Sample records for hafnates

  1. Pressure-induced structural modifications of rare-earth hafnate pyrochlore

    NASA Astrophysics Data System (ADS)

    Turner, Katlyn M.; Rittman, Dylan R.; Heymach, Rachel A.; Tracy, Cameron L.; Turner, Madison L.; Fuentes, Antonio F.; Mao, Wendy L.; Ewing, Rodney C.

    2017-06-01

    Complex oxides with the pyrochlore (A2B2O7) and defect-fluorite ((A,B)4O7) structure-types undergo structural transformations under high-pressure. Rare-earth hafnates (A2Hf2O7) form the pyrochlore structure for A  =  La-Tb and the defect-fluorite structure for A  =  Dy-Lu. High-pressure transformations in A2Hf2O7 pyrochlore (A  =  Sm, Eu, Gd) and defect-fluorite (A  =  Dy, Y, Yb) were investigated up to ~50 GPa and characterized by in situ Raman spectroscopy and synchrotron x-ray diffraction (XRD). Raman spectra at ambient pressure revealed that all compositions, including the defect-fluorites, have some pyrochlore-type short-range order. In situ high-pressure synchrotron XRD showed that all of the rare earth hafnates investigated undergo a pressure-induced phase transition to a cotunnite-like (orthorhombic) structure that begins between 18 and 25 GPa. The phase transition to the cotunnite-like structure is not complete at 50 GPa, and upon release of pressure, the hafnates transform to defect-fluorite with an amorphous component. For all compositions, in situ Raman spectroscopy showed that disordering occurs gradually with increasing pressure. Pyrochlore-structured hafnates retain their short-range order to a higher pressure (30 GPa vs.  <10 GPa) than defect-fluorite-structured hafnates. Rare earth hafnates quenched from 50 GPa show Raman spectra consistent with weberite-type structures, as also reported for irradiated rare-earth stannates. The second-order Birch-Murnaghan equation of state fit gives a bulk modulus of ~250 GPa for hafnates with the pyrochlore structure, and ~400 GPa for hafnates with the defect-fluorite structure. Dy2Hf2O7 is intermediate in its response, with some pyrochlore-type ordering, based on Raman spectroscopy and the equation of state, with a bulk modulus of ~300 GPa. As predicted based on the similar ionic radius of Zr4+ and Hf4+, rare-earth hafnates show similar behavior to that

  2. Pressure-induced structural modifications of rare-earth hafnate pyrochlore.

    PubMed

    Turner, Katlyn M; Rittman, Dylan R; Heymach, Rachel A; Tracy, Cameron L; Turner, Madison L; Fuentes, Antonio F; Mao, Wendy L; Ewing, Rodney C

    2017-06-28

    Complex oxides with the pyrochlore (A 2 B 2 O 7 ) and defect-fluorite ((A,B) 4 O 7 ) structure-types undergo structural transformations under high-pressure. Rare-earth hafnates (A 2 Hf 2 O 7 ) form the pyrochlore structure for A  =  La-Tb and the defect-fluorite structure for A  =  Dy-Lu. High-pressure transformations in A 2 Hf 2 O 7 pyrochlore (A  =  Sm, Eu, Gd) and defect-fluorite (A  =  Dy, Y, Yb) were investigated up to ~50 GPa and characterized by in situ Raman spectroscopy and synchrotron x-ray diffraction (XRD). Raman spectra at ambient pressure revealed that all compositions, including the defect-fluorites, have some pyrochlore-type short-range order. In situ high-pressure synchrotron XRD showed that all of the rare earth hafnates investigated undergo a pressure-induced phase transition to a cotunnite-like (orthorhombic) structure that begins between 18 and 25 GPa. The phase transition to the cotunnite-like structure is not complete at 50 GPa, and upon release of pressure, the hafnates transform to defect-fluorite with an amorphous component. For all compositions, in situ Raman spectroscopy showed that disordering occurs gradually with increasing pressure. Pyrochlore-structured hafnates retain their short-range order to a higher pressure (30 GPa vs.  <10 GPa) than defect-fluorite-structured hafnates. Rare earth hafnates quenched from 50 GPa show Raman spectra consistent with weberite-type structures, as also reported for irradiated rare-earth stannates. The second-order Birch-Murnaghan equation of state fit gives a bulk modulus of ~250 GPa for hafnates with the pyrochlore structure, and ~400 GPa for hafnates with the defect-fluorite structure. Dy 2 Hf 2 O 7 is intermediate in its response, with some pyrochlore-type ordering, based on Raman spectroscopy and the equation of state, with a bulk modulus of ~300 GPa. As predicted based on the similar ionic radius of Zr 4+ and Hf 4+ , rare-earth hafnates show

  3. The pressure-induced structural response of rare earth hafnate and stannate pyrochlore from 0.1-50 GPa

    NASA Astrophysics Data System (ADS)

    Turner, K. M.; Rittman, D.; Heymach, R.; Turner, M.; Tracy, C.; Mao, W. L.; Ewing, R. C.

    2017-12-01

    Complex oxides with the pyrochlore (A2B2O7) and defect-fluorite ((A,B)4O7) structure-types undergo structural transformations under high-pressure. These compounds are under consideration for applications including as a proposed waste-form for actinides generated in the nuclear fuel cycle. High-pressure transformations in rare earth hafnates (A2Hf2O7, A=Sm, Eu, Gd, Dy, Y, Yb) and stannates (A2Sn2O7, A=Nd, Gd, Er) were investigated to 50 GPa by in situ Raman spectroscopy and synchrotron x-ray diffraction (XRD). Rare-earth hafnates form the pyrochlore structure for A=La-Tb and the defect-fluorite structure for A=Dy-Lu. Lanthanide stannates form the pyrochlore structure. Raman spectra revealed that at ambient pressure all compositions have pyrochlore-type short-range order. Stannate compositions show a larger degree of pyrochlore-type short-range ordering relative to hafnates. In situ high-pressure synchrotron XRD showed that rare earth hafnates and stannates underwent a pressure-induced phase transition to a cotunnite-like (Pnma) structure that begins between 18-25 GPa in hafnates and between 30-33 GPa in stannates. The phase transition is not complete at 50 GPa, and upon decompression, XRD indicates that all compositions transform to defect-fluorite with an amorphous component. In situ Raman spectroscopy showed that disordering in stannates and hafnates occurs gradually upon compression. Pyrochlore-structured hafnates retain short-range order to a higher pressure (30 GPa vs. <10 GPa) than defect-fluorite-structured hafnates. Hafnates and stannates decompressed from 50 GPa show Raman spectra consistent with weberite-type structures, also reported in irradiated stannates. The second-order Birch-Murnaghan equation of state fit gives a bulk modulus of 250 GPa for hafnate compositions with the pyrochlore structure, and 400 GPa for hafnate compositions with the defect-fluorite structure. Stannates have a lower bulk modulus relative to hafnates (between 80-150 GPa

  4. Europium-Doped Lanthanum Hafnate Nanoparticles: Structure, Photoluminescence, and Radioluminescence

    NASA Astrophysics Data System (ADS)

    Wahid, Kareem; Pokhrel, Madhab; Mao, Yuanbing

    Due to their novel physical properties, nanostructured phosphors are of interest for radiation-based imaging and therapeutics. Herein, the structural and luminescent properties of europium-doped lanthanum hafnate (La2Hf2O7:xmol%Eu3+, x = 0 - 35) nanoparticles are investigated for use as scintillators. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy confirm samples prepared through a combined co-precipitation and low-temperature molten salt synthetic process homogenously form spherical nanocrystals of 36 nm in the ordered pyrochlore phase. Ultraviolet and X-ray excitation of these samples induce strong red emissions in the 580 - 590 and 612 - 630 nm range corresponding to the 5D0->7 F1 magnetic dipole and 5D0->7 F2 electric dipole transitions of Eu3+. Optical response and quantum yield are optimized at 5% Eu3+; a proposed trade-off between quenching mechanisms (defect-states/cross-relaxation) and dopant concentration is discussed. Owing to their high density, large effective atomic number, and bright luminescence, these La2Hf2O7:xmol%Eu3+ nanoparticles warrant further investigation for scintillator applications. The authors thank the support from the Defense Threat Reduction Agency of the U.S. Department of Defense (award #HDTRA1- 10-1-0114).

  5. Coated conductors

    DOEpatents

    Arendt, Paul N.; Foltyn, Stephen R.; Stan, Liliana; Usov, Igor O.; Wang, Haiyan

    2010-06-15

    Articles are provided including a base substrate having a layer of an IBAD oriented material thereon, and, a layer of barium-containing material selected from the group consisting of barium zirconate, barium hafnate, barium titanate, barium strontium titanate, barium dysprosium zirconate, barium neodymium zirconate and barium samarium zirconate, or a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the layer of an IBAD oriented material. Such articles can further include thin films of high temperature superconductive oxides such as YBCO upon the layer of barium-containing material selected from the group consisting of barium zirconate, barium hafnate, barium titanate, barium strontium titanate, barium dysprosium zirconate, barium neodymium zirconate and barium samarium zirconate, or a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates.

  6. Alkali metal hafnium oxide scintillators

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

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Taylor, Scott Edward

    The present invention provides for a composition comprising an inorganic scintillator comprising an alkali metal hafnate, optionally cerium-doped, having the formula A 2HfO 3:Ce; wherein A is an alkali metal having a valence of 1, such as Li or Na; and the molar percent of cerium is 0% to 100%. The alkali metal hafnate are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  7. Buffer layers for coated conductors

    DOEpatents

    Stan, Liliana [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM; Foltyn, Stephen R [Los Alamos, NM

    2011-08-23

    A composite structure is provided including a base substrate, an IBAD oriented material upon the base substrate, and a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the IBAD oriented material. Additionally, an article is provided including a base substrate, an IBAD oriented material upon the base substrate, a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the IBAD oriented material, and a thick film upon the cubic metal oxide material. Finally, a superconducting article is provided including a base substrate, an IBAD oriented material upon the base substrate, a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the IBAD oriented material, and an yttrium barium copper oxide material upon the cubic metal oxide material.

  8. Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, Er) at high pressure

    NASA Astrophysics Data System (ADS)

    Turner, Katlyn M.; Tracy, Cameron L.; Mao, Wendy L.; Ewing, Rodney C.

    2017-12-01

    Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare their response to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant feature that influences their response on compression. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the 〈Sn-O〉 bond in stannate pyrochlore is more covalent than the 〈B-O〉 bonds in titanates, zirconate, and hafnates. In stannates, based on in situ Raman spectroscopy, pyrochlore cation and anion sublattices begin to disorder with the onset of compression, first measured at 0.3 GPa. The extent of sublattice disorder versus pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to an orthorhombic, cotunnite-like structure at ~28 GPa similar transitions have been observed in titanate, zirconate, and hafnate pyrochlores at varying pressures (18-40 GPa) with cation radius ratio. The extent of the phase transition versus pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multi-scale defect-fluorite  +  weberite-type structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlores under similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B 0, of stannates varies linearly and inversely with cation radius ratio from 1 1 1 GPa (Nd2Sn2O7) to 251 GPa (Er2Sn2O7). The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates and suggest that the size of the Ln3+ cation is the primary determining factor of B 0. Additionally, when normalized to r A

  9. Holmium hafnate: An emerging electronic device material

    NASA Astrophysics Data System (ADS)

    Pavunny, Shojan P.; Sharma, Yogesh; Kooriyattil, Sudheendran; Dugu, Sita; Katiyar, Rajesh K.; Scott, James F.; Katiyar, Ram S.

    2015-03-01

    We report structural, optical, charge transport, and temperature properties as well as the frequency dependence of the dielectric constant of Ho2Hf2O7 (HHO) which make this material desirable as an alternative high-k dielectric for future silicon technology devices. A high dielectric constant of ˜20 and very low dielectric loss of ˜0.1% are temperature and voltage independent at 100 kHz near ambient conditions. The Pt/HHO/Pt capacitor exhibits exceptionally low Schottky emission-based leakage currents. In combination with the large observed bandgap Eg of 5.6 eV, determined by diffuse reflectance spectroscopy, our results reveal fundamental physics and materials science of the HHO metal oxide and its potential application as a high-k dielectric for the next generation of complementary metal-oxide-semiconductor devices.

  10. Development of Nanomaterials for Nuclear Energetics

    NASA Astrophysics Data System (ADS)

    Petrunin, V. F.

    Structure and properties peculiarities of the nanocrystalline powders give the opportunity to design new and to develop a modernization of nuclear energy industry materials. It was shown experimentally, that addition of 5-10% uranium dioxide nanocrystalline powder to traditional coarse powder allows to decrease the sintering temperature or to increase the fuel tablets size of grain. Similar perspectives for the technology of neutron absorbing tablets of control-rod modernization are shown by nanopowder of dysprosium hafnate changing instead now using boron carbide. It is powders in nanocrystalline state get an opportunity to sinter them and to receive compact tablet with 8,2-8,4 g/cm2 density for automatic defence system of nuclear reactor. Resource of dysprosium hafnate ceramics can be 18-20 years instead 4-5 years for boron carbide. To step up the radiation-damage stability of fuel element jacket material was suggested to strengthen a heat-resistant ferrite-martensite steel by Y2O3 nanocrystalline powder addition. Nanopowder with size of particles 560 nm and crystallite size 9 nm was prepeared by chemical coprecipitation method. To make lighter the container for transport and provisional disposal of exposed fuel from nuclear reactor a new boron-aluminium alloy called as boral was developed. This composite armed with nanopowders of boron-containing materials and heavy metals oxides can replace succesburnt-up corrosion-resistant steels.

  11. The Pressure-Induced Structural Response of A2Hf2O7 (A=Y, Sm, Eu, Gd, Dy, Yb) Compounds from 0.1-50 GPa

    NASA Astrophysics Data System (ADS)

    Turner, K. M.; Rittman, D.; Heymach, R.; Turner, M.; Tracy, C.; Mao, W. L.; Ewing, R. C.

    2016-12-01

    A2B2O7 (A, B= cations) compounds have structures that make their properties conducive to many applications; for example they are a proposed waste-form for actinides generated in the nuclear fuel cycle. This interest in part is due to their structural responses to extreme environments of high P, T, or under intense irradiation. Depending on their cationic radius ratio, ra/rb, A2B2O7 compounds either crystallize as pyrochlore (ra/rb=1.46-1.7) or "defect fluorite" (ra/rb>1.46). The structure types are similar: they are derivatives of ideal fluorite with two cations and 1/8 missing anions. In pyrochlore, the cations and anion vacancy are ordered. In "defect fluorite"-structured oxides, the cations and anion vacancies are random. A2B2O7 compounds rarely amorphize in extreme environments. Rather, they disorder and undergo phase transitions; this resistance to amorphization contributes to the durability of this potential actinide waste-form. Under high-pressure, A2B2O7 compounds are known to disorder or form a cottunite-like phase. Their radius ratio affects their response to extreme environments; "defect fluorite" type compounds tend to disorder, and pyrochlore type compounds tend to form the cottunite-like phase. We have examined six A2Hf2O7 compounds (A=Y, Sm, Eu, Gd, Dy, Yb) in situ to 50 GPa. By keeping the B-site constant (Hf), we examined the effect of a changing radius ratio on the pressure-induced structural response of hafnates. We used symmetric DACs, ruby fluorescence, stainless steel gaskets, and methanol: ethanol (4:1 by volume) pressure medium. We characterized these materials with in situ Raman spectroscopy at Stanford University, and synchrotron X-Ray Diffraction (XRD) at APS 16 BM-D and ALS 12.2.2. The compounds were pyrochlore structured (Sm, Eu, Gd) and "defect-fluorite" structured (Y, Dy, Yb) hafnates . These compounds undergo a slow phase transition to a high-pressure cotunnite-like phase between 18-30 GPa. They undergo disordering of their cation

  12. Doped Lanthanum Hafnates as Scintillating Materials for High-Energy Photon Detection

    NASA Astrophysics Data System (ADS)

    Wahid, Kareem; Pokhrel, Madhab; Mao, Yuanbing

    Recent years have seen the emergence of nanocrystalline complex oxide scintillators for use in X-ray and gamma-ray detection. In this study, we investigate the structural and optical properties of La2Hf2O7 nanoparticles doped with varying levels of Eu3+ or Ce3+ by use of X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and optical photoluminescence. In addition, scintillation response under X-ray and gamma-ray exposure is reported. The authors thank the support from the Defense Threat Reduction Agency (DTRA) of the U.S. Department of Defense (Award #HDTRA1-10-1-0114).

  13. Effect of Microstructure on the Radioluminescence and Transparency of Ce-Doped Strontium Hafnate Ceramics

    PubMed Central

    van Loef, Edgar V.; Wang, Yimin; Miller, Stuart R.; Brecher, Charles; Rhodes, William H.; Baldoni, Gary; Topping, Stephen; Lingertat, Helmut; Sarin, Vinod K.; Shah, Kanai S.

    2011-01-01

    In this paper we report on the fabrication and characterization of SrHfO3:Ce ceramics. Powders were prepared by solid-state synthesis using metal oxides and carbonates. X-ray diffraction measurements showed that phase-pure SrHfO3 is formed at 1200°C. Inductively coupled plasma spectroscopy confirmed the purity and composition of each batch. SrHfO3 exhibits several phase changes in the solid, but this does not appear to be detrimental to the ceramics. Microprobe experiments showed uniform elemental grain composition, whereas aluminum added as charge compensation for trivalent cerium congregated at grain boundaries and triple points. Radioluminescence spectra revealed that the light yield decreases when the concentration of excess Sr increases. The decrease in the light yield may be related to the change of Ce3+ into Ce4+ ions. For stoichiometric SrHfO3:Ce, the light yield is about four times that of bismuth germanate (BGO), the conventional benchmark, indicating great potential for many scintillator applications. PMID:21339835

  14. Mn 4+ emission in pyrochlore oxides

    DOE PAGES

    Du, Mao-Hua

    2014-08-27

    For the existing Mn 4+ activated red phosphors have relatively low emission energies (or long emission wavelengths) and are therefore inefficient for general lighting. Density functional calculations are performed to study Mn 4+ emission in rare-earth hafnate, zirconate, and stannate pyrochlore oxides (RE 2Hf 2O 7, RE 2Zr 2O 7, and RE 2Sn 2O 7). We show how the different sizes of the RE 3+ cation in these pyrochlores affect the local structure of the distorted MnO 6 octahedron, the Mn–O hybridization, and the Mn 4+ emission energy. The Mn 4+ emission energies of many pyrochlores are found to bemore » higher than those currently known for Mn 4+ doped oxides and should be closer to that of Y 2O 3:Eu 3+ (the current commercial red phosphor for fluorescent lighting). The O–Mn–O bond angle distortion in a MnO6 octahedron is shown to play an important role in weakening Mn–O hybridization and consequently increasing the Mn 4+ emission energy. Our result shows that searching for materials that allow significant O–Mn–O bond angle distortion in a MnO 6 octahedron is an effective approach to find new Mn 4+ activated red phosphors with potential to replace the relatively expensive Y 2O 3:Eu 3+ phosphor.« less

  15. Structural, photoluminescence and radioluminescence properties of Eu{sup 3+} doped La{sub 2}Hf{sub 2}O{sub 7} nanoparticles

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

    Wahid, Kareem; Pokhrel, Madhab; Mao, Yuanbing, E-mail: yuanbing.mao@utrgv.edu

    This study presents the structural, optical, and radioluminescent characterization of newly synthesized europium-doped lanthanum hafnate (La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+}, x=0 to 35) nanoparticles (NPs) for use as phosphors and scintillation materials. Samples prepared through a combined co-precipitation and molten salt synthetic process were found to crystalize in the pyrochlore phase, a radiation tolerant structure related to the fluorite structure. These samples exhibit red luminescence under ultraviolet and X-ray excitation. Under these excitations, the optical intensity and quantum yield of the La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+} NPs depend on the Eu{sup 3+} concentration and are maximized at 5%. It ismore » proposed that there is a trade-off between the quenching due to defect states/cross-relaxation and dopant concentration. An optimal dopant concentration allows the La{sub 2}Hf{sub 2}O{sub 7}:5 mol%Eu{sup 3+} NPs to show the best luminescent properties of all the samples. - Graphical abstract: Incident X-ray and UV photons interact with La{sub 2}Hf{sub 2}O{sub 7}: xmol%Eu{sup 3+}(x=1–35) nanoparticles (NPs) to yield strong red luminescence centered at 612 nm. Colored spheres inside NP diagram represent pyrochlore coordination environment of La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+}. Blue, red, yellow, green and black spheres represent hafnium(IV) atoms, lanthanum(III)/europium(III) atoms, oxygen atoms at 48f site, oxygen atoms at 8b site and oxygen vacancies, respectively. - Highlights: • La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+} (x=0–35) nanoparticles with weakly-ordered pyrochlore structures were synthesized. • Optically and X-ray excited emission spectra showed strong luminescence centered at 612 nm. • Photoluminescence quantum yield increases with doping concentration up to 5% and decreases at higher concentrations.« less