields, while the values of remanent polarization are low (around 5 μC/cm 2). It was found that, at high sweep fields, the contribution of the leakage current to the apparent values of remanent polarization can be large, even for the films with large electrical resistivity (˜10 8-10 9 Ω cm at an electric filed of 1 MV/cm). The measured dielectric constant ranges from 410 to 260 for Pb(Zr 0.33Ti 0.67)O 3 and from 313 to 213 for Pb(Zr 0.2Ti 0.8)O 3 in the frequency range from 100 to 1 MHz.

Influence of alloying elements on the oxidation behavior of NbAl3

NASA Technical Reports Server (NTRS)

Hebsur, M. G.; Stephens, J. R.; Smialek, J. L.; Barrett, C. A.; Fox, D. S.

1988-01-01

NbAL3 is one candidate material for advanced aeropropulsion systems because of its high melting point, low density, and good oxidation resistance. Although NbAl3 has the lowest oxidation rate among the binary Nb-Al alloys, it does not form exclusive layers of protective Al2O3 scales. Recently Perkin et al., have shown the feasibility of forming alumina scales on Nb-Al alloys at greatly reduced Al contents. However, the objective was to maintain the high Al content, and hence low density, while achieving the capability of growing protective alumina scales. Alloy development followed approaches similar to those used successfully for superalloys and oxidation resistant MCrAlY coatings. Among the three elements examined (Ti, Si, and Cr) as ternary additions to Nb-Al3, Cr was the most effective in favoring the selective oxidation of Al. Nb-41Al-8Cr formed exclusive layers of alumina and had a k sub p value of 0.22 mg squared/cm (sup 4)/hr at 1200 C. The addition of 1 wt percent Y to this alloy was also beneficial, resulting in nearly an order of magnitude decrease in K sub p at 1200 C. Further improvements were achieved by adding about 1 wt percent Si to the quaternary alloy. The k sub p value of 0.012 mg squared/cm (sup 4)/hr for Nb-40Al-8Cr-1Y-1Si at 1200 C was identical to the best NiAl + Zr alloys. These NbAl3 alloys also exhibited excellent cyclic oxidation resistance for 100 hr at 1200 C, being nearly equivalent to NiAl + Zr.

Influence of alloying elements on the oxidation behavior of NbAl3

NASA Technical Reports Server (NTRS)

Hebsur, M. G.; Stephens, J. R.; Smialek, J. L.; Barrett, C. A.; Fox, D. S.

1989-01-01

NbAl3 is one candidate material for advanced aeropropulsion systems because of its high melting point, low density, and good oxidation resistance. Although NbAl3 has the lowest oxidation rate among the binary Nb-Al alloys, it does not form exclusive layers of protective Al203 scales. Recently Perkin et al., have shown the feasibility of forming alumina scales on Nb-Al alloys at greatly reduced Al contents. However, the objective was to maintain the high Al content, and hence low density, while achieving the capability of growing protective alumina scales. Alloy development followed approaches similar to those used successfully for superalloys and oxidation resistant MCrAly coatings. Among the three elements examined (Ti, Si, and Cr) as ternary additions to Nb-Al3, Cr was the most effective in favoring the selective oxidation of Al. Nb-41Al-8Cr formed exclusive layers of alumina and had a k sub p value of 0.22 mg squared/cm (sup 4)/hr at 1200 C. The addition of 1 wt percent Y to this alloy was also beneficial, resulting in nearly an order of magnitude decrease in K sub p at 1200 C. Further improvements were achieved by adding about 1 wt percent Si to the quaternary alloy. The k sub p value of 0.012 mg squared/cm (sup 4)/hr for Nb-40Al-8Cr-1Y-1Si at 1200 C was identical to the best NiAl + Zr alloys. These NbAl3 alloys also exhibited excellent cyclic oxidation resistance for 100 hr at 1200 C, being nearly equivalent to NiAl + Zr.

Evolution of magnetic properties and microstructure of Hf2Co11B alloys

DOE PAGES

McGuire, Michael A.; Rios, Orlando

2015-02-05

Amorphous Hf 2Co 11B alloys produced by melt-spinning have been crystallized by annealing at 500-800 °C, and the products have been investigated using magnetization measurements, x-ray diffraction, and scanning electron microscopy. The results reveal the evolution of the phase fractions, microstructure, and magnetic properties with both annealing temperature and time. Crystallization of the phase denoted HfCo 7, which is associated with the development of coercivity, occurs slowly at 500 °C. Annealing at intermediate temperatures produces mixed phase samples containing some of the HfCo 7 phase with the highest values of remanent magnetization and coercivity. The equilibrium structure at 800 °Cmore » contains HfCo3B 2, Hf 6Co 23 and Co, and displays soft ferromagnetism. Maximum values for the remanent magnetization, intrinsic coercivity, and magnetic energy product among the samples are approximately 5.2 kG, 2.0 kOe, and 3.1 MGOe, respectively, which indicates that the significantly higher values observed in crystalline, melt-spun Hf 2Co 11B ribbons are a consequence of the non-equilibrium solidification during the melt-spinning process. Application of high magnetic fields during annealing is observed to strongly affect the microstructural evolution, which may provide access to higher performance materials in Zr/Hf-Co hard ferromagnets. The crystal structure of HfCo 7 and the related Zr analogues is unknown, and without knowledge of atomic positions powder diffraction cannot distinguish among proposed unit cells and symmetries found in the literature.« less

Multilayer ultra-high-temperature ceramic coatings

DOEpatents

Loehman, Ronald E [Albuquerque, NM; Corral, Erica L [Tucson, AZ

2012-03-20

A coated carbon-carbon composite material with multiple ceramic layers to provide oxidation protection from ultra-high-temperatures, where if the carbon-carbon composite material is uninhibited with B.sub.4C particles, then the first layer on the composite material is selected from ZrB.sub.2 and HfB.sub.2, onto which is coated a layer of SiC coated and if the carbon-carbon composite material is inhibited with B.sub.4C particles, then protection can be achieved with a layer of SiC and a layer of either ZrB.sub.2 and HfB.sub.2 in any order.

High temperature solid electrolyte fuel cell with ceramic electrodes

DOEpatents

Marchant, David D.; Bates, J. Lambert

1984-01-01

A solid oxide electrolyte fuel cell is described having a central electrolyte comprised of a HfO.sub.2 or ZrO.sub.2 ceramic stabilized and rendered ionically conductive by the addition of Ca, Mg, Y, La, Nd, Sm, Gd, Dy Er, or Yb. The electrolyte is sandwiched between porous electrodes of a HfO.sub.2 or ZrO.sub.2 ceramic stabilized by the addition of a rare earth and rendered electronically conductive by the addition of In.sub.2 O.sub.3. Alternatively, the anode electrode may be made of a metal such as Co, Ni, Ir Pt, or Pd.

High temperature solid electrolyte fuel cell with ceramic electrodes

DOEpatents

Bates, J.L.; Marchant, D.D.

A solid oxide electrolyte fuel cell is described having a central electrolyte comprised of a HfO/sub 2/ or ZrO/sub 2/ ceramic stabilized and rendered ionically conductive by the addition of Ca, Mg, Y, La, Nd, Sm, Gd, Dy Er, or Yb. The electrolyte is sandwiched between porous electrodes of a HfO/sub 2/ or ZrO/sub 2/ ceramic stabilized by the addition of a rare earth and rendered electronically conductive by the addition of In/sub 2/O/sub 3/. Alternatively, the anode electrode may be made of a metal such as Co, Ni, Ir Pt, or Pd.