Review of A2B2O7 Pyrochlore Response to Irradiation and Pressure

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

Lang, M.; Zhang, F; Zhang, J

2010-01-01

This article reviews recent research on swift heavy-ion irradiations and high-pressure studies on pyrochlores of the Gd{sub 2}Zr{sub 2-x}Ti{sub x}O{sub 7} binary. Applying three complementary analytical techniques (synchrotron X-ray diffraction, Raman spectroscopy and transmission electron microscopy) allowed for the investigation of the response of pyrochlore to irradiation and/or pressure. The chemical composition of pyrochlore has a strong effect on the character and energetics of the type of structural modifications that can be obtained under pressure or irradiation: For Ti-rich pyrochlores, the crystalline-to-amorphous transition is the dominant process. When Zr is substituted for Ti, an order-disorder transformation to the defect-fluorite structuremore » becomes the increasingly dominant process. Except for Gd{sub 2}Zr{sub 2}O{sub 7}, single ion tracks in pyrochlore consist of an amorphous core, surrounded by a crystalline, but disordered, defect-fluorite shell. This shell is surrounded by a defect-rich pyrochlore region. In contrast to similar effects observed when pressure or irradiation are applied separately, the response of the pyrochlore structure is significantly different when it is exposed simultaneously to pressure and irradiation. The combination of relativistic heavy ions with high pressure results in the formation of a new metastable pyrochlore phase. TEM and quantum-mechanical calculations suggest that these novel structural modifications are caused by the formation of nanocrystals and the modified energetics of nanomaterials.« less

Self-propagating high-temperature synthesis of Ce-bearing zirconolite-rich minerals using Ca(NO3)2 as the oxidant

NASA Astrophysics Data System (ADS)

Zhang, Kuibao; Wen, Guanjun; Yin, Dan; Zhang, Haibin

2015-12-01

Synroc is recognized as the second generation waste form for the immobilization of high-level radioactive waste (HLW). Zirconolite-rich (CaZrTi2O7) Synroc minerals were attempted by self-propagating high-temperature synthesis (SHS) using Fe2O3, CrO3, Ca(NO3)2 as the oxidants and Ti as the reductant. All designed reactions were ignited and sustained using Ca(NO3)2 as the oxidant, and zirconolite-rich ceramic matrices were successfully prepared with pyrochlore (Ca2Ti2O6), perovskite (CaTiO3) and rutile (TiO2) as the minor phases. The sample CN-4, which was designed using Ca(NO3)2 as the oxidant with TiO2/Ti ratio of 7:9, was readily solidified with density of 4.62 g/cm3 and Vickers hardness of 1052 HV. CeO2 was successfully stabilized by the CN-4 sample with resultant phase constituent of 2M-CaZrTi2O7 and CaTiO3.

Structure, thermal expansion coefficient and phase stability of La2(Zr0.7Ce0.3)2O7 studied by molecular dynamic simulation and experiment

NASA Astrophysics Data System (ADS)

Che, JunWei; Liu, XiangYang; Wang, XueZhi; Liang, GongYing

2018-04-01

This paper presents structure, thermal expansion coefficient and phase stability of La2(Zr0.7Ce0.3)2O7 (LZ7C3) ceramic by both theoretical and experimental results. It was found out that LZ7C3 powders had a pyrochlore structure after being heat-treated at temperatures higher than 1473 K or higher according to XRD and TEM results. The calculated average thermal expansion coefficient (TEC) was 7.12 × 10-6 K-1, which is a little smaller than experiment result, but changes of calculated average TECs of LZ, YSZ and LZ7C3 had the same trend with experimental results. Finally, the radial distribution function (RDF) was calculated to study the phase stability of LZ7C3.

Enhance the photoluminescence and radioluminescence of La2Zr2O7:Eu3+ core nanoparticles by coating with a thin Y2O3 shell

NASA Astrophysics Data System (ADS)

Pokhrel, Madhab; Burger, Arnold; Groza, Michael; Mao, Yuanbing

2017-06-01

We report the generation of La2Zr2O7:5%Eu3+@Y2O3 (LZO5E@YO) core@shell crystalline inorganic-inorganic heterogeneous nanoparticles (NPs). The Y2O3 (YO) shell coating process based on a chemical sol-gel method led to the growth of a thin YO shell on the ordered pyrochlore La2Zr2O7:5%Eu3+ (LZO5E) core NPs. Photoluminescence (PL) analyses demonstrated a blue shift of 15 nm on charge transfer (CT) excitation band of the core@shell NPs from that of the core NPs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) along x-ray diffraction (XRD), Fourier-transform Infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) studies confirmed the formation of the thin YO layer over the LZO5E core NPs. The PL intensity of the LZO5E@YO core@shell NPs was enhanced by three fold compared to that of the LZO5E core NPs, and higher quantum yield (QY) was observed for the former compared to the original NPs by more than 70%. Higher radioluminescence (RL) emission was also observed for the core@shell NPs compared to the core NPs. Our ability of obtaining near-perfect core@shell heterostructure with enhanced luminescence performance opens the door for the development of efficient La2Zr2O7:5%Eu3+@Y2O3 NPs for both optical and x-ray scintillation applications.

Strain engineered pyrochlore at high pressure

DOE PAGES

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye; ...

2017-05-22

Strain engineering is a promising method for next-generation materials processing techniques. Here, we use mechanical milling and annealing followed by compression in diamond anvil cell to tailor the intrinsic and extrinsic strain in pyrochlore, Dy 2Ti 2O 7 and Dy 2Zr 2O 7. Raman spectroscopy, X-ray pair distribution function analysis, and X-ray diffraction were used to characterize atomic order over short-, medium-, and long-range spatial scales, respectively, under ambient conditions. Raman spectroscopy and X-ray diffraction were further employed to interrogate the material in situ at high pressure. High-pressure behavior is found to depend on the species and concentration of defectsmore » in the sample at ambient conditions. Overall, we show that defects can be engineered to lower the phase transformation onset pressure by ~50% in the ordered pyrochlore Dy 2Ti 2O 7, and lower the phase transformation completion pressure by ~20% in the disordered pyrochlore Dy 2Zr 2O 7. Lastly, these improvements are achieved without significantly sacrificing mechanical integrity, as characterized by bulk modulus.« less

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

Aldridge, James D.; Womick, Jordan M.; Rosmus, Kimberly A.

Novel quaternary lanthanide-substituted oxides of stoichiometry LnxY2-xTi2O7 (where Ln is lanthanum, neodymium, samarium, gadolinium, or ytterbium) were prepared by traditional high-temperature, solid-state techniques and characterized by X-ray powder diffraction. Samples with nominal values of x up to 1.0 were attempted. The well-studied ternary cubic pyrochlore compound yttrium titanium oxide (Y2Ti2O7, space group Fd-3m, Z = 8), served as a parent structural framework in which Ln3+ cations were substituted on the Y3+ site. Laboratory-grade X-ray powder diffraction data revealed pure quaternary pyrochlore phases for LnxY2-xTi2O7 with x ≤ 0.2. Pyrochlore phase purity was verified by Rietveld analysis using high-resolution synchrotron X-raymore » powder diffraction data when x ≤ 0.2, however, for La3+ substitution specifically, pure quaternary pyrochlore formed at x<0.1. Band gap energies on selected samples were determined using optical diffuse reflectance spectroscopy and showed that these materials can be classified as electrical insulators with indirect band gap energies around 3.7 eV.« less

Sintering Characteristics of Multilayered Thermal Barrier Coatings Under Thermal Gradient and Isothermal High Temperature Annealing Conditions

NASA Technical Reports Server (NTRS)

Rai, Amarendra K.; Schmitt, Michael P.; Bhattacharya, Rabi; Zhu, Dongming; Wolfe, Douglas E.

2014-01-01

Pyrochlore oxides have most of the relevant attributes for use as next generation thermal barrier coatings such as phase stability, low sintering kinetics and low thermal conductivity. One of the issues with the pyrochlore oxides is their lower toughness and therefore higher erosion rate compared to the current state-of-the-art TBC material, yttria (6 to 8 wt%) stabilized zirconia (YSZ). In this work, sintering characteristics were investigated for novel multilayered coating consisted of alternating layers of pyrochlore oxide viz Gd2Zr2O7 and t' low k (rare earth oxide doped YSZ). Thermal gradient and isothermal high temperature (1316 C) annealing conditions were used to investigate sintering and cracking in these coatings. The results are then compared with that of relevant monolayered coatings and a baseline YSZ coating.

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

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

Strain engineering is a promising method for next-generation materials processing techniques. Here, we use mechanical milling and annealing followed by compression in diamond anvil cell to tailor the intrinsic and extrinsic strain in pyrochlore, Dy 2Ti 2O 7 and Dy 2Zr 2O 7. Raman spectroscopy, X-ray pair distribution function analysis, and X-ray diffraction were used to characterize atomic order over short-, medium-, and long-range spatial scales, respectively, under ambient conditions. Raman spectroscopy and X-ray diffraction were further employed to interrogate the material in situ at high pressure. High-pressure behavior is found to depend on the species and concentration of defectsmore » in the sample at ambient conditions. Overall, we show that defects can be engineered to lower the phase transformation onset pressure by ~50% in the ordered pyrochlore Dy 2Ti 2O 7, and lower the phase transformation completion pressure by ~20% in the disordered pyrochlore Dy 2Zr 2O 7. Lastly, these improvements are achieved without significantly sacrificing mechanical integrity, as characterized by bulk modulus.« less

Ion beam irradiation of lanthanum and thorium-doped yttrium titanates

NASA Astrophysics Data System (ADS)

Lian, J.; Zhang, F. X.; Peters, M. T.; Wang, L. M.; Ewing, R. C.

2007-05-01

Y2Ti2O7 pyrochlores doped with La have been sintered at 1373 K for 12 h with the designed compositions of the (LaxY1-x)2Ti2O7 system (x = 0, 0.08, 0.5, and 1), and the phase compositions were analyzed by X-ray diffraction. Limited amounts of La were incorporated into yttrium titanate pyrochlore structure for La-doped samples; while, the end member composition of La2Ti2O7 formed a layered perovskite structure. Ion beam-induced amorphization occurred for all compositions in the (LaxY1-x)2Ti2O7 binary under 1 MeV Kr2+ irradiation at room temperature, and the critical amorphization dose decreased with increasing amounts of La3+. The critical amorphization temperatures for Y2Ti2O7, (La0.162Y0.838)2Ti2O7 and La2Ti2O7 were determined to be ∼780, 890 and 920 K, respectively. Th4+ and Fe3+-doped yttrium titanate pyrochlores were synthesized at 1373 K by sintering Y2Ti2O7 with (ThO2 + Fe2O3). Pyrochlore structures and the chemical compositions were primarily identified by the X-ray diffraction and energy dispersive X-ray (EDX) measurements. The lattice parameter and the critical amorphization dose (1 MeV Kr2+ at room temperature) increase for yttrium titanate pyrochlores with the addition of Th. The increasing 'resistance' to amorphization with less La and greater Th and Fe contents for (Y1-xLax)2Ti2O7 and Y2Ti2O7-Fe2O3-ThO2 systems, respectively, are consistent with the changes in the average ionic radius ratio at the A-sites and B-sites. These results suggest that the addition of lanthanides and actinides (e.g., Th, U, or Pu) will affect the structural stability, as well as the radiation response behavior of the pyrochlore structure-type.

Atomic scale simulations of pyrochlore oxides with a tight-binding variable-charge model: implications for radiation tolerance.

PubMed

Sattonnay, G; Tétot, R

2014-02-05

Atomistic simulations with new interatomic potentials derived from a tight-binding variable-charge model were performed in order to investigate the lattice properties and the defect formation energies in Gd2Ti2O7 and Gd2Zr2O7 pyrochlores. The main objective was to determine the role played by the defect stability on the radiation tolerance of these compounds. Calculations show that the titanate has a more covalent character than the zirconate. Moreover, the properties of oxygen Frenkel pairs, cation antisite defects and cation Frenkel pairs were studied. In Gd2Ti2O7 the cation antisite defect and the Ti-Frenkel pair are not stable: they evolve towards more stable defect configurations during the atomic relaxation process. This phenomenon is driven by a decrease of the Ti coordination number down to five which leads to a local atomic reorganization and strong structural distortions around the defects. These kinds of atomic rearrangements are not observed around defects in Gd2Zr2O7. Therefore, the defect stability in A2B2O7 depends on the ability of B atoms to accommodate high coordination number (higher than six seems impossible for Ti). The accumulation of structural distortions around Ti-defects due to this phenomenon could drive the Gd2Ti2O7 amorphization induced by irradiation.

Phase transition in lithium garnet oxide ionic conductors Li7La3Zr2O12: The role of Ta substitution and H2O/CO2 exposure

NASA Astrophysics Data System (ADS)

Wang, Yuxing; Lai, Wei

2015-02-01

High Li-content lithium garnet oxides are promising solid electrolyte materials for lithium batteries. Being the highest Li-content lithium garnet oxides, Li7La3Zr2O12 has been reported to crystallize in either the tetragonal or cubic phase with no consensus on the exact conditions under which these two phases are formed, which may be due to unintentional Al contamination and air exposure. In this work, the effects of Ta substitution and H2O/CO2 exposure have been studied under Al-contamination free conditions with minimal air exposure. We showed that 1) the Ta-substitution induced phase transition occurred through a two-phase mechanism and a minimum 0.6 mol of Ta substitution to Zr is needed to stabilize the cubic phase; 2) H2O and CO2 can individually induce the tetragonal-cubic phase transition in Li7La3Zr2O12 through proton exchange and Li extraction, respectively, which can have great influence on the transport properties of Li7La3Zr2O12.

Fluctuations and All-In-All-Out Ordering in Dipole-Octupole Nd2Zr2O7

NASA Astrophysics Data System (ADS)

Lhotel, E.; Petit, S.; Guitteny, S.; Florea, O.; Ciomaga Hatnean, M.; Colin, C.; Ressouche, E.; Lees, M. R.; Balakrishnan, G.

2015-11-01

By means of neutron scattering and magnetization measurements down to 90 mK, we determine the magnetic ground state of the spin-ice candidate Nd2Zr2O7. We show that, despite ferromagnetic interactions, Nd2Zr2O7 undergoes a transition around 285 mK towards an all-in-all-out antiferromagnetic state, with a strongly reduced ordered magnetic moment. We establish the (H ,T ) phase diagram in the three directions of the applied field and reveal a metamagnetic transition around 0.1 T, associated with an unexpected shape of the magnetization curves. We propose that this behavior results from the peculiar nature of the Nd3 + doublet, a dipolar-octupolar doublet, different from the standard Kramers doublet studied to date, thus revealing the importance of multipolar correlations in the properties of pyrochlore oxides.

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/r B, the bulk moduli of stannates are comparable to those of zirconates and hafnates, which vary from titanates. Our results suggest that the cation radius ratio strongly influences the bulk moduli of stannates, as well as their overall compression response.

Response of Gd 2 Ti 2 O 7 and La 2 Ti 2 O 7 to swift-heavy ion irradiation and annealing

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

Park, Sulgiye; Lang, Maik; Tracy, Cameron L.

2015-07-01

Swift heavy ion (2 GeV 181Ta) irradiation-induced amorphization and temperature-induced recrystallization of cubic pyrochlore Gd2Ti2O7 (Fd3¯m) are compared with the response of a compositionally-similar material with a monoclinic-layered perovskite-type structure, La2Ti2O7 (P21). The averaged electronic energy loss, dE/dx, was 37 keV/nm and 35 keV/nm in Gd2Ti2O7 and La2Ti2O7, respectively. Systematic analysis of the structural modifications was completed using transmission electron microscopy, synchrotron X-ray diffraction, Raman spectroscopy, and small-angle X-ray scattering. Increasing ion-induced amorphization with increasing ion fluence was evident in the X-ray diffraction patterns of both compositions by a reduction in the intensity of the diffraction maxima concurrent with themore » growth in intensity of a broad diffuse scattering halo. Transmission electron microscopy analysis showed complete amorphization within ion tracks (diameter: ~10 nm) for the perovskite-type material; whereas a concentric, core–shell morphology was evident in the ion tracks of the pyrochlore, with an outer shell of disordered yet still crystalline material with the fluorite structure surrounding an amorphous track core (diameter: ~9 nm). The radiation response of both titanate oxides with the same stoichiometry can be understood in terms of differences in their structures and compositions. While the radiation damage susceptibility of pyrochlore A2B2O7 materials decreases as a function of the cation radius ratio rA/rB, the current study correlates this behavior with the stability field of monoclinic structures, where rLa/rTi > rGd/rTi. Isochronal annealing experiments of the irradiated materials showed complete recrystallization of La2Ti2O7 at 775 °C and of Gd2Ti2O7 at 850 °C. The annealing behavior is discussed in terms of enhanced damage recovery in La2Ti2O7, compared to the pyrochlore compounds Gd2Ti2O7. The difference in the recrystallization behavior may be related to structural constraints, i.e., reconstructing a low symmetry versus a high symmetry phase.« less

Transmission electron microscopic study of pyrochlore to defect-fluorite transition in rare-earth pyrohafnates

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

Karthik, Chinnathambi, E-mail: Karthikchinnathambi@boisestate.edu; Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415; Anderson, Thomas J.

2012-10-15

A structural transition in rare earth pyrohafnates, Ln{sub 2}Hf{sub 2}O{sub 7} (Ln=Y, La, Pr, Nd, Tb, Dy, Yb and Lu), has been identified. Neutron diffraction showed that the structure transforms from well-ordered pyrochloric to fully fluoritic through the lanthanide series from La to Lu with a corresponding increase in the position parameter x of the 48f (Fd3{sup Macron }m) oxygen site from 0.330 to 0.375. As evidenced by the selected area electron diffraction, La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} exhibited a well-ordered pyrocholoric structure with the presence of intense superlattice spots, which becamemore » weak and diffuse (in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}) before disappearing completely as the series progressed towards the Lu end. High resolution electron microscopic studies showed the breakdown of the pyrochlore ordering in the form of antiphase domains resulting in diffused smoke-like superlattice spots in the case of Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. - Graphical abstract: Transmission electron microscopic studies showed the ordered pyrochlore to defect fluorite transition in rare-earth pyrohafnates to occur via the formation of anti-phase domains to start with. Highlights: Black-Right-Pointing-Pointer Pyrochlore to fluorite structural transition in rare earth pyrohafnates. Black-Right-Pointing-Pointer La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} showed well ordered pyrochlore structure. Black-Right-Pointing-Pointer Short range ordering in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Break down of pyrochlore ordering due to antiphase boundaries. Black-Right-Pointing-Pointer Rest of the series showed fluoritic structure.« less

Zirconia ceramics for excess weapons plutonium waste

NASA Astrophysics Data System (ADS)

Gong, W. L.; Lutze, W.; Ewing, R. C.

2000-01-01

We synthesized a zirconia (ZrO 2)-based single-phase ceramic containing simulated excess weapons plutonium waste. ZrO 2 has large solubility for other metallic oxides. More than 20 binary systems A xO y-ZrO 2 have been reported in the literature, including PuO 2, rare-earth oxides, and oxides of metals contained in weapons plutonium wastes. We show that significant amounts of gadolinium (neutron absorber) and yttrium (additional stabilizer of the cubic modification) can be dissolved in ZrO 2, together with plutonium (simulated by Ce 4+, U 4+ or Th 4+) and impurities (e.g., Ca, Mg, Fe, Si). Sol-gel and powder methods were applied to make homogeneous, single-phase zirconia solid solutions. Pu waste impurities were completely dissolved in the solid solutions. In contrast to other phases, e.g., zirconolite and pyrochlore, zirconia is extremely radiation resistant and does not undergo amorphization. Baddeleyite (ZrO 2) is suggested as the natural analogue to study long-term radiation resistance and chemical durability of zirconia-based waste forms.

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

2017-01-24

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A = Eu, Dy; B = Ti, Zr) up to ~50 GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B = Ti and ~16 GPa B = Zr. But, the A-site cation affected the kinetics of the phase transformation,more » with the transformation for compositions with the smaller ionic radii, i.e., A = Dy, proceeding faster than those with a larger ionic radii, i.e., A = Eu. Our results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B = Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A = Eu than A = Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

2017-01-28

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr) up to ~50GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B=Ti and ~16 GPa B=Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionicmore » radii, i.e., A=Dy, proceeding faster than those with a larger ionic radii, i.e., A=Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B=Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A=Eu than A=Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

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

Silyukov, Oleg I., E-mail: olegsilyukov@yandex.ru; Abdulaeva, Liliia D.; Burovikhina, Alena A.

2015-03-15

Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}

Active three-way catalysis of rhodium particles with a low oxidation state maintained under an oxidative atmosphere on a La-containing ZrO2 support.

PubMed

Kawabata, Hisaya; Koda, Yuki; Sumida, Hirosuke; Shigetsu, Masahiko; Takami, Akihide; Inumaru, Kei

2013-05-11

Rhodium on a La-containing ZrO2 support effectively eliminated NOx from a synthetic auto exhaust gas under fluctuating oxygen conditions. Rhodium particles maintained a low oxidation state on the ZrO2-La2O3 mixed oxide even after treatment with 5% O2 at 773 K, highlighting the significant effect of the La addition.

17O solid-state NMR spectroscopy of A2B2O7 oxides: quantitative isotopic enrichment and spectral acquisition?

PubMed

Fernandes, Arantxa; Moran, Robert F; Sneddon, Scott; Dawson, Daniel M; McKay, David; Bignami, Giulia P M; Blanc, Frédéric; Whittle, Karl R; Ashbrook, Sharon E

2018-02-13

The potential of 17 O NMR spectroscopy for the investigation of A 2 B 2 O 7 ceramic oxides important in the encapsulation of radioactive waste is demonstrated, with post-synthetic enrichment by exchange with 17 O 2 gas. For Y 2 Sn 2 O 7 , Y 2 Ti 2 O 7 and La 2 Sn 2 O 7 pyrochlores, enrichment of the two distinct O species is clearly non quantitative at lower temperatures (∼700 °C and below) and at shorter times, despite these being used in prior work, with preferential enrichment of OA 2 B 2 favoured over that of OA 4 . At higher temperatures, the 17 O NMR spectra suggest that quantitative enrichment has been achieved, but the integrated signal intensities do not reflect the crystallographic 1 : 6 (O1 : O2) ratio until corrected for differences in T 1 relaxation rates and, more importantly, the contribution of the satellite transitions. 17 O NMR spectra of Y 2 Zr 2 O 7 and Y 2 Hf 2 O 7 defect fluorites showed little difference with any variation in enrichment temperature or time, although an increase in the absolute level of enrichment (up to ∼7.5%) was observed at higher temperature. DFT calculations show that the six distinct resonances observed cannot be assigned unambiguously, as each has contributions from more than one of the five possible next nearest neighbour environments. For La 2 Ti 2 O 7 , which adopts a layered perovskite-like structure, little difference in the spectral intensities is observed with enrichment time or temperature, although the highest absolute levels of enrichment (∼13%) were obtained at higher temperature. This work demonstrates that 17 O NMR has the potential to be a powerful probe of local structure and disorder in oxides, but that considerable care must be taken both in choosing the conditions for 17 O enrichment and the experimental acquisition parameters if the necessary quantitative measurements are to be obtained for more complex systems.

Bubble Formation and Lattice Parameter Changes Resulting from He Irradiation of Defect-Fluorite Gd2Zr2O7

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

Taylor, Caitlin A.; Patel, Maulik K.; Aguiar, Jeffery A.

2016-08-15

Pyrochlores have long been considered as potential candidates for advanced ceramic waste-forms for the immobilization of radioactive waste nuclides. This work provides evidence that Gd2Zr2O7, often considered the most radiation tolerant pyrochlore, could be susceptible to radiation damage in the form of bubble nucleation at the highest He doses expected over geological time. Ion irradiations were utilized to experimentally simulate the radiation damage and He accumulation produced by ..alpha..-decay. Samples were pre-damaged using 7 MeV Au3+ to induce the pyrochlore to defect-fluorite phase transformation, which would occur due to ..alpha..-recoil damage within several hundred years of storage in a Gd2Zr2O7more » waste-form. These samples were then implanted to various He concentrations in order to study the long-term effects of He accumulation. Helium bubbles 1-3 nm in diameter were observed in TEM at a concentration of 4.6 at.% He. Some bubbles remained isolated, while others formed chains 10-30 nm in length parallel to the surface. GIXRD measurements showed lattice swelling after irradiating pristine Gd2Zr2O7 with 7 MeV Au3+ to a fluence of 2.2 x 1015 Au/cm2. An increase in lattice swelling was also measured after 2.2 x 1015 Au/cm2 + 2 x 1015 He/cm2 and 2.2 x 1015 Au/cm2 + 2 x 1016 He/cm2. A decrease in lattice swelling was measured after irradiation with 2.2 x 1015 Au/cm2 + 2 x 1017 He/cm2, the fluence where bubbles and bubble chains were observed in TEM. Bubble chains are thought to form in order to reduce lattice strain normal to the surface, which is produced by the Au and He irradiation damage.« less

Air Plasma-Sprayed La2Zr2O7-SrZrO3 Composite Thermal Barrier Coating Subjected to CaO-MgO-Al2O3-SiO2 (CMAS)

NASA Astrophysics Data System (ADS)

Cai, Lili; Ma, Wen; Ma, Bole; Guo, Feng; Chen, Weidong; Dong, Hongying; Shuang, Yingchai

2017-08-01

La2Zr2O7-SrZrO3 composite thermal barrier coatings (TBCs) were prepared by air plasma spray (APS). The La2Zr2O7-SrZrO3 composite TBCs covered with calcium-magnesium-aluminum-silicate (CMAS) powder, as well as the powder mixture of CMAS and spray-dried La2Zr2O7-SrZrO3 composite powder, were heat-treated at 1250 °C in air for 1, 4, 8, and 12 h. The phase constituents and microstructures of the reaction products were characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. Experimental results showed that the La2Zr2O7-SrZrO3 composite TBCs had higher CMAS resistance than 8YSZ coating. A dense new layer developed between CMAS and La2Zr2O7-SrZrO3 composite TBCs during interaction, and this new layer consisted mostly of apatite (Ca2La8(SiO4)6O2) and c-ZrO2. The newly developed layer effectively protected the La2Zr2O7-SrZrO3 composite TBCs from further CMAS attack.

Structural and magnetic investigations of single-crystalline neodymium zirconate pyrochlore Nd2Zr2O7

NASA Astrophysics Data System (ADS)

Hatnean, M. Ciomaga; Lees, M. R.; Petrenko, O. A.; Keeble, D. S.; Balakrishnan, G.; Gutmann, M. J.; Klekovkina, V. V.; Malkin, B. Z.

2015-05-01

We report structural and magnetic properties studies of large high-quality single crystals of the frustrated magnet Nd2Zr2O7 . Powder x-ray diffraction analysis confirms that Nd2Zr2O7 adopts the pyrochlore structure. Room-temperature x-ray diffraction and time-of-flight neutron-scattering experiments show that the crystals are stoichiometric in composition with no measurable site disorder. The temperature dependence of the magnetic susceptibility shows no magnetic ordering at temperatures down to 0.5 K. Fits to the magnetic susceptibility data using a Curie-Weiss law reveal a ferromagnetic coupling between the Nd moments. Magnetization versus field measurements show a local Ising anisotropy along the <111 > axes of the Nd3 + ions in the ground state. Specific heat versus temperature measurements in zero applied magnetic field indicate the presence of a thermal anomaly below T ˜7 K, but no evidence of magnetic ordering is observed down to 0.5 K. The experimental temperature dependence of the single-crystal bulk dc susceptibility and isothermal magnetization are analyzed using crystal field theory and the crystal field parameters and exchange coupling constants determined.

Thermal barrier coating having high phase stability

DOEpatents

Subramanian, Ramesh

2001-01-01

A device (10) comprising a substrate (22) having a deposited ceramic thermal barrier coating layer (20) characterized by a microstructure having gaps (28) where the thermal barrier coating (20) consists essentially of a pyrochlore crystal structure having a chemical formula consisting essentially of A.sup.n+.sub.2-x B.sup.m+.sub.2+x O.sub.7-y, where A is selected from the group of elements selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and mixtures thereof; where B is selected from the group of elements selected from Zr, Hf, Ti and mixtures thereof; n and m are the valence of A and B respectively, and for -0.5.ltoreq.x.ltoreq.0.5, ##EQU1## and excluding the following combinations for x=0, y=0: A=La and B=Zr; A=La and B=Hf; A=Gd and B=Hf; and A=Yb and B=Ti.

Uranium luminescence in La2 Zr2 O7 : effect of concentration and annealing temperature.

PubMed

Mohapatra, M; Rajeswari, B; Hon, N S; Kadam, R M

2016-12-01

The speciation of a particular element in any given matrix is a prerequisite to understanding its solubility and leaching properties. In this context, speciation of uranium in lanthanum zirconate pyrochlore (La 2 Zr 2 O 7  = LZO), prepared by a low-temperature combustion route, was carried out using a simple photoluminescence lifetime technique. The LZO matrix is considered to be a potential ceramic host for fixing nuclear and actinide waste products generated during the nuclear fuel cycle. Special emphasis has been given to understanding the dynamics of the uranium species in the host as a function of annealing temperature and concentration. It was found that, in the LZO host, uranium is stabilized as the commonly encountered uranyl species (UO 2 2+ ) up to a heat treatment of 500 °C at the surface. Above 500 °C, the uranyl ion is diffused into the matrix as the more symmetric octahedral uranate species (UO 6 6- ). The uranate ions thus formed replace the six-coordinated 'Zr' atoms at regular lattice positions. Further, it was observed that concentration quenching takes place beyond 5 mol% of uranium doping. The mechanism of the quenching was found to be a multipolar interaction. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Computational and Experimental Studies of the Radiation Response of Gd2Ti2O7 Pyrochlore

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

Devanathan, Ram; Weber, William J.

2005-12-16

The structure and property changes in Gd2Ti2O7 (polycrystalline pyrochlore) were examined following irradiation with 1 MeV Kr+, 0.6 MeV Bi+ and 4 MeV Au2+ ions over the temperature range 30-950 K. Gd2Ti2O7 readily amorphizes with a low temperature (30 K) critical dose for amorphization of {approx} 0.15 displacements per atom (dpa). The critical temperature above which amorphization does not occur is about 1190 K. Nano-indentation studies reveal that the structural changes were accompanied by decreases of 15% in the Young's modulus. 1 MeV Kr+ irradiation of amorphous Gd2Ti2O7 at 1065 K resulted in ion-beam-assisted recrystallization. These experimental studies were complementedmore » with molecular dynamics simulations of low energy recoils in Gd2Ti2O7 and Gd2Zr2O7 using a Buckingham type potential. The displacement threshold energy surface in both pyrochlores is highly anisotropic. Displacement energies are higher for all sublattices in the titanate pyrochlore compared to the zirconate. Ti sublattice displacements require energies in excess of 100 eV, and result in multiple displacements and defect clusters. The formation of these clusters might impede dynamic defect recovery and facilitate amorphization.« less

Novel Functionally Graded Thermal Barrier Coatings in Coal-Fired Power Plant Turbines

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

Zhang, Jing

This project presents a detailed investigation of a novel functionally graded coating material, pyrochlore oxide, for thermal barrier coating (TBC) in gas turbines used in coal-fired power plants. Thermal barrier coatings are refractory materials deposited on gas turbine components, which provide thermal protection for metallic components at operating conditions. The ultimate goal of this research is to develop a manufacturing process to produce the novel low thermal conductivity and high thermal stability pyrochlore oxide based coatings with improved high-temperature durability. The current standard TBC, yttria stabilized zirconia (YSZ), has service temperatures limited to <1200°C, due to sintering and phase transitionmore » at higher temperatures. In contrast, pyrochlore oxide, e.g., lanthanum zirconate (La 2Zr 2O 7, LZ), has demonstrated lower thermal conductivity and better thermal stability, which are crucial to high temperature applications, such as gas turbines used in coal-fired power plants. Indiana University – Purdue University Indianapolis (IUPUI) has collaborated with Praxair Surface Technologies (PST), and Changwon National University in South Korea to perform the proposed research. The research findings are critical to the extension of current TBCs to a broader range of high-temperature materials and applications. Several tasks were originally proposed and accomplished, with additional new opportunities identified during the course of the project. In this report, a description of the project tasks, the main findings and conclusions are given. A list of publications and presentations resulted from this research is listed in the Appendix at the end of the report.« less

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). Stannate and hafnate pyrochlore compositions taken to high pressure show structural transformations consistent with irradiated pyrochlore, and compositionally disordered pyrochlore: a long-range structure best described by defect-fluorite, and a short-range structure best described by weberite.

Mechanical Properties of Layered La2Zr2O7 Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Guo, Xingye; Li, Li; Park, Hyeon-Myeong; Knapp, James; Jung, Yeon-Gil; Zhang, Jing

2018-04-01

Lanthanum zirconate (La2Zr2O7) has been proposed as a promising thermal barrier coating (TBC) material due to its low thermal conductivity and high stability at high temperatures. In this work, both single and double-ceramic-layer (DCL) TBC systems of La2Zr2O7 and 8 wt.% yttria-stabilized zirconia (8YSZ) were prepared using air plasma spray (APS) technique. The thermomechanical properties and microstructure were investigated. Thermal gradient mechanical fatigue (TGMF) tests were applied to investigate the thermal cycling performance. The results showed that DCL La2Zr2O7 + 8YSZ TBC samples lasted fewer cycles compared with single-layered 8YSZ TBC samples in TGMF tests. This is because DCL La2Zr2O7 TBC samples had higher residual stress during the thermal cycling process, and their fracture toughness was lower than that of 8YSZ. Bond strength test results showed that 8YSZ TBC samples had higher bond strength compared with La2Zr2O7. The erosion rate of La2Zr2O7 TBC samples was higher than that of 8YSZ samples, due to the lower critical erodent velocity and fracture toughness of La2Zr2O7. DCL porous 8YSZ + La2Zr2O7 had a lower erosion rate than other SCL and DCL La2Zr2O7 coatings, suggesting that porous 8YSZ serves as a stress-relief buffer layer.

Oxidant effect of La(NO3)3·6H2O solution on the crystalline characteristics of nanocrystalline ZrO2 films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Oh, Nam Khen; Kim, Jin-Tae; Kang, Goru; An, Jong-Ki; Nam, Minwoo; Kim, So Yeon; Park, In-Sung; Yun, Ju-Young

2017-02-01

Nanocrystalline ZrO2 films were synthesized by atomic layer deposition method using CpZr[N(CH3)2]3 (Cp = C5H5) as the metal precursor and La(NO3)3·6H2O solution as the oxygen source. La element in the deposited ZrO2 films could not be detected as its content was below the resolution limit of the X-ray photoelectron spectroscopy. The alternative introduction of La(NO3)3·6H2O solution to conventionally used H2O as the oxidant effectively altered the crystalline structure, grain size, and surface roughness of the grown ZrO2 films. Specifically, the crystalline structure of the ZrO2 film changed from a mixture of tetragonal and monoclinic phases to monoclinic phase. The average grain size also increased, and the resulting film surface became rougher. The average grain sizes of the ZrO2 films prepared from La(NO3)3·6H2O solution at concentrations of 10, 20, 30, and 40% were 280, 256, 208, and 200 nm, respectively, whereas that prepared using H2O oxidant was 142 nm. However, the concentration of La(NO3)3·6H2O solution minimally influenced the crystalline characteristics of the nanocrystalline ZrO2 films i.e., the crystalline structure, grain size, and surface roughness except for crystallite size.

Swift heavy ion track formation in Gd2Zr2-xTixO7 pyrochlore: Effect of electronic energy loss

NASA Astrophysics Data System (ADS)

Lang, Maik; Toulemonde, Marcel; Zhang, Jiaming; Zhang, Fuxiang; Tracy, Cameron L.; Lian, Jie; Wang, Zhongwu; Weber, William J.; Severin, Daniel; Bender, Markus; Trautmann, Christina; Ewing, Rodney C.

2014-10-01

The morphology of swift heavy ion tracks in the Gd2Zr2-xTixO7 pyrochlore system has been investigated as a function of the variation in chemical composition and electronic energy loss, dE/dx, over a range of energetic ions: 58Ni, 101Ru, 129Xe, 181Ta, 197Au, 208Pb, and 238U of 11.1 MeV/u specific energy. Bright-field transmission electron microscopy, synchrotron X-ray diffraction, and Raman spectroscopy reveal an increasing degree of amorphization with increasing Ti-content and dE/dx. The size and morphology of individual ion tracks in Gd2Ti2O7 were characterized by high-resolution transmission electron microscopy revealing a core-shell structure with an outer defect-fluorite dominated shell at low dE/dx to predominantly amorphous tracks at high dE/dx. Inelastic thermal-spike calculations have been used together with atomic-scale characterization of ion tracks in Gd2Ti2O7 by high resolution transmission electron microscopy to deduce critical energy densities for the complex core-shell morphologies induced by ions of different dE/dx.

Complex oxides: Intricate disorder

DOE PAGES

Uberuaga, Blas Pedro

2016-02-29

In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations 1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder 2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought 4.« less

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

Uberuaga, Blas Pedro

In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations 1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder 2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought 4.« less

Magnetic and charge transport properties of the Na-based Os oxide pyrochlore

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

Shi, Y.G., E-mail: SHI.Youguo@nims.go.j; International Center for Materials Nanoarchitectonics; JST, Transformative Research-Project on Iron Pnictides

2009-04-15

The Na-based osmium oxide pyrochlore was synthesized for the first time by an ion-exchange method using KOs{sub 2}O{sub 6} as a host. The composition was identified as Na{sub 1.4}Os{sub 2}O{sub 6}.H{sub 2}O by electron probe micro-analysis, thermogravimetric analysis, and structural analysis using synchrotron X-ray diffraction. Na{sub 1.4}Os{sub 2}O{sub 6}.H{sub 2}O crystallizes in a regular pyrochlore structure with some defects (space group: Fd-3m, a=10.16851(1) A). Electrical resistivity, heat capacity, and magnetization measurements clearly showed absence of superconductivity down to 2 K, being in large contrast to what was found for the beta-type pyrochlore superconductor AOs{sub 2}O{sub 6} (A=Cs, Rb, and K).more » The Sommerfeld coefficient is 22 mJ K{sup -2} mol{sup -1}, being the smallest among AOs{sub 2}O{sub 6}. A magnetic anomaly at {approx}57 K and associated magneto-resistance (+3.7% at 2 K in 70 kOe) were found. - Graphical abstract: Crystal structure of the Na-based Os oxide pyrochlore Na{sub 1.4}Os{sub 2}O{sub 6}.H{sub 2}O.« less

Thermal barrier coating having high phase stability

DOEpatents

Subramanian, Ramesh

2002-01-01

A device (10) comprising a substrate (22) having a deposited ceramic thermal barrier coating characterized by a microstructure having gaps (28) where the thermal barrier coating comprises a first thermal barrier layer (40), and a second thermal barrier layer (30) with a pyrochlore crystal structure having a chemical formula of A.sup.n+.sub.2-x B.sup.m+.sub.2+x O.sub.7-y, where A is selected from the group of elements consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and mixtures thereof, where B is selected from the group of elements consisting of Zr, Hf, Ti and mixtures thereof, where n and m are the valence of A and B respectively, and for -0.5.ltoreq.x.ltoreq.0.5, ##EQU1## and excluding the following combinations for x=0, y=0: A=La and B=Zr; A=La and B=Hf; A=Gd and B=Hf; and A=Yb and B=Ti.

About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

PubMed

Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

2016-10-12

The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets

PubMed Central

Rettenwander, D.; Geiger, C.A.; Tribus, M.; Tropper, P.; Wagner, R.; Tippelt, G.; Lottermoser, W.; Amthauer, G.

2015-01-01

A series of Fe3+-bearing Li7La3Zr2O12 (LLZO) garnets was synthesized using solid-state synthesis methods. The synthetic products were characterized compositionally using electron microprobe analysis and inductively coupled plasma optical emission spectroscopy (ICP-OES) and structurally using X-ray powder diffraction and 57Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe3+ pfu could be incorporated in Li7−3xFexLa3Zr2O12 garnet solid solutions. At Fe3+ concentrations lower than about 0.16 pfu, both tetragonal and cubic garnets were obtained in the synthesis experiments. X-ray powder diffraction analysis showed only a garnet phase for syntheses with starting materials having intended Fe3+ contents lower than 0.52 Fe3+ pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a0, for all solid-solution garnets is similar with a value of a0≈12.98 Å regardless of the amount of Fe3+. 57Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe3+ contents greater than 0.16 Fe3+ pfu. The composition of different phase pure Li7−3xFexLa3Zr2O12 garnets, as determined by electron microprobe (Fe, La, Zr) and ICP-OES (Li) measurements, give Li6.89Fe0.03La3.05Zr2.01O12, Li6.66Fe0.06La3.06Zr2.01O12, Li6.54Fe0.12La3.01Zr1.98O12, and Li6.19Fe0.19La3.02Zr2.04O12. The 57Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe3+ occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe3+ in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li6.54Fe0.12La3.01Zr1.98O12 this Fe3+ has a distorted 4-fold coordination. PMID:26435549

Quantum spin ices and magnetic states from dipolar-octupolar doublets on the pyrochlore lattice

NASA Astrophysics Data System (ADS)

Chen, Gang

We consider a class of electron systems in which dipolar-octupolar Kramers doublets arise on the pyrochlore lattice. In the localized limit, the Kramers doublets are described by the effective spin 1/2 pseudospins. The most general nearest-neighbor exchange model between these pseudospins is the XYZ model. In additional to dipolar ordered and octupolar ordered magnetic states, we show that this XYZ model exhibits two distinct quantum spin ice (QSI) phases, that we dub dipolar QSI and octupolar QSI. These two QSIs are distinct symmetry enriched U(1) quantum spin liquids, enriched by the lattice symmetry. Moreover, the XYZ model is absent from the notorious sign problem for a quantum Monte Carlo simulation in a large parameter space. We discuss the potential relevance to real material systems such as Dy2Ti2O7, Nd2Zr2O7, Nd2Hf2O7, Nd2Ir2O7, Nd2Sn2O7 and Ce2Sn2O7. chggst@gmail.com, Refs: Y-P Huang, G Chen, M Hermele, Phys. Rev. Lett. 112, 167203 (2014).

Enhanced Hydrothermal Stability and Catalytic Activity of La x Zr y O z Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase

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

Lopez-Ruiz, Juan A.; Cooper, Alan R.; Li, Guosheng

Common ketonization catalysts such as ZrO2, CeO2, CexZryOz, and TiO2-based catalysts have been reported to lose surface area, undergo phase-transformation, and lose catalytic activity when utilized in the condensed aqueous phase. In this work, we synthesized and tested a series of LaxZryOz mixed metal oxides with different La:Zr atomic ratios with the goal of enhancing the catalytic activity and stability for the ketonization of acetic acid in condensed aqueous media at 568 K. We synthesized a hydrothermally stable LaxZryOz mixed-metal oxide catalyst with enhanced ketonization activities 360 and 40 times more active than La2O3 and ZrO2, respectively. Catalyst characterization techniquesmore » suggest that the formation of a hydrothermally stable catalyst which is isomorphic with tetragonal-ZrO2 under hydrothermal reaction conditions.« less

Dopant concentration dependent optical and X-Ray induced photoluminescence in Eu3+ doped La2Zr2O7

NASA Astrophysics Data System (ADS)

Pokhrel, Madhab; Brik, Mikhail; Mao, Yuanbing

2015-03-01

Herein, we will be presenting the dopant (Eu) concentration dependent high density La2Zr2O7 nanoparticles for optical and X-ray scintillation applications by use of X - ray diffraction, Raman, FTIR, scanning electron microscope (SEM), transmission electron microscopy (TEM), optically and X-ray excited photoluminescence (PL). Several theoretical methods have been used in order to investigate the structural, electronic, optical, elastic, dynamic properties of Eu doped La2Zr2O7. It is observed that Eu: La2Zr2O7 shows an intense red luminescence under 258, 322, 394 and 465 nm excitation. The optical intensity of Eu: La2Zr2O7 depends on the dopant concentration of Eu3+. Following high energy excitation with X-rays, Eu: La2Zr2O7 shows an atypical Eu PL response (scintillation) with a red emission. The intense color emission of Eu obtained under 258 nm excitation, the X-ray induced luminescence property along with reportedly high density of La2Zr2O7, makes these nanomaterials attractive for optical and X-ray applications. The authors thank the support from the Defense Threat Reduction Agency (DTRA) of the U.S. Department of Defense (Award #HDTRA1-10-1-0114).

Two-magnon scattering in the 5d all-in-all-out pyrochlore magnet Cd2Os2O7.

PubMed

Nguyen, Thi Minh Hien; Sandilands, Luke J; Sohn, C H; Kim, C H; Wysocki, Aleksander L; Yang, In-Sang; Moon, S J; Ko, Jae-Hyeon; Yamaura, J; Hiroi, Z; Noh, Tae Won

2017-08-15

5d pyrochlore oxides with all-in-all-out magnetic order are prime candidates for realizing strongly correlated, topological phases of matter. Despite significant effort, a full understanding of all-in-all-out magnetism remains elusive as the associated magnetic excitations have proven difficult to access with conventional techniques. Here we report a Raman spectroscopy study of spin dynamics in the all-in-all-out magnetic state of the 5d pyrochlore Cd 2 Os 2 O 7 . Through a comparison between the two-magnon scattering and spin-wave theory, we confirm the large single ion anisotropy in this material and show that the Dzyaloshinskii-Moriya and exchange interactions play a significant role in the spin-wave dispersions. The Raman data also reveal complex spin-charge-lattice coupling and indicate that the metal-insulator transition in Cd 2 Os 2 O 7 is Lifshitz-type. Our work establishes Raman scattering as a simple and powerful method for exploring the spin dynamics in 5d pyrochlore magnets.Pyrochlore 5d transition metal oxides are expected to have interesting forms of magnetic order but are hard to study with conventional probes. Here the authors show that Raman scattering can be used to measure magnetic excitations in Cd 2 Os 2 O 7 and that it exhibits complex spin-charge-lattice coupling.

Phase transformation and microstructural evolution of nanostructured oxides and nitrides under ion irradiations

NASA Astrophysics Data System (ADS)

Lu, Fengyuan

Material design at the nanometer scale is an effective strategy for developing advanced materails with enhanced radiation tolerance for advanced nuclear energy systems as high densities of surfaces and interfaces of the nanostructured materials may behave as effective sinks for defect recovery. However, nanostructured materials may not be intrinsically radiation tolerant, and the interplay among the factors of crystal size, temperature, chemical composition, surface energy and radiation conditions may eventually determine material radiation behaviors. Therefore, it is necessary to understand the radiation effects of nanostructured materials and the underlying physics for the design of advanced nanostructured nuclear materials. The main objective of this doctoral thesis is to study the behavior of nanostructured oxides and nitrides used as fuel matrix and waste forms under extreme radiation conditions with the focus of phase transformation, microstructural evolution and damage mechanisms. Radiation experiments were performed using energetic ion beam techniques to simulate radiation damage resulting from energetic neutrons, alpha-decay events and fission fragments, and various experimental approaches were employed to characterize materials’ microstructural evolution and phase stability upon intense radiation environments including transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. Thermal annealing experiments indicated that nanostructured ZrO2 phase stability is strongly affected by the grain size. Radiation results on nanostructured ZrO2 indicated that thermodynamically unstable or metastable high temperature phases can be induced by energetic beam irradiation at room temperature. Various phase transformation among different polymorphs of monoclinic, tetragonal and amorphous states can be induced, and different mechanisms are responsible for structural transformations including oxygen vacancies accumulation upon displacive damage, radiation-assistant recrystallization and thermal spike by ionization radiation. The radiation response of nanosized pyrochlores indicated that the radiation tolerance of nanoceramics is highly dependent on the composition and size. Nanosized tantalate pyrochlores KxLnyTa2O 7-v (Ln = Gd, Y, Lu) with the average grain size around 10 - 15 nm are highly sensitive to radiation-induced amorphization. The pyrochlore A to B site ionic radius ratio rA/rB is crucial in determining the radiation tolerance of pyrochlores, and a minimum rA/rB of 1.605 exists for the occurring of radiation induced amorphization. The interplay among chemical compositions, structural deviation and grain size eventually determines the phase stability and structural transformation processes of tantalate pyrochlores under intense radiation environments. ZrN shows extremely high phase stability under both displacive ion irradiation and ionizing swift heavy ion irradiation. However, a contraction in lattice constant up to ~ 1.42 % can be induced in nanocrystalline ZrN irradiated with displacive ion beams. In contrast, the strongly ionizing swift heavy ions cannot induce any lattice contraction. Such lattice contractions may be due to a negative strain field in the ZrN nanograins related to N vacancies built up upon displacive radiation. Ion irradiations also lead to the formation of orthorhombic ZrSi phase at the interface between ZrN and Si substrate, resulting from atom mixing and precipitation upon ion irradiations. The fundamental knowledge provides critical data for assessing and quantifying nanostructured ceramics as fuel matrix and waste forms utilized in the extreme environments of advanced nuclear energy systems. Further possibilities are being pursued in manipulating microstructure at the nano-scale, controlling phase stability and tailoring the physical properties of materials for various important engineering applications.

Development and Optimization of Tailored Composite TBC Design Architectures for Improved Erosion Durability

NASA Astrophysics Data System (ADS)

Schmitt, Michael P.; Schreiber, Jeremy M.; Rai, Amarendra K.; Eden, Timothy J.; Wolfe, Douglas E.

2017-08-01

Rare-earth pyrochlores, RE2Zr2O7, have been identified as potential thermal barrier coating (TBC) materials due to their attractive thermal properties and CMAS resistance. However, they possess a low fracture toughness which results in poor erosion durability/foreign object damage resistance. This research focuses on the development of tailored composite air plasma spray (APS) TBC design architectures utilizing a t' Low-k secondary toughening phase (ZrO2-2Y2O3-1Gd2O3-1Yb2O3; mol.%) to enhance the erosion durability of a hyper-stoichiometric pyrochlore, NZO (ZrO2-25Nd2O3-5Y2O3-5Yb2O3; mol.%). In this study, composite coatings have been deposited with 30, 50, and 70% (wt.%) t' Low-k toughening phase in a horizontally aligned lamellar morphology which enhances the toughening response of the coating. The coatings were characterized via SEM and XRD and were tested for erosion durability before and after isothermal heat treatment at 1100 °C. Analysis with mixing laws indicated improved erosion performance; however, a lack of long-term thermal stability was shown via isothermal heat treatments at 1316 °C. An impact stress analysis was performed using finite element analysis of a coating cross section, representing the first microstructurally realistic study of mechanical properties of TBCs with the results correlating well with observed behavior.

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

Hanc, Emil; Zając, Wojciech, E-mail: wojciech.zajac@agh.edu.pl; Lu, Li

Ceramic oxides exhibiting high lithium-ion mobility at room temperature receive broad attention as candidate electrolytes for lithium batteries. Lithium-stuffed garnets from the Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} group seem to be especially promising because of their high ionic conductivity at room temperature and their electrochemical stability. In this work, we discuss factors that affect formation of the garnet in its bulk form or in the form of thick and thin films. We demonstrate that zinc oxide can be applied as a sintering aid that facilitate the formation of the highly conducting cubic Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} garnet phase inmore » a single-step sintering procedure. Based on our experience with the single-step sintering experiments, we successfully fabricated a thick-film membrane consisting of a garnet solid electrolyte using the tape casting technique. In order to reduce the thickness of the electrolyte even further we investigated the fabrication of a thin-film Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} electrolyte by means of the pulsed laser deposition technique.« less

On fabrication procedures of Li-ion conducting garnets

NASA Astrophysics Data System (ADS)

Hanc, Emil; Zając, Wojciech; Lu, Li; Yan, Binggong; Kotobuki, Masashi; Ziąbka, Magdalena; Molenda, Janina

2017-04-01

Ceramic oxides exhibiting high lithium-ion mobility at room temperature receive broad attention as candidate electrolytes for lithium batteries. Lithium-stuffed garnets from the Li7La3Zr2O12 group seem to be especially promising because of their high ionic conductivity at room temperature and their electrochemical stability. In this work, we discuss factors that affect formation of the garnet in its bulk form or in the form of thick and thin films. We demonstrate that zinc oxide can be applied as a sintering aid that facilitate the formation of the highly conducting cubic Li7La3Zr2O12 garnet phase in a single-step sintering procedure. Based on our experience with the single-step sintering experiments, we successfully fabricated a thick-film membrane consisting of a garnet solid electrolyte using the tape casting technique. In order to reduce the thickness of the electrolyte even further we investigated the fabrication of a thin-film Li7La3Zr2O12 electrolyte by means of the pulsed laser deposition technique.

A Synthesis and Crystal Chemical Study of the Fast Ion Conductor Li7–3xGaxLa3 Zr2O12 with x = 0.08 to 0.84

PubMed Central

2014-01-01

Fast-conducting phase-pure cubic Ga-bearing Li7La3Zr2O12 was obtained using solid-state synthesis methods with 0.08 to 0.52 Ga3+ pfu in the garnet. An upper limit of 0.72 Ga3+ pfu in garnet was obtained, but the synthesis was accompanied by small amounts of La2Zr2O12 and LiGaO3. The synthetic products were characterized by X-ray powder diffraction, electron microprobe and SEM analyses, ICP-OES measurements, and 71Ga MAS NMR spectroscopy. The unit-cell parameter, a0, of the various garnets does not vary significantly as a function of Ga3+ content, with a value of about 12.984(4) Å. Full chemical analyses for the solid solutions were obtained giving: Li7.08Ga0.06La2.93Zr2.02O12, Li6.50Ga0.15La2.96Zr2.05O12, Li6.48Ga0.23La2.93Zr2.04O12, Li5.93Ga0.36La2.94Zr2.01O12, Li5.38Ga0.53La2.96Zr1.99O12, Li4.82Ga0.60La2.96Zr2.00O12, and Li4.53Ga0.72La2.94Zr1.98O12. The NMR spectra are interpreted as indicating that Ga3+ mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet. PMID:24874559

Insights on dramatic radial fluctuations in track formation by energetic ions

DOE PAGES

Sachan, Ritesh; Lang, Maik; Trautmann, Christina; ...

2016-06-02

We discuss the insights on the unexpected dramatic radial variations in the ion tracks formed by energetic ion (2.3 GeV 208Pb) irradiation at a constant electronic energy-loss (~42 keV/nm) in pyrochlore structured Gd 2TiZrO 7. Though previous studies have shown track formation and average track diameter measurements, this work brings further clarity on why quantitative analysis of ion track formation in Gd 2Ti xZr (1-x)O 7 systems can be more complicated than the currently accepted behavior for ion tracks. The ion track profile is usually considered to be diametrically uniform at constant values of the electronic energy-loss. This study showsmore » the diameter variations to be as large as ~40% within an extremely short incremental track length of ~20 nm. Our molecular dynamics simulations show that these fluctuations in diameter of amorphous core and overall track diameter are attributed to (i) the stochastic nature of inelastic energy loss along the track and (ii) the random substitution of Ti atoms by Zr atoms on the B-site in the pyrochlore lattice. Furthermore, the partial substitution of Ti by Zr increases the favorability of the defect-fluorite structure formation over amorphous phase stochastically, by introducing localized inhomogeneity in atomic structure, density and strain.« less

Insights on dramatic radial fluctuations in track formation by energetic ions

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

Sachan, Ritesh; Lang, Maik; Trautmann, Christina

We discuss the insights on the unexpected dramatic radial variations in the ion tracks formed by energetic ion (2.3 GeV 208Pb) irradiation at a constant electronic energy-loss (~42 keV/nm) in pyrochlore structured Gd 2TiZrO 7. Though previous studies have shown track formation and average track diameter measurements, this work brings further clarity on why quantitative analysis of ion track formation in Gd 2Ti xZr (1-x)O 7 systems can be more complicated than the currently accepted behavior for ion tracks. The ion track profile is usually considered to be diametrically uniform at constant values of the electronic energy-loss. This study showsmore » the diameter variations to be as large as ~40% within an extremely short incremental track length of ~20 nm. Our molecular dynamics simulations show that these fluctuations in diameter of amorphous core and overall track diameter are attributed to (i) the stochastic nature of inelastic energy loss along the track and (ii) the random substitution of Ti atoms by Zr atoms on the B-site in the pyrochlore lattice. Furthermore, the partial substitution of Ti by Zr increases the favorability of the defect-fluorite structure formation over amorphous phase stochastically, by introducing localized inhomogeneity in atomic structure, density and strain.« less

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

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, Donald A.; Yeager, E.

1992-01-01

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined.

Thermodynamics of radiation induced amorphization and thermal annealing of Dy 2Sn 2O 7 pyrochlore

DOE PAGES

Chung, Cheng-Kai; Lang, Maik; Xu, Hongwu; ...

2018-06-14

Thermodynamics and annealing behavior of swift heavy ion amorphized Dy 2Sn 2O 7 pyrochlore were studied. Its amorphization enthalpy, defined as the total energetic difference between the irradiation amorphized and undamaged Dy 2Sn 2O 7 states, was determined to be 283.6 ± 6.5 kJ/mol by high temperature oxide melt drop solution calorimetry. It has been an enigma that stannate and some other pyrochlores do not follow the general r A/r B-radiation resistance relation seen in most pyrochlore systems. In this paper, we use the amorphization enthalpy, which reflects all the complex chemical and structural characteristics, as a more effective parametermore » to correlate the radiation damage resistance of pyrochlores with their compositions. It successfully explains the superior radiation damage resistance of the stannate pyrochlores compared with titanate pyrochlores. Differential scanning calorimetry (DSC) reveals a strong exothermic event starting at 978 K, which is attributed to long-range recrystallization based on X-ray diffraction (XRD) analysis, similar to the effect previously observed in Dy 2Ti 2O 7. A second pronounced heat event beginning at ~1148 K, which results from local structural rearrangement, is clearly decoupled from the first event for irradiated Dy 2Sn 2O 7. Both the heat releases measured by DSC on heating to 1023 and 1473 K, and the excess enthalpies of the annealed samples indicate that the recovery to the original, ordered state was not fully achieved up to even 1473 K, despite XRD showing the apparent restoration of crystalline pyrochlore structure. The remaining metastability may be attributed to local disorder in the form of weberite-like short-range domains in the recrystallized material. Intriguingly, the second event for different pyrochlores generally starts at similar temperatures while the onset of the long range recrystallization is compositionally dependent. Finally, the amorphization and thermal annealing behavior observed in irradiated Dy 2Sn 2O 7 may provide insights into the general mechanisms of radiation damage and recovery of pyrochlores relevant to their nuclear applications.« less

Pyrochlore Ce2Zr2O7 decorated over rGO: a photocatalyst that proves to be efficient towards the reduction of 4-nitrophenol and degradation of ciprofloxacin under visible light.

PubMed

Mansingh, Sriram; Acharya, Rashmi; Martha, Satyabadi; Parida, K M

2018-04-18

In the present study, a series of Ce2Zr2O7@rGO nanocomposites were synthesized using a simple solution combustion method followed by a photoreduction technique. The as-prepared samples were well characterised using various analytical techniques to determine the morphological, optical, structural, electrochemical and compositional properties. The presence of oxygen defects was observed from Raman and photoluminescence spectra. The photoreduction of GO to rGO was determined from Raman and Fourier-transform infrared (FTIR) spectroscopy results. The role of rGO proved to be quite significant for the enhanced photocatalytic activity of the nanocomposites. The synergistic communication between Ce2Zr2O7 and rGO accelerates the photoreduction of 4-nitrophenol along with the degradation of ciprofloxacin under visible light irradiation. Of the rGO nanocomposites, 3 wt% GO loaded Ce2Zr2O7 reduces 99% of 20 ppm of 4-nitrophenol to 4-aminophenol in 120 min and decomposes 10 ppm of ciprofloxacin by up to 89% in 60 min. The significant enhancement in the activity of the Ce2Zr2O7@rGO nanocomposite was ascribed to the effective charge separation of excitons through π-conjugation of graphene at the interface, which is well supported by the impedance, photoluminescence and photocatalytic results.

Study of Pt-Rh/CeO2-ZrO2-MxOy (M = Y, La)/Al2O3 three-way catalysts

NASA Astrophysics Data System (ADS)

Jiaxiu, Guo; Zhonghua, Shi; Dongdong, Wu; Huaqiang, Yin; Maochu, Gong; Yaoqiang, Chen

2013-05-01

CeO2-ZrO2-MxOy (M = Y; La) mixed oxides, prepared by co-precipitation method and characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Raman spectra (RM) and oxygen pulse reaction, were comparatively investigated to elucidate the combinational effects of Y and/or La oxide promoters on the catalytic activity and anti-aging performance of monolithic cordierite honeycomb catalysts with low Pt and Rh content. The catalytic activities, water-gas shift (WGS) and steam reforming reaction (SR) were studied under a simulated gas mixture. The catalysts were also characterized by H2-temperature-programmed reduction (H2-TPR) and O2-temperature-programmed desorption (O2-TPD). The results showed that the prepared CeO2-ZrO2-MxOy oxides have a face-centered cubic fluorite structure and are nanosize. La3+ ions can significantly improve thermal stability and efficiently retard CeO2-ZrO2 crystal sintering and growth. Doped CeO2-ZrO2 with Y3+ and La3+ has 105 and 60 m2/g surface area and 460 and 390 μmol/g OSC before and after aging. The T50 of fresh Pt-Rh/CZYL/LA is 170 °C for CO, 222 °C for C3H8 and 189 °C for NO, and shift to 205, 262 and 228 °C after hydrothermal aging, which are better than those of Pt-Rh/CZY/LA or Pt-Rh/CZL/LA. WGS and SR are relate to the OSC of oxygen storage materials and absorbed oxygen species on the catalyst surface and affect the three-way catalytic activities of catalysts. The reductive property of noble metals and the dissociatively adsorbed O2 on the surface of catalysts are closely related to the catalytic activities.

Solid-state NMR calculations for metal oxides and gallates: Shielding and quadrupolar parameters for perovskites and related phases

NASA Astrophysics Data System (ADS)

Middlemiss, Derek S.; Blanc, Frédéric; Pickard, Chris J.; Grey, Clare P.

2010-05-01

The NMR parameters obtained from solid-state DFT calculations within the GIPAW approach for 17O- and 69/71Ga-sites in a range of predominantly oxide-based (group II monoxides, SrTiO 3, BaZrO 3, BaSnO 3, BaTiO 3, LaAlO 3, LaGaO 3, SrZrO 3, MgSiO 3 and Ba 2In 2O 5), and gallate (α- and β-Ga 2O 3, LiGaO 2, NaGaO 2, GaPO 4 and LaGaO 3) materials are compared with experimental values, with a view to the future application of a similar approach to doped phases of interest as candidate intermediate temperature solid oxide fuel cell (ITSOFC) electrolytes. Isotropic and anisotropic chemical shift parameters, quadrupolar coupling constants, and associated asymmetries are presented and analyzed. The unusual GaO 5 site occurring in LaGaGe 2O 7 is also fully characterised. In general, it is found that the theoretical results closely track the experimental trends, though some deviations are identified and discussed, particularly in regard to quadrupolar ηQ-values. The high quality of the computed results suggests that this approach can be extended to study more complex and disordered phases.

The role of surfaces, chemical interfaces, and disorder on plutonium incorporation in pyrochlores

DOE PAGES

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

2016-07-27

Pyrochlores, a class of complex oxides with formula A 2B 2O 7, are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu 3+ and Pu 4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound.more » We also find that pyrochlore/pyrochlore bicrystals A 2B 2O 7/A 2'B 2'O 7 can be used to immobilize Pu 3+ and Pu 4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu 4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu 3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. Particularly, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.« less

The low temperature synthesis, characterization and properties of ferroelectrics

NASA Astrophysics Data System (ADS)

Xu, Jie

2000-10-01

PZT 50:50 xerogels prepared by two different sol-gel routes crystallized in a similar fashion to give a mixture of tetragonal and rhombohedral at high temperature (1000°C). Both the diffraction and EXAFS data suggest that the compositional inhomogeneity of the samples prepared by the two routes is similar. The crystallization of CZT gels is complicated. Crystalline CaCO 3 was always detected in the dry gels regardless of the sample composition and preparation methods. At intermediate temperatures a fluorite related phase was always formed and it transformed to perovskite at higher temperatures. The EXAFS data suggest that perovskite CZT samples prepared using alkoxide sol-gel chemistry may not be random solid solutions. All the solution processed ZrTiO4 materials crystallized in the range 600--700°C. The KTN samples prepared using a conventional alkoxide sol-gel route crystallized completely to perovskite at lower temperatures than those prepared using prehydrolyzed precursors. The EXAFS data for the KTN samples prepared using a conventional alkoxide sol-gel route are consistent with a random distribution of tantalum and niobium in the solid solution. However, materials prepared using the inhomogeneous sol-gel route and by the direct reaction of mixed oxides were shown to be compositionally inhomogeneous. The heterogeneity could not be removed by regrinding and heating the mixed oxide samples several times. K2Ta4-xNbxO11 (x = 0, 2, 4) samples were prepared using alkoxide sol-gel chemistry and their crystallization was examined by powder X-ray diffraction. A Rietveld structure analysis of the pyrochlore formed from a gel with bulk composition K2Ta 2Nb2O11 indicated that it was rich in potassium relative to the bulk sample. On heating to high temperatures tetragonal tungsten bronzes were formed. A Rietveld analysis was also performed for K2Ta 2Nb2O11 with tetragonal tungsten bronze structure. The defect pyrochlores "AgTaO3" and GaTaO 3 were synthesized by ion-exchange using pyrochlore KTaO3 as a starting material. The structures of the pyrochlores were examined using the Rietveld method. The pyrochlore-to-perovskite transformations were also explored.

Orange-red emitting Gd2Zr2O7:Sm3+: Structure-property correlation, optical properties and defect spectroscopy

NASA Astrophysics Data System (ADS)

Gupta, Santosh K.; Reghukumar, C.; Sudarshan, K.; Ghosh, P. S.; Pathak, Nimai; Kadam, R. M.

2018-05-01

Local structure analysis of dopant ion, understanding host to dopant energy transfer dynamics and defects characterization in a doped material which plays an important role in the designing a highly efficient opto-electronic material. In this connection a new Sm3+ doped Gd2Zr2O7 pyrochlore material was synthesized using gel-combustion technique and was characterized systematically using X-ray diffraction (XRD), time resolved photoluminescence spectroscopy (TRPLS), positron annihilation lifetime spectroscopy (PALS) and density functional theory (DFT) based ab-initio calculation. Based on DFT site selective energetics calculation and luminescence decay measurement, it was observed that the Sm3+ was distributed at both Gd3+ and Zr4+ site with higher Sm3+ fraction at the Gd3+ site. PALS was used to probe the presence of defects in the phosphor. In this work intense orange-red emission is realized through manipulating the energy transfer from host defect emission (oxygen vacancies) to Sm3+ which allows color emission from green in undoped to orange-red in doped samples. Effect of dopant concentration and annealing temperature was probed using TRPLS and PALS. These all information is highly important for researcher looking to achieve pyrochlore based phosphor materials with high quantum yield.

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

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

Pyrochlores, a class of complex oxides with formula A 2B 2O 7, are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu 3+ and Pu 4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound.more » We also find that pyrochlore/pyrochlore bicrystals A 2B 2O 7/A 2'B 2'O 7 can be used to immobilize Pu 3+ and Pu 4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu 4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu 3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. Particularly, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.« less

Vibrational and elastic properties of Ln2Sn2O7 (Ln = La, Sm, Gd, Dy, Ho, Er, Yb, or Lu)

NASA Astrophysics Data System (ADS)

Akbudak, S.; Kushwaha, A. K.

2018-04-01

In this study, an eight-parameter bond-bending force constant model was used to calculate the zone center phonon frequencies, elastic constants, and related properties of the stannate compounds Ln2Sn2O7 (Ln = La, Sm, Gd, Dy, Ho, Er, Yb, or Lu) with a pyrochlore structure. We found that the Snsbnd O bond strengths dominate the Ln-O and Osbnd O bonds. We also found that all of the materials are ductile and anisotropic in nature. The anisotropic nature of the compounds increases in the order of: La2Sn2O7 < Sm2Sn2O7 < Gd2Sn2O7 < Dy2Sn2O7 < Ho2Sn2O7 < Er2Sn2O7 < Yb2Sn2O7 < Lu2Sn2O7.

Solid-state NMR calculations for metal oxides and gallates: shielding and quadrupolar parameters for perovskites and related phases.

PubMed

Middlemiss, Derek S; Blanc, Frédéric; Pickard, Chris J; Grey, Clare P

2010-05-01

The NMR parameters obtained from solid-state DFT calculations within the GIPAW approach for (17)O- and (69/71)Ga-sites in a range of predominantly oxide-based (group II monoxides, SrTiO(3), BaZrO(3), BaSnO(3), BaTiO(3), LaAlO(3), LaGaO(3), SrZrO(3), MgSiO(3) and Ba(2)In(2)O(5)), and gallate (alpha- and beta-Ga(2)O(3), LiGaO(2), NaGaO(2), GaPO(4) and LaGaO(3)) materials are compared with experimental values, with a view to the future application of a similar approach to doped phases of interest as candidate intermediate temperature solid oxide fuel cell (ITSOFC) electrolytes. Isotropic and anisotropic chemical shift parameters, quadrupolar coupling constants, and associated asymmetries are presented and analyzed. The unusual GaO(5) site occurring in LaGaGe(2)O(7) is also fully characterised. In general, it is found that the theoretical results closely track the experimental trends, though some deviations are identified and discussed, particularly in regard to quadrupolar eta(Q)-values. The high quality of the computed results suggests that this approach can be extended to study more complex and disordered phases. Copyright 2010 Elsevier Inc. All rights reserved.

High- and low-Am RE inclusion phases in a U-Np-Pu-Am-Zr alloy

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

Janney, Dawn E.; Madden, James W.; O'Holleran, Thomas P.

2015-03-01

Structural, microstructural, and microchemical data were collected from rare-earth inclusions in an as-cast U-Pu-Zr alloy with ~3 at% Am, 2% Np, and 9% rare-earth elements (La, Ce, Pr, and Nd). Two RE phases with different concentrations of Am were identified. The composition of high-Am RE inclusions is ~2-5 at% La, 15-20 % Ce, 5-10% Pr, 25-45% Nd, 1% Np, 5-10% Pu, and 10-20% Am. Some areas also have O, although this does not appear to be an essential part of the high-Am RE phase. The inclusions have a face-centered cubic structure with a lattice parameter a ~ 0.54 nm. Themore » composition of the only low-Am RE inclusion studied in detail is ~~35-40 at% O, 40-45 % Nd, 1-2% Zr, 4-5% La, 9-10% Ce, and 6-7% Pr. This inclusion is an oxide with a crystal structure similar to the room-temperature structure of Nd 2O 3. Microstructural features suggest that oxidation occurred during casting, and that early crystallization of high-temperature oxides led to formation of two distinct RE phases.« less

Chlorination of UO 2, PuO 2 and rare earth oxides using ZrCl 4 in LiCl-KCl eutectic melt

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

2005-04-01

A new chlorination method using ZrCl 4 in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl 4 has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La 2O 3, CeO 2, Nd 2O 3 and Y 2O 3) and actinide oxides (UO 2 and PuO 2) were allowed to react with ZrCl 4 in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO 2. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl 4 chlorination method, free from corrosive gas, was very simple and useful.

Phase Composition and Disorder in La2(Sn,Ti)2O7 Ceramics: New Insights from NMR Crystallography.

PubMed

Fernandes, Arantxa; McKay, David; Sneddon, Scott; Dawson, Daniel M; Lawson, Sebastian; Veazey, Richard; Whittle, Karl R; Ashbrook, Sharon E

2016-09-15

An NMR crystallographic approach, involving the combination of 119 Sn NMR spectroscopy, XRD, and DFT calculations, is demonstrated for the characterization of La 2 Sn 2- x Ti x O 7 ceramics. A phase change from pyrochlore (La 2 Sn 2 O 7 ) to a layered perovskite phase (La 2 Ti 2 O 7 ) is predicted (by radius ratio rules) to occur when x ≈ 0.95. However, the sensitivity of NMR spectroscopy to the local environment is able to reveal a significant two-phase region is present, extending from x = 1.8 to ∼0.2, with limited solid solution at the two extremes, in broad agreement with powder XRD measurements. DFT calculations reveal that there is preferential site substitution of Sn in La 2 Ti 2 O 7 , with calculated shifts for Sn substitution onto Ti1 and Ti2 sites (in the "bulk" perovskite layers) in better agreement with experiment than those for Ti3 and Ti4 ("edge" sites). Substitution onto these two sites also produces structural models with lower relative enthalpy. As the Sn content decreases, there is a further preference for substitution onto Sn2. In contrast, the relative intensities of the spectral resonances suggest that Ti substitution into the pyrochlore phase is random, although only a limited solid solution is observed (up to ∼7% Ti). DFT calculations predict very similar 119 Sn shifts for Sn substitution into the two proposed models of La 2 Ti 2 O 7 (monoclinic ( P 2 1 ) and orthorhombic ( Pna 2 1 )), indicating it is not possible to distinguish between them. However, the relative energy of the Sn-substituted orthorhombic phase was higher than that of substituted monoclinic cells, suggesting that the latter is the more likely structure.

Crystal chemistry of pyrochlore from the Mesozoic Panda Hill carbonatite deposit, western Tanzania

NASA Astrophysics Data System (ADS)

Boniface, Nelson

2017-02-01

The Mesozoic Panda Hill carbonatite deposit in western Tanzania hosts pyrochlore, an ore and source of niobium. This study was conducted to establish the contents of radioactive elements (uranium and thorium) in pyrochlore along with the concentration of niobium in the ore. The pyrochlore is mainly hosted in sövite and is structurally controlled by NW-SE (SW dipping) or NE-SW (NW dipping) magmatic flow bands with dip angles of between 60° and 90°. Higher concentrations of pyrochlore are associated with magnetite, apatite and/or phlogopite rich flow bands. Electron microprobe analyses on single crystals of pyrochlore yield very low UO2 concentrations that range between 0 and 0.09 wt% (equivalent to 0 atoms per formula unit: a.p.f.u.) and ThO2 between 0.55 and 1.05 wt% (equivalent to 0.1 a.p.f.u.). The analyses reveal high concentrations of Nb2O5 (ranging between 57.13 and 65.50 wt%, equivalent to a.p.f.u. ranging between 1.33 and 1.43) and therefore the Panda Hill Nb-oxide is classified as pyrochlore sensu stricto. These data point to a non radioactive pyrochlore and a deposit rich in Nb at Panda Hill. The Panda Hill pyrochlore has low concentrations of REEs as displayed by La2O3 that range between 0.10 and 0.49 wt% (equivalent to a.p.f.u. ranging between 0 and 0.01) and Ce2O3 ranging between 0.86 and 1.80 wt% (equivalent to a.p.f.u. ranging between 0.02 and 0.03), Pr2O3 concentrations range between 0 and 0.23 wt% (equivalent to 0 a.p.f.u.), and Y2O3 is 0 wt% (equivalent to 0 a.p.f.u.). The abundance of the REEs in pyroclore at the Panda Hill Carbonatite deposit is of no economic significance.

Crystal structure of the pyrochlore oxide superconductor KOs{sub 2}O{sub 6}

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

Yamaura, Jun-Ichi; Yonezawa, Shigeki; Muraoka, Yuji

2006-01-15

We report the single-crystal X-ray analysis of the structure of the pyrochlore oxide superconductor KOs{sub 2}O{sub 6}. The structure was identified as the {beta}-pyrochlore structure with space group Fd3-bar m and lattice constant a=10.089(2)A at 300K: the K atom is located at the 8b site, not at the 16d site as in conventional pyrochlore oxides. We found an anomalously large atomic displacement parameter U{sub iso}=0.0735(8)A{sup 2} at 300K for the K cation, which suggests that the K cation weakly bound to an oversized Os{sub 12}O{sub 18} cage exhibits intensive rattling, as recently observed for clathrate compounds. The rattling of Amore » cations is a common feature in the series of {beta}-pyrochlore oxide superconductors AOs{sub 2}O{sub 6} (A=Cs, Rb and K), and is greatest for the smallest K cation.« less

Modifying the Surface of γ-Al2 O3 with Y2 Sn2 O7 Pyrochlore: Monolayer Dispersion Behaviour of Composite Oxides.

PubMed

Xu, Xianglan; Liu, Fang; Tian, Jinshu; Peng, Honggen; Liu, Wenming; Fang, Xiuzhong; Zhang, Ning; Wang, Xiang

2017-06-20

To investigate the dispersion behaviour of composite oxides on supports, and to obtain better supports for Pd for CO oxidation, a series of Y 2 Sn 2 O 7 /Al 2 O 3 composite oxides with different Y 2 Sn 2 O 7 loadings were prepared by a deposition-precipitation method. XRD and X-ray photoelectron spectroscopic extrapolation methods revealed that, similar to single-component metal oxides, composite oxides can also disperse spontaneously on support surfaces to form a monolayer with a certain capacity. The monolayer dispersion capacity/threshold for Y 2 Sn 2 O 7 on the surface of γ-Al 2 O 3 is 0.109 mmol per 100 m 2 γ-Al 2 O 3 , corresponding to 7.2 wt % Y 2 Sn 2 O 7 loading. This is the first work to demonstrate monolayer dispersion of a composite oxide on a support. After combining Y 2 Sn 2 O 7 with γ-Al 2 O 3 , active oxygen species can be introduced onto the catalyst surfaces. Thus, the interaction between Pd and the support is strengthened, the dispersion of Pd is improved in comparison with the single-component Y 2 Sn 2 O 7 support, and a synergistic effect is induced between Pd and the composite support, which is beneficial to catalyst activity. By tuning the γ-Al 2 O 3 surface with different amounts of pyrochlore Y 2 Sn 2 O 7 , CO oxidation activity on 1 % Pd/Y 2 Sn 2 O 7 /Al 2 O 3 was improved. These findings may provide new insights into the design and preparation of effective supported noble metal catalysts with lower contents of noble metals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin-orbit-driven magnetic structure and excitation in the 5d pyrochlore Cd 2Os 2O 7

DOE PAGES

Calder, Stuart A; Vale, James G.; Bogdanov, Nikolay; ...

2016-06-07

Here, much consideration has been given to the role of spin-orbit coupling (SOC) in 5d oxides, particularly on the formation of novel electronic states and manifested metal-insulator transitions (MITs). SOC plays a dominant role in 5d 5 iridates (Ir 4+), undergoing MITs both concurrent (pyrochlores) and separated (perovskites) from the onset of magnetic order. However, the role of SOC for other 5d configurations is less clear. For example, 5d 3 (Os 5+) systems are expected to have an orbital singlet with reduced effective SOC. The pyrochlore Cd 2Os 2O 7 nonetheless exhibits a MIT entwined with magnetic order phenomenologically similarmore » to pyrochlore iridates. Here, we resolve the magnetic structure in Cd 2Os 2O 7 with neutron diffraction and then via resonant inelastic X-ray scattering determine the salient electronic and magnetic energy scales controlling the MIT. In particular, SOC plays a subtle role in creating the electronic ground state but drives the magnetic order and emergence of a multiple spin-flip magnetic excitation.« less

Two-magnon scattering in the 5d all-in-all-out pyrochlore magnet Cd 2Os 2O 7

DOE PAGES

Nguyen, Thi Minh Hien; Sandilands, Luke J.; Sohn, C. H.; ...

2017-08-15

5d pyrochlore oxides with all-in-all-out magnetic order are prime candidates for realizing strongly correlated, topological phases of matter. Despite significant effort, a full understanding of all-in-all-out magnetism remains elusive as the associated magnetic excitations have proven difficult to access with conventional techniques. Here we report a Raman spectroscopy study of spin dynamics in the all-in-all-out magnetic state of the 5d pyrochlore Cd 2Os 2O 7. Through a comparison between the two-magnon scattering and spin-wave theory, we confirm the large single ion anisotropy in this material and show that the Dzyaloshinskii–Moriya and exchange interactions play a significant role in the spin-wavemore » dispersions. The Raman data also reveal complex spin–charge–lattice coupling and indicate that the metal–insulator transition in Cd 2Os 2O 7 is Lifshitz-type. In conclusion, our work establishes Raman scattering as a simple and powerful method for exploring the spin dynamics in 5d pyrochlore magnets.« less

Photocatalytic water oxidation by a pyrochlore oxide upon irradiation with visible light: rhodium substitution into yttrium titanate.

PubMed

Kiss, Borbala; Didier, Christophe; Johnson, Timothy; Manning, Troy D; Dyer, Matthew S; Cowan, Alexander J; Claridge, John B; Darwent, James R; Rosseinsky, Matthew J

2014-12-22

A stable visible-light-driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y2 Ti2 O7 is demonstrated by monitoring Vegard's law evolution of the unit-cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible-light active. The overall rate of oxygen evolution is comparable to WO3 but with superior light-harvesting and surface-area-normalized turnover rates, making Y2 Ti1.94 Rh0.06 O7 an excellent candidate for use in a Z-scheme water-splitting system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Metaloxide--ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel

DOEpatents

Kim, Manhoe; Salley, Steven O.; Ng, K. Y. Simon

2016-09-06

Mixed metal oxide catalysts (ZnO, CeO, La2O3, NiO, Al203, SiO2, TiO2, Nd2O3, Yb2O3, or any combination of these) supported on zirconia (ZrO2) or hydrous zirconia are provided. These mixed metal oxide catalysts can be prepared via coprecipitation, impregnation, or sol-gel methods from metal salt precursors with/without a Zirconium salt precursor. Metal oxides/ZrO2 catalyzes both esterification and transesterification of oil containing free fatty acids in one batch or in single stage. In particular, these mixed metal oxides supported or added on zirconium oxide exhibit good activity and selectivity for esterification and transesterification. The low acid strength of this catalyst can avoid undesirable side reaction such as alcohol dehydration or cracking of fatty acids. Metal oxides/ZrO2 catalysts are not sensitive to any water generated from esterification. Thus, esterification does not require a water free condition or the presence of excess methanol to occur when using the mixed metal oxide catalyst. The FAME yield obtained with metal oxides/ZrO2 is higher than that obtained with homogeneous sulfuric acid catalyst. Metal oxides/ZrO2 catalasts can be prepared as strong pellets and in various shapes for use directly in a flow reactor. Furthermore, the pellet has a strong resistance toward dissolution to aqueous or oil phases.

Structural transformations and disordering in zirconolite (CaZrTi2O7) at high pressure.

PubMed

Salamat, Ashkan; McMillan, Paul F; Firth, Steven; Woodhead, Katherine; Hector, Andrew L; Garbarino, Gaston; Stennett, Martin C; Hyatt, Neil C

2013-02-04

There is interest in identifying novel materials for use in radioactive waste applications and studying their behavior under high pressure conditions. The mineral zirconolite (CaZrTi(2)O(7)) exists naturally in trace amounts in diamond-bearing deep-seated metamorphic/igneous environments, and it is also identified as a potential ceramic phase for radionuclide sequestration. However, it has been shown to undergo radiation-induced metamictization resulting in amorphous forms. In this study we probed the high pressure structural properties of this pyrochlore-like structure to study its phase transformations and possible amorphization behavior. Combined synchrotron X-ray diffraction and Raman spectroscopy studies reveal a series of high pressure phase transformations. Starting from the ambient pressure monoclinic structure, an intermediate phase with P2(1)/m symmetry is produced above 15.6 GPa via a first order transformation resulting in a wide coexistence range. Upon compression to above 56 GPa a disordered metastable phase III with a cotunnite-related structure appears that is recoverable to ambient conditions. We examine the similarity between the zirconolite behavior and the structural evolution of analogous pyrochlore systems under pressure.

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

Li, Kuo; Hu, Yufei; Wang, Yingxia, E-mail: Wangyx@pku.edu.cn

Isostructural compounds RE{sub 3}Sb{sub 3}Co{sub 2}O{sub 14} (RE=La, Pr, Nd, Sm–Ho) with an ordered pyrochlore structure were synthesized. The structure of La{sub 3}Sb{sub 3}Co{sub 2}O{sub 14} was solved ab initio based on powder XRD data, and refined by combining with high resolution neutron diffraction data. La{sub 3}Sb{sub 3}Co{sub 2}O{sub 14} crystallizes in the space group R-3m with the unit cell parameters a=7.52954(2) Å and c=17.59983(6) Å. The structures of other members in this family are confirmed by Rietveld refinement using powder X-ray diffraction data. The cations (RE, Sb and Co) in RE{sub 3}Sb{sub 3}Co{sub 2}O{sub 14} are orderly distributed, presentingmore » as [RE{sub 3}Co][Sb{sub 3}Co]O{sub 14} formula, and giving rise to two distinctive Kagome lattices constructed by RE{sup 3+} and Sb{sup 5+}, respectively. Co{sup 2+} occupies 8-coordinated and 6-coordinated environments, showing low spin (S=1/2) and high spin (S=3/2) states respectively. The magnetic susceptibility and UV–visual spectroscopy supports the magnetic observation. TDDFT calculation was performed to interpret the electronic states. The compounds [RE{sub 3}Co][Sb{sub 3}Co]O{sub 14} provide a profound example in which the ideal 2D Kagome lattice is derived from the 3D pyrochlore-type structure by an ordered distribution of the metal cations. - Graphical abstract: La{sub 3}Sb{sub 3}Co{sub 2}O{sub 14} crystallizes in a pyrochlore related structure with an ordered distribution of cations, giving rise to two sets of ideal 2D Kagome lattices formed by La{sup 3+} or Sb{sup 5+} respectively. This rhombohedral pyrochlore is a tolerant structure for stable compounds composed by many light rare-earth and d-transition elements. Substituting Zn{sup 2+} or Mg{sup 2+} for Co{sup 2+} will provide a series of compounds useful for studying magnetic interactions in the rare-earth Kagome lattices. - Highlights: • Pyrochlore-type La{sub 3}Sb{sub 3}Co{sub 2}O{sub 14} shows an ordered distribution of cations in its structure. • It presents two sets of ideal 2D Kagome lattices formed by La{sup 3+} or Sb{sup 5+}, respectively. • A family of isostructural compounds RE{sub 3}Sb{sub 3}Co{sub 2}O{sub 14} (RE=Pr, Nd, Sm–Ho) were realized. • Co{sup 2+} presents two spin states with S=1/2, 3/2 due to two coordinated environments.« less

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 and anionic sites as pressure is increased. The pressure of their phase transitions correlates directly with their radius ratio. Our results are comparable to many high-pressure studies of rare earth zirconates and titanates, but contrast from previous experiments performed on rare earth hafnates, specifically La2Hf2O7.

High-pressure Raman study on the superconducting pyrochlore oxide Cd2Re2O7

NASA Astrophysics Data System (ADS)

Matsubayashi, Yasuhito; Hasegawa, Takumi; Ogita, Norio; Yamaura, Jun-ichi; Hiroi, Zenji

2018-05-01

The superconducting pyrochlore oxide Cd2Re2O7 (Tc = 1 K), which is now considered as a candidate of the spin-orbit-coupled metal, shows an inversion-symmetry-breaking structural transition at Ts1 = 200 K . Ts1 decreases with increasing pressure and disappears at around Pc = 4.2 GPa , where at least four high-pressure phases with tiny structural distortions are suggested by means of powder X-ray diffraction [Yamaura PRB 2017]. We have carried out Raman scattering experiments to investigate changes in the crystal symmetry under high pressures up to 4.8 GPa. A structural transition at 1.9-3.0 GPa and the recovery of inversion symmetry above Pc are observed at 12 K.

Disappearance of the metal-insulator transition in iridate pyrochlores on approaching the ideal R2Ir2O7 stoichiometry

NASA Astrophysics Data System (ADS)

Sleight, Arthur W.; Ramirez, Arthur P.

2018-07-01

Recently, rare earth iridates, R2Ir2O7, with the pyrochlore structure have been intensively investigated due to their promise as either topological Mott insulators or Weyl semimetals. Single crystals of such pyrochlores with R = Nd, Sm, Eu, and Dy were prepared hydrothermally in sealed gold tubes at 975 K and show significantly higher electrical resistivities than previously reported for either crystals or polycrystalline samples. Furthermore, none of the present crystals exhibit the metal-insulator transition found for some samples of these phases. Lower resistivities are ascribed to lack of control of x and y in R2-xIr2O7-y in other more commonly used synthesis methods, yielding uncertainty in the Ir oxidation state. We also report resistivity of R2Ru2O7 crystals for R = Yb, Gd, Eu, and Nd, prepared in the same manner. These results suggest that the observed charge transport in hydrothermally grown iridate crystals is that of essentially stoichiometric phases and is consistent a with the existence of Weyl nodes.

Investigation of Thermal Conductivities and Expansion Coefficients of (Yb1 - x La x )2AlTaO7 Ceramics

NASA Astrophysics Data System (ADS)

Xiaoge, Chen; Hongsong, Zhang; Sai, Su; Yongde, Zhao; An, Tang; Haoming, Zhang

2017-12-01

The (Yb1 - x La x )2AlTaO7 ( x = 0, 0.1, 0.3, 0.5) ceramics were prepared by solid-state reaction method. The phase composition, microstructure, thermophysical properties of (Yb1 - x La x )2AlTaO7 ceramics were investigated. Results reveal that (Yb1 - x La x )2AlTaO7 ( x = 0, 0.1, 0.3) ceramics exhibit a single pyrochlore-type structure, and the (Yb0.5La0.5)2AlTaO7 has an orthorhombic weberite structure. The thermal conductivities of (Yb1 - x La x )2AlTaO7 ( x = 0, 0.1, 0.3) ceramics decrease with increasing Yb2O3 contents. (Yb0.5La0.5)2AlTaO7 has the highest thermal conductivity among all the ceramics studied, within the range of 1.48-1.75 W/m K (20-1200 °C). The thermal expansion coefficients of (Yb1 - x La x )2AlTaO7 ceramics decrease gradually with increasing La2O3 fractions, and the thermal expansion coefficients are close to those of YSZ.

Advances in Understanding of Swift Heavy-Ion Tracks in Complex Ceramics

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

Lang, Maik; Devanathan, Ram; Toulemonde, Marcel

2015-02-01

Tracks produced by swift heavy ions in ceramics are of interest for fundamental science as well as for applications covering different fields such as nanotechnology or fission-track dating of minerals. In the case of pyrochlores with general formula A2B2O7, the track structure and radiation sensitivity shows a clear dependence on the composition. Ion irradiated Gd2Zr2O7, e.g., retains its crystallinity while amorphous tracks are produced in Gd2Ti2O7. Tracks in Ti-containing compositions have a complex morphology consisting of an amorphous core surrounded by a shell of a disordered, defect-fluorite phase. The size of the amorphous core decreases with decreasing energy loss andmore » with increasing Zr content, while the shell thickness seems to be similar over a wide range of energy loss values. The large data set and the complex track structure has made pyrochlore an interesting model system for a general theoretical description of track formation including thermal spike calculations (providing the spatial and temporal evolution of temperature around the ion trajectory) and molecular dynamics (MD) simulations (describing the response of the atomic system).Recent MD advances consider the sudden temperature increase by inserting data from the thermal spike. The combination allows the reproduction of the core-shell track characteristic and sheds light on the early stages of track formation including recrystallization of the molten material produced by the thermal spike.« less

Alkali oxide-tantalum, niobium and antimony oxide ionic conductors

NASA Technical Reports Server (NTRS)

Roth, R. S.; Brower, W. S.; Parker, H. S.; Minor, D. B.; Waring, J. L.

1975-01-01

The phase equilibrium relations of four systems were investigated in detail. These consisted of sodium and potassium antimonates with antimony oxide and tantalum and niobium oxide with rubidium oxide as far as the ratio 4Rb2O:llB2O5 (B=Nb, Ta). The ternary system NaSbO3-Sb2O4-NaF was investigated extensively to determine the actual composition of the body centered cubic sodium antimonate. Various other binary and ternary oxide systems involving alkali oxides were examined in lesser detail. The phases synthesized were screened by ion exchange methods to determine mobility of the mobility of the alkali ion within the niobium, tantalum or antimony oxide (fluoride) structural framework. Five structure types warranted further investigation; these structure types are (1) hexagonal tungsten bronze (HTB), (2) pyrochlore, (3) the hybrid HTB-pyrochlore hexagonal ordered phases, (4) body centered cubic antimonates and (5) 2K2O:3Nb2O5. Although all of these phases exhibit good ion exchange properties only the pyrochlore was prepared with Na(+) ions as an equilibrium phase and as a low porosity ceramic. Sb(+3) in the channel interferes with ionic conductivity in this case, although relatively good ionic conductivity was found for the metastable Na(+) ion exchanged analogs of RbTa2O5F and KTaWO6 pyrochlore phases.

The solubility and site preference of Fe{sup 3+} in Li{sub 7−3x}Fe{sub x}La{sub 3}Zr{sub 2}O{sub 12} garnets

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

Rettenwander, D., E-mail: daniel.rettenwander@sbg.ac.at; Geiger, C.A.; Tribus, M.

2015-10-15

A series of Fe{sup 3+}-bearing Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZO) garnets was synthesized using solid-state synthesis methods. The synthetic products were characterized compositionally using electron microprobe analysis and inductively coupled plasma optical emission spectroscopy (ICP-OES) and structurally using X-ray powder diffraction and {sup 57}Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe{sup 3+} pfu could be incorporated in Li{sub 7−3x}Fe{sub x}La{sub 3}Zr{sub 2}O{sub 12} garnet solid solutions. At Fe{sup 3+} concentrations lower than about 0.16 pfu, both tetragonal and cubic garnets were obtained in the synthesis experiments. X-ray powder diffraction analysis showed only a garnet phase for syntheses withmore » starting materials having intended Fe{sup 3+} contents lower than 0.52 Fe{sup 3+} pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a{sub 0}, for all solid-solution garnets is similar with a value of a{sub 0}≈12.98 Å regardless of the amount of Fe{sup 3+}. {sup 57}Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO{sub 3} in syntheses with Fe{sup 3+} contents greater than 0.16 Fe{sup 3+} pfu. The composition of different phase pure Li{sub 7−3x}Fe{sub x}La{sub 3}Zr{sub 2}O{sub 12} garnets, as determined by electron microprobe (Fe, La, Zr) and ICP-OES (Li) measurements, give Li{sub 6.89}Fe{sub 0.03}La{sub 3.05}Zr{sub 2.01}O{sub 12}, Li{sub 6.66}Fe{sub 0.06}La{sub 3.06}Zr{sub 2.01}O{sub 12}, Li{sub 6.54}Fe{sub 0.12}La{sub 3.01}Zr{sub 1.98}O{sub 12}, and Li{sub 6.19}Fe{sub 0.19}La{sub 3.02}Zr{sub 2.04}O{sub 12}. The {sup 57}Fe Mössbauer spectrum of cubic Li{sub 6.54}Fe{sub 0.12}La{sub 3.01}Zr{sub 1.98}O{sub 12} garnet indicates that most Fe{sup 3+} occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe{sup 3+} in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li{sub 6.54}Fe{sub 0.12}La{sub 3.01}Zr{sub 1.98}O{sub 12} this Fe{sup 3+} has a distorted 4-fold coordination. - Graphical abstract: Cubic nominally Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZO) garnet is a promising candidate to be used as a solid electrolyte in Li-ion batteries. A series of Fe{sup 3+}-bearing LLZO garnets was synthesized and characterized compositionally and structurally. {sup 57}Mössbauer measurements were made to determine where Fe is incorporated in the crystal structure. X-ray diffraction, electron microprobe, ICP-OES and {sup 57}Mössbauer measurements are needed to obtain a full description of the synthetic products, some of which contain small amounts of nano- or poorly crystalline FeLaO{sub 3}. - Highlights: • A series of Fe{sup 3+}-bearing Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZO) garnets was synthesized and characterized compositionally and structurally. • {sup 57}Mössbauer measurements were made to determine where Fe is incorporated in the crystal structure. • Most Fe{sup 3+} substitutes for Li{sup +} in LLZO at the 24d and 96h sites in the cubic phase (Ia-3d). • No more than about 0.25 Fe{sup 3+} pfu can be incorporated into the LLZO garnet structure. • X-ray powder diffractions measurements indicate the presence of both cubic and tetragonal garnets phases in some syntheses. • The probable presence of small amounts of poorly or nano-crystalline FeLaO3 can only be identified by Mössbauer spectroscopy.« less

Long-range magnetic order in the Heisenberg pyrochlore antiferromagnets G d2G e2O7 and G d2P t2O7 synthesized under high pressure

NASA Astrophysics Data System (ADS)

Li, X.; Cai, Y. Q.; Cui, Q.; Lin, C. J.; Dun, Z. L.; Matsubayashi, K.; Uwatoko, Y.; Sato, Y.; Kawae, T.; Lv, S. J.; Jin, C. Q.; Zhou, J.-S.; Goodenough, J. B.; Zhou, H. D.; Cheng, J.-G.

2016-12-01

G d2S n2O7 and G d2T i2O7 have been regarded as good experimental realizations of the classical Heisenberg pyrochlore antiferromagnet with dipolar interaction. The former was found to adopt the Palmer-Chalker state via a single, first-order transition at TN≈1 K , while the latter enters a distinct, partially ordered state through two successive transitions at TN 1≈1 K and TN 2= 0.75 K . To shed more light on their distinct magnetic ground states, we have synthesized two more gadolinium-based pyrochlore oxides, G d2G e2O7 and G d2P t2O7 , under high-pressure conditions and performed detailed characterizations via x-ray powder diffraction, dc and ac magnetic susceptibility, and specific heat measurements down to 100 mK. We found that both compounds enter a long-range antiferromagnetically ordered state through a single, first-order transition at TN= 1.4 K for G d2G e2O7 and TN= 1.56 K for G d2P t2O7 , with the specific heat anomaly similar to that of G d2S n2O7 rather than G d2T i2O7 . Interestingly, the low-temperature magnetic specific heat values of both G d2G e2O7 and G d2P t2O7 were found to follow nicely the T3 dependence as expected for a three-dimensional antiferromagnet with gapless spin-wave excitations. We have rationalized the enhancement of TN in terms of the reduced Gd-Gd distances for the chemically pressurized G d2G e2O7 and the addition of extra superexchange pathways through the empty Pt -eg orbitals for G d2P t2O7 . Our current study has expanded the family of gadolinium-based pyrochlores and permits us to achieve a better understanding of their distinct magnetic properties in a more comprehensive perspective.

Investigation of thermodynamic properties of metal-oxide catalysts

NASA Astrophysics Data System (ADS)

Shah, Parag Rasiklal

An apparatus for Coulometric Titration was developed and used to measure the redox isotherms (i.e. oxygen fugacity P(O2) vs oxygen stoichiometry) of ceria-zirconia solid solutions, mixed oxides of vanadia, and vanadia supported on ZrO2. This data was used to correlate the redox thermodynamics of these oxides to their structure and catalytic properties. From the redox isotherms measured between 873 K and 973 K, the differential enthalpies of oxidation (DeltaH) for Ce0.81Zr0.19O 2.0 and Ce0.25Zr0.75O2.0 were determined, and they were found to be independent of extent of reduction or composition of the solid solution. They were also lower than DeltaH for ceria, which explains the better redox properties of ceria-zirconia solid solutions. The oxidation was driven by entropy in the low reduction region, and a structural model was proposed to explain the observed entropy effects. Redox isotherms were also measured for a number of bulk vanadates between 823 K and 973 K. DeltaG, DeltaH and DeltaS were reported for V 2O5, Mg3(VO4)2, CeVO 4 and ZrV2O7 along with DeltaG values for AlVO 4, LaVO4, CrVO4. V2O5 and ZrV2O7, which were the only oxides having V-O-V bonds, showed a two-step transition of vanadium for V+3↔V +4 and V+4↔V+5 equilibrium in the redox isotherms. The other oxides, all of which have only M-O-V (M=cation other than V), showed a direct one-step transition, V+3↔V +5. The nature of the M-atom also influenced the P(O2) at which the V+3↔V+5 transition occurs. Redox isotherms at 748 K were measured for vanadia supported on ZrO 2; with two different vanadia loadings corresponding to isolated vanadyls and polymeric vanadyls. The isotherm for the sample with isolated vanadyls showed a single-step transition, similar to the one seen in bulk vanadates with M-O-V linkages, while no such one-step transition was observed in the isotherm of the other sample. To study the affect of the varying redox properties of the vanadium-based catalysts on oxidation rates, kinetic studies were performed for methanol and propane oxidation reactions on some of these catalysts. The results suggested that there was no effect of thermodynamic properties of these catalysts on the rates of these oxidation reactions.

New dielectric ceramics Pb(Cd)BiM/sup IV/SbO/sub 7/ (M/sup IV/ = Ti, Zr, Sn) with the pyrochlore structure

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

Lambachri, A.; Monier, M.; Mercurio, J.P.

1988-04-01

Dielectric ceramics have been obtained by natural sintering of pyrochlore phases with general formula Pb(Cd)BiM/sup IV/SbO/sub 7/ (M/sup IV/ = Ti, Zr, Sn). Low frequency dielectric characteristics have been studied with respect to the processing conditions: sintering without additive and in the presence of some low melting compounds (PbO, Pb/sub 5/Ge/sub 3/O/sub 11/, Bi/sub 12/PbO/sub 19/ and Bi/sub 12/CdO/sub 19/). The dielectric constants of these ceramics lie between 30 and 60, the dielectric losses range from 10 to 30.10/sup -4/ and the temperature coefficient of the dielectric constants (20 - 100/sup 0/C) can be tailored by means of additives inmore » the +- 30 ppm K/sup -1/ range.« less

Possibility of Flat-Band Ferromagnetism in Hole-Doped Pyrochlore Oxides Sn2 Nb2 O7 and Sn2 Ta2 O7

NASA Astrophysics Data System (ADS)

Hase, I.; Yanagisawa, T.; Aiura, Y.; Kawashima, K.

2018-05-01

Quantum mechanics tells us that the hopping integral between local orbitals makes the energy band dispersive. In a lattice with geometric frustration, however, dispersionless flat bands may appear due to quantum interference. Several models possessing flat bands have been proposed theoretically, and many attracting magnetic and electronic properties are predicted. However, despite many attempts to realize these models experimentally, compounds that are appropriately described by this model have not been found so far. Here we show that pyrochlore oxides Sn2 Nb2 O7 and Sn2Ta2O7 are such examples, by performing first-principles band calculation and several tight-binding analyses. Moreover, spin-polarized band calculation shows that the hole-doped systems Sn2 Nb2 O6 N and Sn2 Ta2 O6 N have complete spin polarization, and their magnetic moments are mostly carried by Sn-s and N-p orbitals, which are usually nonmagnetic. These compounds are not only candidates for ferromagnets without a magnetic element, but also will provide an experimental platform for a flat-band model which shows a wide range of physical properties.

Coulomb spin liquid in anion-disordered pyrochlore Tb 2Hf 2O 7

DOE PAGES

Sibille, Romain; Lhotel, Elsa; Hatnean, Monica Ciomaga; ...

2017-10-12

Here, the charge ordered structure of ions and vacancies characterizing rare-earth pyrochlore oxides serves as a model for the study of geometrically frustrated magnetism. The organization of magnetic ions into networks of corner-sharing tetrahedra gives rise to highly correlated magnetic phases with strong fluctuations, including spin liquids and spin ices. It is an open question how these ground states governed by local rules are affected by disorder. Here we demonstrate in the pyrochlore Tb 2Hf 2O 7, that the vicinity of the disordering transition towards a defective fluorite structure translates into a tunable density of anion Frenkel disorder while cationsmore » remain ordered. Quenched random crystal fields and disordered exchange interactions can therefore be introduced into otherwise perfect pyrochlore lattices of magnetic ions. We show that disorder can play a crucial role in preventing long-range magnetic order at low temperatures, and instead induces a strongly fluctuating Coulomb spin liquid with defect-induced frozen magnetic degrees of freedom.« less

Fabrication and characterization of La2Zr2O7 films on different buffer architectures for YBa2Cu3O7-δ coated conductors by RF magnetron sputtering.

PubMed

Xu, Da; Liu, Linfei; Xiao, Guina; Li, Yijie

2013-02-27

La2Zr2O7 (LZO) films were grown on different buffer architectures by radio frequency magnetron sputtering for the large-scale application of YBa2Cu3O7-x (YBCO)-coated conductors. The three different buffer architectures were cerium oxide (CeO2), yttria-stabilized zirconia (YSZ)/CeO2, and CeO2/YSZ/CeO2. The microstructure and surface morphology of the LZO film were studied by X-ray diffraction, optical microscopy, field emission scanning electron microscopy, and atomic force microscopy. The LZO films prepared on the CeO2, YSZ/CeO2, and CeO2/YSZ/CeO2 buffer architectures were preferentially c-axis-oriented and highly textured. The in-plane texture of LZO film on CeO2 single-buffer architecture was ∆ φ = 5.5° and the out-of-plane texture was ∆ ω = 3.4°. All the LZO films had very smooth surfaces, but LZO films grown on YSZ/CeO2 and CeO2/YSZ/CeO2 buffer architectures had cracks. The highly textured LZO film grown on CeO2-seed buffered NiW tape was suitable for the epitaxial growth of YBCO film with high currents.

Thermal Spray Deposition, Phase Stability and Mechanical Properties of La2Zr2O7/LaAlO3 Coatings

NASA Astrophysics Data System (ADS)

Lozano-Mandujano, D.; Poblano-Salas, C. A.; Ruiz-Luna, H.; Esparza-Esparza, B.; Giraldo-Betancur, A. L.; Alvarado-Orozco, J. M.; Trápaga-Martínez, L. G.; Muñoz-Saldaña, J.

2017-08-01

This paper deals with the deposition of La2Zr2O7 (LZO) and LaAlO3 (LAO) mixtures by air plasma spray (APS). The raw material for thermal spray, single phase LZO and LAO in a 70:30 mol.% ratio mixture was prepared from commercial metallic oxides by high-energy ball milling (HEBM) and high-temperature solid-state reaction. The HEBM synthesis route, followed by a spray-drying process, successfully produced spherical agglomerates with adequate size distribution and powder-flow properties for feeding an APS system. The as-sprayed coating consisted mainly of a crystalline LZO matrix and partially crystalline LAO, which resulted from the high cooling rate experienced by the molten particles as they impact the substrate. The coatings were annealed at 1100 °C to promote recrystallization of the LAO phase. The reduced elastic modulus and hardness, measured by nanoindentation, increased from 124.1 to 174.7 GPa and from 11.3 to 14.4 GPa, respectively, after the annealing treatment. These values are higher than those reported for YSZ coatings; however, the fracture toughness ( K IC) of the annealed coating was only 1.04 MPa m0.5.

Effect of Gallium Substitution on Lithium-Ion Conductivity and Phase Evolution in Sputtered Li7-3 xGa xLa3Zr2O12 Thin Films.

PubMed

Rawlence, M; Filippin, A N; Wäckerlin, A; Lin, T-Y; Cuervo-Reyes, E; Remhof, A; Battaglia, C; Rupp, J L M; Buecheler, S

2018-04-25

Replacing the liquid electrolyte in conventional lithium-ion batteries with thin-film solid-state lithium-ion conductors is a promising approach for increasing energy density, lifetime, and safety. In particular, Li 7 La 3 Zr 2 O 12 is appealing due to its high lithium-ion conductivity and wide electrochemical stability window. Further insights into thin-film processing of this material are required for its successful integration into solid-state batteries. In this work, we investigate the phase evolution of Li 7-3 x Ga x La 3 Zr 2 O 12 in thin films with various amounts of Li and Ga for stabilizing the cubic phase. Through this work, we gain valuable insights into the crystallization processes unique to thin films and are able to form dense Li 7-3 x Ga x La 3 Zr 2 O 12 layers stabilized in the cubic phase with high in-plane lithium-ion conductivities of up to 1.6 × 10 -5 S cm -1 at 30 °C. We also note the formation of cubic Li 7 La 3 Zr 2 O 12 at the relatively low temperature of 500 °C.

Quantum origins of moment fragmentation in Nd2Zr2O7

NASA Astrophysics Data System (ADS)

Benton, Owen

2016-09-01

Spin-liquid states are often described as the antithesis of magnetic order. Recently, however, it has been proposed that in certain frustrated magnets the magnetic degrees of freedom may "fragment" in such a way as to give rise to a coexistence of spin liquid and ordered phases. Recent neutron-scattering results [S. Petit, E. Lhotel, B. Canals, M. Ciomaga Hatnean, J. Ollivier, H. Muttka, E. Ressouche, A. R. Wildes, M. R. Lees, and G. Balakrishnan, Nat. Phys. 12, 746 (2016), 10.1038/nphys3710] suggest that this scenario may be realized in the pyrochlore magnet Nd2Zr2O7 . These observations show the characteristic pinch-point features of a Coulombic spin liquid occurring alongside the Bragg peaks of an "all-in-all-out" ordered state. Here we explain the quantum origins of this apparent magnetic moment fragmentation, within the framework of a quantum model of nearest-neighbor exchange, appropriate to Nd2Zr2O7 . This model is able to capture both the ground-state order and the pinch points observed at finite energy. The observed fragmentation arises due to the combination of the unusual symmetry properties of the Nd3 + ionic wave functions and the structure of equations of motion of the magnetic degrees of freedom. The results of our analysis suggest that Nd2Zr2O7 is proximate to a U (1 ) spin-liquid phase and is a promising candidate for the observation of a Higgs transition in a magnetic system.

Electrical Characteristics and Preparation of Nanostructured Pb(Zr0.5Ti0.5)O3 Films by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Koo, Horng-Show; Chen, Mi; Hotta, Yoichi; Kawai, Tomoji

2007-07-01

Nanostructured thin films of Pb(Zr0.5Ti0.5)O3 on Pt (1000 Å)/Ti (100 Å)/SiO2 (2000 Å)/Si substrates are prepared by spray pyrolysis and subsequently rapid thermal annealing. Lead nitrate, zirconium nitrate and titanium isopropoxide are used as starting material with ethylene glycol as solvent. The crystal structure of the as-sprayed films are transformed from the amorphous, pyrochlore and multiple phases of pyrochlore and perovskite to the single phase of perovskite as the annealing temperature is increased up to 500 °C. For the formation of single phase perovskite, excess lead of 10 mol % is required to compensate the loss of lead during the processing of the primitive films. The physical characteristics of the resultant films show the dielectric constant (\\varepsilonr) of 400, remanent polarization (2Pr) of 30.0 μC/cm2 and coercive field (2Ec) of 70.0 kV/cm, respectively.

Fast crystallization of amorphous Gd{sub 2}Zr{sub 2}O{sub 7} induced by thermally activated electron-beam irradiation

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

Huang, Zhangyi; Qi, Jianqi, E-mail: qijianqi@scu.edu.cn; Zhou, Li

2015-12-07

We investigate the ionization and displacement effects of an electron-beam (e-beam) on amorphous Gd{sub 2}Zr{sub 2}O{sub 7} synthesized by the co-precipitation and calcination methods. The as-received amorphous specimens were irradiated under electron beams at different energies (80 keV, 120 keV, and 2 MeV) and then characterized by X-ray diffraction and transmission electron microscopy. A metastable fluorite phase was observed in nanocrystalline Gd{sub 2}Zr{sub 2}O{sub 7} and is proposed to arise from the relatively lower surface and interface energy compared with the pyrochlore phase. Fast crystallization could be induced by 120 keV e-beam irradiation (beam current = 0.47 mA/cm{sup 2}). The crystallization occurred on the nanoscale upon ionizationmore » irradiation at 400 °C after a dose of less than 10{sup 17} electrons/cm{sup 2}. Under e-beam irradiation, the activation energy for the grain growth process was approximately 10 kJ/mol, but the activation energy was 135 kJ/mol by calcination in a furnace. The thermally activated ionization process was considered the fast crystallization mechanism.« less

The thermal stability and catalytic application of manganese oxide-zirconium oxide powders

NASA Astrophysics Data System (ADS)

Zhao, Qiang

MnOx-ZrO2 mixed oxide is an active catalyst for combustion, oxidation, and oxygen storage applications. MnOx-ZrO 2 mixture also has large reversible adsorption capability for NO x, which makes it a promising candidate for NOx abatement in automobile emission control. However, MnOx-ZrO 2 mixed oxide has not been used extensively because the processing and the thermal stability of resulting powders have not been studied systematically. It is critical to have thermally stable catalytic material because the application temperature can reach as high as 1000°C during service. In this study, we focused on improving the thermal stability of oxide powders, such as MnO x, ZrO2, and MnOx-ZrO2, by controlling the processing methods and parameters. For pure MnOx made from the precipitation method using Mn(NO3)2 aqueous solution and ammonium hydroxide, we found that lower concentration of Mn(NO3) 2 solution and larger amount of ammonium hydroxide resulted in higher surface area powders. For pure ZrO2, we found curing hydrous zirconia in the mother liquid produced ZrO2 powders with larger pore volume and pore size. The specific surface area was also significantly enhanced by curing for the synthesized powders before calcination or after low temperature calcinations, and this improvement could be preserved to high temperatures if SiO2 was doped in ZrO2. A Monte Carlo simulation model examining the effect of primary particle packing on the specific surface area was used to explain the curing result. MnOx-ZrO2 mixtures had higher surface area than the single component oxide at 500 and 700°C because composite powders sintered less. The sintering behavior of composite powders at 900°C was opposite to that at 500°C and the specific surface area of MnOx-ZrO2 decreased drastically at 900°C. Curing ZrO2 first or using La dopant could significantly enhance the specific surface area of MnOx-ZrO2 at 900°C. Through the tests of the redox property and NO storage capability we found a close relationship between the enhanced thermal stability and better catalytic performance.

Abnormal Pressure-Induced Photoluminescence Enhancement and Phase Decomposition in Pyrochlore La2 Sn2 O7.

PubMed

Zhao, Yongsheng; Li, Nana; Xu, Cong; Li, Yan; Zhu, Hongyu; Zhu, Pinwen; Wang, Xin; Yang, Wenge

2017-09-01

La 2 Sn 2 O 7 is a transparent conducting oxide (TCO) material and shows a strong near-infrared fluorescent at ambient pressure and room temperature. By in situ high-pressure research, pressure-induced visible photoluminescence (PL) above 2 GPa near 2 eV is observed. The emergence of unusual visible PL behavior is associated with the seriously trigonal lattice distortion of the SnO 6 octehedra, under which the Sn-O1-Sn exchange angle θ is decreased below 22.1 GPa, thus enhancing the PL quantum yield leading to Sn 3 P 1 → 1 S 0 photons transition. Besides, bandgap closing followed by bandgap opening and the visible PL appearing at the point of the gap reversal, which is consistent with high-pressure phase decomposition, are discovered. The high-pressure PL results demonstrate a well-defined pressure window (7-17 GPa) with flat maximum PL yielding and sharp edges at both ends, which may provide a great calibration tool for pressure sensors for operation in the deep sea or at extreme conditions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structure, stoichiometry, and dielectric relaxation in Bi 3.32Nb 7.09O 22.7 and structurally related ternary phases

NASA Astrophysics Data System (ADS)

Grey, I. E.; Vanderah, T. A.; Mumme, W. G.; Roth, R. S.; Guzman, J.; Nino, J. C.; Levin, I.

2008-03-01

The crystal structure of the phase previously reported to occur at 4:9 Bi 2O 3:Nb 2O 5 has been determined using single-crystal X-ray and powder neutron diffraction ( P6 3/ mmc; a=7.4363(1) Å, c=19.7587(5) Å; Z=2). The structural study combined with phase equilibrium analyses indicate that the actual composition is Bi 3.32Nb 7.09O 22.7. This binary compound is the end-member of a family of four phases which form along a line between it and the pyrochlore phase field in the Bi 2O 3:Fe 2O 3:Nb 2O 5 system. The structures are derived from the parent pyrochlore end-member by chemical twinning, and can also be described as unit-cell intergrowths of the pyrochlore and hexagonal tungsten bronze (HTB) structures. The dielectric properties of the three chemically twinned pyrochlore phases, Bi 3.32Nb 7.09O 22.7, Bi 9.3Fe 1.1Nb 16.9O 57.8 and Bi 5.67FeNb 10O 35, were characterized. All exhibit low-temperature, broad dielectric relaxation similar to that of the Bi-Fe-Nb-O pyrochlore. At 1 MHz and ≈175 K the observed relative permittivites were 345, 240, and 205, respectively, compared to 125 for the Bi-Fe-Nb-O pyrochlore. The higher relative permittivities observed for the chemically twinned pyrochlore derivatives are ascribed to the presence of HTB blocks in their structures: The Bi atoms located in the HTB blocks feature highly asymmetric coordination environments compared to pyrochlore, and the magnitude of the relative permittivity increases with the proportion of Bi located within the HTB portions of the structures.

Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

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

Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

DOE PAGES

Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

2017-07-19

Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

Radiation-induced disorder in compressed lanthanide zirconates.

PubMed

Park, Sulgiye; Tracy, Cameron L; Zhang, Fuxiang; Park, Changyong; Trautmann, Christina; Tkachev, Sergey N; Lang, Maik; Mao, Wendy L; Ewing, Rodney C

2018-02-28

The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln 2 Zr 2 O 7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197 Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 . For irradiated Er 2 Zr 2 O 7 , which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

Epitaxial growth of iridate pyrochlore Nd 2Ir 2O 7 films

DOE PAGES

Gallagher, J. C.; Esser, B. D.; Morrow, R.; ...

2016-02-29

Epitaxial films of the pyrochlore Nd 2Ir 2O 7 have been grown on (111)-oriented yttria-stabilized zirconia (YSZ) substrates by off-axis sputtering followed by post-growth annealing. X-ray diffraction (XRD) results demonstrate phase-pure epitaxial growth of the pyrochlore films on YSZ. Scanning transmission electron microscopy (STEM) investigation of an Nd 2Ir 2O 7 film with a short post-annealing provides insight into the mechanism for crystallization of Nd 2Ir 2O 7 during the post-annealing process. STEM images reveal clear pyrochlore ordering of Nd and Ir in the films. As a result, the epitaxial relationship between the YSZ and Nd 2Ir 2O 7 ismore » observed clearly while some interfacial regions show a thin region with polycrystalline Ir nanocrystals.« less

Oxidation/reduction studies on Zr yU 1-yO 2+x and delineation of a new orthorhombic phase in U-Zr-O system

NASA Astrophysics Data System (ADS)

Sali, S. K.; Kulkarni, N. K.; Krishnan, K.; Achary, S. N.; Tyagi, A. K.

2008-08-01

In this communication, we report the oxidation and reduction behavior of fluorite type solid solutions in U-Zr-O. The maximum solubility of ZrO 2 in UO 2 lattice could be achieved with a mild oxidizing followed by reducing conditions. The role of valency state of U is more dominating in controlling the unit cell parameters than the incorporated interstitial oxygen in the fluorite lattice. The controlled oxidation studies on U-Zr-O solid solutions led to the delineation of a new distorted fluorite lattice at the U:Zr=2:1 composition. The detailed crystal structure analysis of this ordered composition Zr 0.33U 0.67O 2.33 (ZrU 2O 7) has been carried from the powder XRD data. This phase crystallizes in an orthorhombically distorted fluorite type lattice with unit cell parameters: a=5.1678(2), b=5.4848(2), c=5.5557(2) Å and V=157.47(1) Å 3 (Space group: Cmcm, No. 63). The metal ions have distorted cubical polyhedra with anion similar to the fluorite structure. The excess anions are occupied in the interstitial (empty cubes) of the fluorite unit cell. The crystal structure and chemical analyses suggest approximately equal fractions of U 4+ and U 6+ in this compound. The details of the thermal stability as well as kinetics of formation and oxidation of ZrU 2O 7 are also studied using thermogravimetry.

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.

Metal-Insulator Transition in Epitaxial Pyrochlore Iridates Bi2Ir2O7 thin Films

NASA Astrophysics Data System (ADS)

Chu, Jiun-Haw; Liu, Jian; Yi, Di; Rayan-Serrao, C.; Suresha, S.; Marti, Xavi; Riggs, Scott; Shapiro, Max; Ian, Fisher; Ramesh, R.

2013-03-01

Recently there is a surge of interest in searching for topological order in correlated electronic systems such as transition metal oxides. The strong spin-orbit interaction of 5d electrons and the geometric frustration in the crystal lattice make the pyrochlore iridate(A2Ir2O7) an ideal candidate to achieve this goal. Pioneering experiments on bulk polycrystalline and single crystal samples revealed a temperature dependent metal-insulator transition coupled to a long range magnetic order, and the transition temperature can be tuned by either A-site ionic radius or an external pressure. In this talk we present our efforts to understand and control the metal-insulator transition and the underlying electronic structure of pyrochlore iridates via epitaxial Bi2Ir2O7 thin films. Bulk Bi2Ir2O7 is located at the metallic side of the phase diagram. However as the film's thickness decreases the transport evolves from a metallic to a strongly localized character. Resonant X-ray spectroscopy suggests that the density of states near Fermi level is dominated by the Ir Je ff =1/2 states. Intriguingly, the magnetoresistance shows a linear field dependence over a wide range of fields at low temperatures, which is possibly consistent with the existence of Dirac nodes.

Steam Reforming of CH4 Using Ni- Substituted Pyrochlore Catalysts

NASA Astrophysics Data System (ADS)

Haynes, Daniel J.

The steam reforming of methane (SMR) continues to remain an important industrial reaction for large-scale production of H2 as well as synthesis gas mixtures which can be used for the production of useful chemicals (e.g. methanol). Although SMR is a rather mature technology, traditional nickel based catalysts used industrially are subjected to severe temperatures and reaction conditions, which lead to irreversible activity loss through sintering, support collapse, and carbon formation. Pyrochlore-based mixed oxide have been identified as refractory materials that can be modified through the substitution of catalytic metals and other promoting species into the structure to mitigate these issues causing deactivation. For this study, a lanthanum zirconate pyrochlore catalyst was substituted with Ni to determine whether the oxide structure could effectively stabilize the activity of the catalytic metal during the SMR. The effect of different variables including calcination temperature, a comparison of a substituted versus supported Ni pyrochlore catalyst, Ni weight loading, and Sr promotion have been evaluated to determine the location of the Ni in the structure, and their effect on catalytic behavior. It was revealed that the effect of calcination temperature on a 6wt% Ni substituted pyrochlore produced by the Pechini method demonstrated very little Ni was soluble in the pyrochlore lattice. It was further revealed that by XRD, TEM, and atom probe tomography that, despite the metal loading, Ni exsolves from the structure upon crystallization of the pyrochlore at 700°C, and forms NiO at the surface and grain boundaries. An additional separate La2ZrNiO6 perovskite phase also began to form at higher temperatures (>800°C). Increasing calcination temperature was found to lead to slight sintering of the NiO at the surface, which made the NiO more reducible. Meanwhile decreasing the Ni weight loading was found to produce a lower reduction temperature due to the presence of less lanthanum at the surface. Comparing the XANES and EXAFS profiles for the supported and substituted Ni catalysts showed no detectable difference between the spectra, further confirming the Ni to be present as NiO after substitution. Activity testing found the NiO on the surface to be the active catalytic form. However, the Ni proved to be highly sensitive to sintering and oxidation by steam, especially under high pressures (1.8 MPa), which caused all catalysts to suffer irreversible activity loss. Low reaction pressures (0.23 MPa) elicited an activation effect in which the Ni initially lost activity, but then recovered to near equilibrium yields after nearly 10 hours time on stream. The activation was correlated with an increase in Ni particle size, as observed by XRD. It is speculated from similar behavior reported in the literature that ability to recovery activity was linked to a redox cycling of the Ni particles under reaction conditions, in which a small amount of the Ni was redistributed over the surface through the volatilization with steam, as well as the exsolution of the Sr from the structure which helped stabilize the Ni. A comparison of the supported and substituted forms of Ni showed the substituted form to have a weaker interaction with the pyrochlore surface, which is the likely cause for the rapid sintering and deactivation by steam. It was also found that the substitution of more Sr into the structure produced only strong basic sites, which resulted in a lower degree of activity loss and more stable activity under high pressure conditions (1.8 MPa) compared to the catalyst with less Sr. Carbon formation was not an issue for these materials, due to the rapid sintering and oxidation of the metal in-situ. Fitting the Ni particle size growth with time showed a parabolic relationship with growth proportional to time by the power 0.28. This value is close to results observed in the literature which indicates the Ni agglomerates via atomic migration.

First-principles density functional calculation of electrochemical stability of fast Li ion conducting garnet-type oxides.

PubMed

Nakayama, Masanobu; Kotobuki, Masashi; Munakata, Hirokazu; Nogami, Masayuki; Kanamura, Kiyoshi

2012-07-28

The research and development of rechargeable all-ceramic lithium batteries are vital to realize their considerable advantages over existing commercial lithium ion batteries in terms of size, energy density, and safety. A key part of such effort is the development of solid-state electrolyte materials with high Li(+) conductivity and good electrochemical stability; lithium-containing oxides with a garnet-type structure are known to satisfy the requirements to achieve both features. Using first-principles density functional theory (DFT), we investigated the electrochemical stability of garnet-type Li(x)La(3)M(2)O(12) (M = Ti, Zr, Nb, Ta, Sb, Bi; x = 5 or 7) materials against Li metal. We found that the electrochemical stability of such materials depends on their composition and structure. The electrochemical stability against Li metal was improved when a cation M was chosen with a low effective nuclear charge, that is, with a high screening constant for an unoccupied orbital. In fact, both our computational and experimental results show that Li(7)La(3)Zr(2)O(12) and Li(5)La(3)Ta(2)O(12) are inert to Li metal. In addition, the linkage of MO(6) octahedra in the crystal structure affects the electrochemical stability. For example, perovskite-type La(1/3)TaO(3) was found, both experimentally and computationally, to react with Li metal owing to the corner-sharing MO(6) octahedral network of La(1/3)TaO(3), even though it has the same constituent elements as garnet-type Li(5)La(3)Ta(2)O(12) (which is inert to Li metal and features isolated TaO(6) octahedra).

Image-based multi-scale simulation and experimental validation of thermal conductivity of lanthanum zirconate

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

Guo, Xingye; Hu, Bin; Wei, Changdong

Lanthanum zirconate (La2Zr2O7) is a promising candidate material for thermal barrier coating (TBC) applications due to its low thermal conductivity and high-temperature phase stability. In this work, a novel image-based multi-scale simulation framework combining molecular dynamics (MD) and finite element (FE) calculations is proposed to study the thermal conductivity of La2Zr2O7 coatings. Since there is no experimental data of single crystal La2Zr2O7 thermal conductivity, a reverse non-equilibrium molecular dynamics (reverse NEMD) approach is first employed to compute the temperature-dependent thermal conductivity of single crystal La2Zr2O7. The single crystal data is then passed to a FE model which takes into accountmore » of realistic thermal barrier coating microstructures. The predicted thermal conductivities from the FE model are in good agreement with experimental validations using both flash laser technique and pulsed thermal imaging-multilayer analysis. The framework proposed in this work provides a powerful tool for future design of advanced coating systems. (C) 2016 Elsevier Ltd. All rights reserved.« less

Structural vs. intrinsic carriers: contrasting effects of cation chemistry and disorder on ionic conductivity in pyrochlores

DOE PAGES

Perriot, Romain; Uberuaga, Blas P.

2015-04-21

We use molecular dynamics simulations to investigate the role of cation disorder on oxygen diffusion in Gd 2Zr 2O 7 (GZO) and Gd 2Ti 2O 7 (GTO) pyrochlores, a class of complex oxides which contain a structural vacancy relative to the basic fluorite structure. The introduction of disorder has distinct effects depending on the chemistry of the material, increasing the mobility of structural carriers by up to four orders of magnitude in GZO. In contrast, in GTO, there is no mobility at zero or low disorder on the ns timescale, but higher disorder liberates the otherwise immobile carriers, allowing diffusionmore » with rates comparable to GZO for the fully disordered material. Here, we show that the cation disorder enhances the diffusivity by both increasing the concentration of mobile structural carriers and their individual mobility. The disorder also influences the diffusion in materials containing intrinsic carriers, such as additional vacancies VO or oxygen interstitials OI. And while in ordered GZO and GTO the contribution of the intrinsic carriers dominates the overall diffusion of oxygen, OI in GZO contributes along with structural carriers, and the total diffusion rate can be calculated by assuming simple additive contributions from the two sources. Although the disorder in the materials with intrinsic defects usually enhances the diffusivity as in the defect-free case, in low concentrations, cation antisites AB or BA, where A = Gd and B = Zr or Ti, can act as traps for fast intrinsic defects. The trapping results in a lowering of the diffusivity, and causes a non-monotonic behavior of the diffusivity with disorder. Conversely, in the case of slow intrinsic defects, the main effect of the disorder is to liberate the structural carriers, resulting in an increase of the diffusivity regardless of the defect trapping.« less

Pyrochlore Oxide Superconductor Cd2Re2O7 Revisited

NASA Astrophysics Data System (ADS)

Hiroi, Zenji; Yamaura, Jun-ichi; Kobayashi, Tatsuo C.; Matsubayashi, Yasuhito; Hirai, Daigorou

2018-02-01

The superconducting pyrochlore oxide Cd2Re2O7 is revisited with a particular emphasis on the sample-quality issue. The compound has drawn attention as the only superconductor (Tc = 1.0 K) that has been found in the family of α-pyrochlore oxides since its discovery in 2001. Moreover, it exhibits two characteristic structural transitions from the cubic pyrochlore structure, with the inversion symmetry broken at the first one at 200 K. Recently, it has attracted increasing attention as a candidate spin-orbit coupled metal (SOCM), in which specific Fermi liquid instability is expected to lead to an odd-parity order with spontaneous inversion-symmetry breaking [L. Fu, Phys. Rev. Lett. 115, 026401 (2015)] and parity-mixing superconductivity [V. Kozii and L. Fu, Phys. Rev. Lett. 115, 207002 (2015); Y. Wang et al., Phys. Rev. B 93, 134512 (2016)]. We review our previous experimental results in comparison with those of other groups in the light of the theoretical prediction of the SOCM, which we consider meaningful and helpful for future progress in understanding this unique compound.

Electrical characteristics of SiO2/ZrO2 hybrid tunnel barrier for charge trap flash memory

NASA Astrophysics Data System (ADS)

Choi, Jaeho; Bae, Juhyun; Ahn, Jaeyoung; Hwang, Kihyun; Chung, Ilsub

2017-08-01

In this paper, we investigate the electrical characteristics of SiO2/ZrO2 hybrid tunnel oxide in metal-Al2O3-SiO2-Si3N4-SiO2-silicon (MAONOS) structure in an effort to improve program and erase speed as well as retention characteristics. Inserting ZrO2 into the conventional MAONOS structure increased the programmed V th variation to 6.8 V, and increased the erased V th variation to -3.7 V at 17 MV/cm. The results can be understood in terms of reducing the Fowler-Nordheim (F/N) tunneling barrier due to high-k ZrO2 in the tunneling oxide. In addition, Zr diffusion in SiO2 caused the formation of Zr x Si1- x O2 at the interface region, which reduced the energy band gap of SiO2. The retention property of the hybrid tunnel oxide varied depending on the thickness of SiO2. For thin SiO2 less than 30 Å, the retention properties of the tunneling oxides were poor compared with those of the SiO2 only tunneling oxides. However, the hybrid tunneling oxides with SiO2 thickness thicker than 40 Å yielded improved retention behavior compared with those of the SiO2-only tunneling oxides. The detailed analysis in charge density of ZrO2 was carried out by ISPP test. The obtained charge density was quite small compared to that of the total charge density, which indicates that the inserted ZrO2 layer serves as a tunneling material rather than charge storage dielectric.

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, D.; Yeager, E.; Shingler, M.; Aldred, W.; Wang, C.

1990-01-01

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

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

High thermal stability of La 2O 3 and CeO 2-stabilized tetragonal ZrO 2

DOE PAGES

Wang, Shichao; Xie, Hong; Lin, Yuyuan; ...

2016-02-15

Catalyst support materials of tetragonal ZrO 2, stabilized by either La 2O 3 (La 2O 3-ZrO 2) or CeO 2 (CeO 2-ZrO 2), were synthesized under hydrothermal conditions at 200 °C with NH 4OH or tetramethylammonium hydroxide as the mineralizer. From In Situ synchrotron powder X-ray diffraction and small-angle X-ray scattering measurements, the calcined La 2O 3-ZrO 2 and CeO 2-ZrO 2 supports were nonporous nanocrystallites that exhibited rectangular shapes with thermal stability up to 1000 °C in air. These supports had an average size of ~10 nm and a surface area of 59-97 m 2/g. The catalysts Pt/La 2Omore » 3-ZrO 2 and Pt/CeO 2-ZrO 2 were prepared by using atomic layer deposition with varying Pt loadings from 6.3-12.4 wt %. Mono-dispersed Pt nanoparticles of ~3 nm were obtained for these catalysts. As a result, the incorporation of La 2O 3 and CeO 2 into the t-ZrO 2 structure did not affect the nature of the active sites for the Pt/ZrO 2 catalysts for the water-gas-shift (WGS) reaction.« less

Structure and Thermal Expansion of YSZ and La 2Zr 2O 7 Above 1500°C from Neutron Diffraction on Levitated Samples

DOE PAGES

Ushakov, Sergey V.; Navrotsky, Alexandra; Weber, Richard J. K.; ...

2015-07-28

High-temperature time-of-flight neutron diffraction experiments were performed in this paper on cubic yttria-stabilized zirconia (YSZ, 10 mol% YO 1.5) and lanthanum zirconate (LZ) prepared by laser melting. Three spheroids of each composition were aerodynamically levitated and rotated in argon flow and heated with a CO 2 laser. Unit cell, positional and atomic displacement parameters were obtained by Rietveld analysis. Below ~1650°C the mean thermal expansion coefficient (TEC) for YSZ is higher than for LZ (13 ± 1 vs. 10.3 ± 0.6) × 10 -6/K. From ~1650°C to the onset of melting of LZ at ~2250°C, TEC for YSZ and LZmore » are similar and within (7 ± 2) × 10 -6/K. LZ retains the pyrochlore structure up to the melting temperature with Zr coordination becoming closer to perfectly octahedral. Congruently melting LZ is La deficient. The occurrence of thermal disordering of oxygen sublattice (Bredig transition) in defect fluorite structure was deduced from the rise in YSZ TEC to ~25 × 10 -6/K at 2350°C–2550°C with oxygen displacement parameters (U iso) reaching 0.1 Å 2, similar to behavior observed in UO 2. Acquisition of powder-like high-temperature neutron diffraction data from solid-levitated samples is feasible and possible improvements are outlined. Finally, this methodology should be applicable to a wide range of materials for high-temperature applications.« less

Crystal-field, exchange interactions and magnetism in pyrochlore ferromagnet R2V2O7 (R3+=Y, Lu)

NASA Astrophysics Data System (ADS)

Ali Biswas, A.; Jana, Y. M.

2013-03-01

The temperature dependence of the observed bulk magnetic susceptibility, magnetization, paramagnetic Curie temperature θCW, magnetic specific heat of ferromagnetic semi-conducting pyrochlore-based vanadate compounds Y2V2O7 and Lu2V2O7, which are the simplest of R2M2O7 pyrochlore series of oxides, are simulated and analyzed, simultaneously and consistently, within the frame work of the appropriate crystal-field (CF) theory and a mean-field approximation by introducing effective anisotropic molecular-field tensors and also taking account of appreciable spin-orbit coupling. The electronic and magnetic properties are correlated to the structural parameters. Ten-fold degenerate 2D term of 3d1 V4+-ions is split into five Kramers doublets with overall CF splitting Δ1≈2 eV and the total splitting of the 2T2g state Δ0≈0.4 eV under combined actions of octahedral CF, trigonal (D3d) distortion at V-site and spin-orbit coupling. The ground doublet is a well-isolated effectively spin s=1/2 state, characterized by the anisotropic g-tensors and directional magnetic moments. The degeneracy of the ground state is lifted by the spin-spin correlations among V4-tetrahedra at T∼170 K, which causes the formation of ferromagnetic clusters in these pyrochlores. The temperature dependence of the calculated directional site-susceptibilities shows that the V4+ ions have a substantial easy-axis single-ion anisotropy along local <111> axis of a given V4-tetrahedron in the magnetic phase where ferromagnetic clusters coexist with paramagnetic phase.

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

Nguyen, Thi Minh Hien; Sandilands, Luke J.; Sohn, C. H.

5d pyrochlore oxides with all-in-all-out magnetic order are prime candidates for realizing strongly correlated, topological phases of matter. Despite significant effort, a full understanding of all-in-all-out magnetism remains elusive as the associated magnetic excitations have proven difficult to access with conventional techniques. Here we report a Raman spectroscopy study of spin dynamics in the all-in-all-out magnetic state of the 5d pyrochlore Cd 2Os 2O 7. Through a comparison between the two-magnon scattering and spin-wave theory, we confirm the large single ion anisotropy in this material and show that the Dzyaloshinskii–Moriya and exchange interactions play a significant role in the spin-wavemore » dispersions. The Raman data also reveal complex spin–charge–lattice coupling and indicate that the metal–insulator transition in Cd 2Os 2O 7 is Lifshitz-type. In conclusion, our work establishes Raman scattering as a simple and powerful method for exploring the spin dynamics in 5d pyrochlore magnets.« less

Comparing XPS on bare and capped ZrN films grown by plasma enhanced ALD: Effect of ambient oxidation

NASA Astrophysics Data System (ADS)

Muneshwar, Triratna; Cadien, Ken

2018-03-01

In this article we compare x-ray photoelectron spectroscopy (XPS) measurements on bare- and capped- zirconium nitride (ZrN) films to investigate the effect of ambient sample oxidation on the detected bound O in the form of oxide ZrO2 and/or oxynitride ZrOxNy. ZrN films in both bare- and Al2O3/AlN capped- XPS samples were grown by plasma-enhanced atomic layer deposition (PEALD) technique using tetrakis dimethylamino zirconium (TDMAZr) precursor, forming gas (5% H2, rest N2) inductively coupled plasma (ICP), and as received research grade process gases under identical process conditions. Capped samples were prepared by depositing 1 nm thick PEALD AlN on ZrN, followed by additional deposition of 1 nm thick ALD Al2O3, without venting of ALD reactor. On bare ZrN sample at room temperature, spectroscopic ellipsometry (SE) measurements with increasing ambient exposure times (texp) showed a self-limiting surface oxidation with the oxide thickness (dox) approaching 3.7 ± 0.02 nm for texp > 120 min. In XPS data measured prior to sample sputtering (tsput = 0), ZrO2 and ZrOxNy were detected in bare- samples, whereas only ZrN and Al2O3/AlN from capping layer were detected in capped- samples. For bare-ZrN samples, appearance of ZrO2 and ZrOxNy up to sputter depth (dsput) of 15 nm in depth-profile XPS data is in contradiction with measured dox = 3.7 nm, but explained from sputtering induced atomic inter-diffusion within analyzed sample. Appearance of artifacts in the XPS spectra from moderately sputtered (dsput = 0.2 nm and 0.4 nm) capped-ZrN sample, provides an evidence to ion-bombardment induced modifications within analyzed sample.

Symmetry and light stuffing of H o 2 T i 2 O 7 ,   E r 2 T i 2 O 7 , and Y b 2 T i 2 O 7 characterized by synchrotron x-ray diffraction

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

Baroudi, Kristen; Gaulin, Bruce D.; Lapidus, Saul H.

2015-07-01

The Ho2Ti2O7, Er2Ti2O7 and Yb2Ti2O7 pyrochlores were studied by synchrotron X-ray diffraction to determine whether the (002) peak, forbidden in the pyrochlore space group Fd-3m but observed in single crystal neutron scattering measurements, is present due to a deviation of their pyrochlore structure from Fd-3m symmetry. Synchrotron diffraction measurements on precisely synthesized stoichiometric and non-stoichiometric powders and a crushed floating zone crystal of Ho2Ti2O7 revealed that the (002) reflection is absent in all cases to a sensitivity of approximately one part in 30,000 of the strongest X-ray diffraction peak. This indicates to high sensitivity that the structural space group ofmore » these rare earth titanate pyrochlores is Fd-3m, and that thus the (002) peak observed in the neutron scattering experiments has a non-structural origin. The cell parameters and internal strain for lightly stuffed Ho2+xTi2-xO7 are also presented.« less

Partial Oxidation of Hydrocarbons in a Segmented Bed Using Oxide-based Catalysts and Oxygen-conducting Supports

NASA Astrophysics Data System (ADS)

Smith, Mark W.

Two objectives for the catalytic reforming of hydrocarbons to produce synthesis gas are investigated herein: (1) the effect of oxygen-conducting supports with partially substituted mixed-metal oxide catalysts, and (2) a segmented bed approach using different catalyst configurations. Excess carbon deposition was the primary cause of catalyst deactivation, and was the focus of the experiments for both objectives. The formation and characterization of deposited carbon was examined after reaction for one of the selected catalysts to determine the quantity and location of the carbon on the catalyst surface leading to deactivation. A nickel-substituted barium hexaaluminate (BNHA), with the formula BaAl 11.6Ni0.4O18.8, and a Rh-substituted lanthanum zirconate pyrochlore (LCZR) with the formula La1.89Ca0.11 Zr1.89Rh0.11, were combined with two different doped ceria supports. These supports were gadolinium-doped ceria (GDC) and zirconium-doped ceria (ZDC). The active catalyst phases were combined with the supports in different ratios using different synthesis techniques. The catalysts were characterized using several different techniques and were tested under partial oxidation (POX) of n-tetradecane (TD), a diesel fuel surrogate. It was found that the presence of GDC and ZDC reduced the formation of carbon for both catalysts; the optimal ratio of catalyst to support was different for the hexaaluminate and the pyrochlore; a loading of 20 wt% of the pyrochlore with ZDC produced the most stable performance in the presence of common fuel contaminants (>50 h); and, the incipient wetness impregnation synthesis method of applying the active catalyst to the support produced more stable product yields than the catalyst prepared by a solid-state mixing technique. Different hexaaluminate and pyrochlore catalysts were used in different configurations in a segmented bed approach. The first strategy was to promote the indirect reforming mechanism by placing a combustion catalyst in the reactor inlet, followed by a reforming catalyst. This approach demonstrated that BNHA can be used in the reactor inlet to promote combustion with 1 wt% Rh-substituted pyrochlore in the reactor outlet, but the combustion catalyst should fill less than 50% of the reactor. The second approach placed specific catalysts in regions of the reactor that have conditions in which they are less likely to deactivate. This showed the most benefit in the use of a sulfur-tolerant noble metal catalyst in the reactor outlet. The carbon formation study was conducted on a 2 wt% Rh-substituted pyrochlore. POX of TD for various run times, followed by temperature programmed oxidation, revealed two different types of carbon deposits in the catalyst bed: carbon that burned off at relatively low temperature (LTC), and carbon that burned off at higher temperatures (HTC). The LTC reached a steady state level within two hours of reaction, and was determined not to lead to catalyst deactivation. The HTC continued to accumulate with time on stream. A mathematical expression was developed to predict the rate of formation of the HTC for a given set of reaction conditions (O/C = 1.25). This expression was modified from data from a test under different reaction conditions (O/C = 1.1) for one length of time, and was found to predict the carbon formation for a different run time within 3%.

Heavy ion irradiation-induced microstructural evolution in pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} at room temperature and 723 K

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

Xie, Q.R.; Zhang, J., E-mail: zhangjian@xmu.edu.cn; Dong, X.N.

Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} at room temperature and 723 K to a fluence of 4×10{sup 15} ions/cm{sup 2}, corresponding to an average ballistic damage dose of 10 displacements per atom in the peak damage region. Irradiation-induced microstructural evolution was examined by grazing incidence X-ray diffraction, and cross-sectional transmission electron microscopy. Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal which has the identical structure of pyrochlore, and the formation of nano-crystal is attributed to the mechanism of epitaxial recrystallization. However, an orderedmore » pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Graphical Abstract: Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} to a fluence of 4×10{sup 15} ions/cm{sup 2} at room temperature and 723 K, Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal. However, an ordered pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Highlights: Pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated by heavy ions at RT and 723 K. At RT irradiation, ~75% of amorphization was achieved. The nano-crystals were formed in the damage layer at RT irradiation. The formed nano-crystals enhanced the radiation tolerance of Lu{sub 2}Ti{sub 2}O{sub 7}. A pyrochlore to fluorite phase transformation was observed at 723 K irradiation.« less

Tuning Frustration in Rare Earth Pyrochlores by Platinum Substitution

NASA Astrophysics Data System (ADS)

Hallas, Alannah; Gaudet, Jonathan; Sharma, Arzoo; Wilson, Murray; Cai, Yipeng; Tachibana, Makoto; Wiebe, Chris; Gaulin, Bruce; Luke, Graeme

A successful mechanism for exploring the rich physics of rare earth pyrochlores, R2B2O7, is to substitute the non-magnetic B-site. Varying the ionic radius of the B-site induces an internal chemical pressure. Some rare earths are robust to substitutions; for example, the holmium-based pyrochlores all exhibit a dipolar spin ice state. In the case of other rare earths such as ytterbium, the ground states are remarkably fragile to chemical pressure. In this talk, I will introduce two materials with a new non-magnetic B-site: platinum. The ionic radius of platinum is comparable to that of titanium, which occupies the B-site in the most well-studied family of pyrochlores. Thus, platinum does not induce a strong chemical pressure on the lattice. Nevertheless, using Gd2Pt2O7 and Er2Pt2O7 as examples, I will show that platinum does affect a dramatic change on the magnetic properties. We trace this effect to platinum's empty eg orbitals, which mediate superexchange pathways not available in other rare earth pyrochlores. In Gd2Pt2O7, this results in a striking 160% enhancement of TN as compared to other Gd-based pyrochlores. In Er2Pt2O7, the ordering temperature is strongly suppressed and the ground state is altered.

Pentavalent iridium pyrochlore C d2I r2O7 : A prototype material system for competing crystalline field and spin-orbit coupling

NASA Astrophysics Data System (ADS)

Dai, Jianhong; Yin, Yunyu; Wang, Xiao; Shen, Xudong; Liu, Zhehong; Ye, Xubin; Cheng, Jinguang; Jin, Changqing; Zhou, Guanghui; Hu, Zhiwei; Weng, Shihchang; Wan, Xiangang; Long, Youwen

2018-02-01

A new pyrochlore oxide C d2I r2O7 with an I r5 + charge state was prepared by high-pressure techniques. Although strong spin-orbit coupling (SOC) dominates the electronic states in most iridates so that a SOC-Mott state is proposed in S r2Ir O4 in the assumption of an undistorted Ir O6 octahedral crystalline field, the strongly distorted one in the current C d2I r2O7 exhibits a competing interaction with the SOC. Unexpected from a strong SOC limit, C d2I r2O7 deviates from a nonmagnetic and insulating J =0 ground state. It displays short-range ferromagnetic correlations and metallic electrical transport properties. First-principles calculations well reproduce the experimental observation, revealing the large mixture between the jeff=1 /2 and jeff=3 /2 bands near the Fermi surface due to the significant distortion of Ir O6 octahedra. This work sheds light on the critical role of a noncubic crystalline field in electronic properties which has been ignored in past studies of 5 d -electron systems.

Stabilizing nanostructured solid oxide fuel cell cathode with atomic layer deposition.

PubMed

Gong, Yunhui; Palacio, Diego; Song, Xueyan; Patel, Rajankumar L; Liang, Xinhua; Zhao, Xuan; Goodenough, John B; Huang, Kevin

2013-09-11

We demonstrate that the highly active but unstable nanostructured intermediate-temperature solid oxide fuel cell cathode, La0.6Sr0.4CoO3-δ (LSCo), can retain its high oxygen reduction reaction (ORR) activity with exceptional stability for 4000 h at 700 °C by overcoating its surfaces with a conformal layer of nanoscale ZrO2 films through atomic layer deposition (ALD). The benefits from the presence of the nanoscale ALD-ZrO2 overcoats are remarkable: a factor of 19 and 18 reduction in polarization area-specific resistance and degradation rate over the pristine sample, respectively. The unique multifunctionality of the ALD-derived nanoscaled ZrO2 overcoats, that is, possessing porosity for O2 access to LSCo, conducting both electrons and oxide-ions, confining thermal growth of LSCo nanoparticles, and suppressing surface Sr-segregation is deemed the key enabler for the observed stable and active nanostructured cathode.

Thermoluminescence (TL) of europium-doped ZrO2 obtained by sol-gel method

NASA Astrophysics Data System (ADS)

Rivera, T.; Furetta, C.; Azorín, J.; Barrera, M.; Soto, A. M.

This article reports the preparation and characterization of europium-doped zirconium oxide (ZrO2:Eu3+) formed by homogeneous precipitation from propoxyde of zirconium [Zr(OC3H7)4]. The alkoxide sol gel process is an efficient method to prepare the zirconium oxide matrix by the hydrolysis of alkoxide precursors followed by condensation to yield a polymeric oxo-bridged ZrO2 network. All compounds were characterized by thermal analysis and the X-ray diffractometry method. The thermoluminescence (TL) emission properties of ZrO2:Eu3+ under beta radiation effects are studied. The europium-doped sintered zirconia powder presents a TL glow curve with two peaks (Tmax) centered at around 204 and around 292 °C, respectively. TL response of ZrO2:Eu3+ as a function of beta-absorbed dose was linear from 2 Gy up to 90 Gy. The europium ion (Eu3+)-doped ZrO2 was found to be more sensitive to beta radiation than undoped ZrO2 obtained by the same method and presented a little fading of the TL signal compared with undoped zirconium oxide.

Growth of an Ultrathin Zirconia Film on Pt3Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory.

PubMed

Li, Hao; Choi, Joong-Il Jake; Mayr-Schmölzer, Wernfried; Weilach, Christian; Rameshan, Christoph; Mittendorfer, Florian; Redinger, Josef; Schmid, Michael; Rupprechter, Günther

2015-02-05

Ultrathin (∼3 Å) zirconium oxide films were grown on a single-crystalline Pt 3 Zr(0001) substrate by oxidation in 1 × 10 -7 mbar of O 2 at 673 K, followed by annealing at temperatures up to 1023 K. The ZrO 2 films are intended to serve as model supports for reforming catalysts and fuel cell anodes. The atomic and electronic structure and composition of the ZrO 2 films were determined by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HR-XPS) (including depth profiling), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. Oxidation mainly leads to ultrathin trilayer (O-Zr-O) films on the alloy; only a small area fraction (10-15%) is covered by ZrO 2 clusters (thickness ∼0.5-10 nm). The amount of clusters decreases with increasing annealing temperature. Temperature-programmed desorption (TPD) of CO was utilized to confirm complete coverage of the Pt 3 Zr substrate by ZrO 2 , that is, formation of a closed oxide overlayer. Experiments and DFT calculations show that the core level shifts of Zr in the trilayer ZrO 2 films are between those of metallic Zr and thick (bulklike) ZrO 2 . Therefore, the assignment of such XPS core level shifts to substoichiometric ZrO x is not necessarily correct, because these XPS signals may equally well arise from ultrathin ZrO 2 films or metal/ZrO 2 interfaces. Furthermore, our results indicate that the common approach of calculating core level shifts by DFT including final-state effects should be taken with care for thicker insulating films, clusters, and bulk insulators.

New rare earth hafnium oxynitride perovskites with photocatalytic activity in water oxidation and reduction.

PubMed

Black, Ashley P; Suzuki, Hajime; Higashi, Masanobu; Frontera, Carlos; Ritter, Clemens; De, Chandan; Sundaresan, A; Abe, Ryu; Fuertes, Amparo

2018-02-06

RHfO 2 N perovskites with R = La, Nd and Sm show a GdFeO 3 -type structure and are semiconductors with band gaps of 3.35, 3.40 and 2.85 eV and relative dielectric constants of 30, 16 and 28 respectively. These compounds have adequate reduction and oxidation potentials to conduct the overall water splitting reaction, and the analogous perovskite LaZrO 2 N with a band gap of 2.8 eV shows photocatalytic activity under visible light irradiation for O 2 evolution.

Frequency dependent dielectric properties of combustion synthesized Dy2Ti2O7 pyrochlore oxide

NASA Astrophysics Data System (ADS)

Jeyasingh, T.; Saji, S. K.; Kavitha, V. T.; Wariar, P. R. S.

2018-05-01

Nanocrystalline pyrochlore material Dysprosium Titanate (Dy2Ti2O7) has been synthesized through a single step optimized combustion route. The phase purity and phase formation of the combustion product has been characterized using X-Ray diffraction analysis (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR) analysis. X-Ray diffraction analysis (XRD) reveal that Dy2Ti2O7 is highly crystalline in nature with cubic structure in the Fd3m space group. The microstructures and average particle size of the prepared nanopowder were examined by High Resolution Transmission Electron Microscopy (HR-TEM). The optical band gap of the Dy2Ti2O7 nanoparticles is determined from the absorption spectrum, was attributed to direct allowed transitions through optical band gap of 3.98 eV. The frequency dependent dielectric measurements have been carried out on the sintered pellet in the frequency range 1 Hz-10 MHz. The measured value of dielectric constant (ℇ') was ˜ 43 and loss tangent (tan δ) was 4×10-3 at 1 MHz, at room temperature.

Synthesis and structural studies on cerium substituted La0.4Ca0.6MnO3 as solid oxide fuel cell electrode material

NASA Astrophysics Data System (ADS)

Singh, Monika; Kumar, Dinesh; Singh, Akhilesh Kumar

2018-04-01

For solid oxide fuel cell electrode material, calcium doped lanthanum manganite La0.4Ca0.6MnO3 (LCMO) and cerium-incorporated on Ca-site with composition La0.40Ca0.55Ce0.05MnO3 (LCCMO) were synthesized using most feasible and efficient glycine-nitrate method. The formation of crystalline single phase was confirmed by x-ray diffraction (XRD). The Rietveld analysis reveals that both systems crystallize into orthorhombic crystal structure with Pnma space group. Additionally, 8 mole % Y2O3 stabilized ZrO2 (8YSZ) solid electrolyte was also synthesized using high energy ball mill to check the reaction with electrode materials. It was found that the substitution of Ce+4 cations in LCMO perovskite suppressed formation of undesired insulating CaZrO3 phase.

Effect of CMAS composition on hot corrosion behavior of gadolinium zirconate thermal barrier coating materials

DOE PAGES

Deng, Wenzhuo; Fergus, Jeffrey W.

2017-07-06

The resistance of synthesized pyrochlore-type Gd 2Zr 2O 7 bulk specimens to four calcium-magnesium aluminosilicate (CMAS) compositions at different temperatures was investigated. The reaction products were identified by x-ray diffraction and penetration depths were examined using scanning electron microscopy. A dense reaction layer is comprised mainly of Ca 2Gd 8(SiO 4) 6O 2 and a cubic fluorite phase formed during the CMAS attack, and some unreacted CMAS was found in a transition layer below the reaction layer. The overall infiltration depth changed slightly with temperature, however, the thickness of the reaction layer and the morphology of the transition layer variedmore » distinctly with temperature. The sintered sample underwent the most severe degradation by the CaO-lean CMAS, whereas the effect of CaSO 4 and CaCO 3 was not significant. Furthermore, the Gd content of the ZrO 2-based cubic fluorite phase depends on the temperature and the molar ratio of Ca:Si in the CMAS.« less

Formation and reduction behaviors of zirconium oxide compounds in LiCl-Li2O melt at 923 K

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Iizuka, Masatoshi; Kitawaki, Shinichi; Nakayoshi, Akira; Kofuji, Hirohide

2015-11-01

The reduction behaviors of ZrO2, Li2ZrO3 and (U,Pu,Zr)O2 in a LiCl-Li2O salt bath at 923 K were investigated. This study was conducted as part of a feasibility study on the pyrochemical treatment of damaged fuel debris generated by severe accidents at light water reactors. It was demonstrated in electrolytic reduction tests that the uranium in synthetic corium specimens of (U,Pu,Zr)O2 with various ZrO2 contents could be reduced to the metallic form and that part of the zirconium was converted to Li2ZrO3. Zirconium metal and Li2ZrO3 were obtained by the reduction of ZrO2. The reduction of Li2ZrO3 did not proceed even in LiCl containing no Li2O. Moreover, the stable chemical forms of the ZrO2-Li2O complex oxide were investigated as a function of the Li2O concentration in LiCl. ZrO2 was converted to Li2ZrO3 at a Li2O concentration of 0.018 wt%. As the Li2O concentration was increased, Li2ZrO3 was converted to Li6Zr2O7 and then to Li8ZrO6. It is suggested that the removal of Li2ZrO3 from the reduction product is a key point in the pyrochemical treatment of corium.

Multilayer Thermal Barrier Coating (TBC) Architectures Utilizing Rare Earth Doped YSZ and Rare Earth Pyrochlores

NASA Technical Reports Server (NTRS)

Schmitt, Michael P.; Rai, Amarendra K.; Bhattacharya, Rabi; Zhu, Dongming; Wolfe, Douglas E.

2014-01-01

To allow for increased gas turbine efficiencies, new insulating thermal barrier coatings (TBCs) must be developed to protect the underlying metallic components from higher operating temperatures. This work focused on using rare earth doped (Yb and Gd) yttria stabilized zirconia (t' Low-k) and Gd2Zr2O7 pyrochlores (GZO) combined with novel nanolayered and thick layered microstructures to enable operation beyond the 1200 C stability limit of current 7 wt% yttria stabilized zirconia (7YSZ) coatings. It was observed that the layered system can reduce the thermal conductivity by approximately 45 percent with respect to YSZ after 20 hr of testing at 1316 C. The erosion rate of GZO is shown to be an order to magnitude higher than YSZ and t' Low-k, but this can be reduced by almost 57 percent when utilizing a nanolayered structure. Lastly, the thermal instability of the layered system is investigated and thought is given to optimization of layer thickness.

Intermixing and thermal oxidation of ZrO2 thin films grown on a-Si, SiN, and SiO2 by metallic and oxidic mode magnetron sputtering

NASA Astrophysics Data System (ADS)

Coloma Ribera, R.; van de Kruijs, R. W. E.; Sturm, J. M.; Yakshin, A. E.; Bijkerk, F.

2017-03-01

The initial growth of DC sputtered ZrO2 on top of a-Si, SiN, and SiO2 layers has been studied by in vacuo high-sensitivity low energy ion scattering for two gas deposition conditions with different oxygen contents (high-O and low-O conditions). This unique surface sensitive technique allowed the determination of surface composition and thicknesses required to close the ZrO2 layer on all three substrates for both conditions. The ZrO2 layer closes similarly on all substrates due to more favorable enthalpies of formation for ZrO2 and ZrSiO4, resulting in passivation of the Si from the substrate. However, this layer closes at about half of the thickness (˜1.7 nm) for low-O conditions due to less oxidative conditions and less energetic particles arriving at the sample, which leads to less intermixing via silicate formation. In contrast, for high-O conditions, there is more ZrSiO4 and/or SiOx formation, giving more intermixing (˜3.4 nm). In vacuo X-ray photoelectron spectroscopy (XPS) measurements revealed similar stoichiometric ZrO2 layers deposited by both conditions and a higher interaction of the ZrO2 layer with the underlying a-Si for high-O conditions. In addition, oxygen diffusion through low-O ZrO2 films on a-Si has been investigated by ex situ angular-resolved XPS of samples annealed in atmospheric oxygen. For temperatures below 400 °C, no additional oxidation of the underlying a-Si was observed. This, together with the amorphous nature and smoothness of these samples, makes ZrO2 a good candidate as an oxidation protective layer on top of a-Si.

Elastic modulus and internal friction of SOFC electrolytes at high temperatures under controlled atmospheres

NASA Astrophysics Data System (ADS)

Kushi, Takuto; Sato, Kazuhisa; Unemoto, Atsushi; Hashimoto, Shinichi; Amezawa, Koji; Kawada, Tatsuya

2011-10-01

Mechanical properties such as Young's modulus, shear modulus, Poisson's ratio and internal friction of conventional electrolyte materials for solid oxide fuel cells, Zr0.85Y0.15 O1.93 (YSZ), Zr0.82Sc0.18O1.91 (ScSZ), Zr0.81Sc0.18Ce0.01O2-δ (ScCeSZ), Ce0.9Gd0.1O2-δ (GDC), La0.8Sr0.2Ga0.8Mg0.15Co0.05O3-δ (LSGMC), La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM), were evaluated by a resonance method at temperatures from room temperature to 1273 K in various oxygen partial pressures. The Young's modulus of GDC gradually decreased with increasing temperature in oxidizing conditions. The Young's moduli of the series of zirconia and lanthanum gallate based materials drastically decreased in an intermediate temperature range and increased slightly with increasing temperature at higher temperatures. The Young's modulus of GDC considerably decreased above 823 K in reducing atmospheres in response to the change of oxygen nonstoichiometry. However, temperature dependences of the Young's moduli of ScCeSZ and LSGMC in reducing atmospheres did not show any significant differences with those in oxidizing atmospheres.

George E. Valley, Jr. Prize Talk: Quantum Frustrated Magnetism and its Expression in the Ground State Selection of Pyrochlore Magnets

NASA Astrophysics Data System (ADS)

Ross, Kate

In the search for novel quantum states of matter, such as highly entangled Quantum Spin Liquids, ``geometrically frustrated'' magnetic lattices are essential for suppressing conventional magnetic order. In three dimensions, the pyrochlore lattice is the canonical frustrated geometry. Magnetic materials with pyrochlore structures have the potential to realize unusual phases such as ``quantum spin ice'', which is predicted to host emergent magnetic monopoles, electrons, and photons as its fundamental excitations. Even in pyrochlores that form long range ordered phases, this often occurs through unusual routes such as ``order by disorder'', in which the fluctuation spectrum dictates the preferred ordered state. The rare earth-based pyrochlore series R2Ti2O7 provides a fascinating variety of magnetic ground states. I will introduce the general anisotropic interaction Hamiltonian that has been successfully used to describe several materials in this series. Using inelastic neutron scattering, the relevant anisotropic interaction strengths can be extracted quantitatively. I will discuss this approach, and its application to two rare earth pyrochlore materials, Er2Ti2O7 and Yb2Ti<2O7, whose ground state properties have long been enigmatic. From these studies, ErTi2O7 and Yb2Ti2O7 have been suggested to be realizations of "quantum order by disorder" and "quantum spin ice", respectively. This research was supported by NSERC of Canada and the National Science Foundation.

Preparation and characterization of mesoporous ZnO-ZrO2 doped by Cr, Nd and Dy as a catalyst for conversion of coumarin using ultrasensitive fluorometric method

NASA Astrophysics Data System (ADS)

Ibrahim, M. M.

2017-04-01

Doping of mesoporous ZnO-ZrO2 nanoparticles with transition metal and lanthanides (Cr, Nd, Dy) were used as a catalyst to develop an ultrasensitive fluorometric method for the conversion of non fluorescent coumarin to highly fluorescent 7-hydroxycoumarin using H2O2 or light. It was found that doped- ZnO-ZrO2 mixed oxide can catalyze the decomposition of H2O2 to produce •OH radicals, which in turn convert coumarin to 7-hydroxycoumarin. At contrast, the doping has deleterious effect on conversion of coumarin by light due to high band gap and high concentrations of doping increase the recombination rate of electron and holes. Doped mixed oxides prepared by impregnation method and characterized by studying their structural, surface and optical properties. Chromium doped ZnO-ZrO2 had the highest rate of formation of hydroxyl radical due to decomposition of H2O2 and therefore 7-hydroxycoumarin due to surface area, small crystal size and high redox potential.

Structural and electrical properties of Pb(Zr ,Ti)O3 grown on (0001) GaN using a double PbTiO3/PbO bridge layer

NASA Astrophysics Data System (ADS)

Xiao, Bo; Gu, Xing; Izyumskaya, Natalia; Avrutin, Vitaliy; Xie, Jinqiao; Liu, Huiyong; Morkoç, Hadis

2007-10-01

Pb(Zr0.52Ti0.48)O3 films were deposited by rf magnetron sputtering on silicon-doped GaN(0001)/c-sapphire with a PbTiO3/PbO oxide bridge layer grown by molecular beam epitaxy. X-ray diffraction data showed the highly (111)-oriented perovskite phase in lead zirconate titanate (PZT) films with PbTiO3/PbO bridge layers, compared to the pyrochlore phase grown directly on GaN. The in-plane epitaxial relationships were found from x-ray pole figures to be PZT[112¯]‖GaN[11¯00] and PZT[11¯0]‖GaN[112¯0]. The polarization-electric field measurements revealed the ferroelectric behavior with remanent polarization of 30-40μC /cm2 and asymmetric hysteresis loops due to the depletion layer formed in GaN under reverse bias which resulted in a high negative coercive electric field (950kV/cm).

Efficient removal of arsenite through photocatalytic oxidation and adsorption by ZrO2-Fe3O4 magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Sun, Tianyi; Zhao, Zhiwei; Liang, Zhijie; Liu, Jie; Shi, Wenxin; Cui, Fuyi

2017-09-01

Bifunctional ZrO2-Fe3O4 magnetic nanoparticles were synthesized and characterized, to remove As(III) through photocatalyic oxidation and adsorption. With a saturation magnetization of 27.39 emu/g, ZrO2-Fe3O4 nanoparticles with size of 10-30 nm could be easily separated from solutions with a simple magnetic process. Under UV light, As(III) could be completely oxidized to less toxic As(V) by ZrO2-Fe3O4 nanoparticles within 40 min in the photocatalytic reaction. Simultaneously, As(V) could be adsorbed onto the surface of nanoparticles with high efficiency. The adsorption of As(V) was well fitted by the pseudo-second-order model and the Freundlich isotherm model, respectively, and the maximum adsorption capacities of the nanoparticles was 133.48 mg/g at pH 7.0. As(III) could be effectively removed by ZrO2-Fe3O4 nanoparticles at initial pH range from 4 to 8. Among all the common coexisting ions investigated, except for chloride and sulfate, carbonate, silicate and phosphate decreased the As(III) removal by competing with arsenic species for adsorption sites. The synthesized magnetic ZrO2-Fe3O4 combined the photocatalytic oxidation property of ZrO2 and the high adsorption capacity of both ZrO2 and Fe3O4, which make it have significant potential applications in the As(III)-contaminated water treatment.

Epitaxial thin films of pyrochlore iridate Bi 2+xIr 2-yO 7-δ: structure, defects and transport properties

DOE PAGES

Yang, W. C.; Xie, Y. T.; Zhu, W. K.; ...

2017-08-10

While pyrochlore iridate thin films are theoretically predicted to possess a variety of emergent topological properties, experimental verification of these predictions can be obstructed by the challenge in thin film growth. We report on the pulsed laser deposition and characterization of thin films of a representative pyrochlore compound Bi 2Ir 2O 7. Moreover, the films were epitaxially grown on yttria-stabilized zirconia substrates and have lattice constants that are a few percent larger than that of the bulk single crystals. The film composition shows a strong dependence on the oxygen partial pressure. Density-functional-theory calculations indicate the existence of BiIr antisite defects,more » qualitatively consistent with the high Bi: Ir ratio found in the films. Both Ir and Bi have oxidation states that are lower than their nominal values, suggesting the existence of oxygen deficiency. The iridate thin films show a variety of intriguing transport characteristics, including multiple charge carriers, logarithmic dependence of resistance on temperature, antilocalization corrections to conductance due to spin-orbit interactions, and linear positive magnetoresistance.« less

Epitaxial thin films of pyrochlore iridate Bi 2+xIr 2-yO 7-δ: structure, defects and transport properties

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

Yang, W. C.; Xie, Y. T.; Zhu, W. K.

While pyrochlore iridate thin films are theoretically predicted to possess a variety of emergent topological properties, experimental verification of these predictions can be obstructed by the challenge in thin film growth. We report on the pulsed laser deposition and characterization of thin films of a representative pyrochlore compound Bi 2Ir 2O 7. Moreover, the films were epitaxially grown on yttria-stabilized zirconia substrates and have lattice constants that are a few percent larger than that of the bulk single crystals. The film composition shows a strong dependence on the oxygen partial pressure. Density-functional-theory calculations indicate the existence of BiIr antisite defects,more » qualitatively consistent with the high Bi: Ir ratio found in the films. Both Ir and Bi have oxidation states that are lower than their nominal values, suggesting the existence of oxygen deficiency. The iridate thin films show a variety of intriguing transport characteristics, including multiple charge carriers, logarithmic dependence of resistance on temperature, antilocalization corrections to conductance due to spin-orbit interactions, and linear positive magnetoresistance.« less

Chemical expansion affected oxygen vacancy stability in different oxide structures from first principles calculations

DOE PAGES

Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; ...

2015-01-21

We study the chemical expansion for neutral and charged oxygen vacancies in fluorite, rocksalt, perovskite and pyrochlores materials using first principles calculations. We show that the neutral oxygen vacancy leads to lattice expansion whereas the charged vacancy leads to lattice contraction. In addition, we show that there is a window of strain within which an oxygen vacancy is stable; beyond that range, the vacancy can become unstable. Using CeO 2|ZrO 2 interface structure as an example, we show that the concentration of oxygen vacancies can be manipulated via strain, and the vacancies can be preferentially stabilized. Furthermore, these results couldmore » serve as guiding principles in predicting oxygen vacancy stability in strained systems and in the design of vacancy stabilized materials.« less

Relief of frustration in the Heisenberg pyrochlore antiferromagnet Gd2Pt2O7

NASA Astrophysics Data System (ADS)

Hallas, A. M.; Sharma, A. Z.; Cai, Y.; Munsie, T. J.; Wilson, M. N.; Tachibana, M.; Wiebe, C. R.; Luke, G. M.

2016-10-01

The gadolinium pyrochlores Gd2B2O7 are among the best realizations of antiferromagnetically coupled Heisenberg spins on a pyrochlore lattice. We present a magnetic characterization of Gd2Pt2O7 , a unique member of this family. Magnetic susceptibility, heat capacity, and muon spin relaxation measurements show that Gd2Pt2O7 undergoes an antiferromagnetic ordering transition at TN=1.6 K. This transition is strongly first order, as indicated by the sharpness of the heat capacity anomaly, thermal hysteresis in the magnetic susceptibility, and a nondivergent relaxation rate in μ SR . The form of the heat capacity below TN suggests that the ground state is an anisotropic collinear antiferromagnet with an excitation spectrum that is gapped by 0.245(1) meV. The ordering temperature in Gd2Pt2O7,TN=1.6 K, is a substantial 160% increase from other gadolinium pyrochlores, which are all known to order at 1 K or lower. We attribute this enhancement in TN to the B -site cation, platinum. Despite being nonmagnetic, platinum has a filled 5 d t2 g orbital and an empty 5 d eg orbital that can facilitate superexchange. Thus, the magnetic frustration in Gd2Pt2O7 is partially "relieved," thereby promoting magnetic order.

Microstructure and dielectric properties of pyrochlore Bi2Ti2O7 thin films

NASA Astrophysics Data System (ADS)

Cagnon, Joël; Boesch, Damien S.; Finstrom, Nicholas H.; Nergiz, Saide Z.; Keane, Sean P.; Stemmer, Susanne

2007-08-01

Bi2Ti2O7 thin films were grown by radio-frequency magnetron sputtering on bare and Pt-coated sapphire substrates at low substrate temperatures (˜200 °C). Postdeposition anneals were carried out at different temperatures to crystallize the films. Nearly phase-pure Bi2Ti2O7 thin films with the cubic pyrochlore structure were obtained at annealing temperatures up to 800 °C. Impurity phases, in particular Bi4Ti3O12, formed at higher temperatures. At 1 MHz, the dielectric constants were about 140-150 with a very small tunability and the dielectric loss was about 4×10-3. The dielectric loss increased with frequency. The dielectric properties of Bi2Ti2O7 films are compared to those of pyrochlore bismuth zinc niobate films.

Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

NASA Technical Reports Server (NTRS)

Klettlinger, Jennifer Lindsey Suder

2012-01-01

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the active site density; on the other hand, by increasing the size of the cobalt clusters, there is less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the extent of reduction while increasing the particle size slightly may be beneficial for maintaining the sites, even if there is a slight decrease in overall initial active site density.

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

New insights on ion track morphology in pyrochlores by aberration corrected scanning transmission electron microscopy

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

Sachan, Ritesh; Zhang, Yanwen; Ou, Xin

Here we demonstrate the enhanced imaging capabilities of an aberration corrected scanning transmission electron microscope to advance the understanding of ion track structure in pyrochlore structured materials (i.e., Gd 2Ti 2O 7 and Gd 2TiZrO 7). Track formation occurs due to the inelastic transfer of energy from incident ions to electrons, and atomic-level details of track morphology as a function of energy-loss are revealed in the present work. A comparison of imaging details obtained by varying collection angles of detectors is discussed in the present work. A quantitative analysis of phase identification using high-angle annular dark field imaging is performedmore » on the ion tracks. Finally, a novel 3-dimensional track reconstruction method is provided that is based on depth dependent imaging of the ion tracks. The technique is used in extracting the atomic-level details of nanoscale features, such as the disordered ion tracks, which are embedded in relatively thicker matrix. Another relevance of the method is shown by measuring the tilt of the ion tracks relative to the electron beam incidence that helps in knowing the structure and geometry of ion tracks quantitatively.« less

New insights on ion track morphology in pyrochlores by aberration corrected scanning transmission electron microscopy

DOE PAGES

Sachan, Ritesh; Zhang, Yanwen; Ou, Xin; ...

2016-12-13

Here we demonstrate the enhanced imaging capabilities of an aberration corrected scanning transmission electron microscope to advance the understanding of ion track structure in pyrochlore structured materials (i.e., Gd 2Ti 2O 7 and Gd 2TiZrO 7). Track formation occurs due to the inelastic transfer of energy from incident ions to electrons, and atomic-level details of track morphology as a function of energy-loss are revealed in the present work. A comparison of imaging details obtained by varying collection angles of detectors is discussed in the present work. A quantitative analysis of phase identification using high-angle annular dark field imaging is performedmore » on the ion tracks. Finally, a novel 3-dimensional track reconstruction method is provided that is based on depth dependent imaging of the ion tracks. The technique is used in extracting the atomic-level details of nanoscale features, such as the disordered ion tracks, which are embedded in relatively thicker matrix. Another relevance of the method is shown by measuring the tilt of the ion tracks relative to the electron beam incidence that helps in knowing the structure and geometry of ion tracks quantitatively.« less

Evidence for percolation diffusion of cations and reordering in disordered pyrochlore from accelerated molecular dynamics

DOE PAGES

Perriot, Romain; Uberuaga, Blas P.; Zamora, Richard J.; ...

2017-09-20

Diffusion in complex oxides is critical to ionic transport, radiation damage evolution, sintering, and aging. In complex oxides such as pyrochlores, anionic diffusion is dramatically affected by cation disorder. However, little is known about how disorder influences cation transport. Here, we report results from classical and accelerated molecular dynamics simulations of vacancy-mediated cation diffusion in Gd 2Ti 2O 7 pyrochlore, on the microsecond timescale. We find that diffusion is slow at low levels of disorder, while higher disorder allows for fast diffusion, which is then accompanied by antisite annihilation and reordering, and thus a slowing of cation transport. Cation diffusivitymore » is therefore not constant, but decreases as the material reorders. We also show that fast cation diffusion is triggered by the formation of a percolation network of antisites. This is in contrast with observations from other complex oxides and disordered media models, suggesting a fundamentally different relation between disorder and mass transport.« less

Hot corrosion behavior of YSZ, Gd2Zr2O7 and YSZ/Gd2Zr2O7 thermal barrier coatings exposed to molten sulfate and vanadate salt

NASA Astrophysics Data System (ADS)

Ozgurluk, Yasin; Doleker, Kadir Mert; Karaoglanli, Abdullah Cahit

2018-04-01

Thermal barrier coatings (TBCs) are mostly used in critical components of aircraft gas turbine engines. Hot corrosion is among the main deteriorating factors in TBCs which results from the effect of molten salt on the coating-gas interface. This type of corrosion is observed as a result of contamination accumulated during combustion processes. Fuels used in aviation industry generally contain impurities such as vanadium oxide (V2O5) and sodium sulfate (Na2SO4). These impurities damage turbines' inlet at elevated temperatures because of chemical reaction. Yttria stabilized zirconia (YSZ) is a conventional top coating material for TBCs while Gd2Zr2O7 is a new promising top coating material for TBCs. In this study, CoNiCrAlY metallic bond coat was deposited on Inconel 718 nickel based superalloy substrate material with a thickness about 100 μm using cold gas dynamic spray (CGDS) method. Production of TBCs were done with deposition of YSZ, Gd2Zr2O7, YSZ/Gd2Zr2O7 ceramic top coating materials using EB-PVD method, having a total thickness of 300 μm. Hot corrosion behavior of YSZ, Gd2Zr2O7, YSZ/Gd2Zr2O7 TBC systems were exposed to 45 wt.% Na2SO4 and 55 wt.% V2O5 molten salt mixtures at 1000 °C temperature. TBC samples were investigated and compared using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) analysis and X-ray diffractometer (XRD). The hot corrosion failure mechanisms of YSZ, Gd2Zr2O7 and YSZ/Gd2Zr2O7 TBCs in the molten salts were evaluated.

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La).

PubMed

Solomon, Jonathan M; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

2016-12-12

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho 2 Zr 2 O 7 . In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE 2 Th 2 O 7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

NASA Astrophysics Data System (ADS)

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

2016-12-01

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho2Zr2O7. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE2Th2O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

DOE PAGES

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh; ...

2017-07-27

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge to produce hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y 2Ru 2O 7-δ) electrocatalyst that has significantly enhanced performance toward OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1 M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y 2Ru 2O 7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band centermore » energy for the overlap between Ru 4d and O 2p orbitals and is therefore more stable Ru–O bond than RuO 2, highlighting the effect of yttrium on the enhancement in stability. Finally, the Y 2Ru 2O 7-δ pyrochlore is also free of expensive iridium metal and thus is a cost-effective candidate for practical applications.« less

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

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

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap betweenmore » Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.« less

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

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

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge to produce hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y 2Ru 2O 7-δ) electrocatalyst that has significantly enhanced performance toward OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1 M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y 2Ru 2O 7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band centermore » energy for the overlap between Ru 4d and O 2p orbitals and is therefore more stable Ru–O bond than RuO 2, highlighting the effect of yttrium on the enhancement in stability. Finally, the Y 2Ru 2O 7-δ pyrochlore is also free of expensive iridium metal and thus is a cost-effective candidate for practical applications.« less

Oxygen miscibility gap and spin glass formation in the pyrochlore Lu{sub 2}Mo{sub 2}O{sub 7}

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

Clark, L.; Ritter, C.; Harrison, A.

2013-07-15

Rare earth (R) molybdate pyrochlores, R{sub 2}Mo{sub 2}O{sub 7}, are of interest as frustrated magnets. Polycrystalline samples of Lu{sub 2}Mo{sub 2}O{sub 7−x} prepared at 1600 °C display a coexistence of cubic pyrochlore phases. Rietveld fits to powder neutron diffraction data and chemical analyses show that the miscibility gap is between a stoichiometric x=0 and an oxygen-deficient x≈0.4 phase. Lu{sub 2}Mo{sub 2}O{sub 7} behaves as a spin glass material, with a divergence of field cooled and zero field cooled DC magnetic susceptibilities at a spin freezing temperature T{sub f}=16 K, that varies with frequency in AC measurements following a Vogel–Fulcher law.more » Lu{sub 2}Mo{sub 2}O{sub 6.6} is more highly frustrated spin glass and has T{sub f}=20 K. - Graphical abstract: The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system exhibits a miscibility gap between coexisting pyrochlore phases at 1600 °C. Neutron powder diffraction refinement and chemical analysis shows that the gap separates stoichiometric x=0 and oxygen-deficient x≈0.4 phases. Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content. - Highlights: • The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system has a miscibility gap between coexisting pyrochlore phases at 1600 °C. • Neutron powder diffraction shows that the gap separates x=0 and oxygen-deficient x≈0.4 phases. • Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content.« less

Crystal Structure of Garnet-Related Li-Ion Conductor Li7–3xGaxLa3Zr2O12: Fast Li-Ion Conduction Caused by a Different Cubic Modification?

PubMed Central

2016-01-01

Li-oxide garnets such as Li7La3Zr2O12 (LLZO) are among the most promising candidates for solid-state electrolytes to be used in next-generation Li-ion batteries. The garnet-structured cubic modification of LLZO, showing space group Ia-3d, has to be stabilized with supervalent cations. LLZO stabilized with Ga3+ shows superior properties compared to LLZO stabilized with similar cations; however, the reason for this behavior is still unknown. In this study, a comprehensive structural characterization of Ga-stabilized LLZO is performed by means of single-crystal X-ray diffraction. Coarse-grained samples with crystal sizes of several hundred micrometers are obtained by solid-state reaction. Single-crystal X-ray diffraction results show that Li7–3xGaxLa3Zr2O12 with x > 0.07 crystallizes in the acentric cubic space group I-43d. This is the first definite record of this cubic modification for LLZO materials and might explain the superior electrochemical performance of Ga-stabilized LLZO compared to its Al-stabilized counterpart. The phase transition seems to be caused by the site preference of Ga3+. 7Li NMR spectroscopy indicates an additional Li-ion diffusion process for LLZO with space group I-43d compared to space group Ia-3d. Despite all efforts undertaken to reveal structure–property relationships for this class of materials, this study highlights the potential for new discoveries. PMID:27019548

Effects of sintering temperature on the pyrochlore phase in PZT nanotubes and their transformation to the perovskite phase by coating with PbO multilayers.

PubMed

Han, Jin Kyu; Choi, Yong Chan; Jeon, Do Hyen; Lee, Min Ku; Bu, Sang Don

2014-11-01

We report the phase evolution of Pb(Zr0.52Ti0.48)O3 nanotubes (PZT-NTs), from the pyrochlore to perovskite phase, with an outer diameter of about 420 nm and a wall thickness of about 10 nm. The PZT-NTs were fabricated in pores of porous anodic alumina membrane (PAM) using a spin coating of PZT sol-gel solution and subsequent annealing at 500-700 degrees C in oxygen gas. The pyrochlore phase was found to be formed at 500 degrees C, and also found not to be transformed into the perovskite phase, even though annealing was performed at higher temperatures to 700 degrees C. Elementary distribution analysis of PZT-NTs embedded in PAM reveal that Pb diffusion from nanotubes into pore walls of PAM is one of the main reasons. By employing firstly an additional PbO coating on the pyrochlore nanotubes and then subsequent annealing at 700 degrees C, we have successfully achieved an almost pure perovskite phase in nanotubes. These results suggest that PbO acts as a Pb-compensation agent in the Pb- deficient PZT-NTs. Moreover, our method can be used in the synthesis of all metal-oxide materials, including volatile elements.

Processing of La(1.8)Sr(0.2)CuO4 and YBa2Cu3O7 superconducting thin films by dual-ion-beam sputtering

NASA Astrophysics Data System (ADS)

Madakson, P.; Cuomo, J. J.; Yee, D. S.; Roy, R. A.; Scilla, G.

1988-03-01

High-quality La(1.8)Sr(0.2)CuO4 and YBa2Cu3O7 superconducting thin films, with zero resistance at 88 K, have been made by dual-ion-beam sputtering of metal and oxide targets at elevated temperatures. The films are about 1.0 micron thick and are single phase after annealing. The substrates investigated are Nd-YAP, MgO, SrF2, Si, CaF2, ZrO2-(9 pct)Y2O3, BaF2, Al2O3, and SrTiO3. Characterization of the films was carried out using Rutherford backscattering spectroscopy, resistivity measurements, TEM, X-ray diffraction, and SIMS. Substrate/film interaction was observed in every case. This generally involves diffusion of the substrate into the film, which is accompanied by, for example, the replacement of Ba by Sr in the YBa2Cu2O7 structure, in the case of SrTiO3 substrate. The best substrates were those that did not significantly diffuse into the film and which did not react chemically with the film.

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

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

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

DOE PAGES

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

2016-08-26

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

Adsorption of Anionic, Cationic and Nonionic Surfactants on Carbonate Rock in Presence of ZrO 2 Nanoparticles

NASA Astrophysics Data System (ADS)

Esmaeilzadeh, Pouriya; Bahramian, Alireza; Fakhroueian, Zahra

The adsorption of surfactants at the solid-water interface is important for the control of wetting, lubrication, detergency and in mineral flotation.We have studied the adsorptions of different types of surfactants, cationic (Dodecyl trimethylammonium bromide, DTAB), anionic (sodium dodecyl sulfate, SDS) and non-anionic (lauryl alcohol-7 mole ethoxylate, LA7) on carbonate rock in presence of zirconium oxide spherical nanoparticles (17-19 nm). ZrO2 nanoparticles with tetrahedral structure have significant effect on adsorption of surfactants on the carbonate rock. We have used the measured conductivities to determine the rate of adsorption of surfactants at rock-water interfaces. The conductivity of DTAB in aqueous solutions containing calcite powder decreases more than the other surfactants in contact with ZrO2 nanoparticles. We have also investigated the adsorption of surfactants at the air-water interface. The presence of nanoparticles, as demonstrated by our experiments, enhances the surface activity and surface adsorption of the surfactants through electrostatic forces or formation of nanostructures. Dynamic light structuring data shows similar aggregation number of nanoparticles in presence of nanoparticles.

High conducting oxide--sulfide composite lithium superionic conductor

DOEpatents

Liang, Chengdu; Rangasamy, Ezhiylmurugan; Dudney, Nancy J.; Keum, Jong Kahk; Rondinone, Adam Justin

2017-01-17

A solid electrolyte for a lithium-sulfur battery includes particles of a lithium ion conducting oxide composition embedded within a lithium ion conducting sulfide composition. The lithium ion conducting oxide composition can be Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO). The lithium ion conducting sulfide composition can be .beta.-Li.sub.3PS.sub.4 (LPS). A lithium ion battery and a method of making a solid electrolyte for a lithium ion battery are also disclosed.

Preparation of Zr(Mo,W)2O8 with a larger negative thermal expansion by controlling the thermal decomposition of Zr(Mo,W)2(OH,Cl)2∙2H2O.

PubMed

Petrushina, Mariya Yu; Dedova, Elena S; Filatov, Eugeny Yu; Plyusnin, Pavel E; Korenev, Sergei V; Kulkov, Sergei N; Derevyannikova, Elizaveta A; Sharafutdinov, Marat R; Gubanov, Alexander I

2018-03-28

Solid solutions of Zr(Mo,W) 2 O 7 (OH,Cl) 2 ∙2H 2 O with a preset ratio of components were prepared by a hydrothermal method. The chemical composition of the solutions was determined by energy dispersive X-ray spectroscopy (EDX). For all the samples of ZrMo x W 2-x O 7 (OH,Cl) 2 ∙2H 2 O (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, and 2.0), TGA and in situ powder X-ray diffraction (PXRD) studies (300-1100 K) were conducted. For each case, the boundaries of the transformations were determined: Zr(Mo,W) 2 O 7 (OH,Cl) 2 ∙2H 2 O → orthorhombic-ZrMo x W 2-x O 8 (425-525 K), orthorhombic-ZrMo x W 2-x O 8  → cubic-ZrMo x W 2-x O 8 (700-850 K), cubic-ZrMo x W 2-x O 8  → trigonal-ZrMo x W 2-x O 8 (800-1050 K for x > 1) and cubic-ZrMo x W 2-x O 8  → oxides (1000-1075 K for x ≤ 1). The cell parameters of the disordered cubic-ZrMo x W 2-x O 8 (space group Pa-3) were measured within 300-900 K, and the thermal expansion coefficients were calculated: -3.5∙10 -6  - -4.5∙10 -6  K -1 . For the ordered ZrMo 1.8 W 0.2 O 8 (space group P2 1 3), a negative thermal expansion (NTE) coefficient -9.6∙10 -6  K -1 (300-400 K) was calculated. Orthorhombic-ZrW2O 8 is formed upon the decomposition of ZrW 2 O 7 (OH,Cl) 2 ∙2H 2 O within 500-800 K.

In situ electrochemical synthesis of highly loaded zirconium nanoparticles decorated reduced graphene oxide for the selective determination of dopamine and paracetamol in presence of ascorbic acid.

PubMed

Ezhil Vilian, A T; Rajkumar, Muniyandi; Chen, Shen-Ming

2014-03-01

Highly loaded zirconium oxide (ZrO2) nanoparticles were supported on graphene oxide (ERGO/ZrO2) via an in situ, simple and clean strategy on the basis of the electrochemical redox reaction between zirconyl chloride and graphene oxide (ZrOCl2 and GO). The electrochemical measurements and surface morphology of the as prepared nanocomposite were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and field emission scanning electron microscopy (FESEM). This ZrO2 decorated reduced graphene oxide nanocomposite modified GCE (ERGO/ZrO2) exhibits a prominent electrocatalytic activity toward the selective detection and determination of dopamine (DA) and paracetamol (PA) in presence of ascorbic acid (AA). The peaks of linear sweep voltammetry (LSV) for DA and PA oxidation at ERGO/ZrO2 modified electrode surface were clearly separated from each other when they co-existed in the physiological pH (pH 7.0) with a potential value of 140 mV (between AA and DA) and 330 mV (between AA and PA). It was, therefore, possible to simultaneously determine DA and PA in the samples at ERGO/ZrO2 nanocomposite modified GCE. Linear calibration curves were obtained for 9-237 μM of PA and DA. The ERGO/ZrO2 nanocomposite electrode has been satisfactorily used for the determination of DA and PA in the presence of AA at pharmaceutical formulations in human urine samples with a linear range of 3-174 μM. The proposed biosensor shows a wide linear range, low detection limit, good reproducibility and acceptable stability, providing a biocompatible platform for bio sensing and bio catalysis. Copyright © 2013 Elsevier B.V. All rights reserved.

Investigation of the Structural Stability of Ion-Implanted Gd 2Ti 2-xSn xO 7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy

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

Aluri, Esther Rani; Hayes, John R.; Walker, James D.S.

2016-03-24

Rare-earth titanate and stannate pyrochlore-type oxides have been investigated in the past for the sequestration of nuclear waste elements because of their resistance to radiation-induced structural damage. In order to enhance this property, it is necessary to understand the effect of radioactive decay of the incorporated actinide elements on the local chemical environment. In this study, Gd 2Ti 2–xSn xO 7 materials have been implanted with Au– ions to simulate radiation-induced structural damage. Glancing angle X-ray absorption near-edge spectroscopy (GA-XANES), glancing angle X-ray absorption fine structure (GA-EXAFS) analysis, and powder X-ray diffraction have been used to investigate changes in themore » local coordination environment of the metal atoms in the damaged surface layer. Examination of GA-XANES/EXAFS spectra from the implanted Gd 2Ti 2–xSn xO 7 materials collected at various glancing angles allowed for an investigation of how the local coordination environment around the absorbing atoms changed at different depths in the damaged surface layer. This study has shown the usefulness of GA-XANES to the examination of ion-implanted materials and has suggested that Gd 2Ti 2–xSn xO 7 becomes more susceptible to ion-beam-induced structural damage with increasing Sn concentration.« less

[Preliminary study on DNA damage of ZrO(2)/LaPO(4) diphase ceramics on human peripheral blood lymphocytes in vitro].

PubMed

Zhu, Hui-fang; Chen, Li-ping; Zhang, Xiu-li; Zhang, Bao-wei

2009-06-01

To detect the genotoxicity of dental machinable ZrO(2)/LaPO(4) diphase ceramics on human peripheral blood lymphocytes in vitro. The evaluation of DNA damage on human lymphocytes was performed by comet assay for three groups of ZrO(2)/LaPO(4) diphase ceramics with 30wt% of LaPO(4) (with 3wt% and 5wt% of Y(2)O(3)) and 40wt% of LaPO(4) (with 5wt% of Y(2)O(3)). The results were analyzed with SPSS16.0 software package for one-factor ANOVA and LSD. Three experimental groups with different concentration of LaPO(4) of ZrO(2)/LaPO(4) diphase ceramics, the negative control of IPS Empress II ceramics and the blank behaved little migration of the DNA strands respectively after six-day test, and there was no significant difference in all the groups except the positive control (P>0.05). The study indicates little effect of DNA damage of ZrO(2)/LaPO(4) diphase ceramics.

A room temperature process for the fabrication of amorphous indium gallium zinc oxide thin-film transistors with co-sputtered Zr x Si1- x O2 Gate dielectric and improved electrical and hysteresis performance

NASA Astrophysics Data System (ADS)

Hung, Chien-Hsiung; Wang, Shui-Jinn; Liu, Pang-Yi; Wu, Chien-Hung; Wu, Nai-Sheng; Yan, Hao-Ping; Lin, Tseng-Hsing

2017-04-01

The use of co-sputtered zirconium silicon oxide (Zr x Si1- x O2) gate dielectrics to improve the gate controllability of amorphous indium gallium zinc oxide (α-IGZO) thin-film transistors (TFTs) through a room-temperature fabrication process is proposed and demonstrated. With the sputtering power of the SiO2 target in the range of 0-150 W and with that of the ZrO2 target kept at 100 W, a dielectric constant ranging from approximately 28.1 to 7.8 is obtained. The poly-structure formation immunity of the Zr x Si1- x O2 dielectrics, reduction of the interface trap density suppression, and gate leakage current are examined. Our experimental results reveal that the Zr0.85Si0.15O2 gate dielectric can lead to significantly improved TFT subthreshold swing performance (103 mV/dec) and field effect mobility (33.76 cm2 V-1 s-1).

Similar local order in disordered fluorite and aperiodic pyrochlore structures

DOE PAGES

Shamblin, Jacob; Tracy, Cameron; Palomares, Raul; ...

2017-10-01

A major challenge to understanding the response of materials to extreme environments (e.g., nuclear fuels/waste forms and fusion materials) is to unravel the processes by which a material can incorporate atomic-scale disorder, and at the same time, remain crystalline. While it has long been known that all condensed matter, even liquids and glasses, possess short-range order, the relation between fully-ordered, disordered, and aperiodic structures over multiple length scales is not well understood. For example, when defects are introduced (via pressure or irradiation) into materials adopting the pyrochlore structure, these complex oxides either disorder over specific crystallographic sites, remaining crystalline, ormore » become aperiodic. Here we present neutron total scattering results characterizing the irradiation response of two pyrochlores, one that is known to disorder (Er2Sn2O7) and the other to amorphize (Dy2Sn2O7) under ion irradiation. The results demonstrate that in both cases, the local pyrochlore structure is transformed into similar short range configurations that are best fit by the orthorhombic weberite structure, even though the two compositions have distinctly different structures, aperiodic vs. disordered-crystalline, at longer length scales. Thus, a material's resistance to amorphization may not depend primarily on local defect formation energies, but rather on the structure's compatibility with meso-scale modulations of the local order in a way that maintains long-range periodicity.« less

Antiferroquadrupolar correlations in the quantum spin ice candidate Pr2Zr2O7

NASA Astrophysics Data System (ADS)

Petit, S.; Lhotel, E.; Guitteny, S.; Florea, O.; Robert, J.; Bonville, P.; Mirebeau, I.; Ollivier, J.; Mutka, H.; Ressouche, E.; Decorse, C.; Ciomaga Hatnean, M.; Balakrishnan, G.

2016-10-01

We present an experimental study of the quantum spin ice candidate pyrochlore compound Pr2Zr2O7 by means of magnetization measurements, specific heat, and neutron scattering up to 12 T and down to 60 mK. When the field is applied along the [111 ] and [1 1 ¯0 ] directions, k =0 field-induced structures settle in. We find that the ordered moment rises slowly, even at very low temperature, in agreement with macroscopic magnetization. Interestingly, for H ∥[1 1 ¯0 ] , the ordered moment appears on the so-called α chains only. The spin excitation spectrum is essentially inelastic and consists in a broad flat mode centered at about 0.4 meV with a magnetic structure factor which resembles the spin ice pattern. For H ∥[1 1 ¯0 ] (at least up to 2.5 T), we find that a well-defined mode forms from this broad response, whose energy increases with H , in the same way as the temperature of the specific-heat anomaly. We finally discuss these results in the light of mean field calculations and propose an interpretation where quadrupolar interactions play a major role, overcoming the magnetic exchange. In this picture, the spin ice pattern appears shifted up to finite energy because of those interactions. We then propose a range of acceptable parameters for Pr2Zr2O7 that allow to reproduce several experimental features observed under field. With these parameters, the actual ground state of this material would be an antiferroquadrupolar liquid with spin-ice-like excitations.

Oxidative coupling of methane over supported La{sub 2}O{sub 3} and La-promoted MgO catalysts: Influence of catalyst-support interactions

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

Choudhary, V.R.; Mulla, S.A.R.; Uphade, B.S.

1997-06-01

Methane-to-C{sub 2}-hydrocarbon conversion activity and selectivity (or yield) of MgO and La-promoted MgO catalysts in the oxidative coupling of methane and strong basicity of the catalysts are decreased appreciably when these catalysts are deposited on commonly used commercial low surface area porous catalyst carriers containing Al{sub 2}O{sub 3}, SiO{sub 2}, SiC, or ZrO{sub 2} + HfO{sub 2} as the main components. The decrease in the strong basicity and catalytic activity/selectivity or yield is mostly due to strong chemical interactions between the active catalyst component (viz., MgO and La{sub 2}O{sub 3}) and the reactive components of the catalyst support (viz., Al{submore » 2}O{sub 3} and SiO{sub 2}), resulting in the formation of catalytically inactive binary metal oxides on the support surface. However, the influence of support on the activity/selectivity of La{sub 2}O{sub 3} is relatively very small, and also the chemical interactions of La{sub 2}O{sub 3} with the supports (except that containing a high concentration of SiO{sub 2}) are almost absent. The catalyst-support interactions are thus found to be strongly dependent upon the nature (chemical composition) of both catalyst and support. For developing better supported catalysts for the oxidative coupling of methane, supported La{sub 2}O{sub 3} with some promoters shows high promise.« less

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

Pyrochlore-rich titanate ceramics for the immobilization of plutonium: redox effects on phase equilibria in cerium- and thorium- substituted analogs

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

Ryerson, F J; Ebbinghaus, B

2000-05-25

Three compositions representing plutonium-free analogs of a proposed Ca-Ti-Gd-Hf-U-PU oxide ceramic for the immobilization of plutonium were equilibrated at 1 atm, 1350 C over a range of oxygen fugacities between air and that equivalent to the iron-wuestite buffer. The cerium analog replaces Pu on a mole-per-mole basic with Ce; the thorium analog replaces Pu with Th. A third material has 10 wt% Al{sub 2}O{sub 3} added to the cerium analog to encourage the formation of a Hf-analog of, CaHfTi{sub 2}O{sub 7}, zirconolite, which is referred to as hafnolite. The predominant phase produced in each formulation under all conditions is pyrochlore,more » A{sub 2}T{sub 2}O{sub 7}, where the T site is filled by Ti, and Ca, the lanthanides, Hf, U and Pu are accommodated on the A-site. Other lanthanide and uranium-bearing phases encountered include brannerite (UTi{sub 2}O{sub 6}), hafnolite (CaHfTi{sub 2}O{sub 7}), perovskite (CaTiO{sub 3}) and a calcium-lanthanide aluminotitanate with nominal stoichiometry (Ca,Ln)Ti{sub 2}Al{sub 9}O{sub 19}, where Ln is a lanthanide. The phase compositions show progressive shifts with decreasing oxygen fugacity. All of the phases observed have previously been identified in titanate-based high-level radioactive waste ceramics and demonstrate the flexibility of these ceramics to variations in processing parameters. The main variation is an increase in the uranium concentrations of pyrochlore and brannerite which must be accommodated by variations in modal abundance. Pyrochlore compositions are consistent with existing spectroscopic data suggesting that uranium is predominantly pentavalent in samples synthesized in air. A simple model based on ideal stoichiometry suggests the U{sup +4}/{Sigma}U varies linearly with log fO{sub 2} and that all of the uranium is quadravalent at the iron-wuestite buffer.« less

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.

Mixed conductivity, structural and microstructural characterization of titania-doped yttria tetragonal zirconia polycrystalline/titania-doped yttria stabilized zirconia composite anode matrices

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

Colomer, M.T., E-mail: tcolomer@icv.csic.e; Maczka, M.

2011-02-15

Taking advantage of the fact that TiO{sub 2} additions to 8YSZ cause not only the formation of a titania-doped YSZ solid solution but also a titania-doped YTZP solid solution, composite materials based on both solutions were prepared by solid state reaction. In particular, additions of 15 mol% of TiO{sub 2} give rise to composite materials constituted by 0.51 mol fraction titania-doped yttria tetragonal zirconia polycrystalline and 0.49 mol fraction titania-doped yttria stabilized zirconia (0.51TiYTZP/0.49TiYSZ). Furthermore, Y{sub 2}(Ti{sub 1-y}Zr{sub y}){sub 2}O{sub 7} pyrochlore is present as an impurity phase with y close to 1, according to FT-Raman results. Lower and highermore » additions of titania than that of 15 mol%, i.e., x=0, 5, 10, 20, 25 and 30 mol% were considered to study the evolution of 8YSZ phase as a function of the TiO{sub 2} content. Furthermore, zirconium titanate phase (ZrTiO{sub 4}) is detected when the titania content is equal or higher than 20 mol% and this phase admits Y{sub 2}O{sub 3} in solid solution according to FE-SEM-EDX. The 0.51TiYTZP/0.49TiYSZ duplex material was selected in this study to establish the mechanism of its electronic conduction under low oxygen partial pressures. In the pO{sub 2} range from 0.21 to 10{sup -7.5} atm. the conductivity is predominantly ionic and constant over the range and its value is 0.01 S/cm. The ionic plus electronic conductivity is 0.02 S/cm at 1000 {sup o}C and 10{sup -12.3} atm. Furthermore, the onset of electronic conductivity under reducing conditions exhibits a -1/4 pO{sub 2} dependence. Therefore, it is concluded that the n-type electronic conduction in the duplex material can be due to a small polaron-hopping between Ti{sup 3+} and Ti{sup 4+}. -- Graphical abstract: FE-SEM micrograph of a polished and thermal etched surface of a Ti-doped YTZP/Ti-doped YSZ composite material. Display Omitted Research highlights: {yields} Ti-doped YTZP/Ti-doped YSZ composite materials are mixed conductors under low partial pressures. {yields} From 5 mol% of TiO{sub 2}, Y{sub 2}(Ti{sub 1-y},Zr{sub y}){sub 2}O{sub 7} pyrochlore is present as a minor phase, being y close to 1 according to FT-Raman studies. {yields} The onset of the electronic conductivity under reducing conditions exhibit a -1/4 pO{sub 2} dependence. The n-type electronic conduction is due to a small polaron-hopping between Ti{sup 3+} and Ti{sup 4+}.« less

Modifications of structural and physical properties induced by swift heavy ions in Gd2Ti2O7 and Y2Ti2O7 pyrochlores

NASA Astrophysics Data System (ADS)

Sellami, N.; Sattonnay, G.; Grygiel, C.; Monnet, I.; Debelle, A.; Legros, C.; Menut, D.; Miro, S.; Simon, P.; Bechade, J. L.; Thomé, L.

2015-12-01

The structural transformations induced by ionization processes in Gd2Ti2O7 and Y2Ti2O7 pyrochlores irradiated with swift heavy ions have been studied using XRD and Raman experiments. Results show that irradiation induces amorphization and that the phase transformation build-up can be accounted for in the framework of a model involving a single-impact mechanism. The radiation induced amorphization build-up is faster in Gd2Ti2O7 than in Y2Ti2O7. Moreover, a decrease of the thermal conductivity (measured by the laser flash method) is induced by irradiation both in Gd2Ti2O7 and Y2Ti2O7.

Experimental Insights into Ground-State Selection of Quantum XY Pyrochlores

NASA Astrophysics Data System (ADS)

Hallas, Alannah M.; Gaudet, Jonathan; Gaulin, Bruce D.

2018-03-01

Extensive experimental investigations of the magnetic structures and excitations in the XY pyrochlores have been carried out over the past decade. Three families of XY pyrochlores have emerged: Yb2B2O7, Er2B2O7, and, most recently, [Formula: see text]Co2F7. In each case, the magnetic cation (either Yb, Er, or Co) exhibits XY anisotropy within the local pyrochlore coordinates, a consequence of crystal field effects. Materials in these families display rich phase behavior and are candidates for exotic ground states, such as quantum spin ice, and exotic ground-state selection via order-by-disorder mechanisms. In this review, we present an experimental summary of the ground-state properties of the XY pyrochlores, including evidence that they are strongly influenced by phase competition. We empirically demonstrate the signatures for phase competition in a frustrated magnet: multiple heat capacity anomalies, suppressed TN or TC, sample- and pressure-dependent ground states, and unconventional spin dynamics.

High-pressure synthesis and characterizations of the R2Pt2O7 pyrochlores.

NASA Astrophysics Data System (ADS)

Cai, Yunqi; Cui, Qi; Cheng, Jinguang; Dun, Zhiling; Zhou, Haidong; Ma, Jie; Cruz, C. Dela; Yan, Jiaqiang; Li, Xiang; Zhou, Jianshi

Pyrochlore R2B2O7 where R3 + stands for rear-earth ion and B4 + for a nonmagnetic cation such as Sn4 +or Ti4 +consist of an important family of geometrically frustrated magnets, which have been the focus of extensive investigations over last decades. To further enlarge the R2B2O7, we have chosen to stabilize the Pt-based cubic pyrochlores under HPHT conditions for two reasons: (1) Pt4 + is in a low-spin state which ionic radius is located in between Ti4 + (0.605\\x85) and Sn4 + (0.69\\x85), and (2) Pt4 + has a spatially much more extended 5d orbitals and thus enhanced Pt 5d-O 2p hybridizations that might modify the local anisotropic exchange interactions. Such an effect has never been taken into account in the previous studies. In this work, we will present the detailed characterizations on the pyrochlores R2Pt2O7 obtained under HPHT conditions. This work is supported by the National Science Foundation of China (Grant Nos.11304371, 11574377), part of the work was supported by the CEM, and NSF MRSEC, under Grant DMR-1420451, and Grant No. NSF-DMR-1350002.

Stoichiometry determination of (Pb,La)(Zr,Ti)O3-type nano-crystalline ferroelectric ceramics by wavelength-dispersive X-ray fluorescence spectrometry.

PubMed

Sitko, Rafał; Zawisza, Beata; Kita, Andrzej; Płońska, Małgorzata

2006-07-01

Analysis of small samples of lanthanum-doped lead zirconate titanate (PLZT) by wavelength-dispersive X-ray fluorescence spectrometry (WDXRF) is presented. The powdered material in ca. 30 mg was suspended in water and collected on the membrane filter. The pure oxide standards (PbO, La2O3, ZrO2 and TiO2) were used for calibration. The matrix effects were corrected using a theoretical influence coefficients algorithm for intermediate-thickness specimens. The results from XRF method were compared with the results from the inductively coupled plasma optical emission spectrometry (ICP-OES). Agreement between XRF and ICP-OES analysis was satisfactory and indicates the usefulness of XRF method for stoichiometry determination of PLZT.

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho 2Zr 2O 7 and RE 2Th 2O 7 (RE=Ho, Y, Gd, Nd, La)

DOE PAGES

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; ...

2016-12-12

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho 2Zr 2O 7. In a recentmore » neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE 2Th 2O 7'' fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. Finally, the results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.« less

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

PubMed Central

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

2016-01-01

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho2Zr2O7. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE2Th2O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination. PMID:27941870

Batievaite-(Y), Y2Ca2Ti[Si2O7]2(OH)2(H2O)4, a new mineral from nepheline syenite pegmatite in the Sakharjok massif, Kola Peninsula, Russia

NASA Astrophysics Data System (ADS)

Lyalina, L. M.; Zolotarev, A. A.; Selivanova, E. A.; Savchenko, Ye. E.; Krivovichev, S. V.; Mikhailova, Yu. A.; Kadyrova, G. I.; Zozulya, D. R.

2016-12-01

Batievaite-(Y), Y2Ca2Ti[Si2O7]2(OH)2(H2O)4, is a new mineral found in nepheline syenite pegmatite in the Sakharjok alkaline massif, Western Keivy, Kola Peninsula, Russia. The pegmatite mainly consists of nepheline, albite, alkali pyroxenes, amphiboles, biotite and zeolites. Batievaite-(Y) is a late-pegmatitic or hydrothermal mineral associated with meliphanite, fluorite, calcite, zircon, britholite-group minerals, leucophanite, gadolinite-subgroup minerals, titanite, smectites, pyrochlore-group minerals, zirkelite, cerianite-(Ce), rutile, behoite, ilmenite, apatite-group minerals, mimetite, molybdenite, and nickeline. Batievaite-(Y) is pale-cream coloured with white streak and dull, greasy or pearly luster. Its Mohs hardness is 5-5.5. No cleavage or parting was observed. The measured density is 3.45(5) g/cm3. Batievaite-(Y) is optically biaxial positive, α 1.745(5), β 1.747(5), γ 1.752(5) (λ 589 nm), 2 V meas. = 60(5)°, 2 V calc. = 65°. Batievaite-(Y) is triclinic, space group P-1, a 9.4024(8), b 5.5623(5), c 7.3784(6) Å, α 89.919(2), β 101.408(2), γ 96.621(2)°, V 375.65(6) Å3 and Z = 1. The eight strongest lines of the X-ray powder diffraction pattern [ d(Å)(I)( hkl)] are: 2.991(100)(11-2), 7.238(36)(00-1), 3.061(30)(300), 4.350(23)(0-1-1), 9.145(17)(100), 4.042(16)(11-1), 2.819(16)(3-10), 3.745(13)(2-10). The chemical composition determined by electron probe microanalysis (EPMA) is (wt.%): Nb2O5 2.25, TiO2 8.01, ZrO2 2.72, SiO2 29.96, Al2O3 0.56, Fe2O3 0.43, Y2O3 11.45, La2O3 0.22, Ce2O3 0.33, Nd2O3 0.02, Gd2O3 0.07, Dy2O3 0.47, Er2O3 1.07, Tm2O3 0.25, Yb2O3 2.81, Lu2O3 0.45, CaO 24.98, MnO 1.31, MgO 0.01, Na2O 1.13, K2O 0.02, F 2.88, Cl 0.19, H2O 6.75 (determined on the basis of crystal structure data), O = (F,Cl) -1.25, total 97.09 wt.%. The empirical formula based on the EPMA and single-crystal structure analyses is (Y0.81Ca0.65Mn0.15Zr0.12Yb0.11Er0.04Fe3+ 0.04Ce0.02Dy0.02Lu0.02La0.01Tm0.01)Σ2.00((H2O)0.75Ca0.70□0.55)Σ2.00Ca2.00(□0.61Na0.25( H2O)0.14)Σ1.00(Ti0.76Nb0.15Zr0.09)Σ1.00[(Si3.91Al0.09)Σ4.00O14]((OH)1.56F0.44)Σ2.00((H2O)1.27F0.73)Σ2.00. The infrared spectrum of the mineral contains the following bands (cm-1): 483, 584, 649, 800, 877, 985, 1630, 1646, 1732, 3426. Batievaite-(Y) belongs to the rosenbuschite group minerals and is the Na-deficient Y-analogue of hainite. The mineral is named in honour of the Russian geologist Iya Dmitrievna Batieva (1922-2007) in recognition of her remarkable contribution into the geology and petrology of metamorphic and alkaline complexes of the Kola Peninsula.

High modulus invert analog glass compositions containing beryllia

NASA Technical Reports Server (NTRS)

Bacon, J. F. (Inventor)

1974-01-01

Glass compositions having a Young's modulus of at least 15 million psi and a specific modulus of at least 110 million inches consisting essentially of, in mols, 10-45% SiO2, 2-15% Li2O, 3-34% BeO, 12-36% of at least one bivalent oxide selected from the group consisting of CaO, ZnO, MgO and CuO, 10-39% of at least one trivalent oxide selected from the group consisting of Al2O3, B2O3, La2O3, Y2O3 and the mixed rare earth oxides, the total number of said bivalent and trivalent oxides being at least three, and up to 10% of a tetravalent oxide selected from the group consisting of ZrO2, TiO2 and CeO2.

Effect of chemical pressure on the crystal electric field states of erbium pyrochlore magnets

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

Gaudet, J; Hallas, A. A.; Kolesnikov, Alexander I.

We have carried out a systematic study of the crystal electric field excitations in the family of cubic pyrochlores Er 2B 2O 7 with B=Ge, Ti, Pt, and Sn, using neutron spectroscopy. All members of this family are magnetic insulators based on 4f 11Er 3+ and nonmagnetic B 4+. At sufficiently low temperatures, long-range antiferromagnetic order is observed in each of these Er 2B 2O 7 pyrochlores. The different ionic sizes associated with different nonmagnetic B 4+ cations correspond to positive or negative chemical pressure, depending on the relative contraction or expansion of the crystal lattice, which gives rise tomore » different local environments at the Er 3+ site. Our results show that the g-tensor components are XY-like for all four members of the Er 2B 2O 7 series. However, the XY anisotropy is much stronger for Er 2Pt 2O 7 and Er 2Sn 2O 7(g⊥/gz>25) than for Er 2Ge 2O 7 and Er 2Ti 2O 7(g⊥/gz<4). The variation in the nature of the XY anisotropy in these systems correlates strongly with their ground states as Er 2Ge 2O 7 and Er 2Ti 2O 7 order into Γ 5 magnetic structures, whereas Er 2Pt 2O 7 and Er 2Sn 2O 7 order in the Γ 7 Palmer-Chalker structure.« less

Effect of chemical pressure on the crystal electric field states of erbium pyrochlore magnets

NASA Astrophysics Data System (ADS)

Gaudet, J.; Hallas, A. M.; Kolesnikov, A. I.; Gaulin, B. D.

2018-01-01

We have carried out a systematic study of the crystal electric field excitations in the family of cubic pyrochlores Er2B2O7 with B =Ge , Ti, Pt, and Sn, using neutron spectroscopy. All members of this family are magnetic insulators based on 4 f11Er3 + and nonmagnetic B4 +. At sufficiently low temperatures, long-range antiferromagnetic order is observed in each of these Er2B2O7 pyrochlores. The different ionic sizes associated with different nonmagnetic B4 + cations correspond to positive or negative chemical pressure, depending on the relative contraction or expansion of the crystal lattice, which gives rise to different local environments at the Er3 + site. Our results show that the g -tensor components are X Y -like for all four members of the Er2B2O7 series. However, the X Y anisotropy is much stronger for Er2Pt2O7 and Er2Sn2O7(g⊥/gz>25 ) than for Er2Ge2O7 and Er2Ti2O7(g⊥/gz<4 ) . The variation in the nature of the X Y anisotropy in these systems correlates strongly with their ground states as Er2Ge2O7 and Er2Ti2O7 order into Γ5 magnetic structures, whereas Er2Pt2O7 and Er2Sn2O7 order in the Γ7 Palmer-Chalker structure.

Effect of chemical pressure on the crystal electric field states of erbium pyrochlore magnets

DOE PAGES

Gaudet, J; Hallas, A. A.; Kolesnikov, Alexander I.; ...

2018-01-17

We have carried out a systematic study of the crystal electric field excitations in the family of cubic pyrochlores Er 2B 2O 7 with B=Ge, Ti, Pt, and Sn, using neutron spectroscopy. All members of this family are magnetic insulators based on 4f 11Er 3+ and nonmagnetic B 4+. At sufficiently low temperatures, long-range antiferromagnetic order is observed in each of these Er 2B 2O 7 pyrochlores. The different ionic sizes associated with different nonmagnetic B 4+ cations correspond to positive or negative chemical pressure, depending on the relative contraction or expansion of the crystal lattice, which gives rise tomore » different local environments at the Er 3+ site. Our results show that the g-tensor components are XY-like for all four members of the Er 2B 2O 7 series. However, the XY anisotropy is much stronger for Er 2Pt 2O 7 and Er 2Sn 2O 7(g⊥/gz>25) than for Er 2Ge 2O 7 and Er 2Ti 2O 7(g⊥/gz<4). The variation in the nature of the XY anisotropy in these systems correlates strongly with their ground states as Er 2Ge 2O 7 and Er 2Ti 2O 7 order into Γ 5 magnetic structures, whereas Er 2Pt 2O 7 and Er 2Sn 2O 7 order in the Γ 7 Palmer-Chalker structure.« less

Pyrochlore structure and spectroscopic studies of titanate ceramics. A comparative investigation on SmDyTi2O7 and YDyTi2O7 solid solutions

NASA Astrophysics Data System (ADS)

Garbout, A.; Férid, M.

2018-06-01

Considering the features in changing the structure and properties of rare earth titanates pyrochlores, the substituted Dy2Ti2O7 may be very attractive for various applications. Effect of Sm and Y substitution on the structural properties of Dy2Ti2O7 ceramic was established. These ceramics were prepared by solid-state reaction and characterized by X-ray diffraction and Raman spectroscopy. Both analysis show that YDyTi2O7 with the pyrochlore structure is obtained after heating at 1400 °C, but SmDyTi2O7 has already formed after sintering at 1200 °C. SEM images revealed that the average grain size was increased with the increase of heating temperature, and an un-homogeneous grain growth was detected. The average size was about 37 nm and 135 nm for the SmDyTi2O7 and YDyTi2O7 particles, respectively. Structural Rietveld refinements indicate that all prepared ceramics crystallize in cubic structure with space group of Fd3m. The refined cell parameters demonstrate an almost linear correlation with the ionic radius of Ln3+. The vibrational spectra revealed that the positions of bands are sensitive to the Ln3+-ionic radius, and the Tisbnd O bond strength decreased linearly with the increase of cubic lattice parameter. Raman spectra indicate that the wavenumber of Osbnd Tisbnd O bending mode is considerably shifted to lower region with increasing in mass of the Ln atom. This paper provides solid foundations for additional research of these solid solutions, which are very attractive for different fields as promising catalytic compounds for combustion applications or as frustrated magnetic pyrochlore ceramics.

Growth of self-textured Ga3+-substituted Li7La3Zr2O12 ceramics by solid state reaction and their significant enhancement in ionic conductivity

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming'en; Hu, Zhiwei; Zhu, Jiliang

2018-03-01

A highly self-textured Ga2O3-substituted Li7La3Zr2O12 (LLZO-Ga) solid electrolyte with a nominal composition of Li6.55Ga0.15La3Zr2O12 is obtained by a simple and low-cost solid-state reaction technique, requiring no seed crystals to achieve grain orientation. The as-prepared self-textured LLZO-Ga shows a strong (420) preferred orientation with a high Lotgering factor of 0.91. Coherently, a terrace-shaped microstructure consisting of many parallel layers, indicating a two-dimensional-like growth mode, is clearly observed in the self-textured sample. As a result, the highly self-textured garnet-type lithium-ion conducting solid electrolyte of LLZO-Ga exhibits an extremely high ionic conductivity, reaching a state-of-the-art level of 2.06 × 10-3 S cm-1 at room temperature (25 °C) and thus shedding light on an important strategy for improving the structure and ionic conductivity of solid electrolytes.

A-site deficient La0.2Sr0.7TiO3-δ anode material for proton conducting ethane fuel cell to cogenerate ethylene and electricity

NASA Astrophysics Data System (ADS)

Liu, Subiao; Behnamian, Yashar; Chuang, Karl T.; Liu, Qingxia; Luo, Jing-Li

2015-12-01

A site deficient La0.2Sr0.7TiO3-δ (LSTA) and a highly proton conductive electrolyte BaCe0.7Zr0.1Y0.2O3-δ (BCZY) are synthesized by using solid state reaction method. The performance of the electrolyte-supported single cell, comprised of LSTA + Cr2O3 + Cu//BCZY//(La0.60Sr0.40)0.95Co0.20Fe0.80O3-δ (LSCF)+BCZY, is fabricated and investigated. LSTA shows remarkably high electrical performance, with a conductivity as high as 27.78 Scm-1 at 1150 °C in a 10% H2/N2 reducing atmosphere. As a main anode component, it shows good catalytic activity towards the oxidation of ethane, causing the power density to considerably increase from 158.4 mW cm-2 to 320.9 mW cm-2 and the ethane conversion to significantly rise from 12.6% to 30.9%, when the temperature increases from 650 °C to 750 °C. These changes agree well with the polarization resistance which dramatically decreases from 0.346 Ωcm2 to 0.112 Ωcm2. EDX measurement shows that no element diffusion exists (chemical compatibility) between anode (LSTA + Cr2O3+Cu) and electrolyte (BCZY). With these properties, the pure phase LSTA is evaluated as a high electro-catalytic activity anode material for ethane proton conducting solid oxide fuel cell (PC-SOFC).

Pulsed laser deposition of {CeO_2} and {Ce_{1-x}M_xO_2} (M = La, Zr): Application to insulating barrier in cuprate heterostructures

NASA Astrophysics Data System (ADS)

Berger, S.; Contour, J.-P.; Drouet, M.; Durand, O.; Khodan, A.; Michel, D.; Régi, F.-X.

1998-03-01

SrTiO_3 had been often tentatively used as an insulating barrier for HT superconductor/insulator heterostructures. Unfortunately, the deposition of SrTiO_3 on the YBa_2Cu_3O_7 inverse interface results in a poor epitaxial regrowth producing a high roughness dislocated titanate layer. Taking into account the good matching with YBa_2Cu_3O_7 and LaAlO_3, CeO_2 and Ce_{1-x}M_xO_2 (M = La, Zr), epitaxial layers were grown by pulsed laser deposition on LaAlO_3 substrates and introduced into YBa_2Cu_3O_7 based heterostructures as insulating barrier. After adjusting the growth parameters from RHEED oscillations, epitaxial growth is achieved, the oxide crystal axes being rotated by 45^circ from those of the substrate. The surface roughness of 250 nm thick films is very low with a rms value lower than 0.5 nm over 1;μ m^2. The YBa_2Cu_3O_7 layers of a YBa_2Cu_3O_7/CeO_2 /YBa_2Cu_3O_7 heterostructures grown using these optimized parameters show an independent resistive transition, when the thickness is larger than 25 nm, respectively at T_c_1 = 89.6;K and T_c_2 = 91.4;{K}. SrTiO3 est souvent utilisé comme barrière isolante dans des hétérostructures SIS de cuprates supraconducteurs, cependant les défauts générés lors de la croissance de ce titanate sur l'interface inverse de YBa2Cu3O7 conduisent à un matériau dont la qualité cristalline et les propriétés physiques sont médiocres. L'oxyde de cérium CeO2 est également une barrière isolante potentielle intéressante pour ces structures SIS basées sur YBa2Cu3O7 car cet oxyde cubique (a = 0,5411 nm, asqrt{2}/2 = 0,3825 nm) qui est peu désaccordé par rapport au plan ab du cuprate (Δ a/a = - 0,18 %, Δ b/a = 1,6 %) présente de plus un coefficient de dilatation thermique (10,6 × 10^{-6 circ}C^{-1}) très voisin de celui de YBa2Cu3O7 (13 × 10^{-6 circ}C^{-1}). Nous avons donc étudié l'épitaxie de CeO2 et des oxydes de type Ce{1-x}MxO2 (M = La, Zr) en ablation laser pulsée afin de définir des conditions de croissance optimisées pour la réalisation de barrières isolantes ultra-minces à faible rugosité d'interface. L'interface de croissance a été caractérisée par analyse en diffraction d'électrons rapides en incidence rasante (RHEED) en temps réel et par analyse ex-situ en microscopie par force atomique (AFM) et diffraction de rayons X (DRX). Lorsque les paramètres de la croissance (T, p_O_2, fréquence du laser, distance cible-substrat...) sont optimisés par observation des oscillations d'intensité de RHEED, les films sont épitaxiés à 45^{circ} des axes du substrat. La rugosité rms d'un film de 250 nm d'épaisseur déterminée par AFM sur 1 μ m^2 est alors inférieure à 0,5 nm, c'est-à-dire de l'ordre de la hauteur d'une maille élémentaire. Ces conditions optimisées ont été utilisées pour la réalisation d'hétérostructures YBa2Cu3O7/CeO2/YBa2Cu3O7, lorsque l'épaisseur est supérieure à 25 nm, les couches élémentaires de YBa2Cu3O7 présentent des transitions résistive indépendantes respectivement à T_c_1 = 89,6 K et T_c_2 = 91,4 K.

Photoemission properties of Eu-doped Zr1- x Ce x O2 (x = 0-0.2) nanoparticles prepared by hydrothermal method

NASA Astrophysics Data System (ADS)

Ozawa, Masakuni; Matsumoto, Masashi; Hattori, Masatomo

2018-01-01

Photoluminescent Eu-doped ZrO2 and Zr1- x Ce x O2 (x = 0-0.2) nanoparticles were prepared by a hydrothermal method. X-ray diffraction and Raman spectra indicated the formation of tetragonal crystals of ZrO2 and its solid solutions with a grain size of less than 10 nm diameter after heat treatment at 400 °C. The photoemission spectra of Zr1- x Ce x O2:Eu3+ nanocrystalline samples showed the typical emission of Eu3+ ions assigned to 5D0 → 7F1 (590 nm) and 5D0 → 7F2 (610 nm) transitions and additional emissions of 5D0 → 7F J with higher J of 3-5. Increasing the CeO2 concentration reduced the emission intensity, and the emission peak shift was affected by a local lattice distortion, i.e., CeO2 concentration. The present study provided fundamental knowledge that is expected to enable the fabrication of ZrO2-based nanocrystal phosphor materials and a measure for controlling the emission peak shift and intensity in oxide fluorite-based phosphor.

Doped ZrO2 for future lead free piezoelectric devices

NASA Astrophysics Data System (ADS)

Starschich, S.; Böttger, U.

2018-01-01

The ferroelectric and piezoelectric properties of doped ZrO2 prepared by chemical solution deposition (CSD) are investigated. Doping with different elements such as Mg, In, La, and Y leads to a stabilization of the constricted hysteresis. As shown in a previous work, for the constricted hysteresis of ZrO2, the piezoelectric response is significantly larger compared to ZrO2 with a normal hysteresis. The Mg doped ZrO2 shows a strong temperature and cycle stability. For the piezoelectric properties, a magnesium concentration of 7% shows the largest piezoelectric response with a piezoelectric coefficient of >10 pm/V, as well as the best cycle stability. Due to thicker films, which can be realized by the CSD technique, the shown doped ZrO2 films are a promising candidate for energy related applications such as piezoelectric energy harvesting as well as for microelectromechanical systems.

The formation of crystals in glasses containing rare earth oxides

NASA Astrophysics Data System (ADS)

Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

2014-02-01

Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd2O3-22.7CeO2-11.7La2O3-10.9PrO2-1.3Eu2O3-1.3Gd2O3-8.1Sm2O3-4.8Y2O3 with a baseline glass of composition 60.2SiO2-16.0B2O3-12.6Na2O-3.8Al2O3-5.7CaO-1.7ZrO2. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La2O3 and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO5) and oxyapatite (Ca2La8Si6O26) were found in glasses containing La2O3, while oxyapatite (Ca2La8Si6O26 and NaNd9Si6O26) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (TL) of the glasses containing 5%, 10% and 15% La2O3 were 800°C, 959°C and 986°C, respectively; while TL was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients TB2O3, TSiO2, TCaO, and TRE2O3 were also evaluated using a recently published study.

Structure, morphology and reducibility of ceria-doped zirconia

NASA Astrophysics Data System (ADS)

Aribi, Koubra; Soltani, Zohra; Ghelamallah, Madani; Granger, Pascal

2018-03-01

Zr1-xCexOx has been prepared by hydrolysis, in neutral medium, starting from rough ZrO2 and CeO2 materials as simple and cheaper synthesis method compared to sol-gel routes. The oxy-hydroxide precursors thus obtained were calcined under air at 450 °C, 900 °C and 1200 °C. The impact of those thermal treatments on the structure, texture and related redox properties has been investigated. Higher specific surface area than those observed on ceria were observed after calcination at low temperature, i.e., 450 °C. Above that temperature thermal sintering occurs having a detrimental effect on the specific surface area related to crystal growth more accentuated on CeO2. The formation of several Zrsbnd Ce mixed oxide phases formed by incorporation and substitution of Zr in the structure of ceria was characterized. A complete loss of specific surface area is noticeable after calcination at 1200 °C. XRD and SEM analysis revealed the formation of two mixed oxides structure, i.e. Ce2Zr2O7.04 and Ce2Zr2O7 corresponding to different redox behavior evidenced from H2-TPR experiments.

Band gap tuning of amorphous Al oxides by Zr alloying

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

Canulescu, S., E-mail: stec@fotonik.dtu.dk; Schou, J.; Jones, N. C.

2016-08-29

The optical band gap and electronic structure of amorphous Al-Zr mixed oxides with Zr content ranging from 4.8 to 21.9% were determined using vacuum ultraviolet and X-ray absorption spectroscopy. The light scattering by the nano-porous structure of alumina at low wavelengths was estimated based on the Mie scattering theory. The dependence of the optical band gap of the Al-Zr mixed oxides on the Zr content deviates from linearity and decreases from 7.3 eV for pure anodized Al{sub 2}O{sub 3} to 6.45 eV for Al-Zr mixed oxides with a Zr content of 21.9%. With increasing Zr content, the conduction band minimum changes non-linearlymore » as well. Fitting of the energy band gap values resulted in a bowing parameter of ∼2 eV. The band gap bowing of the mixed oxides is assigned to the presence of the Zr d-electron states localized below the conduction band minimum of anodized Al{sub 2}O{sub 3}.« less

Comparison of fracture strength and failure mode of different ceramic implant abutments.

PubMed

Elsayed, Adham; Wille, Sebastian; Al-Akhali, Majed; Kern, Matthias

2017-04-01

The whitish color of zirconia (ZrO 2 ) abutments offers favorable esthetics compared with the grayish color of titanium (Ti) abutments. Nonetheless, ZrO 2 has greater opacity, making it difficult to achieve natural tooth color. Therefore, lithium disilicate (LaT) abutments have been suggested to replace metal abutments. The purpose of this in vitro study was to evaluate the fracture strength and failure mode of single-tooth implant restorations using ZrO 2 and LaT abutments, and to compare them with titanium (Ti) abutments. Five different types of abutments, Ti; ZrO 2 with no metal base; ZrO 2 with a metal base (ZrT); LaT; and LaT combination abutment and crown (LcT) were assembled on 40 Ti implants and restored with LaT crowns. Specimens were subjected to quasistatic loading using a universal testing machine, until the implant-abutment connection failed. As bending of the metal would be considered a clinical failure, the values of force (N) at which the plastic deformation of the metal occurred were calculated, and the rate of deformation was analyzed. Statistical analysis was done using the Mann-Whitney U test (α=.05). Group ZrO 2 revealed the lowest resistance to failure with a mean of 202 ±33 N. Groups ZrT, LaT, and LaC withstood higher forces without fracture or debonding of the ceramic suprastructure, and failure was due to deformation of metal bases, with no statistically significant differences between these groups regarding the bending behavior. Within the limitations of this in vitro study, it was concluded that LaT abutments have the potential to withstand the physiological occlusal forces that occur in the anterior region and that ZrO 2 abutments combined with Ti inserts have much higher fracture strength than pure ZrO 2 abutments. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Photocatalytic activity of nanostructured ZnO-ZrO2 binary oxide using fluorometric method

NASA Astrophysics Data System (ADS)

Ibrahim, M. M.

2015-06-01

Evaluation of the photocatalytic activity of ZnO-ZrO2 nanomaterials using fluorescence based technique has rarely been reported. In the present work, ZnO-ZrO2 mixed oxides coupled with various ZnO dosages (0, 10, 30, 50, 70 wt%) were prepared by impregnation method. These nanomaterials were characterized by studying their structural, surface and optical properties. The photocatalytic activity in term of quantitative determination of the active oxidative species (radOH) produced on the surface of binary oxide was evaluated using fluorescent probe method. The interaction between ZnO and ZrO2 was affected on the photocatalytic efficiency of mixture. The results show that, the addition of ZnO to ZrO2 decreased the electron-hole recombination and increased the rate of radOH radicals formation. 50 wt% ZnO-ZrO2 photocatalyst exhibited much higher photocatalytic activity. The profound effect of binary oxide catalyst was generally considered due to the high surface area, small particle size, high monoclinic phase of ZrO2 content, low band gap and the presence of surface OH groups.

Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

NASA Astrophysics Data System (ADS)

Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

2018-06-01

Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

Status of plutonium ceramic immobilization processes and immobilization forms

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

Ebbinghaus, B.B.; Van Konynenburg, R.A.; Vance, E.R.

1996-05-01

Immobilization in a ceramic followed by permanent emplacement in a repository or borehole is one of the alternatives currently being considered by the Fissile Materials Disposition Program for the ultimate disposal of excess weapons-grade plutonium. To make Pu recovery more difficult, radioactive cesium may also be incorporated into the immobilization form. Valuable data are already available for ceramics form R&D efforts to immobilize high-level and mixed wastes. Ceramics have a high capacity for actinides, cesium, and some neutron absorbers. A unique characteristic of ceramics is the existence of mineral analogues found in nature that have demonstrated actinide immobilization over geologicmore » time periods. The ceramic form currently being considered for plutonium disposition is a synthetic rock (SYNROC) material composed primarily of zirconolite (CaZrTi{sub 2}O{sub 7}), the desired actinide host phase, with lesser amounts of hollandite (BaAl{sub 2}Ti{sub 6}O{sub 16}) and rutile (TiO{sub 2}). Alternative actinide host phases are also being considered. These include pyrochlore (Gd{sub 2}Ti{sub 2}O{sub 7}), zircon (ZrSiO{sub 4}), and monazite (CePO{sub 4}), to name a few of the most promising. R&D activities to address important technical issues are discussed. Primarily these include moderate scale hot press fabrications with plutonium, direct loading of PuO{sub 2} powder, cold press and sinter fabrication methods, and immobilization form formulation issues.« less

Creep Resistance of ZrO2 Ceramic Improved by the Addition of a Small Amount of Er2O3

NASA Technical Reports Server (NTRS)

Martinez-Fernandez, Julian; Sayir, Ali; Farmer, Serene C.

2003-01-01

Zirconia (ZrO2) has great technological importance in structural, electrical, and chemical applications. It is the crucial component for state-of-the art thermal barrier coatings and an enabling component as a solid electrolyte for solid-oxide fuel cell systems. Pure ZrO2 is of limited use for industrial applications because of the phase transformations that occur. Upon the addition of stabilizers, cubic (c-ZrO2) and tetragonal (t-ZrO2) forms can be preserved. It is the stabilized and partially stabilized forms of zirconia that function as thermal barrier coatings, solid electrolytes, and oxygen sensors and that have numerous applications in the electrochemical industry. The cubic form of ZrO2 is typically stabilized through Y2O3 additions. However, Y2O3-stabilized zirconia is susceptible to deformation at high temperatures (greater than 900 C) because of the large number of slip systems and the high oxygen diffusion rates, which result in high creep rates at high temperatures. Successful use of ZrO2 at high temperatures requires that new dopant additives be found that will retain or enhance the desirable properties of cubic ZrO2 and yet produce a material with lower creep rates. At the NASA Glenn Research Center, erbium oxide (Er2O3) was identified as a promising dopant for improving the creep resistance of. ZrO2. The selection of Er2O3 was based on the strong interactions of point defects and dislocations. Single crystals of 5 mol% Er2O3- doped ZrO2 rods (4 mm in diameter) and monofilaments (200 to 300 mm in diameter and 30 cm long) were grown using the laser-heated float zone technique, and their creep behavior was measured as a function of temperature. The addition of 5 mol% Er2O3 to single-crystal ZrO2 improved its creep resistance at high temperatures by 2 to 3 orders of magnitude over state-of-the-art Y2O3-doped crystals. Detailed microstructural characterization of ZrO2-Er2O3 single crystals has identified new mechanisms for improving the creep resistance of this class of materials. Adding Er2O3 to ZrO2 results in microstructure of stable and metastable tetragonal precipitates that with thermal treatment evolve to a tweed structure of nanosize tetragonal lamellae. The superior high-temperature creep resistance of Er2O3-doped ZrO2 is attributed to nanoscale precipitation hardening. Doping with Er2O3 will significantly increase the upper-use temperature limit of ZrO2. Potential applications include using Er2O3-doped ZrO2 as a high-temperature fiber for structural applications and adding Er2O3 to reduce the sintering rates of ZrO2 thermal barrier coatings. This work was conducted at Dpto. de F sica de la Materia Condensada, Universidad de Sevilla, Spain, and at NASA Glenn.

Effects of interfacial layer on characteristics of TiN/ZrO2 structures.

PubMed

Kim, Younsoo; Kang, Sang Yeol; Choi, Jae Hyoung; Lim, Jae Soon; Park, Min Young; Chung, Suk-Jin; Chung, Jaegwan; Lee, Hyung Ik; Kim, Ki Hong; Kyoung, Yong Koo; Heo, Sung; Yoo, Cha Young; Kang, Ho-Kyu

2011-09-01

To minimize the formation of unwanted interfacial layers, thin interfacial layer (ZrCN layer) was deposited between TiN bottom electrode and ZrO2 dielectric in TiN/ZrO2/TiN capacitor. Carbon and nitrogen were also involved in the layer because ZrCN layer was thermally deposited using TEMAZ without any reactant. Electrical characteristics of TiN/ZrO2/TiN capacitor were improved by insertion of ZrCN layer. The oxidation of TiN bottom electrode was largely inhibited at TiN/ZrCN/ZrO2 structure compared to TiN/ZrO2 structure. While the sheet resistance of TiN/ZrCN/ZrO2 structure was constantly sustained with increasing ZrO2 thickness, the large increase of sheet resistance was observed in TiN/ZrO2 structure after 6 nm ZrO2 deposition. When ZrO2 films were deposited on ZrCN layer, the deposition rate of ZrO2 also increased. It is believed that ZrCN layer acted both as a protection layer of TiN oxidation and a seed layer of ZrO2 growth.

Chemical pressure effects on magnetism in the quantum spin liquid candidates Yb2X2O7 (X =Sn, Ti, Ge)

NASA Astrophysics Data System (ADS)

Dun, Z. L.; Lee, M.; Choi, E. S.; Hallas, A. M.; Wiebe, C. R.; Gardner, J. S.; Arrighi, E.; Freitas, R. S.; Arevalo-Lopez, A. M.; Attfield, J. P.; Zhou, H. D.; Cheng, J. G.

2014-02-01

The linear and nonlinear ac susceptibility measurements of Yb-pyrochlores, Yb2X2O7 (X =Sn, Ti, and Ge), show transitions with a ferromagnetic nature at 0.13 and 0.25 K for Yb2Sn2O7 and Yb2Ti2O7, respectively, and an antiferromagnetic ordering at 0.62 K for Yb2Ge2O7. These systematical results (i) provided information about the nature of the unconventional magnetic ground state in Yb2Ti2O7; (ii) realized a distinct antiferromagnetic ordering state in Yb2Ge2O7; and (iii) demonstrated that the application of chemical pressure through the series of Yb-pyrochlores can efficiently perturb the fragile quantum spin fluctuations of the Yb3+ ions and lead to very different magnetic ground states.

Resolving the grain boundary and lattice impedance of hot-pressed Li 7La 3Zr 2O 12 garnet electrolytes

DOE PAGES

Tenhaeff, Wyatt E.; Wang, Yangyang; Sokolov, Alexei P.; ...

2013-07-24

Here, the cubic-stabilized garnet solid electrolyte with a nominal composition of Li 6.28Al 0.24La 3Zr 2O 12 is thoroughly characterized by impedance spectroscopy. By varying the frequency of the applied AC signal over 11 orders of magnitude for characterizations from –100 to +60 °C, the relative contributions of grain and grain boundary conduction are unambiguously resolved.

High modulus rare earth and beryllium containing silicate glass compositions. [for glass reinforcing fibers

NASA Technical Reports Server (NTRS)

Bacon, J. F. (Inventor)

1976-01-01

Glass compositions having a Young's modulus of at least 16 million psi and a specific modulus of at least 110 million inches consisting essentially of approximately, by weight, 20 to 43% SiO2, 8 to 21% Al2O3, 4 to 10% BeO, 27 to 58% of at least one oxide selected from a first group consisting of Y2O3, La2O3, Nd2O3, Ce2O3, Ce2O3, and the mixed rare earth oxides, and 3 to 12% of at least one oxide selected from a second group consisting of MgO, ZrO2, ZnO and CaO are described. The molar ratio of BeO to the total content of the first group oxides is from 1.0 to 3.0.

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

Perriot, Romain; Uberuaga, Blas P.; Zamora, Richard J.

Diffusion in complex oxides is critical to ionic transport, radiation damage evolution, sintering, and aging. In complex oxides such as pyrochlores, anionic diffusion is dramatically affected by cation disorder. However, little is known about how disorder influences cation transport. Here, we report results from classical and accelerated molecular dynamics simulations of vacancy-mediated cation diffusion in Gd 2Ti 2O 7 pyrochlore, on the microsecond timescale. We find that diffusion is slow at low levels of disorder, while higher disorder allows for fast diffusion, which is then accompanied by antisite annihilation and reordering, and thus a slowing of cation transport. Cation diffusivitymore » is therefore not constant, but decreases as the material reorders. We also show that fast cation diffusion is triggered by the formation of a percolation network of antisites. This is in contrast with observations from other complex oxides and disordered media models, suggesting a fundamentally different relation between disorder and mass transport.« less

Development of Novel Garnet-Type Solid Electrolytes for Potential Application in Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Narayanan, Sumaletha

The development of promising solid electrolytes having a garnet-like structure has been successfully achieved through solid state (ceramic) method. Various approaches to improve the Li ion conductivity were employed. The first approach involved creating oxide ion vacancies into the crystal structure of parent garnet-like oxide, Li5La3Nb2O 12 to create a novel family of compounds with nominal composition, Li 5La3Nb2-xYxO12-δ (0 ≤ x ≤ 1). The second approach was Li stuffing into the garnet-like oxides to develop a series of Li stuffed novel Li5+2xLa3Nb 2-xYxO12 (0.05 ≤ x ≤ 0.75) and Li6.5 La2.5Ba0.5ZrTaO12. Powder X-ray diffraction (PXRD), thermo gravimetric analysis (TGA), scanning electron microscopy (SEM), electron probe microanalysis (EPMA) coupled with a wavelength-dispersive spectrometer (WDS), 7Li nuclear magnetic resonance (Li-NMR), and AC impedance spectroscopy were employed to characterize the structure, morphology, elemental composition, Li ion sites, and Li ion conductivity. Studies have shown that Li5+2xLa 3Nb2-xYxO12 have turned out to be promising solid electrolytes with high Li ion conductivity (10-4 Scm -1 at ambient temperatures). In addition, all families of garnets are found to be chemically stable with Li cathode materials (Li2MMn 3O8, where M = Fe, Co) up to 400 °C in air. The developed electrolyte materials have the potential to be used in all-solid-state Li ion batteries.

Extremely fine structured cathode for solid oxide fuel cells using Sr-doped LaMnO3 and Y2O3-stabilized ZrO2 nano-composite powder synthesized by spray pyrolysis

NASA Astrophysics Data System (ADS)

Shimada, Hiroyuki; Yamaguchi, Toshiaki; Sumi, Hirofumi; Nomura, Katsuhiro; Yamaguchi, Yuki; Fujishiro, Yoshinobu

2017-02-01

A solid oxide fuel cell (SOFC) for high power density operation was developed with a microstructure-controlled cathode using a nano-composite powder of Sr-doped LaMnO3 (LSM) and Y2O3-stabilized ZrO2 (YSZ) synthesized by spray pyrolysis. The individual LSM-YSZ nano-composite particles, formed by crystalline and amorphous nano-size LSM and YSZ particles, showed spherical morphology with uniform particle size. The use of this powder for cathode material led to an extremely fine microstructure, in which all the LSM and YSZ grains (approximately 100-200 nm) were highly dispersed and formed their own network structures. This microstructure was due to the two phase electrode structure control using the powder, namely, nano-order level in each particle and micro-order level between particles. An anode-supported SOFC with the LSM-YSZ cathode using humidified H2 as fuel and ambient air as oxidant exhibited high power densities, such as 1.29 W cm-2 under a voltage of 0.75 V and a maximum power density of 2.65 W cm-2 at 800 °C. Also, the SOFC could be stably operated for 250 h with no degradation, even at a high temperature of 800 °C.

Forging Fast Ion Conducting Nanochannels with Swift Heavy Ions: The Correlated Role of Local Electronic and Atomic Structure

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

Sachan, Ritesh; Cooper, Valentino R.; Liu, Bin

2016-12-19

Atomically disordered oxides have attracted significant attention in recent years due to the possibility of enhanced ionic conductivity. However, the correlation between atomic disorder, corresponding electronic structure, and the resulting oxygen diffusivity is not well understood. The disordered variants of the ordered pyrochlore structure in gadolinium titanate (Gd 2Ti 2O 7) are seen as a particularly interesting prospect due to intrinsic presence of a vacant oxygen site in the unit atomic structure, which could provide a channel for fast oxygen conduction. In this paper, we provide insights into the subangstrom scale on the disordering-induced variations in the local atomic environmentmore » and its effect on the electronic structure in high-energy ion irradiation-induced disordered nanochannels, which can be utilized as pathways for fast oxygen ion transport. With the help of an atomic plane-by-plane-resolved analyses, the work shows how the presence of various types of TiO x polyhedral that exist in the amorphous and disordered crystalline phase modify the electronic structures relative to the ordered pyrochlore phase in Gd 2Ti 2O 7. Finally, the correlated molecular dynamics simulations on the disordered structures show a remarkable enhancement in oxygen diffusivity as compared with ordered pyrochlore lattice and make that a suitable candidate for applications requiring fast oxygen conduction.« less

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

Perriot, Romain; Uberuaga, Blas P.

We use molecular dynamics simulations to investigate the role of cation disorder on oxygen diffusion in Gd 2Zr 2O 7 (GZO) and Gd 2Ti 2O 7 (GTO) pyrochlores, a class of complex oxides which contain a structural vacancy relative to the basic fluorite structure. The introduction of disorder has distinct effects depending on the chemistry of the material, increasing the mobility of structural carriers by up to four orders of magnitude in GZO. In contrast, in GTO, there is no mobility at zero or low disorder on the ns timescale, but higher disorder liberates the otherwise immobile carriers, allowing diffusionmore » with rates comparable to GZO for the fully disordered material. Here, we show that the cation disorder enhances the diffusivity by both increasing the concentration of mobile structural carriers and their individual mobility. The disorder also influences the diffusion in materials containing intrinsic carriers, such as additional vacancies VO or oxygen interstitials OI. And while in ordered GZO and GTO the contribution of the intrinsic carriers dominates the overall diffusion of oxygen, OI in GZO contributes along with structural carriers, and the total diffusion rate can be calculated by assuming simple additive contributions from the two sources. Although the disorder in the materials with intrinsic defects usually enhances the diffusivity as in the defect-free case, in low concentrations, cation antisites AB or BA, where A = Gd and B = Zr or Ti, can act as traps for fast intrinsic defects. The trapping results in a lowering of the diffusivity, and causes a non-monotonic behavior of the diffusivity with disorder. Conversely, in the case of slow intrinsic defects, the main effect of the disorder is to liberate the structural carriers, resulting in an increase of the diffusivity regardless of the defect trapping.« less

The incorporation of plutonium in lanthanum zirconate pyrochlore

NASA Astrophysics Data System (ADS)

Gregg, Daniel J.; Zhang, Yingjie; Middleburgh, Simon C.; Conradson, Steven D.; Triani, Gerry; Lumpkin, Gregory R.; Vance, Eric R.

2013-11-01

The incorporation of plutonium (Pu) within lanthanum zirconate pyrochlore was investigated using air, argon, and N2-3.5%H2 sintering atmospheres together with Ca2+ and Sr2+ incorporation for charge compensation. The samples have been characterised in the first instance by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectroscopy (DRS). The results show Pu can be exchanged for La3+ on the A-site with and without charge compensation and for Zr4+ on the B-site. DRS measurements were made over the wavenumber range of 4000-19,000 cm-1 and the Pu in all air- and argon-sintered samples was found to be present as Pu4+ while that in samples sintered in N2-3.5%H2 was present as Pu3+. The Pu valence was confirmed for three of the samples using X-ray near-edge absorption spectroscopy (XANES). Pu valences >4+ were not observed in any of the samples.

Electrical characteristics and thermal stability of n+ polycrystalline- Si/ZrO2/SiO2/Si metal-oxide-semiconductor capacitors

NASA Astrophysics Data System (ADS)

Lim, Kwan-Yong; Park, Dae-Gyu; Cho, Heung-Jae; Kim, Joong-Jung; Yang, Jun-Mo; Ii, Choi-Sang; Yeo, In-Seok; Park, Jin Won

2002-01-01

We have investigated the thermal stability of n+ polycrystalline-Si(poly-Si)/ZrO2(50-140 Å)/SiO2(7 Å)/p-Si metal-oxide-semiconductor (MOS) capacitors via electrical and material characterization. The ZrO2 gate dielectric was prepared by atomic layer chemical vapor deposition using ZrCl4 and H2O vapor. Capacitance-voltage hysteresis as small as ˜12 mV with the flatband voltage of -0.5 V and the interface trap density of ˜5×1010cm-2 eV-1 were attained with activation anneal at 750 °C. A high level of gate leakage current was observed at the activation temperatures over 750 °C and attributed to the interfacial reaction of poly-Si and ZrO2 during the poly-Si deposition and the following high temperature anneal. Because of this, the ZrO2 gate dielectric is incompatible with the conventional poly-Si gate process. In the MOS capacitors having a smaller active area (<50×50 μm2), fortunately, the electrical degradation by further severe silicidation does not occur up to an 800 °C anneal in N2 for 30 min.

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.

Structural and mechanical properties of lanthanide doped La1/3Nb0.8Ta0.2O3 thin films prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Brunckova, Helena; Medvecky, Lubomir; Kovalcikova, Alexandra; Fides, Martin; Mudra, Erika; Durisin, Juraj; Skvarla, Jiri; Kanuchova, Maria

2017-04-01

Transparent Eu and Nd doped lanthanum niobate tantalate La1/3Nb0.8Ta0.2O3 (LNT) thin films (˜150 nm) were prepared by sol-gel/spin-coating process on Pt/SiO2/Si substrates and annealing at 1100 °C. The x-ray diffraction analysis of films confirmed formation of the perovskite La1/3NbO3 and La1/3TaO3 phases with traces of pyrochlore LaNbO4. Eu and Nd doped LNT films were smoother with roughness 17.1 and 25.4 nm in comparison with LNT (43.3 nm). In all films was observed heterogeneous microstructure with the perovskite spherical and pyrochlore needle-like particles. The mechanical properties of films were characterized for the first time by conventional and continuous stiffness (CSM) nanoindentation. The Eu and Nd doped LNT film modulus (E) and hardness (H) were higher than LNT (˜99.8 and 4.4 GPa) determined by conventional nanoindentation. It was measured the significant effect of substrate on properties of Eu or Nd films (H ˜ 5.9 or 4.9 GPa and E ˜ 107.3 or 104.1 GPa) by CSM nanoindentation.

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. .

JPRS Report, Science & Technology, USSR: Materials Science

DTIC Science & Technology

1988-03-17

mentally on heat-resistant ceramic coatings, ZrO £ coatings with Y2O3 stabilizer, for determination of the yttrium content which largely contributes to the...with carbon filler in a ceramic matrix was made for the purpose of determining the effect of a hot oxidizing ambient medium on their load capacity... admixture of refractory oxides such as MgO, Si02, C^Oß, N10, SnÜ2 and La203 or excess AI2O3 and Ti02 on the stability of this ceramic material at

Facile synthesis and unique physicochemical properties of three-dimensionally ordered macroporous magnesium oxide, gamma-alumina, and ceria-zirconia solid solutions with crystalline mesoporous walls.

PubMed

Li, Huining; Zhang, Lei; Dai, Hongxing; He, Hong

2009-05-18

Three-dimensionally (3D) ordered macroporous (3DOM) MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) with polycrystalline mesoporous walls have been successfully fabricated with the triblock copolymer EO(106)PO(70)EO(106) (Pluronic F127) and regularly packed monodispersive polymethyl methacrylate (PMMA) microspheres as the template and magnesium, aluminum, cerium and zirconium nitrate(s), or aluminum isopropoxide as the metal source. The as-synthesized metal oxides were characterized by means of techniques such as X-ray diffraction (XRD), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), Fourier transform infrared (FT-IR), high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy/selected area electron diffraction (HRTEM/SAED), BET, carbon dioxide temperature-programmed desorption (CO(2)-TPD), and hydrogen temperature-programmed reduction (H(2)-TPR). It is shown that the as-fabricated MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples possessed single-phase polycrystalline structures and displayed a 3DOM architecture; the MgO, Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples exhibited worm-hole-like mesoporous walls, whereas the gamma-Al(2)O(3) samples exhibited 3D ordered mesoporous walls. The solvent (ethanol or water) nature and concentration, metal precursor, surfactant, and drying condition have an important impact on the pore structure and surface area of the final product. The introduction of surfactant F127 to the synthesis system could significantly enhance the surface areas of the 3DOM metal oxides. With PMMA and F127 in a 40% ethanol solution, one can generate well-arrayed 3DOM MgO with a surface area of 243 m(2)/g and 3DOM Ce(0.6)Zr(0.4)O(2) with a surface area of 100 m(2)/g; with PMMA and F127 in an ethanol-HNO(3) solution, one can obtain 3DOM gamma-Al(2)O(3)with a surface area of 145 m(2)/g. The 3DOM MgO and 3DOM gamma-Al(2)O(3) samples showed excellent CO(2) adsorption behaviors, whereas the 3DOM Ce(0.6)Zr(0.4)O(2) sample exhibited exceptional low-temperature reducibility. The unique physicochemical properties associated with the copresence of 3DOM and mesoporous walls make these porous materials ideal candidates for applications in heterogeneous catalysis and CO(2) adsorption.

Tm-doped TiO2 and Tm2Ti2O7 pyrochlore nanoparticles: enhancing the photocatalytic activity of rutile with a pyrochlore phase.

PubMed

De Los Santos, Desiré M; Navas, Javier; Aguilar, Teresa; Sánchez-Coronilla, Antonio; Fernández-Lorenzo, Concha; Alcántara, Rodrigo; Piñero, Jose Carlos; Blanco, Ginesa; Martín-Calleja, Joaquín

2015-01-01

Tm-doped TiO2 nanoparticles were synthesized using a water-controlled hydrolysis reaction. Analysis was performed in order to determine the influence of the dopant concentration and annealing temperature on the phase, crystallinity, and electronic and optical properties of the resulting material. Various characterization techniques were utilized such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and UV-vis spectroscopy. For the samples annealed at 773 and 973 K, anatase phase TiO2 was obtained, predominantly internally doped with Tm(3+). ICP-AES showed that a doping concentration of up to 5.8 atom % was obtained without reducing the crystallinity of the samples. The presence of Tm(3+) was confirmed by X-ray photoelectron spectroscopy and UV-vis spectroscopy: the incorporation of Tm(3+) was confirmed by the generation of new absorption bands that could be assigned to Tm(3+) transitions. Furthermore, when the samples were annealed at 1173 K, a pyrochlore phase (Tm2Ti2O7) mixed with TiO2 was obtained with a predominant rutile phase. The photodegradation of methylene blue showed that this pyrochlore phase enhanced the photocatalytic activity of the rutile phase.

Synchrotron X-ray studies of model SOFC cathodes, part II: Porous powder cathodes

DOE PAGES

Chang, Kee-Chul; Ingram, Brian; Ilavsky, Jan; ...

2017-10-28

Infiltrated La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) sintered porous powder cathodes for solid oxide fuel cells have been investigated by synchrotron ultra-small angle x-ray scattering (USAXS). Here, we demonstrated that atomic layer deposition (ALD) is the method for a uniform coating and liquid-phase infiltration for growing nanoscale particles on the porous LSCF surfaces. The MnO infiltrate, grown by ALD, forms a conformal layer with a uniform thickness throughout the pores evidenced by USAXS thickness fringes. The La 0.6Sr 0.4CoO 3 (LSC) and La 2Zr 2O 7 (LZO) infiltrates, grown by liquid-phase infiltration, were found to form nanoscale particles onmore » the surfaces of LSCF particles resulting in increased surface areas. In conclusion, impedance measurements suggest that the catalytic property of LSC infiltrate, not the increased surface area of LZO, is important for increasing oxygen reduction activities.« less

Synchrotron X-ray studies of model SOFC cathodes, part II: Porous powder cathodes

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

Chang, Kee-Chul; Ingram, Brian; Ilavsky, Jan

Infiltrated La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) sintered porous powder cathodes for solid oxide fuel cells have been investigated by synchrotron ultra-small angle x-ray scattering (USAXS). Here, we demonstrated that atomic layer deposition (ALD) is the method for a uniform coating and liquid-phase infiltration for growing nanoscale particles on the porous LSCF surfaces. The MnO infiltrate, grown by ALD, forms a conformal layer with a uniform thickness throughout the pores evidenced by USAXS thickness fringes. The La 0.6Sr 0.4CoO 3 (LSC) and La 2Zr 2O 7 (LZO) infiltrates, grown by liquid-phase infiltration, were found to form nanoscale particles onmore » the surfaces of LSCF particles resulting in increased surface areas. In conclusion, impedance measurements suggest that the catalytic property of LSC infiltrate, not the increased surface area of LZO, is important for increasing oxygen reduction activities.« less

Exceptional capability of nanosized CeO(2) materials to "dissolve" lanthanide oxides established by time-gated excitation and emission spectroscopy.

PubMed

Tiseanu, Carmen; Parvulescu, Vasile; Avram, Daniel; Cojocaru, Bogdan; Sanchez-Dominguez, Margarita

2014-05-28

The atomic scale homogeneity of Ce and Zr oxygen bonds represents the main reason for enhanced total oxygen storage capability of CeO2-ZrO2 (Ce/Zr = 1) as compared to that of CeO2. Here, we demonstrate that the addition of 10% Eu(3+) by wet impregnation on preformed nanosized CeO2-ZrO2 (Ce/Zr = 1) followed by calcination induces a remarkable homogeneity of 10% Eu(3+)-CeO2-ZrO2 solid solution. By use of time-resolved emission and excitation spectroscopies, the improvement of the nanoscale chemical and structural homogeneity of 10% Eu(3+)-CeO2-ZrO2 calcined at 1000 as compared to sample calcined at 750 °C is demonstrated. Based on the comparison of luminescence properties of 10% Eu(3+) impregnated on preformed nanosized CeO2-ZrO2 and CeO2, we also show that the presence of zirconium does not only preserve the ability of cerium oxide to "dissolve" lanthanide oxide, but also determines an important stabilization of defects (oxygen vacancies) generated upon Eu(3+) doping.

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.

Oxidation of ZrB2 SiC TaSi2 Materials at Ultra High Temperatures

NASA Technical Reports Server (NTRS)

Opila, E.; Smith, J.; Levine, S.; Lorincz, J.; Reigel, M.

2008-01-01

ZrB2 - 20v% SiC - 20v% TaSi2 was oxidized in stagnant air for ten minute cycles for times up to 100 minutes at 1627 C and 1927 C. The sample oxidized at 1627 C showed oxidation resistance better than that of the standard ZrB2 - 20v% SiC. The sample oxidized at 1927 C, however, showed evidence of liquid phase formation and complex oxidation products. The sample exposed at 1927 C was analyzed in detail by scanning electron microprobe and wavelength dispersive spectroscopy to understand the complex oxidation and melting reactions occurring during exposure. The as hot-pressed material shows the formation of a Zr(Ta)B2 phase in addition to the three phases in the nominal composition already noted. After oxidation, the TaSi2 in the matrix was completely reacted to form Ta(Zr)C. The layered oxidation products included SiO2, ZrO2, Ta2O5, and a complex oxide containing both Zr and Ta. Likely reactions are proposed based on thermodynamic phase stability and phase morphology.

Thermodynamic Assessment of the Y2o3-yb2o3-zro2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2002-01-01

Yttria-zirconia (Y2O3-ZrO2) is the most widely used of the rare earth oxide-zirconia systems. There are numerous experimental studies of the phase boundaries in this system. In this paper, we assess these data and derive parameters for the solution models in this system. There is current interest in other rare earth oxide-zirconia systems as well as systems with several rare earth oxides and zirconia, which may offer improved properties over the Y2O3-ZrO2 system. For this reason, we also assess the ytterbia-zirconia (Yb2O3-ZrO2) and Y2O3-Yb2O3-ZrO2 system.

Initial stages of oxide formation on the Zr surface at low oxygen pressure: An in situ FIM and XPS study

PubMed Central

Bespalov, I.; Datler, M.; Buhr, S.; Drachsel, W.; Rupprechter, G.; Suchorski, Y.

2015-01-01

An improved methodology of the Zr specimen preparation was developed which allows fabrication of stable Zr nanotips suitable for FIM and AP applications. Initial oxidation of the Zr surface was studied on a Zr nanotip by FIM and on a polycrystalline Zr foil by XPS, both at low oxygen pressure (10−8–10−7 mbar). The XPS data reveal that in a first, fast stage of oxidation, a Zr suboxide interlayer is formed which contains three suboxide components (Zr+1, Zr+2 and Zr+3) and is located between the Zr surface and a stoichiometric ZrO2 overlayer that grows in a second, slow oxidation stage. The sole suboxide layer has been observed for the first time at very early states of the oxidation (oxygen exposure ≤4 L). The Ne+ FIM observations are in accord with a two stage process of Zr oxide formation. PMID:25766998

Highly-translucent, strong and aging-resistant 3Y-TZP ceramics for dental restoration by grain boundary segregation.

PubMed

Zhang, Fei; Vanmeensel, Kim; Batuk, Maria; Hadermann, Joke; Inokoshi, Masanao; Van Meerbeek, Bart; Naert, Ignace; Vleugels, Jef

2015-04-01

Latest trends in dental restorative ceramics involve the development of full-contour 3Y-TZP ceramics which can avoid chipping of veneering porcelains. Among the challenges are the low translucency and the hydrothermal stability of 3Y-TZP ceramics. In this work, different trivalent oxides (Al2O3, Sc2O3, Nd2O3 and La2O3) were selected to dope 3Y-TZP ceramics. Results show that dopant segregation was a key factor to design hydrothermally stable and high-translucent 3Y-TZP ceramics and the cation dopant radius could be used as a controlling parameter. A large trivalent dopant, oversized as compared to Zr(4+), exhibiting strong segregation at the ZrO2 grain boundary was preferred. The introduction of 0.2 mol% La2O3 in conventional 0.1-0.25 wt.% Al2O3-doped 3Y-TZP resulted in an excellent combination of high translucency and superior hydrothermal stability, while retaining excellent mechanical properties. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Extremely dense microstructure and enhanced ionic conductivity in hot-isostatic pressing treated cubic garnet-type solid electrolyte of Ga2O3-doped Li7La3Zr2O12

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming’En; Hu, Zhiwei; Zhu, Jiliang

A large number of pores and a low relative density that are frequently observed in solid electrolytes reduce severely their ionic conductivity and thus limit their applicability. Here, we report on the use of hot isostatic pressing (HIP) for ameliorating the garnet-type lithium-ion conducting solid electrolyte of Ga2O3-doped Li7La3Zr2O12 (Ga-LLZO) with nominal composition of Li6.55Ga0.15La3Zr2O12. The Ga-LLZO pellets were conventionally sintered at 1075∘C for 12h, and then were followed by HIP treatment at 120MPa and 1160∘C under an Ar atmosphere. It is found that the HIP-treated Ga-LLZO shows an extremely dense microstructure and a significantly enhanced ionic conductivity. Coherent with the increase in relative density from 90.5% (untreated) to 97.5% (HIP-treated), the ionic conductivity of the HIP-treated Ga-LLZO reaches as high as 1.13×10‑3S/cm at room temperature (25∘C), being two times higher than that of 4.58×10‑4S/cm for the untreated one.

Comparison and mechanism of photocatalytic activities of N-ZnO and N-ZrO2 for the degradation of rhodamine 6G.

PubMed

Sudrajat, Hanggara; Babel, Sandhya

2016-05-01

N-doped ZnO (N-ZnO) and N-doped ZrO2 (N-ZrO2) are synthesized by novel, simple thermal decomposition methods. The catalysts are evaluated for the degradation of rhodamine 6G (R6G) under visible and UV light. N-ZnO exhibits higher dye degradation under both visible and UV light compared to N-ZrO2 due to possessing higher specific surface area, lower crystalline size, and lower band gap. However, it is less reusable than N-ZrO2 and its photocatalytic activity is also deteriorated at low pH. At the same intensity of 3.5 W/m(2), UVC light is shown to be a better UV source for N-ZnO, while UVA light is more suitable for N-ZrO2. At pH 7 with initial dye concentration of 10 mg/L, catalyst concentration of 1 g/L, and UVC light, 94.3 % of R6G is degraded by N-ZnO within 2 h. Using UVA light under identical experimental conditions, 93.5 % degradation of R6G is obtained by N-ZrO2. Moreover, the type of light source is found to determine the reactive species produced in the R6G degradation by N-ZnO and N-ZrO2. Less oxidative reactive species such as superoxide radical and singlet oxygen play a major role in the degradation of R6G under visible light. On the contrary, highly oxidative hydroxyl radicals are predominant under UVC light. Based on the kinetic study, the adsorption of R6G on the catalyst surface is found to be the controlling step.

Facile biological synthetic strategy to morphologically aligned CeO2/ZrO2 core nanoparticles using Justicia adhatoda extract and ionic liquid: Enhancement of its bio-medical properties.

PubMed

Pandiyan, Nithya; Murugesan, Balaji; Sonamuthu, Jegatheeswaran; Samayanan, Selvam; Mahalingam, Sundrarajan

2018-01-01

In this study, a typical green synthesis route has approached for CeO 2 /ZrO 2 core metal oxide nanoparticles using ionic liquid mediated Justicia adhatoda extract. This synthesis method is carried out at simple room temperature condition to obtain the core metal oxide nanoparticles. XRD, SEM and TEM studies employed to study the crystalline and surface morphological properties under nucleation, growth, and aggregation processes. CeO 2 /ZrO 2 core metal oxides display agglomerated nano stick-like structure with 20-45nm size. GC-MS spectroscopy confirms the presence of vasicinone and N,N-Dimethylglycine present in the plant extract, which are capable of converting the corresponding metal ion precursor to CeO 2 /ZrO 2 core metal oxide nanoparticles. In FTIR, the corresponding stretching for Ce-O and Zr-O bands indicated at 498 and 416cm -1 and Raman spectroscopy also supports typical stretching frequencies at 463 and 160cm -1 . Band gap energy of the CeO 2 /ZrO 2 core metal oxide is 3.37eV calculated from UV- DRS spectroscopy. The anti-bacterial studies performed against a set of bacterial strains the result showed that core metal oxide nanoparticles more susceptible to gram-positive (G+) bacteria than gram-negative (G-) bacteria. A unique feature of the antioxidant behaviors core metal oxides reduces the concentration of DPPH radical up to 89%. The CeO 2 /ZrO 2 core metal oxide nanoparticles control the S. marcescent bio-film formation and restrict the quorum sensing. The toxicology behavior of CeO 2 /ZrO 2 core metal oxide NPs is found due to the high oxygen site vacancies, ROS formation, smallest particle size and higher surface area. This type of green synthesis route may efficient and the core metal oxide nanoparticles will possess a good bio-medical agent in future. Copyright © 2017 Elsevier B.V. All rights reserved.

Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study

PubMed Central

Xiao, H. Y.; Weber, W. J.; Zhang, Y.; Zu, X. T.; Li, S.

2015-01-01

The response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser, electron and ion irradiations. PMID:25660219

Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study.

PubMed

Xiao, H Y; Weber, W J; Zhang, Y; Zu, X T; Li, S

2015-02-09

The response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser, electron and ion irradiations.

Stability and Performance of Oxygen Electrodes for Reversible Solid Oxide Cells

NASA Astrophysics Data System (ADS)

Railsback, Justin Gary

Worldwide, governments are beginning to take action to reduce anthropogenic CO2 emissions in order to mitigate the extent of global climate change. The largest fraction of global CO2 emission comes from electrical power generation, which is rapidly being converted to wind and solar installations. The intermittent nature of renewable resources requires that large scale energy storage be implemented to ensure grid stability. Pumped hydro storage is currently the only technology available for large scale energy storage; however, pumped hydro remains geographically confined and susceptible to seasonal fluctuations and offers limited discharge hours. Recent system level models predict that reversible solid oxide cells may be a competitive solution, but two key advancements are required to realize the technology: low cell resistance (<0.2 O•cm2 at <650 °C), particularly low polarization resistance at the oxygen electrode, and low degradation rate (<0.5%/khr for 50,000 hours). The oxygen electrode is typically the largest contributor to the total cell resistance, and when a cell is operated in electrolysis the oxygen electrode is known to degrade quickly. This work focuses on both aspects of the oxygen electrode. A Pr2NiO4 based electrode is developed that has improved phase stability and good polarization resistance ( 0.1 O•cm2 at 650 °C). The electrode is prepared by wet chemical impregnation (infiltration) of Pr2NiO4 precursors into a La0.9Sr 0.1Ga0.8Mg0.2O3 scaffold. Electrochemical data for a number cells is presented and the number of infiltrations is optimized. Preliminary life tests and x-ray data are presented. Pressurization of the oxygen electrode is predicted to decrease its polarization resistance and pressurization of the reversible solid oxide cell system is desirable to achieve high round-trip efficiency. The electrochemical performance of mixed electronic-ionic conducting electrodes has not been reported above 1 atm. Four candidate electrodes are examined under pressurization up to 10 atm: Pr2NiO4 infiltrated La0.9Sr0.1 Ga0.8Mg0.2O3, Sm0.5Sr 0.5CoO3 infiltrated Ce0.9Gd0.1O 2, single phase La0.6Sr0.4Co0.2Fe 0.8O3, and single phase Nd2NiO4. The role of the ion conduction mechanism (vacancy or interstitial) is explored in relation to the decrease in polarization resistance with increased pressure. Current switched life-tests designed to emulate reversible solid oxide cell operating conditions were performed for a range of current densities and overpotentials on three candidate systems: composite La0.7Sr 0.3MnO3-Zr0.84Y0.16O2, single phase La0.6Sr0.4Co0.2Fe0.8O 3, and La2NiO4 infiltrated La0.9Sr 0.1Ga0.8Mg0.2O3. The degradation mode of each system is determined by impedance spectroscopy and post-test microstructural analysis. Operating regions of improved stability are identified for each system based on the measured degradation rates. Overpotential is determined to be the major controlling factor in La0.7Sr0.3MnO 3-Zr0.84Y0.16O2. Analysis and modeling for predicting the long term degradation of an infiltrated electrode is presented. Coarsening of the nanoscale features is thought to be the main contributor to degradation under annealing for infiltrated electrodes and so a combined electrochemical - coarsening model is presented to understand the limitations of such an electrode. The model is fit to prior results to better understand the trade-off between coarsening rate and initial good performance. A figure of merit is presented for selecting materials for infiltration that takes into account the coarsening behavior.

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li7La3Zr2O12 revealed by an internal friction technique.

PubMed

Wang, X P; Gao, Y X; Xia, Y P; Zhuang, Z; Zhang, T; Fang, Q F

2014-04-21

The correlation and transport mechanism of lithium ions with the crystal structure of a fast lithium ion conductor Li7La3Zr2O12 are mainly investigated by internal friction (IF) and AC impedance spectroscopy techniques. Compared with the poor conductivity of tetragonal Li7La3Zr2O12, the Al stabilized cubic phase exhibits a good ionic conductivity that can be up to 1.9 × 10(-4) S cm(-1) at room temperature, which can be ascribed to the disordered distribution of lithium ions in the cubic phase. A well-pronounced relaxation IF peak (labeled as peak PC) is observed in the cubic phase while a very weak IF peak (labeled as PT) is observed in the tetragonal phase, further evidencing the difference in lithium ion migration in the two phases. Peak PC can be decomposed into two sub-peaks with the activation energy and the pre-exponential factor of relaxation time being E1 = 0.41 eV and τ01 = 1.2 × 10(-14) s for the lower temperature peak PC1 and E2 = 0.35 eV and τ02 = 1.9 × 10(-15) s for the higher temperature PC2 peak, respectively. Based on the crystalline structure of a cubic garnet-type Li7La3Zr2O12 compound, an atomistic mechanism of lithium ion diffusion via vacancies is suggested, i.e. 48g(96h) ↔ 48g(96h) for peak PC1 and 48g(96h) ↔ 24d for peak PC2, respectively. The weak PT peak in the tetragonal phase is preliminarily interpreted as due to the short jump process among neighboring octahedral sites and vacant tetrahedral sites.

Physicochemical properties of calcium silicate cements associated with microparticulate and nanoparticulate radiopacifiers.

PubMed

Bosso-Martelo, Roberta; Guerreiro-Tanomaru, Juliane M; Viapiana, Raqueli; Berbert, Fabio Luiz C; Duarte, Marco Antonio Hungaro; Tanomaru-Filho, Mário

2016-01-01

The objective of this paper was to evaluate the physicochemical properties of calcium silicate cements with different chemical compositions, associated with radiopacifying agents. Mineral trioxide aggregate (MTA) Angelus, calcium silicate cement with additives (CSC), and resinous calcium silicate cement (CSCR) were evaluated, with the addition of the following radiopacifiers: microparticles (micro) or nanoparticles (nano) of zirconium oxide (ZrO(2)), niobium oxide (Nb(2)O(5)), bismuth oxide (Bi(2)O(3)), or calcium tungstate (CaWO(4)). Setting time was evaluated using Gilmore needles. Solubility was determined after immersion in water. The pH and calcium ion release were analyzed after 3, 12, and 24 h and 7, 14, and 21 days. The data obtained were submitted to analysis of variance and Tukey's test, at a level of significance of 5 %. CSC + CaWO(4) and CSCR + ZrO(2) micro, Nb(2)O(5) and CaWO(4) presented results similar to MTA, with a shorter final setting time than the other associations. CSC and CSCR+ ZrO(2) micro presented a higher degree of flow. All the cements evaluated presented low solubility. The materials presented alkaline pH and released calcium ions. ZrO(2) micro radiopacifier may be considered a potential substitute for Bi(2)O(3) when associated with CSC or CSCR. The proposed materials, especially when associated with ZrO(2), are potential materials for use as alternatives to MTA.

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide

NASA Astrophysics Data System (ADS)

Mao, Dongsen; Lu, Guanzhong

2007-02-01

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO 2-ZrO 2 mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO 2-ZrO 2 into a crystalline ZrTiO 4 compound, while a larger amount of boria (⩾8 wt%) promotes the crystallization process. FT-IR spectroscopy and 11B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO 4 units delay, while a build-up of trigonal BO 3 promote, the crystallization of amorphous TiO 2-ZrO 2 to form ZrTiO 4 crystals.

A DFT+U study of Pu immobilization in Gd2Zr2O7

NASA Astrophysics Data System (ADS)

Zhao, F. A.; Xiao, H. Y.; Jiang, M.; Liu, Z. J.; Zu, X. T.

2015-12-01

The solubility of Pu in Gd2Zr2O7 has been investigated by the density functional theory plus Hubbard U correction. It is found that the formation of PuGdZr2O7, Gd2PuZrO7 and Gd2Pu1.5Zr0.5O7 are exothermic, whereas Pu0.5Gd1.5Zr2O7, Pu1.5Gd0.5Zr2O7 and Gd2Pu0.5Zr1.5O7 are energetically less stable than their respective separated states. The calculations show that both the Gd and Zr lattice sites can be substituted by the Pu, which is consistent with the immobilization behavior of uranium in Gd2Zr2O7 observed experimentally. The site preference of Pu in Gd2Zr2O7 is found to be dependent on the chemical environment, i.e., Pu prefers to substitute for Gd-site under Gd-rich and O2-rich conditions and for Zr-site under Zr-rich and O2-rich conditions.

An Atomistic-Scale Study for Thermal Conductivity and Thermochemical Compatibility in (DyY)Zr2O7 Combining an Experimental Approach with Theoretical Calculation.

PubMed

Qu, Liu; Choy, Kwang-Leong; Wheatley, Richard

2016-02-18

Ceramic oxides that have high-temperature capabilities can be deposited on the superalloy components in aero engines and diesel engines to advance engine efficiency and reduce fuel consumption. This paper aims to study doping effects of Dy(3+) and Y(3+)on the thermodynamic properties of ZrO2 synthesized via a sol-gel route for a better control of the stoichiometry, combined with molecular dynamics (MD) simulation for the calculation of theoretical properties. The thermal conductivity is investigated by the MD simulation and Clarke's model. This can improve the understanding of the microstructure and thermodynamic properties of (DyY)Zr2O7 (DYZ) at the atomistic level. The phonon-defect scattering and phonon-phonon scattering processes are investigated via the theoretical calculation, which provides an effective way to study thermal transport properties of ionic oxides. The measured and predicted thermal conductivity of DYZ is lower than that of 4 mol % Y2O3 stabilized ZrO2 (4YSZ). It is discovered that DYZ is thermochemically compatible with Al2O3 at 1300 °C, whereas at 1350 °C DYZ reacts with Al2O3 forming a small amount of new phases.

An Atomistic-Scale Study for Thermal Conductivity and Thermochemical Compatibility in (DyY)Zr2O7 Combining an Experimental Approach with Theoretical Calculation

PubMed Central

Qu, Liu; Choy, Kwang-Leong; Wheatley, Richard

2016-01-01

Ceramic oxides that have high-temperature capabilities can be deposited on the superalloy components in aero engines and diesel engines to advance engine efficiency and reduce fuel consumption. This paper aims to study doping effects of Dy3+ and Y3+on the thermodynamic properties of ZrO2 synthesized via a sol-gel route for a better control of the stoichiometry, combined with molecular dynamics (MD) simulation for the calculation of theoretical properties. The thermal conductivity is investigated by the MD simulation and Clarke’s model. This can improve the understanding of the microstructure and thermodynamic properties of (DyY)Zr2O7 (DYZ) at the atomistic level. The phonon-defect scattering and phonon-phonon scattering processes are investigated via the theoretical calculation, which provides an effective way to study thermal transport properties of ionic oxides. The measured and predicted thermal conductivity of DYZ is lower than that of 4 mol % Y2O3 stabilized ZrO2 (4YSZ). It is discovered that DYZ is thermochemically compatible with Al2O3 at 1300 °C, whereas at 1350 °C DYZ reacts with Al2O3 forming a small amount of new phases. PMID:26888438

X-ray scattering studies of structural phase transitions in pyrochlore Cd2Nb2O7

NASA Astrophysics Data System (ADS)

Tachibana, Makoto; Fritsch, Katharina; Gaulin, Bruce D.

2013-10-01

Structural phase transitions in pyrochlore Cd2Nb2O7 were studied by means of single crystal x-ray scattering. On cooling below the ferroelastic transition at T1 = 204 K, the cubic Bragg peaks broaden in a manner consistent with weak orthorhombic distortion. The distortion evolves rather smoothly through the ferroelectric transition at T2 = 196 K, which explains the absence of sharp anomalies in the heat capacity and dielectric constant at this transition. At lower temperatures, the anomalous relaxor-like character of this compound is evident as a gradual reduction in the Bragg peak intensities, which continues down to the onset of another transition at T3 = 85 K. The studies of two Bragg peaks that are forbidden within the cubic phase reveal an interesting disparity: while the intensity for one of them increases in a classical mean-field manner below T1, the other shows unconventional behavior that is reminiscent of the pyrochlore superconductor Cd2Re2O7.

Atomic layer deposition of ZrO2 on W for metal-insulator-metal capacitor application

NASA Astrophysics Data System (ADS)

Lee, Sang-Yun; Kim, Hyoungsub; McIntyre, Paul C.; Saraswat, Krishna C.; Byun, Jeong-Soo

2003-04-01

A metal-insulator-metal (MIM) capacitor using ZrO2 on tungsten (W) metal bottom electrode was demonstrated and characterized in this letter. Both ZrO2 and W metal were synthesized by an atomic layer deposition (ALD) method. High-quality 110˜115 Å ZrO2 films were grown uniformly on ALD W using ZrCl4 and H2O precursors at 300 °C, and polycrystalline ZrO2 in the ALD regime could be obtained. A 13˜14-Å-thick interfacial layer between ZrO2 and W was observed after fabrication, and it was identified as WOx through angle-resolved x-ray photoelectron spectroscopy analysis with wet chemical etching. The apparent equivalent oxide thickness was 20˜21 Å. An effective dielectric constant of 22˜25 including an interfacial WOx layer was obtained by measuring capacitance and thickness of MIM capacitors with Pt top electrodes. High capacitance per area (16˜17 fF/μm2) and low leakage current (10-7 A/cm2 at ±1 V) were achieved.

Formation of ZrO{sub 2} in coating on Mg–3 wt.%Al–1 wt.%Zn alloy via plasma electrolytic oxidation: Phase and structure of zirconia

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

Lee, Kang Min; Kim, Yeon Sung; Yang, Hae Woong

2015-01-15

An investigation of the coating structure formed on Mg–3 wt.%Al–1 wt.%Zn alloy sample subjected to plasma electrolytic oxidation was examined by field-emission transmission electron microscopy. The plasma electrolytic oxidation process was conducted in a phosphoric acid electrolyte containing K{sub 2}ZrF{sub 6} for 600 s. Microstructural observations showed that the coating consisting of MgO, MgF{sub 2}, and ZrO{sub 2} phases was divided into three distinctive parts, the barrier, intermediate, and outer layers. Nanocrystalline MgO and MgF{sub 2} compounds were observed mainly in the barrier layer of ~ 1 μm thick near to the substrate. From the intermediate to outer layers, variousmore » ZrO{sub 2} polymorphs appeared due to the effects of the plasma arcing temperature on the phase transition of ZrO{sub 2} compounds during the plasma electrolytic oxidation process. In the outer layer, MgO compound grew in the form of a dendrite-like structure surrounded by cubic ZrO{sub 2}. - Highlights: • The barrier layer containing MgO and MgF{sub 2} was observed near to the Mg substrate. • In the intermediate layer, m-, t-, and o-ZrO{sub 2} compounds were additionally detected. • The outer layer contained MgO with the dendrite-like structure surrounded by c-ZrO{sub 2}. • The grain sizes of compounds in oxide layer increased from barrier to outer layer.« less

Atomic displacements in the charge ice pyrochlore Bi2Ti2O6O' studied by neutron total scattering

NASA Astrophysics Data System (ADS)

Shoemaker, Daniel P.; Seshadri, Ram; Hector, Andrew L.; Llobet, Anna; Proffen, Thomas; Fennie, Craig J.

2010-04-01

The oxide pyrochlore Bi2Ti2O6O' is known to be associated with large displacements of Bi and O' atoms from their ideal crystallographic positions. Neutron total scattering, analyzed in both reciprocal and real space, is employed here to understand the nature of these displacements. Rietveld analysis and maximum entropy methods are used to produce an average picture of the structural nonideality. Local structure is modeled via large-box reverse Monte Carlo simulations constrained simultaneously by the Bragg profile and real-space pair distribution function. Direct visualization and statistical analyses of these models show the precise nature of the static Bi and O' displacements. Correlations between neighboring Bi displacements are analyzed using coordinates from the large-box simulations. The framework of continuous symmetry measures has been applied to distributions of O'Bi4 tetrahedra to examine deviations from ideality. Bi displacements from ideal positions appear correlated over local length scales. The results are consistent with the idea that these nonmagnetic lone-pair containing pyrochlore compounds can be regarded as highly structurally frustrated systems.

Electrochemical Stability of Li 10GeP 2S 12 and Li 7La 3Zr 2O 12 Solid Electrolytes

DOE PAGES

Han, Fudong; Zhu, Yizhou; He, Xingfeng; ...

2016-01-21

The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk-type solid-state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemicalmore » stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte-carbon cell. The most promising solid electrolytes, Li10GeP2S12 and cubic Li-garnet Li7La3Zr2O12, are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high-performance solid-state batteries.« less

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.

Multiferroic magnetoelectric coupling effect of bilayer La1.2Sr1.8Mn2O7/PbZr0.3Ti0.7O3 complex thin film

NASA Astrophysics Data System (ADS)

Liang, K.; Zhou, P.; Ma, Z. J.; Qi, Y. J.; Mei, Z. H.; Zhang, T. J.

2017-05-01

Magnetoelectric (ME) coupling effect of 2-2-type ferromagnetic/ferroelectric bi-layer multiferroic epitaxial thin film (La1.2Sr1.8Mn2O7/PbZr0.3Ti0.7O3, LSMO/PZT) on SrRuO3 (SRO) substrate is investigated systematically by using Landau-Ginzburg-Devonshire (LGD) thermodynamic theory and modified constitutive equations. The calculating results clarify the detail relationships between ME coupling response and the residual strain, the volume fraction of constituent phases, the interface coupling coefficients, the magnetic field and the temperature. It also shows that improved ME coupling response can be modulated by these parameters. External magnetic fields (H1) induced ME coupling effect could be enhanced around Curie Temperature (Tc) of ferromagnetic phase and ME voltage coefficient (αE31) approaches a maximum at H1 ∼ 4.5 kOe near Tc. The remarkable variations of ME coupling response can be used to provide useful guidelines on the design of multifunctional devices.

Electrochemical performance and carbon deposition resistance of M-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (M = Pd, Cu, Ni or NiCu) anodes for solid oxide fuel cells

PubMed Central

Li, Meng; Hua, Bin; Pu, Jian; Chi, Bo; Jian, Li

2015-01-01

Pd-, Cu-, Ni- and NiCu-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ anodes, designated as M-BZCYYb, were prepared by impregnating M-containing solution into BZCYYb scaffold, and investigated in the aspects of electrocatalytic activity for the reactions of H2 and CH4 oxidation and the resistance to carbon deposition. Impregnation of Pd, Ni or NiCu significantly reduced both the ohmic (RΩ) and polarization (RP) losses of BZCYYb anode exposed to H2 or CH4, while Cu impregnation decreased only RΩ in H2 and the both in CH4. Pd-, Ni- and NiCu-BZCYYb anodes were resistant to carbon deposition in wet (3 mol. % H2O) CH4 at 750°C. Deposited carbon fibers were observed in Pd- and Ni-BZCYYb anodes exposed to dry CH4 at 750°C for 12 h, and not observed in NiCu-BZCYYb exposed to dry CH4 at 750°C for 24 h. The performance of a full cell with NiCu-BZCYYb anode, YSZ electrolyte and La0.6Sr0.4Co0.2Fe0.8O3-δ-Gd doped CeO2 (LSCF-GDC) cathode was stable at 750°C in wet CH4 for 130 h, indicating that NiCu-BZCYYb is a promising anode for direct CH4 solid oxide fuel cells (SOFCs). PMID:25563843

The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

NASA Astrophysics Data System (ADS)

Takano, Hiroyuki; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2011-07-01

The active catalysts for methane formation from the gas mixture of CO 2 + 4H 2 with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO 2 prepared by calcination of aqueous ZrO 2 sol with Sm(NO 3) 3 and Ni(NO 3) 2. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO 2, and the activity for methanation increased by an increase in inclusion of Sm 3+ ions substituting Zr 4+ ions in the tetragonal ZrO 2 lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.

Phase Competition in the Palmer-Chalker X Y Pyrochlore Er2Pt2O7

NASA Astrophysics Data System (ADS)

Hallas, A. M.; Gaudet, J.; Butch, N. P.; Xu, Guangyong; Tachibana, M.; Wiebe, C. R.; Luke, G. M.; Gaulin, B. D.

2017-11-01

We report neutron scattering measurements on Er2Pt2O7 , a new addition to the X Y family of frustrated pyrochlore magnets. Symmetry analysis of our elastic scattering data shows that Er2Pt2O7 orders into the k =0 , Γ7 magnetic structure (the Palmer-Chalker state), at TN=0.38 K . This contrasts with its sister X Y pyrochlore antiferromagnets Er2Ti2O7 and Er2Ge2O7 , both of which order into Γ5 magnetic structures at much higher temperatures, TN=1.2 and 1.4 K, respectively. In this temperature range, the magnetic heat capacity of Er2Pt2O7 contains a broad anomaly centered at T*=1.5 K . Our inelastic neutron scattering measurements reveal that this broad heat capacity anomaly sets the temperature scale for strong short-range spin fluctuations. Below TN=0.38 K , Er2Pt2O7 displays a gapped spin-wave spectrum with an intense, flat band of excitations at lower energy and a weak, diffusive band of excitations at higher energy. The flat band is well described by classical spin-wave calculations, but these calculations also predict sharp dispersive branches at higher energy, a striking discrepancy with the experimental data. This, in concert with the strong suppression of TN, is attributable to enhanced quantum fluctuations due to phase competition between the Γ7 and Γ5 states that border each other within a classically predicted phase diagram.

Nuclear waste disposal—pyrochlore (A2B2O7): Nuclear waste form for the immobilization of plutonium and "minor" actinides

NASA Astrophysics Data System (ADS)

Ewing, Rodney C.; Weber, William J.; Lian, Jie

2004-06-01

During the past half-century, the nuclear fuel cycle has generated approximately 1400 metric tons of plutonium and substantial quantities of the "minor" actinides, such as Np, Am, and Cm. The successful disposition of these actinides has an important impact on the strategy for developing advanced nuclear fuel cycles, weapons proliferation, and the geologic disposal of high-level radioactive waste. During the last decade, there has been substantial interest in the use of the isometric pyrochlore structure-type, A2B2O7, for the immobilization of actinides. Most of the interest has focused on titanate-pyrochlore because of its chemical durability; however, these compositions experience a radiation-induced transition from the crystalline-to-aperiodic state due to radiation damage from the alpha-decay of actinides. Depending on the actinide concentration, the titanate pyrochlore will become amorphous in less than 1000 years of storage. Recently, systematic ion beam irradiations of a variety of pyrochlore compositions has revealed that many zirconate pyrochlores do not become amorphous, but remain crystalline as a defect fluorite structure-type due to disordering of the A- and B-site cations. The zirconate pyrochlores will remain crystalline even to very high doses, greater than 100 displacements per atom. Systematic experimental studies of actinide-doped and ion beam-irradiated pyrochlore, analyses of natural U- and Th-bearing pyrochlore, and simulations of the energetics of the disordering process now provide a rather detailed understanding of the structural and chemical controls on the response of pyrochlore to radiation. These results provide a solid basis for predicting the behavior and durability of pyrochlore used to immobilize plutonium.

Fabrication and electrical properties of a (Pb,La)(Zr,Ti)O3 capacitor with pulsed laser deposited Sn-doped In2O3 bottom electrode on Al2O3(0001)

NASA Astrophysics Data System (ADS)

Takada, Yoko; Tamano, Rika; Okamoto, Naoki; Saito, Takeyasu; Yoshimura, Takeshi; Fujimura, Norifumi; Higuchi, Koji; Kitajima, Akira

2017-07-01

A Sn-doped In2O3 (ITO) electrode was deposited on Al2O3(0001) using pulsed laser deposition at different oxygen pressures to create the bottom electrode of a (Pb,La)(Zr,Ti)O3 (PLZT) capacitor. The crystallographic orientation of the ITO films was controlled via the oxygen pressure. At 600 °C the (111) peak became dominant when the O2 pressure was increased, and when the pressure reached 2.0 Pa the ITO films became preferentially (111) oriented. The remnant polarization was 58.8-90.7 and 46.0-47.5 µC/cm2 for the Pt/PLZT/ITO and ITO/PLZT/ITO capacitors, respectively; the ferroelectric properties of these capacitors were also determined.

Atomic and electronic structures of an extremely fragile liquid.

PubMed

Kohara, Shinji; Akola, Jaakko; Patrikeev, Leonid; Ropo, Matti; Ohara, Koji; Itou, Masayoshi; Fujiwara, Akihiko; Yahiro, Jumpei; Okada, Junpei T; Ishikawa, Takehiko; Mizuno, Akitoshi; Masuno, Atsunobu; Watanabe, Yasuhiro; Usuki, Takeshi

2014-12-18

The structure of high-temperature liquids is an important topic for understanding the fragility of liquids. Here we report the structure of a high-temperature non-glass-forming oxide liquid, ZrO2, at an atomistic and electronic level. The Bhatia-Thornton number-number structure factor of ZrO2 does not show a first sharp diffraction peak. The atomic structure comprises ZrO5, ZrO6 and ZrO7 polyhedra with a significant contribution of edge sharing of oxygen in addition to corner sharing. The variety of large oxygen coordination and polyhedral connections with short Zr-O bond lifetimes, induced by the relatively large ionic radius of zirconium, disturbs the evolution of intermediate-range ordering, which leads to a reduced electronic band gap and increased delocalization in the ionic Zr-O bonding. The details of the chemical bonding explain the extremely low viscosity of the liquid and the absence of a first sharp diffraction peak, and indicate that liquid ZrO2 is an extremely fragile liquid.

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.

High-temperature properties of (La,Ca)(Fe,Mg,Mo)O3-δ perovskites as prospective electrode materials for symmetrical SOFC

NASA Astrophysics Data System (ADS)

Istomin, S. Ya.; Morozov, A. V.; Abdullayev, M. M.; Batuk, M.; Hadermann, J.; Kazakov, S. M.; Sobolev, A. V.; Presniakov, I. A.; Antipov, E. V.

2018-02-01

La1-yCayFe0.5+x(Mg,Mo)0.5-xO3-δ oxides with the orthorhombic GdFeO3-type perovskite structure have been synthesized at 1573 K. Transmission electron microscopy study for selected samples shows the coexistence of domains of perovskite phases with ordered and disordered B-cations. Mössbauer spectroscopy studies performed at 300 K and 573 K show that while compositions with low Ca-content (La0.55Ca0.45Fe0.5Mg0.2625Mo0.2375O3-δ and La0.5Ca0.5Fe0.6Mg0.175Mo0.225O3-δ) are nearly oxygen stoichiometric, La0.2Ca0.8Fe0.5Mg0.2625Mo0.2375O3-δ is oxygen deficient with δ ≈ 0.15. Oxides are stable in reducing atmosphere (Ar/H2, 8%) at 1173 K for 12 h. No additional phases have been observed at XRPD patterns of all studied perovskites and Ce1-xGdxO2-x/2 electrolyte mixtures treated at 1173-1373K, while Fe-rich compositions (x≥0.1) react with Zr1-xYxO2-x/2 electrolyte above 1273 K. Dilatometry studies reveal that all samples show rather low thermal expansion coefficients (TECs) in air of 11.4-12.7 ppm K-1. In reducing atmosphere their TECs were found to increase up to 12.1-15.4 ppm K-1 due to chemical expansion effect. High-temperature electrical conductivity measurements in air and Ar/H2 atmosphere show that the highest conductivity is observed for Fe- and Ca-rich compositions. Moderate values of electrical conductivity and TEC together with stability towards chemical interaction with typical SOFC electrolytes make novel Fe-containing perovskites promising electrode materials for symmetrical solid oxide fuel cell.

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.

Electric-field control of electronic transport properties and enhanced magnetoresistance in La0.7Sr0.3MnO3/0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3 lead-free multiferroic structures

NASA Astrophysics Data System (ADS)

Yan, Jian-Min; Gao, Guan-Yin; Liu, Yu-Kuai; Wang, Fei-Fei; Zheng, Ren-Kui

2017-10-01

We report the fabrication of lead-free multiferroic structures by depositing ferromagnetic La0.7Sr0.3MnO3 (LSMO) polycrystalline films on polished 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3 (BZT-BCT) piezoelectric ceramic substrates. By applying electric fields to the BZT-BCT along the thickness direction, the resistivity of LSMO films can be effectively manipulated via the piezoelectric strain of the BZT-BCT. Moreover, the LSMO polycrystalline films exhibit almost temperature independent and significantly enhanced magnetoresistance (MR) below TC. At T = 2 K and H = 8 T, the MR of polycrystalline films is approximately two orders of magnitude higher than that of LSMO epitaxial films grown on (LaAlO3)0.3(SrAl1/2Ta1/2O3)0.7 single-crystal substrates. The enhanced MR mainly results from the spin-polarized tunneling of charge carriers across grain boundaries. The LSMO/BZT-BCT structures with electric-field controllable modulation of resistivity and enhanced MR effect may have potential applications in low-energy consumption and environmentally friendly electronic devices.

Time-Reversal Symmetry Breaking and Consequent Physical Responses Induced by All-In-All-Out Type Magnetic Order on the Pyrochlore Lattice

NASA Astrophysics Data System (ADS)

Arima, Taka-Hisa

2014-03-01

Pyrochlore-type 5d transition-metal oxide compounds Cd2Os2O7 and R2Ir2O7 (R =rare earth) undergo a metal-insulator transition accompanied by a magnetic transition. Recently, the magnetic structures of Cd2Os2O7 and Eu2Ir2O7 were investigated by means of resonant x-ray magnetic scattering. The x-ray data indicated the all-in/all-out type magnetic order. The all-in/all-out order breaks the time-reversal symmetry, while the spontaneous magnetization is essentially absent. The magnetic order can be viewed as ferroic magnetic octupolar order. The magnetic order is expected to provide several unique physical properties like quadratic magnetization. linear magneto-capacitance, linear magneto-resistance, linear magneto-mechanical coupling and so on. The symmetry breaking results in two non-equivalent domains, ``all-in/all-out'' and ``all-out/all-in.'' Interestingly, some theoretical works predict that a peculiar metallic state would appear on the domain wall. The observation and control of the domain distribution are essential for studying verious exotic physical responses. We have developed an x-ray technique for domain imaging and started studying the effects of external stimuli on the domain distribution. This work was performed in collaboration with S. Tardif, S. Takeshita, H. Ohsumi, D. Uematsu, H. Sagayama, J. J. Ishikawa, S. Nakatsuji, J. Yamaura, and Z. Hiroi.

Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study

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

Xiao, Haiyan Y.; Weber, William J.; Zhang, Yanwen

2015-02-09

In this study, the response of titanate pyrochlores (A 2Ti 2O 7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O 2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization inmore » titanate pyrochlores under laser, electron and ion irradiations.« less

Structural and photoluminescence properties of stannate based displaced pyrochlore-type red phosphors: Ca(3-x)Sn₃Nb₂O₁₄:xEu³⁺.

PubMed

Sreena, T S; Prabhakar Rao, P; Francis, T Linda; Raj, Athira K V; Babu, Parvathi S

2015-05-14

New stannate based displaced pyrochlore-type red phosphors, Ca(3-x)Sn3Nb2O14:xEu(3+), were prepared via a conventional solid state method. The influence of partial occupancy of Sn in both A and B sites of the pyrochlore-type oxides on the photoluminescence properties was studied using powder X-ray diffraction, FT-Raman, transmission electron microscopy, scanning electron microscopy with energy dispersive spectrometry, UV-visible absorption spectroscopy, and photoluminescence excitation and emission spectra with lifetime measurements. The structural analysis establishes that these oxides belong to a cubic displaced pyrochlore type structure with a space group Fd3̄m. These phosphors exhibit strong absorptions at near UV and blue wavelength regions and emit intense multiband emissions due to Eu(3+ 5)D0-(7)F(0, 1, 2) transitions. The absence of characteristic MD transition splitting points out that local cation disorder exists in this type of displaced pyrochlores, reducing the D(3d) inversion symmetry, which is not evidenced by such disorder in the X-ray diffraction analysis. The unusual forbidden intense sharp (5)D0-(7)F0 transition indicates single site occupancy of Eu(3+) with a narrower range of bonding environment, preventing the cluster formation. This is supported by the stable (5)D0 lifetime with Eu(3+) concentration. The Judd-Ofelt intensity parameter assessment corroborates these results. The CIE color coordinates of these phosphors were found to be (0.60, 0.40), which are close to the NTSC standard values (0.67, 0.33) for a potential red phosphor.

Synthesis of nano-scale fast ion conducting cubic Li7La3Zr2O12.

PubMed

Sakamoto, Jeff; Rangasamy, Ezhiylmurugan; Kim, Hyunjoung; Kim, Yunsung; Wolfenstine, Jeff

2013-10-25

A solution-based process was investigated for synthesizing cubic Li7La3Zr2O12 (LLZO), which is known to exhibit the unprecedented combination of fast ionic conductivity, and stability in air and against Li. Sol-gel chemistry was developed to prepare solid metal-oxide networks consisting of 10 nm cross-links that formed the cubic LLZO phase at 600 ° C. Sol-gel LLZO powders were sintered into 96% dense pellets using an induction hot press that applied pressure while heating. After sintering, the average LLZO grain size was 260 nm, which is 13 times smaller compared to LLZO prepared using a solid-state technique. The total ionic conductivity was 0.4 mS cm(-1) at 298 K, which is the same as solid-state synthesized LLZO. Interestingly, despite the same room temperature conductivity, the sol-gel LLZO total activation energy is 0.41 eV, which 1.6 times higher than that observed in solid-state LLZO (0.26 eV). We believe the nano-scale grain boundaries give rise to unique transport phenomena that are more sensitive to temperature when compared to the conventional solid-state LLZO.

Method Using Water-Based Solvent to Prepare Li7La3Zr2O12 Solid Electrolytes.

PubMed

Huang, Xiao; Lu, Yang; Jin, Jun; Gu, Sui; Xiu, Tongping; Song, Zhen; Badding, Michael E; Wen, Zhaoyin

2018-05-09

Li-garnet Li 7 La 3 Zr 2 O 12 (LLZO) is a promising candidate of solid electrolytes for high-safety solid-state Li + ion batteries. However, because of its high reactivity to water, the preparation of LLZO powders and ceramics is not easy for large-scale amounts. Herein, a method applying water-based solvent is proposed to demonstrate a possible solution. Ta-doped LLZO, that is, Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO), and its LLZTO/MgO composite ceramics are made by attrition milling, followed by a spray-drying process using water-based slurries. The impacts of parameters of the method on the structure and properties of green and sintered pellets are studied. A relative density of ∼95%, a Li-ion conductivity of ∼3.5 × 10 -4 S/cm, and uniform grain size LLZTO/MgO garnet composite ceramics are obtained with an attrition-milled LLZTO/MgO slurry that contains 40 wt % solids and 2 wt % polyvinyl alcohol binder. Li-sulfur batteries based on these ceramics are fabricated and work under 25 °C for 20 cycles with a Coulombic efficiency of 100%. This research demonstrates a promising mass production method for the preparation of Li-garnet ceramics.

Effect of La2O3 addition on interface chemistry between 4YSZ top layer and Ni based alloy bond coat in thermal barrier coating by EB PVD.

PubMed

Park, Chan-Young; Yang, Young-Hwan; Kim, Seong-Won; Lee, Sung-Min; Kim, Hyung-Tae; Jang, Byung-Koog; Lim, Dae-Soon; Oh, Yoon-Suk

2014-11-01

The effect of a 5 mol% La2O3 addition on the forming behavior and compositional variation at interface between a 4 mol% Yttria (Y2O3) stabilized ZrO2 (4YSZ) top coat and bond coat (NiCrAlY) as a thermal barrier coating (TBC) has been investigated. Top coats were deposited by electron beam physical vapor deposition (EB PVD) onto a super alloy (Ni-Cr-Co-Al) substrate without pre-oxidation of the bond coat. Top coats are found to consist of dense columnar grains with a thin interdiffusion layer between metallic bond coats. In the as-received 4YSZ coating, a thin interdiffusion zone at the interface between the top and bond coats was found to consist of a Ni-Zr intermetallic compound with a reduced quantity of Y, Al or O elements. On the other hand, in the case of an interdiffusion area of 5 mol% La2O3-added 4YSZ coating, it was found that the complicated composition and structure with La-added YSZ and Ni-Al rich compounds separately. The thermal conductivity of 5 mol% La2O3-added 4YSZ coating (- 1.6 W/m x k at 1100 degrees C) was lower than a 4YSZ coating (- 3.2 W/m x k at 1100 degrees C) alone.

Probing disorder in isometric pyrochlore and related complex oxides

NASA Astrophysics Data System (ADS)

Shamblin, Jacob; Feygenson, Mikhail; Neuefeind, Joerg; Tracy, Cameron L.; Zhang, Fuxiang; Finkeldei, Sarah; Bosbach, Dirk; Zhou, Haidong; Ewing, Rodney C.; Lang, Maik

2016-05-01

There has been an increased focus on understanding the energetics of structures with unconventional ordering (for example, correlated disorder that is heterogeneous across different length scales). In particular, compounds with the isometric pyrochlore structure, A2B2O7, can adopt a disordered, isometric fluorite-type structure, (A, B)4O7, under extreme conditions. Despite the importance of the disordering process there exists only a limited understanding of the role of local ordering on the energy landscape. We have used neutron total scattering to show that disordered fluorite (induced intrinsically by composition/stoichiometry or at far-from-equilibrium conditions produced by high-energy radiation) consists of a local orthorhombic structural unit that is repeated by a pseudo-translational symmetry, such that orthorhombic and isometric arrays coexist at different length scales. We also show that inversion in isometric spinel occurs by a similar process. This insight provides a new basis for understanding order-to-disorder transformations important for applications such as plutonium immobilization, fast ion conduction, and thermal barrier coatings.

New evidence for Cu-decorated binary-oxides mediating bacterial inactivation/mineralization in aerobic media.

PubMed

Rtimi, S; Pulgarin, C; Bensimon, M; Kiwi, J

2016-08-01

Binary oxide semiconductors TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 (TiO2-ZrO2-Cu) uniform films were sputtered on polyester (PES). These films were irradiated under low intensity solar simulated light and led to bacterial inactivation in aerobic and anaerobic media as evaluated by CFU-plate counting. But bacterial mineralization was only induced by TiO2-ZrO2-Cu in aerobic media. The highly oxidative radicals generated on the films surface under light were identified by the use of appropriate scavengers. The hole generated on the TiO2-ZrO2 films is shown to be the main specie leading to bacterial inactivation. TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 films release Zr and Ti <1ppb and Cu 4.6ppb/cm(2) as determined by inductively coupled plasma mass spectrometry (ICP-MS) This level is far below the citotoxicity permitted level allowed for mammalian cells suggesting that bacterial disinfection proceeds through an oligodynamic effect. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR) the systematic shift of the predominating νs(CH2) vibrational-rotational peak making up most of the bacterial cell-wall content in C was monitored. Based on this evidence a mechanism suggested leading to CH bond stretching followed by cell lysis and cell death. Bacterial inactivation cycling was observed on TiO2-ZrO2-Cu showing the stability of these films leading to bacterial inactivation. Copyright © 2016 Elsevier B.V. All rights reserved.

Frustration under pressure: Exotic magnetism in new pyrochlore oxides

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

Wiebe, C. R.; Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2; Department of Physics and Astronomy, McMaster University, Hamilton, Ontario L8S 4M1

2015-04-01

Pyrochlore structures, of chemical formula A{sub 2}B{sub 2}O{sub 7} (A and B are typically trivalent and tetravalent ions, respectively), have been the focus of much activity in the condensed matter community due to the ease of substitution of rare earth and transition metal ions upon the two interpenetrating corner-shared tetrahedral lattices. Over the last few decades, superconductivity, spin liquid states, spin ice states, glassy states in the absence of chemical disorder, and metal-insulator transitions have all been discovered in these materials. Geometric frustration plays a role in the relevant physics of all of these phenomena. In the search for newmore » pyrochlore materials, it is the R{sub A}/R{sub B} cation radius ratio which determines the stability of the lattice over the defect fluorite structure in the lower limit. Under ambient pressure, the pyrochlores are stable for 1.36 ≤ R{sub A}/R{sub B} ≤ 1.71. However, using high pressure synthesis techniques (1-10 GPa of pressure), metastable pyrochlores exist up to R{sub A}/R{sub B} = 2.30. Many of these compounds are stable on a timescale of years after synthesis, and provide a means to greatly enhance exchange, and thus test theories of quantum magnetism and search for new phenomena. Within this article, we review new pyrochlore compounds synthesized via high pressure techniques and show how the ground states are extremely sensitive to chemical pressure.« less

Effect of zirconium oxide nanoparticles addition on the optical and tensile properties of polymethyl methacrylate denture base material

PubMed Central

Gad, Mohammed M; Abualsaud, Reem; Rahoma, Ahmed; Al-Thobity, Ahmad M; Al-Abidi, Khalid S; Akhtar, Sultan

2018-01-01

Background Polymethyl methacrylate (PMMA) is widely used for the fabrication of removable prostheses. Recently, zirconium oxide nanoparticles (nano-ZrO2) have been added to improve some properties of PMMA, but their effect on the optical properties and tensile strength are neglected. Objective The aim of this study was to investigate the effect of nano-ZrO2 addition on the translucency and tensile strength of the PMMA denture base material. Materials and methods Eighty specimens (40 dumbbell-shaped and 40 discs) were prepared out of heat-polymerized acrylic resin and divided into four groups per test (n=10). The control group for each test included unreinforced acrylic, while the test groups were reinforced with 2.5, 5, and 7.5 wt% nano-ZrO2. Acrylic resin was mixed according to manufacturer’s instructions, packed, and processed by conventional method. After polymerization, all specimens were finished, polished, and stored in distilled water at 37°C for 48±2 hours. Tensile strength (MPa) was evaluated using the universal testing machine while the specimens’ translucency was examined using a spectrophotometer. Statistical analysis was carried out by SPSS using the paired sample t-test (p≤0.05). A scanning electron microscope was used to analyze the morphological changes and topography of the fractured surfaces. Results This study showed that the mean tensile strength of the PMMA in the test groups of 2.5%NZ, 5%NZ, and 7.5%NZ was significantly higher than the control group. The tensile strength increased significantly after nano-ZrO2 addition, and the maximum increase seen was in the 7.5%NZ group. The translucency values of the experimental groups were significantly lower than those of the control group. Within the reinforced groups, the 2.5%NZ group had significantly higher translucency values when compared to the 5%NZ and 7.5%NZ groups. Conclusion The addition of nano-ZrO2 increased the tensile strength of the denture base acrylic. The increase was directly proportional to the nano-ZrO2 concentration. The translucency of the PMMA was reduced as the nano-ZrO2 increased. Clinical significance Based on the results of the current study, the tensile strength was improved with different percentages of nano-ZrO2 additions. However, translucency was adversely affected. Therefore, it is important to determine the appropriate amount of reinforcing nano-ZrO2 that will create a balance between achieved properties – mechanical and optical. PMID:29391789

Effect of zirconium oxide nanoparticles addition on the optical and tensile properties of polymethyl methacrylate denture base material.

PubMed

Gad, Mohammed M; Abualsaud, Reem; Rahoma, Ahmed; Al-Thobity, Ahmad M; Al-Abidi, Khalid S; Akhtar, Sultan

2018-01-01

Polymethyl methacrylate (PMMA) is widely used for the fabrication of removable prostheses. Recently, zirconium oxide nanoparticles (nano-ZrO 2 ) have been added to improve some properties of PMMA, but their effect on the optical properties and tensile strength are neglected. The aim of this study was to investigate the effect of nano-ZrO 2 addition on the translucency and tensile strength of the PMMA denture base material. Eighty specimens (40 dumbbell-shaped and 40 discs) were prepared out of heat-polymerized acrylic resin and divided into four groups per test (n=10). The control group for each test included unreinforced acrylic, while the test groups were reinforced with 2.5, 5, and 7.5 wt% nano-ZrO 2 . Acrylic resin was mixed according to manufacturer's instructions, packed, and processed by conventional method. After polymerization, all specimens were finished, polished, and stored in distilled water at 37°C for 48±2 hours. Tensile strength (MPa) was evaluated using the universal testing machine while the specimens' translucency was examined using a spectrophotometer. Statistical analysis was carried out by SPSS using the paired sample t -test ( p ≤0.05). A scanning electron microscope was used to analyze the morphological changes and topography of the fractured surfaces. This study showed that the mean tensile strength of the PMMA in the test groups of 2.5%NZ, 5%NZ, and 7.5%NZ was significantly higher than the control group. The tensile strength increased significantly after nano-ZrO 2 addition, and the maximum increase seen was in the 7.5%NZ group. The translucency values of the experimental groups were significantly lower than those of the control group. Within the reinforced groups, the 2.5%NZ group had significantly higher translucency values when compared to the 5%NZ and 7.5%NZ groups. The addition of nano-ZrO 2 increased the tensile strength of the denture base acrylic. The increase was directly proportional to the nano-ZrO 2 concentration. The translucency of the PMMA was reduced as the nano-ZrO 2 increased. Based on the results of the current study, the tensile strength was improved with different percentages of nano-ZrO 2 additions. However, translucency was adversely affected. Therefore, it is important to determine the appropriate amount of reinforcing nano-ZrO 2 that will create a balance between achieved properties - mechanical and optical.

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

Campbell, Keri R.; Judge, Elizabeth J.; Barefield, James E.

We show the analysis of light water reactor simulated used nuclear fuel using laser-induced breakdown spectroscopy (LIBS) is explored using a simplified version of the main oxide phase. The main oxide phase consists of the actinides, lanthanides, and zirconium. The purpose of this study is to develop a rapid, quantitative technique for measuring zirconium in a uranium dioxide matrix without the need to dissolve the material. A second set of materials including cerium oxide is also analyzed to determine precision and limit of detection (LOD) using LIBS in a complex matrix. Two types of samples are used in this study:more » binary and ternary oxide pellets. The ternary oxide, (U,Zr,Ce)O 2 pellets used in this study are a simplified version the main oxide phase of used nuclear fuel. The binary oxides, (U,Ce)O 2 and (U,Zr)O 2 are also examined to determine spectral emission lines for Ce and Zr, potential spectral interferences with uranium and baseline LOD values for Ce and Zr in a UO 2 matrix. In the spectral range of 200 to 800 nm, 33 cerium lines and 25 zirconium lines were identified and shown to have linear correlation values (R 2) > 0.97 for both the binary and ternary oxides. The cerium LOD in the (U,Ce)O 2 matrix ranged from 0.34 to 1.08 wt% and 0.94 to 1.22 wt% in (U,Ce,Zr)O 2 for 33 of Ce emission lines. The zirconium limit of detection in the (U,Zr)O 2 matrix ranged from 0.84 to 1.15 wt% and 0.99 to 1.10 wt% in (U,Ce,Zr)O 2 for 25 Zr lines. Finally, the effect of multiple elements in the plasma and the impact on the LOD is discussed.« less

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

The formation of crystals in glasses containing rare earth oxides

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

Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod

Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd{sub 2}O{sub 3}–22.7CeO{sub 2}–11.7La{submore » 2}O{sub 3}–10.9PrO{sub 2}–1.3Eu{sub 2}O{sub 3}–1.3Gd{sub 2}O{sub 3}–8.1Sm{sub 2}O{sub 3}–4.8Y{sub 2}O{sub 3} with a baseline glass of composition 60.2SiO{sub 2}–16.0B{sub 2}O{sub 3}–12.6Na{sub 2}O–3.8Al{sub 2}O{sub 3}–5.7CaO–1.7ZrO{sub 2}. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La{sub 2}O{sub 3} and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO{sub 5}) and oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26}) were found in glasses containing La{sub 2}O{sub 3}, while oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26} and NaNd{sub 9}Si{sub 6}O{sub 26}) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (T{sub L}) of the glasses containing 5%, 10% and 15% La{sub 2}O{sub 3} were 800°C, 959°C and 986°C, respectively; while T{sub L} was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients T{sub B2O3}, T{sub SiO2}, T{sub CaO}, and T{sub RE2O3} were also evaluated using a recently published study.« less

A study of suppressed formation of low-conductivity phases in doped Li 7La 3Zr 2O 12 garnets by in situ neutron diffraction

DOE PAGES

Chen, Yan; Rangasamy, Ezhiylmurugan; dela Cruz, Clarina R.; ...

2015-09-28

Doped Li 7La 3Zr 2O 12 garnets, oxide-based solids with good Li + conductivity and compatibility, show great potential as leading electrolyte material candidates for all-solid-state lithium ion batteries. Still yet, the conductive bulk usually suffers from the presence of secondary phases and the transition towards a low-conductivity tetragonal phase during synthesis. Dopants are designed to stabilize the high-conductive cubic phase and suppress the formation of the low-conductivity phases. In situ neutron diffraction enables a direct observation of the doping effects by monitoring the phase evolutions during garnet synthesis. It reveals the reaction mechanism involving the temporary presence of intermediatemore » phases. The off-stoichiometry due to the liquid Li 2CO 3 evaporation leads to the residual of the low-conductivity intermediate phase in the as-synthesized bulk. Appropriate doping of an active element may alter the component of the intermediate phases and promote the completion of the reaction. While the dopants aid to stabilize most of the cubic phase, a small amount of tetragonal phase tends to form under a diffusion process. Lastly, the in situ observations provide the guideline of process optimization to suppress the formation of unwanted low-conductivity phases.« less

Application of novel Ni(II) complex and ZrO2 nanoparticle as mediators for electrocatalytic determination of N-acetylcysteine in drug samples.

PubMed

Karimi-Maleh, Hassan; Salehi, Mehdi; Faghani, Fatemeh

2017-10-01

The electrooxidation of N-acetylcysteine (N-AC) was studied by a novel Ni(II) complex modified ZrO 2 nanoparticle carbon paste electrode [Ni(II)/ZrO 2 /NPs/CPE] using voltammetric methods. The results showed that Ni(II)/ZrO 2 /NPs/CPE had high electrocatalytic activity for the electrooxidation of N-AC in aqueous buffer solution (pH = 7.0). The electrocatalytic oxidation peak currents increase linearly with N-AC concentrations over the concentration ranges of 0.05-600μM using square wave voltammetric methods. The detection limit for N-AC was equal to 0.009μM. The catalytic reaction rate constant, k h , was calculated (7.01 × 10 2  M -1  s -1 ) using the chronoamperometry method. Finally, Ni(II)/ZrO 2 /NPs/CPE was also examined as an ultrasensitive electrochemical sensor for the determination of N-AC in real samples such as tablet and urine. Copyright © 2017. Published by Elsevier B.V.

Effect of TiO2, ZrO2, and TiO2-ZrO2 on the performance of CuO-ZnO catalyst for CO2 hydrogenation to methanol

NASA Astrophysics Data System (ADS)

Xiao, Jie; Mao, Dongsen; Guo, Xiaoming; Yu, Jun

2015-05-01

The influence of TiO2, ZrO2, and TiO2-ZrO2 mixed oxide on the catalytic performance of CuO-ZnO catalyst in the methanol synthesis from CO2 hydrogenation was studied. The catalysts were prepared by oxalate co-precipitation method and characterized by TGA, N2 adsorption, XRD, reactive N2O adsorption, XPS, H2-TPR, H2-TPD, and CO2-TPD techniques. Characterization results reveal that all the additives improve the CuO dispersion in the catalyst body and increase the Cu surface area and adsorption capacities of CO2 and H2. The results of catalytic test reveal that the additives increase both the CO2 conversion and methanol selectivity, and TiO2-ZrO2 mixed oxide is more effective than single components of TiO2 or ZrO2. Moreover, the activity of methanol synthesis is correlated directly with CO2 adsorption capacity over the catalysts.

Trade-off between Zr Passivation and Sn Doping on Hematite Nanorod Photoanodes for Efficient Solar Water Oxidation: Effects of a ZrO2 Underlayer and FTO Deformation.

PubMed

Subramanian, Arunprabaharan; Annamalai, Alagappan; Lee, Hyun Hwi; Choi, Sun Hee; Ryu, Jungho; Park, Jung Hee; Jang, Jum Suk

2016-08-03

Herein we report the influence of a ZrO2 underlayer on the PEC (photoelectrochemical) behavior of hematite nanorod photoanodes for efficient solar water splitting. Particular attention was given to the cathodic shift in onset potential and photocurrent enhancement. Akaganite (β-FeOOH) nanorods were grown on ZrO2-coated FTO (fluorine-doped tin oxide) substrates. Sintering at 800 °C transformed akaganite to the hematite (α-Fe2O3) phase and induced Sn diffusion into the crystal structure of hematite nanorods from the FTO substrates and surface migration, shallow doping of Zr atoms from the ZrO2 underlayer. The ZrO2 underlayer-treated photoanode showed better water oxidation performance compared to the pristine (α-Fe2O3) photoanode. A cathodic shift in the onset potential and photocurrent enhancement was achieved by surface passivation and shallow doping of Zr from the ZrO2 underlayer, along with Sn doping from the FTO substrate to the crystal lattice of hematite nanorods. The Zr based hematite nanorod photoanode achieved 1 mA/cm(2) at 1.23 VRHE with a low turn-on voltage of 0.80 VRHE. Sn doping and Zr passivation, as well as shallow doping, were confirmed by XPS, Iph, and M-S plot analyses. Electrochemical impedance spectroscopy revealed that the presence of a ZrO2 underlayer decreased the deformation of FTO substrate, improved electron transfer at the hematite/FTO interface and increased charge-transfer resistance at the electrolyte/hematite interface. This is the first systematic investigation of the effects of Zr passivation, shallow doping, and Sn doping on hematite nanorod photoanodes through application of a ZrO2 underlayer on the FTO substrate.

Effect of Dopants on the Adsorption of Carbon Dioxide on Ceria Surfaces

DOE PAGES

Li, Meijun; Tumuluri, Uma; Wu, Zili; ...

2015-09-25

Here, high-surface-area nanosized CeO 2 and M-doped CeO 2 (M=Cu, La, Zr, and Mg) prepared by a surfactant-templated method were tested for CO 2 adsorption. Cu, La, and Zr are doped into the lattice of CeO 2, whereas Mg is dispersed on the CeO 2 surface. The doping of Cu and La into CeO 2 leads to an increase of the CO 2 adsorption capacity, whereas the doping of Zr has little or no effect. The addition of Mg causes a decrease of the CO 2 adsorption capacity at a low Mg content and a gradual increase at a highermore » content. The CO 2 adsorption capacity follows the sequence Cu-CeO 2>La-CeO 2>Zr-CeO 2≈CeO 2>Mg-CeO 2 at low dopant contents, in line with the relative amount of defect sites in the samples. It is the defect sites on the surface, not in the bulk of CeO 2, modified by the dopants that play the vital role in CO 2 chemisorption. Lastly, the role of surface oxygen vacancies is further supported by an in situ IR spectroscopic study of the surface chemistry during CO 2 adsorption on the doped CeO 2.« less

Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO 2 supports

DOE PAGES

Kim, Mi -Young; Kyriakidou, Eleni A.; Choi, Jae -Soon; ...

2016-01-18

In this study, we investigated the impact of ZrO 2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO 2 and SiO 2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO 2 surface area and improve sulfur tolerance, a Pd support with ZrO 2-dispersed onto SiO 2 was studied. The physicochemical properties of the catalysts were examined using ICP, N 2 sorption, XRD, SEM, TEM, and NH 3-, CO 2-, and NO x-TPD. The activity of the Pd catalysts were measured frommore » 60 to 600 °C in a flow of 4000 ppm CO, 500 ppm NO, 1000 ppm C 3H 6, 4% O 2, 5% H 2O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO 2-containing catalysts showed considerably higher CO and C 3H 6 oxidation activity than Pd/SiO 2 under the reaction conditions studied.« less

Microstructure-property relationships of chemically vapor deposited zirconia fiber coating for environmentally durable silicon carbide/silicon carbide composites

NASA Astrophysics Data System (ADS)

Li, Hao

In SiC/SiC ceramic matrix composites, toughness is obtained by adding a fiber coating, which provides a weak interface for crack deflection and debonding between the fiber and the matrix. However, the most commonly used fiber coatings, carbon and boron nitride, are unstable in oxidative environments. In the present study, the feasibility of using a chemically vapor deposited zirconia (CVD-ZrO2) fiber coating as an oxidation-resistant interphase for SiC/SiC composites was investigated. A study of morphological evolution in the CVD-ZrO2 coating suggested that a size-controlled displacive phase transformation from tetragonal ZrO2 ( t-ZrO2) to monoclinic ZrO2 (m-ZrO 2) was the key mechanism responsible for the weak interface behavior exhibited by the ZrO2 coating. It appeared that a low oxygen partial pressure in the CVD reactor chamber was essential for the nucleation of t-ZrO2 and therefore was responsible for the delamination behavior. With this understanding of the weak interface mechanism, minicomposite specimens containing various ZrO2 fiber coating morphologies were fabricated and tested. A fractographic analysis showed that in-situ fiber strength and minicomposite failure loads were strongly dependent on the phase contents and microstructure of the ZrO2 coating. We determined that an optimum microstructure of the ZrO2 coating should contain a predelaminated interface surrounded by a dense outer layer. The outer layer was needed to protect the fiber from degradation during the subsequent SiC matrix infiltration procedure. A preliminary tensile stress-rupture study indicated that the ZrO2 coating exhibited promising performance in terms of providing the weak interface behavior and maintaining the thermal and oxidative stability at elevated temperatures.

Enhanced stability of solid oxide fuel cells by employing a modified cathode-interlayer interface with a dense La0.6Sr0.4Co0.2Fe0.8O3-δ thin film

NASA Astrophysics Data System (ADS)

De Vero, Jeffrey C.; Develos-Bagarinao, Katherine; Kishimoto, Haruo; Ishiyama, Tomohiro; Yamaji, Katsuhiko; Horita, Teruhisa; Yokokawa, Harumi

2018-02-01

In La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode/Gd-doped ceria (GDC)/yttria-stabilized zirconia (YSZ)-electrolyte based solid oxide fuel cells (SOFCs), one of the key issues affecting performance and long-term stability is the apparent deactivation of LSCF cathode by the presence of secondary phases such as SrZrO3 at the interfaces. Herein, we report that by modifying the cathode-interlayer interface with a dense LSCF thin film, the severe cation interdiffusion is suppressed especially the fast gas or surface diffusion of Sr into adjacent GDC-interlayer/YSZ-electrolyte resulting in the significant reduction of SrZrO3 formation at the interfaces improving cell stability. In order to understand the present results, the interface chemistry is carefully considered and discussed. The results show that modification of cathode-interlayer interfaces is an important strategy for improving the lifetime of SOFCs.

Garnet-type solid-state fast Li ion conductors for Li batteries: critical review.

PubMed

Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana

2014-07-07

Batteries are electrochemical devices that store electrical energy in the form of chemical energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and electric vehicles. Conventional LiBs use an organic polymer electrolyte, which exhibits several safety issues including leakage, poor chemical stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power density. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compounds are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion conductivity of ∼10(-6) at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion conductivity of 10(-3) S cm(-1) at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chemically stable at higher temperatures and voltages compared to polymer electrolytes. Here, we discuss the chemical composition-structure-ionic conductivity relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.

Synthesis and characterization of insulin/zirconium phosphate@TiO2 hybrid composites for enhanced oral insulin delivery applications.

PubMed

Safari, Mostafa; Kamari, Younes; Ghiaci, Mehran; Sadeghi-Aliabadi, Hojjat; Mirian, Mina

2017-05-01

In this work, a series of composites of insulin (Ins)/zirconium phosphate (ZrP) were synthesized by intercalation method, then, these composites were coated with TiO 2 by sol-gel method to prepare Ins/ZrP@TiO 2 hybrid composites and the drug release of the composites was investigated by using UV-Vis spectroscopy. Ins/ZrP (10, 30, 60 wt%) composites were prepared by intercalation of insulin into the ZrP layers in water. Then Ins/ZrP composites were coated with different amounts of TiO 2 (30, 50, 100 wt %) by using titanium tetra n-butoxide, as precursor. Formation of intercalated Ins/ZrP and Ins/ZrP@TiO 2 hybrid composites was characterized by FT-IR, FE-SEM, BET and XRD analysis. Zeta potential of the optimized Ins/ZrP@TiO 2 hybrid composite was determined -27.2 mV. Cytotoxic effects of the optimized Ins/ZrP@TiO 2 hybrid composite against HeLa and Hek293T cell lines were evaluated using MTT assay and the results showed that designed drug delivery system was not toxic in biological environment. Compared to the Ins/ZrP composites, incorporation of TiO 2 coating enhanced the drug entrapment considerably, and reduced the drug release. The Ins/ZrP composites without TiO 2 coating released the whole drug after 30 min in pH 7.4 (phosphate buffer solution) while the TiO 2 -coated composites released the entrapped drug after 20 h. In addition to increasing the shelf life of hormone, this nanoencapsulation and nanocoating method can convert the insulin utilization from injection to oral and present a painless and more comfortable treatment for diabetics.

Preparation and Characterization of Zirconia-Coated Nanodiamonds as a Pt Catalyst Support for Methanol Electro-Oxidation

PubMed Central

Lu, Jing; Zang, Jianbing; Wang, Yanhui; Xu, Yongchao; Xu, Xipeng

2016-01-01

Zirconia-coated nanodiamond (ZrO2/ND) electrode material was successfully prepared by one-step isothermal hydrolyzing from ND-dispersed ZrOCl2·8H2O aqueous solution. High-resolution transmission electron microscopy reveals that a highly conformal and uniform ZrO2 shell was deposited on NDs by this simple method. The coating obtained at 90 °C without further calcination was mainly composed of monoclinic nanocrystalline ZrO2 rather than common amorphous Zr(OH)4 clusters. The ZrO2/NDs and pristine ND powder were decorated with platinum (Pt) nanoparticles by electrodeposition from 5 mM chloroplatinic acid solution. The electrochemical studies indicate that Pt/ZrO2/ND catalysts have higher electrocatalytic activity and better stability for methanol oxidation than Pt/ND catalysts in acid. PMID:28335361

Structure and radiation effect of Er-stuffed pyrochlore Er2(Ti2-xErx)O7-x/2 (x = 0-0.667)

NASA Astrophysics Data System (ADS)

Yang, D. Y.; Xu, C. P.; Fu, E. G.; Wen, J.; Liu, C. G.; Zhang, K. Q.; Wang, Y. Q.; Li, Y. H.

2015-08-01

Er-stuffed pyrochlore series Er2(Ti2-xErx)O7-x/2 (x = 0, 0.162, 0.286, 0.424 and 0.667) were synthesized using conventional ceramic processing procedures. The structure of Er2(Ti2-xErx)O7-x/2 is effectively tailored by the Er stuffing level (x). In order to study the radiation effect of Er-stuffed pyrochlores, irradiation experiments were performed with 400 keV Ne2+ ions to fluences ranging from 5 × 1014 to 3.0 × 1015 ions/cm2 at cryogenic condition. Irradiation induced microstructural evolution was examined using a grazing incidence X-ray diffraction technique. It is found that the irradiated layer of Er2(Ti2-xErx)O7-x/2 undergoes significant lattice disordering and swelling at fluences of ⩽1.5 × 1015 ions/cm2 and amorphization at fluences of ⩾1.5 × 1015 ions/cm2. The radiation effect depends strongly on the chemical compositions of the samples. Both the lattice swelling percentage and the amorphous fraction decrease with increasing x. The experimental results are discussed in the context of cation antisite defect. The defect formation energy which varies as a function of x is responsible for the difference in the structural behaviors of Er2(Ti2-xErx)O7-x/2 under 400 keV Ne2+ ion irradiation.

Microstructural and mechanical properties of Al2O3/ZrO2 nanomultilayer thin films prepared by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Balakrishnan, G.; Sastikumar, D.; Kuppusami, P.; Babu, R. Venkatesh; Song, Jung Il

2018-02-01

Single layer aluminium oxide (Al2O3), zirconium oxide (ZrO2) and Al2O3/ZrO2 nano multilayer films were deposited on Si (100) substrates at room temperature by pulsed laser deposition. The development of Al2O3/ZrO2 nanolayered structure is an important method used to stabilize the high temperature phase (tetragonal and cubic) of ZrO2 at room temperature. In the Al2O3/ZrO2 multilayer structure, the Al2O3 layer was kept constant at 5 nm, while the ZrO2 layer thickness varied from 5 to 20 nm (5/5, 5/10, 5/15 and 5/20 nm) with a total of 40 bilayers. The X-ray diffraction studies of single layer Al2O3 indicated the γ-Al2O3 of cubic structure, while the single layer ZrO2 indicated both monoclinic and tetragonal phases. The 5/5 and 5/10 nm multilayer films showed the nanocrystalline nature of ZrO2 with tetragonal phase. The high resolution transmission electron microscopy studies indicated the formation of well-defined Al2O3 and ZrO2 layers and that they are of uniform thickness. The atomic force microscopy studies revealed the uniform and dense distribution of nanocrystallites. The nanoindentation studies indicated the hardness of 20.8 ± 1.10 and 10 ± 0.60 GPa, for single layer Al2O3 and ZrO2, respectively, and the hardness of multilayer films varied with bilayer thickness.

Metal Adatoms and Clusters on Ultrathin Zirconia Films

PubMed Central

2016-01-01

Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces. PMID:27213024

Defect-related electroluminescence from metal-oxide-semiconductor devices with ZrO2 films on silicon

NASA Astrophysics Data System (ADS)

Lv, Chunyan; Zhu, Chen; Wang, Canxing; Li, Dongsheng; Ma, Xiangyang; Yang, Deren

2016-11-01

Defect-related electroluminescence (EL) from ZrO2 films annealed under different atmosphere has been realized by means of electrical pumping scheme of metal-oxide-semiconductor (MOS) devices. At the same injection current, the acquired EL from the MOS device with the vacuum-annealed ZrO2 film is much stronger than that from the counterpart with the oxygen-annealed ZrO2 film. This is because the vacuum-annealed ZrO2 film contains more oxygen vacancies and Zr3+ ions. Analysis on the current-voltage characteristic of the ZrO2-based MOS devices indicates the P-F conduction mechanism dominates the electron transportation at the EL-enabling voltages under forward bias. It is tentatively proposed that the recombination of the electrons trapped in multiple oxygen-vacancy-related states with the holes in the defect level pertaining to Zr3+ ions brings about the EL emissions.

Fragile singlet ground-state magnetism in the pyrochlore osmates R 2 Os 2 O 7 ( R = Y and Ho)

DOE PAGES

Zhao, Z. Y.; Calder, S.; Aczel, A. A.; ...

2016-04-25

The singlet ground state magnetism in pyrochlore osmates Y 2Os 2O 7 and Ho 2Os 2O 7 is studied by DC and AC susceptibility, specific heat, and neutron powder diffraction measurements. Despite the expected non-magnetic singlet in the strong spin-orbit coupling (SOC) limit for Os 4+ (5d 4), Y 2Os 2O 7 exhibits a spin-glass (SG) ground state below 4 K with weak magnetism, suggesting possible proximity to a quantum phase transition between the non-magnetic state in the strong SOC limit and the magnetic state in the strong superexchange limit. Ho 2Os 2O 7 has the same structural distortion asmore » occurs in Y 2Os 2O 7. However, the Os sublattice in Ho 2Os 2O 7 shows long- range magnetic ordering below 36 K. We find that the sharp difference of the magnetic ground state between Y 2Os 2O 7 and Ho 2Os 2O 7 signals the singlet ground state magnetism in R 2 Os 2 O 7 is fragile and can be disturbed by the weak 4f—5d interactions.« less

Fragile singlet ground-state magnetism in the pyrochlore osmates R 2 Os 2 O 7 ( R = Y and Ho)

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

Zhao, Z. Y.; Calder, S.; Aczel, A. A.

The singlet ground state magnetism in pyrochlore osmates Y 2Os 2O 7 and Ho 2Os 2O 7 is studied by DC and AC susceptibility, specific heat, and neutron powder diffraction measurements. Despite the expected non-magnetic singlet in the strong spin-orbit coupling (SOC) limit for Os 4+ (5d 4), Y 2Os 2O 7 exhibits a spin-glass (SG) ground state below 4 K with weak magnetism, suggesting possible proximity to a quantum phase transition between the non-magnetic state in the strong SOC limit and the magnetic state in the strong superexchange limit. Ho 2Os 2O 7 has the same structural distortion asmore » occurs in Y 2Os 2O 7. However, the Os sublattice in Ho 2Os 2O 7 shows long- range magnetic ordering below 36 K. We find that the sharp difference of the magnetic ground state between Y 2Os 2O 7 and Ho 2Os 2O 7 signals the singlet ground state magnetism in R 2 Os 2 O 7 is fragile and can be disturbed by the weak 4f—5d interactions.« less

Neutron spectroscopic study of crystal field excitations in Tb 2Ti 2O 7 and Tb 2Sn 2O 7

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

Zhang, J.; Fritsch, Katharina; Hao, Z.

2014-04-01

We present time-of-flight inelastic neutron scattering measurements at low temperature on powder samples of the magnetic pyrochlore oxides Tb 2Ti 2O 7 and Tb 2Sn 2O 7. These two materials possess related, but different ground states, with Tb 2Sn 2O 7 displaying "soft" spin ice order below T N approx 0.87 K, while Tb 2Ti 2O 7 enters a hybrid, glassy-spin ice state below T g approx 0.2 K. Our neutron measurements, performed at T = 1.5 K and 30 K, probe the crystal field states associated with the J = 6 states of Tb 3+ within the appropriate Fd3-barmmore » pyrochlore environment. These crystal field states determine the size and anisotropy of the Tb 3+ magnetic moment in each material's ground state, information that is an essential starting point for any description of the low temperature phase behavior and spin dynamics in Tb 2Ti 2O 7 and Tb 2Sn 2O 7. While these two materials have much in common, the cubic stanate lattice is expanded compared to the cubic titanate lattice. As our measurements show, this translates into a factor of approx 2 increase in the crystal field bandwidth of the 2J +1 = 13 states in Tb 2Ti 2O 7 compared with Tb 2Sn 2O 7. Our results are consistent with previous measurements on crystal field states in Tb 2Sn 2O 7, wherein the ground state doublet corresponds primarily to mJ = {vert_bar}+-5> and the first excited state doublet to mJ = {vert_bar}+-4>. In contrast, our results on Tb 2Ti 2O 7 differ markedly from earlier studies, showing that the ground state doublet corresponds to a significant mixture of mJ = {vert_bar}+-5>, mJ = {vert_bar}+-4> and mJ = {vert_bar}+-2>, while the first excited state doublet corresponds to a mixture of mJ = {vert_bar}+-4>, mJ = {vert_bar}+-5> and mJ = {vert_bar}+-1>. We discuss these results in the context of proposed mechanisms for the failure of Tb 2Ti 2O 7 to develop conventional long range order down to 50 mK.« less

Carbon monoxide formation in UO2 kerneled HTR fuel particles containing oxygen getters

NASA Astrophysics Data System (ADS)

Proksch, E.; Strigl, A.; Nabielek, H.

1986-01-01

Mass spectrometric measurements of CO in irradiated UO2 fuel particles containing oxygen getters are summarized. Uranium carbide addition in the 3% to 15% range reduces the CO release by factors between 25 and 80, up to burn-up levels as high as 70% FIMA. Unintentional gettering by SiC in TRISO coated particles with failed inner pyrocarbon layers results in CO reduction factors between 15 and 110. For ZrC, ambiguous results are obtained; ZrC probably results in CO reduction by a factor of 40; Ce2O3 and La2O3 seem less effective than the carbides; for Ce2O3, reduction factors between 3 and 15 are found. However, the results are possibly incorrect due to premature oxidation of the getter already during fabrication. Addition of SiO2 + Al2O3 has no influence on CO release.

One-pot synthesis and optical properties of Eu3+-doped nanocrystalline TiO2 and ZrO2

NASA Astrophysics Data System (ADS)

Julián, Beatriz; Corberán, Rosa; Cordoncillo, Eloisa; Escribano, Purificación; Viana, Bruno; Sanchez, Clément

2005-11-01

A simple and versatile one-pot sol-gel synthesis of Eu3+-doped nanocrystalline TiO2 and ZrO2 nanomaterials is reported in this paper. It consists of the controlled crystallization of Eu3+-doped TiO2 or ZrO2 nanoparticles from an initial solution containing the metal alkoxide, the lanthanide precursor, a complexing agent and a non-complexing acid. The main interest is that it could be extended to different lanthanide ions and inorganic metal oxides to prepare other multifunctional nanomaterials. The characterization by XRD, HRTEM and SAED techniques showed that the TiO2 and ZrO2 crystallization takes place at very low temperatures (60 °C) and that the crystallite size can be tailored by modifying the synthetic conditions. The optical properties of the resulting materials were studied by emission spectra and decay measurements. Both Eu3+:TiO2 and Eu3+:ZrO2 samples exhibited long lifetime values after removing organic components (τ = 0.7 and 1.3 ms, respectively), but the Eu3+:ZrO2 system is specially promising for photonic applications since its τ value is longer than some reported for other inorganic or hybrid matrices in which Eu3+ ions are complexed. This behaviour has been explained through an effective dispersion of the lanthanide ions within the ZrO2 nanocrystals.

A new generation of zirconia supported metal oxide catalysts for converting low grade renewable feedstocks to biodiesel.

PubMed

Kim, Manhoe; DiMaggio, Craig; Salley, Steven O; Simon Ng, K Y

2012-08-01

A new class of zirconia supported mixed metal oxides (ZnO-TiO(2)-Nd(2)O(3)/ZrO(2) and ZnO-SiO(2)-Yb(2)O(3)/ZrO(2)) has demonstrated the ability to convert low quality, high free fatty acid (FFA) bio-oils into biodiesel. Pelletized catalysts of ZrO(2) supported metal oxides were prepared via a sol-gel process and tested in continuous flow packed bed reactors for up to 6 months. In a single pass, while operating at mild to moderate reaction conditions, 195 °C and 300 psi, these catalysts can perform simultaneous esterification and transesterification reactions on feedstock of 33% FFA and 67% soybean oil to achieve FAME yields higher than 90%. Catalytic activity of the ZrO(2) supported metal oxide catalysts was highly dependent on the metal oxide composition. These heterogeneous catalysts will enable biodiesel manufacturers to avoid problems inherent in homogeneous processes, such as separation and washing, corrosive conditions, and excessive methanol usage. Copyright © 2012 Elsevier Ltd. All rights reserved.

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.

Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2001-01-01

Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.

CO 2 hydrogenation over oxide-supported PtCo catalysts: The role of the oxide support in determining the product selectivity

DOE PAGES

Kattel, Shyam; Yu, Weiting; Yang, Xiaofang; ...

2016-05-09

By simply changing the oxide support, the selectivity of a metal–oxide catalysts can be tuned. For the CO 2 hydrogenation over PtCo bimetallic catalysts supported on different reducible oxides (CeO 2, ZrO 2, and TiO 2), replacing a TiO 2 support by CeO 2 or ZrO 2 selectively strengthens the binding of C,O-bound and O-bound species at the PtCo–oxide interface, leading to a different product selectivity. Lastly, these results reveal mechanistic insights into how the catalytic performance of metal–oxide catalysts can be fine-tuned.

Laser-induced breakdown spectroscopy of light water reactor simulated used nuclear fuel: Main oxide phase

DOE PAGES

Campbell, Keri R.; Judge, Elizabeth J.; Barefield, James E.; ...

2017-04-22

We show the analysis of light water reactor simulated used nuclear fuel using laser-induced breakdown spectroscopy (LIBS) is explored using a simplified version of the main oxide phase. The main oxide phase consists of the actinides, lanthanides, and zirconium. The purpose of this study is to develop a rapid, quantitative technique for measuring zirconium in a uranium dioxide matrix without the need to dissolve the material. A second set of materials including cerium oxide is also analyzed to determine precision and limit of detection (LOD) using LIBS in a complex matrix. Two types of samples are used in this study:more » binary and ternary oxide pellets. The ternary oxide, (U,Zr,Ce)O 2 pellets used in this study are a simplified version the main oxide phase of used nuclear fuel. The binary oxides, (U,Ce)O 2 and (U,Zr)O 2 are also examined to determine spectral emission lines for Ce and Zr, potential spectral interferences with uranium and baseline LOD values for Ce and Zr in a UO 2 matrix. In the spectral range of 200 to 800 nm, 33 cerium lines and 25 zirconium lines were identified and shown to have linear correlation values (R 2) > 0.97 for both the binary and ternary oxides. The cerium LOD in the (U,Ce)O 2 matrix ranged from 0.34 to 1.08 wt% and 0.94 to 1.22 wt% in (U,Ce,Zr)O 2 for 33 of Ce emission lines. The zirconium limit of detection in the (U,Zr)O 2 matrix ranged from 0.84 to 1.15 wt% and 0.99 to 1.10 wt% in (U,Ce,Zr)O 2 for 25 Zr lines. Finally, the effect of multiple elements in the plasma and the impact on the LOD is discussed.« 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.

Atomic and electronic structures of an extremely fragile liquid

PubMed Central

Kohara, Shinji; Akola, Jaakko; Patrikeev, Leonid; Ropo, Matti; Ohara, Koji; Itou, Masayoshi; Fujiwara, Akihiko; Yahiro, Jumpei; Okada, Junpei T.; Ishikawa, Takehiko; Mizuno, Akitoshi; Masuno, Atsunobu; Watanabe, Yasuhiro; Usuki, Takeshi

2014-01-01

The structure of high-temperature liquids is an important topic for understanding the fragility of liquids. Here we report the structure of a high-temperature non-glass-forming oxide liquid, ZrO2, at an atomistic and electronic level. The Bhatia–Thornton number–number structure factor of ZrO2 does not show a first sharp diffraction peak. The atomic structure comprises ZrO5, ZrO6 and ZrO7 polyhedra with a significant contribution of edge sharing of oxygen in addition to corner sharing. The variety of large oxygen coordination and polyhedral connections with short Zr–O bond lifetimes, induced by the relatively large ionic radius of zirconium, disturbs the evolution of intermediate-range ordering, which leads to a reduced electronic band gap and increased delocalization in the ionic Zr–O bonding. The details of the chemical bonding explain the extremely low viscosity of the liquid and the absence of a first sharp diffraction peak, and indicate that liquid ZrO2 is an extremely fragile liquid. PMID:25520236

Non-toxic invert analog glass compositions of high modulus

NASA Technical Reports Server (NTRS)

Bacon, J. F. (Inventor)

1974-01-01

Glass compositions having a Young's modulus of at least 15 million psi are described. They and a specific modulus of at least 110 million inches consist essentially of, in mols, 15 to 40% SiO2, 6 to 15% Li2O, 24 to 45% of at least two bivalent oxides selected from the group consisting of Ca, NzO, MgO and CuO; 13 to 39% of at least two trivalent oxides selected from the group consisting of Al2O3, Fe2O3, B2O3, La2O3, and Y2O3 and up to 15% of one or more tetravelent oxides selected from the group consisting of ZrO2, TiO2 and CeO2. The high modulus, low density glass compositions contain no toxic elements. The composition, glass density, Young's modulus, and specific modulus for 28 representative glasses are presented. The fiber modulus of five glasses are given.

Effect of UV lamp irradiation during oxidation of Zr/Pt/Si structure on electrical properties of Pt/ZrO 2/Pt/Si structure

NASA Astrophysics Data System (ADS)

Bae, Joon Woo; Lim, Jae-Won; Mimura, Kouji; Uchikoshi, Masahito; Miyazaki, Takamichi; Isshiki, Minoru

2010-03-01

Metal-insulator-metal (MIM) capacitors were fabricated using ZrO 2 films and the effects of structural and native defects of the ZrO 2 films on the electrical and dielectric properties were investigated. For preparing ZrO 2 films, Zr films were deposited on Pt/Si substrates by ion beam deposition (IBD) system with/without substrate bias voltages and oxidized at 200 °C for 60 min under 0.1 MPa O 2 atmosphere with/without UV light irradiation ( λ = 193 nm, Deep UV lamp). The ZrO 2(˜12 nm) films on Pt(˜100 nm)/Si were characterized by X-ray diffraction pattern (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HRTEM), capacitance-voltage ( C- V) and current-voltage ( I- V) measurements were carried out on MIM structures. ZrO 2 films, fabricated by oxidizing the Zr film deposited with substrate bias voltage under UV light irradiation, show the highest capacitance (784 pF) and the lowest leakage current density. The active oxygen species formed by UV irradiation are considered to play an important role in the reduction of the leakage current density, because they can reduce the density of oxygen vacancies.

Photocatalytic properties of amine functionalized Bi2Sn2O7/rGO nanocomposites

NASA Astrophysics Data System (ADS)

Gnanamoorthy, G.; Muthamizh, S.; Sureshbabu, K.; Munusamy, S.; Padmanaban, A.; Kaaviya, A.; Nagarajan, R.; Stephen, A.; Narayanan, V.

2018-07-01

The binary metal oxide nanomaterials are having applications in various fields like sensors, optics, electrocatalyst and photocatalyst so on. Bi2Sn2O7 with pyrochlore structure is having low band gap energy; hence it is utilized in battery storage and gas sensor applications. In the present work, we have made an attempt to synthesis amine-functionalized Bi2Sn2O7/rGO nanocomposites by a thermal decomposition method and in-situ method; the synthesized nanocomposites were confirmed by XRD, FT-IR and Raman analysis. The AF-Bi2Sn2O7/rGO nanocomposites morphology was confirmed by FE-SEM along with EDX spectroscopy, we obtained different flowers and nest-like morphology. The pure and composite material band gap energy is decreases from 2.6 eV to 1.6 eV. All three nanomaterials Bi2Sn2O7, AF-Bi2Sn2O7, AF-Bi2Sn2O7/rGO nanocomposites (AF-amine functionalized) were utilized for the photocatalytic degradation of methylene blue dye under visible light irradiation. AF-Bi2Sn2O7/rGO nanocomposite showed an excellent photocatalytic activity than pure Bi2Sn2O7 and AF- Bi2Sn2O7.

Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells

PubMed Central

Chen, Yun; Gerdes, Kirk; Song, Xueyan

2016-01-01

Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1−xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650–800 °C for 400 hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5–1.7 operated at 0.8 V at 750 °C. PMID:27605121

Tensile Strength and Microstructure of Al2O3-ZrO2 Hypo-Eutectic Fibers Studied

NASA Technical Reports Server (NTRS)

Farmer, Serene C.; Sayir, Ali

2001-01-01

Oxide eutectics offer high-temperature strength retention and creep resistance in oxidizing environments. Al2O3-ZrO2 eutectic strengths have been studied since the 1970's. Directionally solidified oxide eutectics exhibit improved resistance to slow crack growth and excellent strength retention at high temperatures up to 1400 C. Materials studied typically contain Y2O3 to metastably retain the high-temperature cubic and tetragonal polymorphs at room temperature. Al2O3-ZrO2 is of fundamental interest for creep studies because it combines a creep-resistant material, Al2O3, with a very low creep resistance material, ZrO2. Results on mechanical properties and microstructures of these materials will be used to define compositions for creep testing in future work. Substantial variations from the eutectic alumina to zirconia ratio can be tolerated without a loss in room-temperature strength. The effect of increasing Y2O3 addition on the room-temperature tensile strength of an Al2O3-ZrO2 material containing excess Al2O3 was examined at the NASA Glenn Research Center, where the materials were grown using Glenn's world-class laser growth facilities.

Effect of lattice-misfit strain on the process-induced imprint behavior in epitaxial Pb (Zr0.52Ti0.48)O3 thin films

NASA Astrophysics Data System (ADS)

Wu, Wenbin; Wang, Y.; Pang, G. K. H.; Wong, K. H.; Choy, C. L.

2004-08-01

The effect of lattice-misfit strain on the process-induced imprint behavior in Pb (Zr0.52Ti0.48)O3 (PZT) capacitors with Pt (top), and SrRuO3, La0.7Sr0.3MnO3 or LaNiO3 (bottom) electrodes has been studied. With the different oxide electrodes and by changing the deposition oxygen pressure, various lattice-misfit strains in the epitaxial PZT films have been produced. It was found that after in situ annealing at reduced oxygen pressures, the capacitors showed an increased voltage offset in the polarization-electric field hysteresis loops with increasing the misfit strain, irrelevant to the oxide electrodes employed, while lattice disorder at the bottom interface can effectively eliminate the voltage shift. Our results suggest that the imprint behavior is caused by oxygen loss via dislocations generated by the misfit strain relaxation at the growth temperature.

Zr/ZrO2 sensors for in situ measurement of pH in high-temperature and -pressure aqueous solutions.

PubMed

Zhang, R H; Zhang, X T; Hu, S M

2008-04-15

The aim of this study is to develop new pH sensors that can be used to test and monitor hydrogen ion activity in hydrothermal conditions. A Zr/ZrO2 oxidation electrode is fabricated for in situ pH measurement of high-temperature aqueous solutions. This sensor responds rapidly and precisely to pH over a wide range of temperature and pressure. The Zr/ZrO2 electrode was made by oxidizing zirconium metal wire with Na2CO3 melt, which produced a thin film of ZrO2 on its surface. Thus, an oxidation-reduction electrode was produced. The Zr/ZrO2 electrode has a good electrochemical stability over a wide range of pH in high-temperature aqueous solutions when used with a Ag/AgCl reference electrode. Measurements of the Zr/ZrO2 sensor potential against a Ag/AgCl reference electrode is shown to vary linearly with pH between temperatures 20 and 200 degrees C. The slope of the potential versus pH at high temperature is slightly below the theoretical value indicated by the Nernst equation; such deviation is attributed to the fact that the sensor is not strictly at equilibrium with the solution to be tested in a short period of time. The Zr/ZrO2 sensor can be calibrated over the conditions that exist in the natural deep-seawater. Our studies showed that the Zr/ZrO2 electrode is a suitable pH sensor for the hydrothermal systems at midocean ridge or other geothermal systems with the high-temperature environment. Yttria-stabilized zirconia sensors have also been used to investigate the pH of hydrothermal fluids in hot springs vents at midocean ridge. These sensors, however, are not sensitive below 200 degrees C. Zr/ZrO2 sensors have wider temperature range and can be severed as good alternative sensors for measuring the pH of hydrothermal fluids.

Structural and electrical properties of atomic layer deposited Al-doped ZrO2 films and of the interface with TaN electrode

NASA Astrophysics Data System (ADS)

Spiga, S.; Rao, R.; Lamagna, L.; Wiemer, C.; Congedo, G.; Lamperti, A.; Molle, A.; Fanciulli, M.; Palma, F.; Irrera, F.

2012-07-01

Al-doped ZrO2 (Al-ZrO2) films deposited by atomic layer deposition onto silicon substrates and the interface with the TaN metal gate are investigated. In particular, structural properties of as-grown and annealed films in the 6-26 nm thickness range, as well as leakage and capacitive behavior of metal-oxide-semiconductor stacks are characterized. As-deposited Al-ZrO2 films in the mentioned thickness range are amorphous and crystallize in the ZrO2 cubic phase after thermal treatment at 900 °C. Correspondingly, the dielectric constant (k) value increases from 20 ± 1 to 27 ± 2. The Al-ZrO2 layers exhibit uniform composition through the film thickness and are thermally stable on Si, whereas chemical reactions take place at the TaN/Al-ZrO2 interface. A transient capacitance technique is adopted for monitoring charge trapping and flat band instability at short and long time scales. The role of traps nearby the TaN/Al-ZrO2 interface is discussed and compared with other metal/high-k oxide films. Further, analytical modeling of the flat band voltage shift with a power-law dependence on time allows extracting features of bulk traps close to the silicon/oxide interface, which exhibit energy levels in the 1.4-1.9 eV range above the valence band of the Al-ZrO2.

Zircon Supported Copper Catalysts for the Steam Reforming of Methanol

NASA Astrophysics Data System (ADS)

Widiastri, M.; Fendy, Marsih, I. N.

2008-03-01

Steam reforming of methanol (SRM) is known as one of the most favorable catalytic processes for producing hydrogen. Current research on zirconia, ZrO2 supported copper catalyst revealed that CuO/ZrO2 as an active catalyst for the SRM. Zircon, ZrSiO4 is available from the by-product of tin mining. In the work presented here, the catalytic properties of CuO/ZrSiO4 with various copper oxide compositions ranging from 2.70% (catalyst I), 4.12% (catalyst II), and 7.12%-mass (catalyst III), synthesized by an incipient wetness impregnation technique, were investigated to methanol conversion, selectivity towards CO formation, and effect of ZnO addition (7.83%CuO/8.01%ZnO/ZrSiO4 = catalyst V). The catalytic activity was obtained using a fixed bed reactor and the zircon supported catalyst activity was compared to those of CuO/ZnO/Al2O3 catalyst (catalyst IV) and commercial Kujang LTSC catalyst. An X-ray powder diffraction (XRD) analysis was done to identify the abundant phases of the catalysts. The catalysts topography and particle diameter were measured with scanning electron microscopy (SEM) and composition of the catalysts was measured by SEM-EDX, scanning electron microscope-energy dispersive using X-ray analysis. The results of this research provide information on the possibility of using zircon (ZrSiO4) as solid support for SRM catalysts.

Cyclic Catalytic Upgrading of Chemical Species Using Metal Oxide Materials

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Rolfe, Sara L. (Inventor); Schutte, Erick J. (Inventor)

2013-01-01

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce(sub x)B(sub y)B'(sub z)B''O(sub gamma; wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Cyclic catalytic upgrading of chemical species using metal oxide materials

DOEpatents

White, James H; Schutte, Erick J; Rolfe, Sara L

2013-05-07

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Single Crystal Fibers of Yttria-Stabilized Cubic Zirconia with Ternary Oxide Additions

NASA Technical Reports Server (NTRS)

Ritzert, F. J.; Yun, H. M.; Miner, R. V.

1997-01-01

Single crystal fibers of yttria (Y2O3)-stabilized cubic zirconia, (ZrO2) with ternary oxide additions were grown using the laser float zone fiber processing technique. Ternary additions to the ZrO2-Y2O3 binary system were studied aimed at increasing strength while maintaining the high coefficient of thermal expansion of the binary system. Statistical methods aided in identifying the most promising ternary oxide candidate (Ta2O5, Sc2O3, and HfO2) and optimum composition. The yttria, range investigated was 14 to 24 mol % and the ternary oxide component ranged from 1 to 5 mol %. Hafnium oxide was the most promising ternary oxide component based on 816 C tensile strength results and ease of fabrication. The optimum composition for development was 81 ZrO2-14 Y203-5 HfO2 based upon the same elevated temperature strength tests. Preliminary results indicate process improvements could improve the fiber performance. We also investigated the effect of crystal orientation on strength.

Competing Spin Liquids and Hidden Spin-Nematic Order in Spin Ice with Frustrated Transverse Exchange

NASA Astrophysics Data System (ADS)

Taillefumier, Mathieu; Benton, Owen; Yan, Han; Jaubert, L. D. C.; Shannon, Nic

2017-10-01

Frustration in magnetic interactions can give rise to disordered ground states with subtle and beautiful properties. The spin ices Ho2 Ti2 O7 and Dy2 Ti2 O7 exemplify this phenomenon, displaying a classical spin-liquid state, with fractionalized magnetic-monopole excitations. Recently, there has been great interest in closely related "quantum spin-ice" materials, following the realization that anisotropic exchange interactions could convert spin ice into a massively entangled, quantum spin liquid, where magnetic monopoles become the charges of an emergent quantum electrodynamics. Here we show that even the simplest model of a quantum spin ice, the XXZ model on the pyrochlore lattice, can realize a still-richer scenario. Using a combination of classical Monte Carlo simulation, semiclassical molecular-dynamics simulation, and analytic field theory, we explore the properties of this model for frustrated transverse exchange. We find not one, but three competing forms of spin liquid, as well as a phase with hidden, spin-nematic order. We explore the experimental signatures of each of these different states, making explicit predictions for inelastic neutron scattering. These results show an intriguing similarity to experiments on a range of pyrochlore oxides.

Fabrication of oxide layer on zirconium by micro-arc oxidation: Structural and antimicrobial characteristics.

PubMed

Fidan, S; Muhaffel, F; Riool, M; Cempura, G; de Boer, L; Zaat, S A J; Filemonowicz, A Czyrska-; Cimenoglu, H

2017-02-01

The aim of this study was to cover the surfaces of zirconium (Zr) with an antimicrobial layer for biomedical applications. For this purpose, the micro-arc oxidation (MAO) process was employed in a sodium silicate and sodium hydroxide containing base electrolyte with and without addition of silver acetate (AgC 2 H 3 O 2 ). In general, synthesized MAO layers were composed of zirconium oxide (ZrO 2 ) and zircon (ZrSiO 4 ). Addition of AgC 2 H 3 O 2 into the base electrolyte caused homogenous precipitation of silver-containing particles in the MAO layer, which exhibited excellent antibacterial efficiency against methicillin-resistant Staphylococcus aureus (MRSA) as compared to the untreated and MAO-treated Zr. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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

The effect of 0.1 atomic percent zirconium on the cyclic oxidation behavior of beta-NiAl for 300 hours at 1200 C

NASA Technical Reports Server (NTRS)

Barrett, C. A.

1988-01-01

The long time effect of 0.1 at percent Zr (0.2 wt percent Zr) on the cyclic oxidation behavior of hipped beta-NiAl was studied. Oxidation testing was performed in static air at 1200 C for up to 3000 one-hour exposure cycles. Specific weight change versus time data was modeled with the COSP computer program to analyze cyclic oxidation behavior. The Zr-free stoichiometric alloy oxidized and spalled randomly to bare metal between cycles at a rate high enough to deplete Al to a low enough level that oxidation breakaway took place as nonprotective NiO replaced the alpha-Al2O3/NiAl2O4 scale as the controlling oxide. The Zr minimized this severe type of spalling maintaining the protective alpha-Al2O3 scale even out to 3000 hours for the stoichiometric alloy with no significant Al depletion. A third beta-NiAl alloy containing 0.1 at percent Zr but with 10 percent less Al than the stoichiometric alloy was also tested and showed some depletion of Al, but the protective Al2O3/NiAl2O4 was still maintained to close to 2700 hours.

Structural, negative thermal expansion and photocatalytic properties of ZrV{sub 2}O{sub 7}: a comparative study between fibers and powders

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

Liu, Qinqin, E-mail: liu_qin_qin@126.com; Yang, Juan; Rong, Xiaoqing

2014-10-15

Novel ZrV{sub 2}O{sub 7} microfibers with diameters about 1–3 μm were synthesized using a sol–gel technique. For comparison, ZrV{sub 2}O{sub 7} powders were prepared by the same method. The resultant structures were studied by X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy. The results indicated that both the pure ZrV{sub 2}O{sub 7} microfibers and powders could be synthesized by the sol–gel technique. The thermal expansion property of the as-prepared ZrV{sub 2}O{sub 7} microfibers and powders was characterized by a thermal mechanical analyzer, both the fibers with cylindrical morphology and irregular powders with average size between 100 and 200more » nm showed negative thermal expansion between 150 °C and 600 °C. The photocatalytic activity of the microfibers was compared to that of powders under UV radiations. The band gap of ZrV{sub 2}O{sub 7} microfibers decreased and its absorption edge exhibited red shift. The microfibers also had a higher surface area compared with the powders, resulting in considerably higher photocatalytic characteristics. The large surface area and the enhanced photocatalytic activity of the ZrV{sub 2}O{sub 7} microfibers also offer potential applications in sensors and inorganic ion exchangers. - Graphical abstract: (a and c) SEM photos of ZrV{sub 2}O{sub 7} powders and fibers. (b and d) TEM images of ZrV{sub 2}O{sub 7} powders and fibers. (e) Thermal expansion curves of ZrV{sub 2}O{sub 7} powders and fibers. (f) Degradation curves of ZrV{sub 2}O{sub 7} powders and ZrV{sub 2}O{sub 7} fibers. - Highlights: • Novel ZrV{sub 2}O{sub 7} fibers could be synthesized using sol–gel technique. • ZrV{sub 2}O{sub 7} powders with irregular shape are also prepared for comparison. • Both ZrV{sub 2}O{sub 7} microfibers and powders exhibit negative thermal expansion property. • ZrV{sub 2}O{sub 7} microfibers show outstanding photocatalytic activity under UV irradiation. • This synthesis technique can be easily extended to many other functional fibers.« less

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

Photoluminescence and cathodoluminescence of Tb-doped Al 2O 3-ZrO 2 nanostructures obtained by sol-gel method

NASA Astrophysics Data System (ADS)

Zawadzki, M.; Hreniak, D.; Wrzyszcz, J.; Miśta, W.; Grabowska, H.; Malta, O. L.; Stręk, W.

2003-07-01

Terbium-doped Al 2O 3-ZrO 2 mixed oxides of 10 wt% zirconia content were prepared by the alkoxide sol-gel method. The obtained samples were characterized by XRD, SEM, thermal analysis, textural and TPR studies. The effect of thermal treatment of Tb-doped Al 2O 3-ZrO 2 samples on photo- and cathodoluminescence spectra was investigated. It was found that the photoluminescence spectrum induced by UV excitation was characterized by a green luminescence pattern arising from the 5D 4 → 7F J ( J=6-0) transitions of the Tb 3+ ion. This photoluminescence became almost completely damped for the samples sintered at 1200 °C. However, these samples have demonstrated an intense cathodoluminescence under high electron accelerating potential (60 kV). Moreover, it was observed that apart of the green luminescence, the blue emission lines arising from 5D 3 → 7F J transitions of Tb 3+ were observed. The nature of such behavior is discussed.

2.7 MeV Ar11+ ion irradiation induced structural evolution in Lu2(Ti2-xLux)O7-x/2 pyrochlores

NASA Astrophysics Data System (ADS)

Yang, D. Y.; Liu, C. G.; Zhang, K. Q.; Xia, Y.; Chen, L. J.; Liu, H.; Li, Y. H.

2015-11-01

This paper aims to study the radiation effects of nonstoichiometric pyrochlore series Lu2(Ti2-xLux)O7-x/2 (x = 0-0.667). Polycrystalline Lu2(Ti2-xLux)O7-x/2 samples were irradiated with 2.7 MeV Ar11+ ions up to a fluence of 8 × 1014 ions/cm2. The irradiated samples were characterized using grazing incidence X-ray diffraction technique. The results reveal that Lu2(Ti2-xLux)O7-x/2 samples undergo significant amorphization and lattice swelling upon irradiation. Specifically, the amorphization process is predominantly driven by ballistic nuclear energy deposition of Ar11+ ions at this energy regime, which can be well described by a direct-impact/defect-stimulated model. Both the amorphization fraction and the relative variation of lattice parameter decrease with increasing x, showing a strong dependence on the chemical composition. The results are then discussed in the framework of the structural disorder and recovery ability from damage, applying an atomic layer model.

Synthesis of nanocrystalline Gd2Ti2O7 by combustion process and its structural, optical and dielectric properties

NASA Astrophysics Data System (ADS)

Jeyasingh, T.; Saji, S. K.; Wariar, P. R. S.

2017-07-01

Nanosized pyrochlore material Gadolinium Titanate (Gd2Ti2O7) powder was prepared by modified single step auto-ignition combustion process. The phase formation has been investigated using X-Ray diffraction analysis (XRD). The crystalline pyrochlore phase is further confirmed by the presence of metal-oxygen bonds in the FT-IR spectra. XRD analysis revealed that Gd2Ti2O7 has a cubic structure with Fd3m space group. The combustion powder was sintered to high density (97% of theoretical density) at ˜13000 C for 4h and the surface morphology was examined by Scanning Electron Microscopy (SEM). The optical band gap of Gd2Ti2O7 determined from the absorption spectrum is found to be 4.2 eV, which corresponds to direct allowed transitions. The dielectric measurements were carried out using LCR meter in the radio frequency region at room temperature. The sintered Gd2Ti2O7 has a dielectric constant (Ɛr) = 40 and dielectric loss (tan δ) = 0.01 at 1MHz.

Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: effect of calcination temperature of catalysts.

PubMed

Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

2012-02-29

Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO(x)/ZrO2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WOx/ZrO2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO2) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO3 and monoclinic ZrO2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WOx/ZrO2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS. Copyright © 2012 Elsevier B.V. All rights reserved.

The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

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

Davidson, Stephen D.; Sun, Junming; Wang, Yong

The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway,more » evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.« less

Experimental investigation of 150-KG-scale corium melt jet quenching in water

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

Magallon, D.; Hohmann, H.

This paper compares and discusses the results of two large scale FARO quenching tests known as L-11 and L-14, which involved, respectively, 151 kg of W% 76.7 UO{sub 2} + 19.2 ZrO{sub 2} + 4.1 Zr and 125 kg of W% 80 UO{sub 2} + 20 ZrO{sub 2} melts poured into 600-kg, 2-m-depth water at saturation at 5.0 MPa. The results are further compared with those of two previous tests performed using a pure oxidic melt, respectively 18 and 44 kg of W% 80 UO{sub 2} + 20 ZrO{sub 2} melt quenched in 1-m-depth water at saturation at 5.0 MPa.more » In all the tests, significant breakup and quenching took place during the melt fall through the water. No steam explosion occurred. In the tests performed with a pure oxide UO{sub 2}-ZrO{sub 2} melt, part of the corium (from 1/6 to 1/3) did not breakup and reached the bottom plate still molten whatever the water depth was. Test L-11 data suggest that full oxidation and complete breakup of the melt occurred during the melt fall through the water. A proportion of 64% of the total energy content of the melt was released to the water during this phase ({approximately}1.5 s), against 44% for L-14. The maximum temperature increase of the bottom plate was 330 K (L-14). The mean particle size of the debris ranged between 2.5 and 4.8mm.« less

Effect of high-pressure H{sub 2}O treatment on elimination of interfacial GeO{sub X} layer between ZrO{sub 2} and Ge stack

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

Huang, Chen-Shuo; Liu, Po-Tsun

2011-08-22

This investigation demonstrates the effect of high-pressure H{sub 2}O treatment on the elimination of the interfacial germanium suboxide (GeO{sub X}) layer between ZrO{sub 2} and Ge. The formation of GeO{sub X} interlayer increases the gate-leakage current and worsen the controllability of the gate during deposition or thermal cycles. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy reveal that high-pressure H{sub 2}O treatment eliminates the interfacial GeO{sub X} layer. The physical mechanism involves the oxidation of non-oxidized Zr with H{sub 2}O and the reduction of GeO{sub X} by H{sub 2}. Treatment with H{sub 2}O reduces the gate-leakage current of a ZrO{submore » 2}/Ge capacitor by a factor of 1000.« less

Ferroelectric Polarization-Modulated Interfacial Fine Structures Involving Two-Dimensional Electron Gases in Pb(Zr,Ti)O3/LaAlO3/SrTiO3 Heterostructures.

PubMed

Wang, Shuangbao; Bai, Yuhang; Xie, Lin; Li, Chen; Key, Julian D; Wu, Di; Wang, Peng; Pan, Xiaoqing

2018-01-10

Interfacial fine structures of bare LaAlO 3 /SrTiO 3 (LAO/STO) heterostructures are compared with those of LAO/STO heterostructures capped with upward-polarized Pb(Zr 0.1 ,Ti 0.9 )O 3 (PZT up ) or downward-polarized Pb(Zr 0.5 ,Ti 0.5 )O 3 (PZT down ) overlayers by aberration-corrected scanning transmission electron microscopy experiments. By combining the acquired electron energy-loss spectroscopy mapping, we are able to directly observe electron transfer from Ti 4+ to Ti 3+ and ionic displacements at the interface of bare LAO/STO and PZT down /LAO/STO heterostructure unit cell by unit cell. No evidence of Ti 3+ is observed at the interface of the PZT up /LAO/STO samples. Furthermore, the confinement of the two-dimensional electron gas (2DEG) at the interface is determined by atomic-column spatial resolution. Compared with the bare LAO/STO interface, the 2DEG density at the LAO/STO interface is enhanced or depressed by the PZT down or PZT up overlayer, respectively. Our microscopy studies shed light on the mechanism of ferroelectric modulation of interfacial transport at polar/nonpolar oxide heterointerfaces, which may facilitate applications of these materials as nonvolatile memory.

Preparation of magnetron sputtered ZrO2 films on Si for gate dielectric application

NASA Astrophysics Data System (ADS)

Kondaiah, P.; Mohan Rao, G.; Uthanna, S.

2012-11-01

Zirconium oxide (ZrO2) thin films were deposited on to p - Si and quartz substrates by sputtering of zirconium target at an oxygen partial pressure of 4x10-2 Pa and sputter pressure of 0.4 Pa by using DC reactive magnetron sputtering technique. The effect of annealing temperature on structural, optical, electrical and dielectric properties of the ZrO2 films was systematically studied. The as-deposited films were mixed phases of monoclinic and orthorhombic ZrO2. As the annealing temperature increased to 1073 K, the films were transformed in to single phase orthorhombic ZrO2. Fourier transform infrared studies conform the presence of interfacial layer between Si and ZrO2. The optical band gap and refractive index of the as-deposited films were 5.82 eV and 1.81. As the annealing temperature increased to 1073 K the optical band gap and refractive index increased to 5.92 eV and 2.10 respectively. The structural changes were influenced the capacitance-voltage and current-voltage characteristics of Al/ZrO2/p-Si capacitors. The dielectric constant was increased from 11.6 to 24.5 and the leakage current was decreased from 1.65×10-7 to 3.30×10-9 A/ cm2 for the as-deposited and annealed at 1073 K respectively.

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.

Incorporation of ZrO2 particles in the oxide layer formed on Mg by anodizing: Influence of electrolyte concentration and current modes.

PubMed

Sankara Narayanan, T S N; Lee, Min Ho

2016-02-15

The objectives of the present study are to ascertain, particle incorporation during the initial stages of microarc oxidation (MAO), feasibility of increasing the level of particle incorporation through manipulation of process variables and, the use of MgO-ZrO2 composite coatings either as a pre-treatment or as a post-treatment for MAO coated Mg. Anodic oxide coatings were prepared using 0.3M NaOH+15g/l ZrO2 and 3M NaOH+15g/l ZrO2 at 10V under direct current, pulsed current (PC) unipolar and PC bipolar modes. MAO coatings were prepared using 5g/l NaOH+15g/l Na2SiO3 at 250V under direct current mode for 2min. The study reveals that it is possible to incorporate ZrO2 particles in the anodic oxide layer, suggesting such a possibility during the initial stages of MAO. When the MgO-ZrO2 composite coating is used as a pre-treatment, it helps to reduce the size and density of the pores of the MAO coatings and increased the corrosion resistance. When it is used as a post-treatment, lamellar shaped Mg(OH)2 with a very high surface area is formed on the surface, which would be beneficial to impart a better bioactivity and to facilitate immobilization of biomolecules. Copyright © 2015. Published by Elsevier Inc.

Influence of the physico-chemical properties of CeO 2-ZrO 2 mixed oxides on the catalytic oxidation of NO to NO 2

NASA Astrophysics Data System (ADS)

Atribak, Idriss; Guillén-Hurtado, Noelia; Bueno-López, Agustín; García-García, Avelina

2010-10-01

Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N 2 adsorption at -196 °C and XPS, and were tested for NO oxidation to NO 2. Among the different physico-chemical properties characterised, the surface composition seems to be the most relevant one in order to explain the NO oxidation capacity of these Ce-Zr catalysts. As a general trend, Ce-Zr catalysts with a cerium-rich surface, that is, high XPS-measured Ce/Zr atomic surface ratios, are more active than those with a Zr-enriched surface. The decrease in catalytic activity of the Ce-Zr mixed oxided upon calcinations at 800 °C with regard to 500 °C is mainly attributed to the decrease in Ce/Zr surface ratio, that is, to the surface segregation of Zr. The phase composition (cubic or t'' for Ce-rich compositions) seems not to be a direct effect on the catalytic activity for NO oxidation in the range of compositions tested. However, the formation of a proper solid solution prevents important surface segregation of Zr upon calcinations at high temperature. The effect of the BET surface area in the catalytic activity for NO oxidation of Ce-Zr mixed oxides is minor in comparison with the effect of the Ce/Zr surface ratio.

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation. Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium).

Magnetic interactions in new fluorite-related rare earth oxides LnLn’{sub 2}RuO{sub 7} (Ln, Ln’=rare earths)

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

Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp; Doi, Yoshihiro

2016-07-15

New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K, which is considerably lowered compared with that for Pr{sub 3}RuO{sub 7}. Analysis of the magnetic specific heat indicates that the magnetic behavior observed at 27 K for Pr{sub 2}YRuO{sub 7} is predominantly due to the magnetic interactions between Ru ions, and that the interactions between the Pr{sup 3+} and Ru{sup 5+} ions are alsomore » important. La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K, which is ascribed to the magnetic ordering between Ru{sup 5+} ions from the analysis of the magnetic specific heat data. - Graphical abstract: New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} show an antiferromagnetic transition at 27 and 9.0 K, respectively. Display Omitted - Highlights: • New fluorite-related quaternary rare earth oxides LnLn’{sub 2}RuO{sub 7} have been prepared. • Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K. • La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K. • Their magnetic exchange mechanism has been elucidated by the magnetic entropy change.« less

Carbon dioxide electrolysis using a ceramic electrolyte. [for space processing

NASA Technical Reports Server (NTRS)

Erstfeld, T. E.; Mullins, O., Jr.; Williams, R. J.

1979-01-01

This paper discusses the results of an experimental study of the electrical aspects of carbon dioxide electrolysis using a ceramic electrolyte. The electrolyte compositions used in this study are 8% Y2O3 stabilized ZrO2, 7.5% CaO stabilized ZrO2, and 5% Y2O3 stabilized ThO2. Results indicate that the 8% Y2O3 stabilized ZrO2 is the best material to use for electrolysis, in terms of current as a function of voltage and temperature, and in terms of efficiency of oxide ion flow through it. The poorest results were obtained with the 5% Y2O3 stabilized ThO2 composition. An electrolysis system which might be employed to reclaim oxygen and carbon from effluents of space manufacturing, assuming that an industry would have to electrolyze 258,000 tonnes of CO2 per year, is predicted to require a total cell area of 110,000 sq m of 1 mm thickness and electrical capacity of 441 MW.

Steam reforming catalyst

DOEpatents

Kramarz, Kurt W.; Bloom, Ira D.; Kumar, Romesh; Ahmed, Shabbir; Wilkenhoener, Rolf; Krumpelt, Michael

2001-01-01

A method of forming a hydrogen rich gas from a source of hydrocarbon fuel. A vapor of the hydrocarbon fuel and steam is brought in contact with a two-part catalyst having a dehydrogenation powder portion and an oxide-ion conducting powder portion at a temperature not less than about 770.degree.C. for a time sufficient to generate the hydrogen rich. The H.sub.2 content of the hydrogen gas is greater than about 70 percent by volume. The dehydrogenation portion of the catalyst includes a group VIII metal, and the oxide-ion conducting portion is selected from a ceramic oxide from the group crystallizing in the fluorite or perovskite structure and mixtures thereof. The oxide-ion conducting portion of the catalyst is a ceramic powder of one or more of ZrO.sub.2, CeO.sub.2, Bi.sub.2 O.sub.3, (BiVO).sub.4, and LaGaO.sub.3.

Stabilization of cubic Li7La3Hf2O12 by Al-doping

NASA Astrophysics Data System (ADS)

Baklanova, Yana V.; Tyutyunnik, Alexander P.; Tarakina, Nadezda V.; Fortes, A. Dominic; Maksimova, Lidiya G.; Korona, Daniil V.; Denisova, Tatyana A.

2018-07-01

In this paper we report on the stabilization of cubic Li7La3Hf2O12 by Al3+ doping and present a detailed crystal structure study and lithium ion conductivity measurements of the obtained compound. Polycrystalline Al-doped Li7La3Hf2O12 was prepared by a modified solid state method. The compound consists of micrometer size grains encapsulated by a glassy phase, which helps preventing the volatilization of lithium during annealing. Al-doped Li7La3Hf2O12 crystallizes in the garnet-related structure with a cubic unit cell (sp. gr. Ia 3 bar d (230)). A structural refinement using X-ray and neutron powder diffraction data showed that the Al3+ ions occupy only tetrahedral Li+ sites in the structure. The presence of overextended leading edges of the peaks on the XRD and NPD data is described by the introduction of an additional phase with rhombohedral distortion that occurs through a stretching of the cubic phase along the body diagonal. The activation energy as well as the total conductivity at room temperature are close to values obtained for un-doped cubic Li7La3Zr2O12 and Li7La3Hf2O12 garnets, which make Al-doped Li7La3Hf2O12 a potential candidate for the application as solid electrolyte in solid-state rechargeable lithium-ion batteries.

Epitaxial growth of YBa2Cu3O7 - delta films on oxidized silicon with yttria- and zirconia-based buffer layers

NASA Astrophysics Data System (ADS)

Pechen, E. V.; Schoenberger, R.; Brunner, B.; Ritzinger, S.; Renk, K. F.; Sidorov, M. V.; Oktyabrsky, S. R.

1993-09-01

A study of epitaxial growth of YBa2Cu3O7-δ films on oxidized Si with yttria- and zirconia-based buffer layers is reported. Using substrates with either SiO2 free or naturally oxidized (100) surfaces of Si it was found that a thin SiO2 layer on top of the Si favors high-quality superconducting film formation. Compared to yttria-stabilized ZrO2 (YSZ) single layers, YSZY2O3 double and YSZ/Y2O3YSZ triple layers allows the deposition of thin YBa2Cu3O7-δ films with improved properties including reduced aging effects. In epitaxial YBa2Cu3O7-δ films grown on the double buffer layers a critical temperature Tc(R=0)=89.5 K and critical current densities of 3.5×106 A/cm2 at 77 K and 1×107 A/cm2 at 66 K were reached.

Compatibility evaluation between La 2Mo 2O 9 fast oxide-ion conductor and Ni-based materials

NASA Astrophysics Data System (ADS)

Corbel, Gwenaël; Lacorre, Philippe

2006-05-01

The chemical reactivity of La 2NiO 4+δ and nickel metal or nickel oxide with fast oxide-ion conductor La 2Mo 2O 9 is investigated in the annealing temperature range between 600 and 1000 °C, using room temperature X-ray powder diffraction. Within the La 2NiO 4+δ/La 2Mo 2O 9 system, subsequent reaction is evidenced at relatively low annealing temperature (600 °C), with formation of La 2MoO 6 and NiO. The reaction is complete at 1000 °C. At reverse, no reaction occurs between Ni or NiO and La 2Mo 2O 9 up to 1000 °C. Together with a previous work [G. Corbel, S. Mestiri, P. Lacorre, Solid State Sci. 7 (2005) 1216], the current study shows that Ni-CGO cermets might be chemically and mechanically compatible anode materials to work with LAMOX electrolytes in solid oxide fuel cells.

In Situ FT-IR Spectroscopic Study of CO2 and CO Adsorption on Y2O3, ZrO2, and Yttria-Stabilized ZrO2

PubMed Central

2013-01-01

In situ FT-IR spectroscopy was exploited to study the adsorption of CO2 and CO on commercially available yttria-stabilized ZrO2 (8 mol % Y, YSZ-8), Y2O3, and ZrO2. All three oxides were pretreated at high temperatures (1173 K) in air, which leads to effective dehydroxylation of pure ZrO2. Both Y2O3 and YSZ-8 show a much higher reactivity toward CO and CO2 adsorption than ZrO2 because of more facile rehydroxylation of Y-containing phases. Several different carbonate species have been observed following CO2 adsorption on Y2O3 and YSZ-8, which are much more strongly bound on the former, due to formation of higher-coordinated polydentate carbonate species upon annealing. As the crucial factor governing the formation of carbonates, the presence of reactive (basic) surface hydroxyl groups on Y-centers was identified. Therefore, chemisorption of CO2 most likely includes insertion of the CO2 molecule into a reactive surface hydroxyl group and the subsequent formation of a bicarbonate species. Formate formation following CO adsorption has been observed on all three oxides but is less pronounced on ZrO2 due to effective dehydroxylation of the surface during high-temperature treatment. The latter generally causes suppression of the surface reactivity of ZrO2 samples regarding reactions involving CO or CO2 as reaction intermediates. PMID:24009780

Carbon monoxide formation in UO 2 kerneled HTR fuel particles containing oxygen getters

NASA Astrophysics Data System (ADS)

Proksch, E.; Strigl, A.; Nabielek, H.

1986-06-01

Mass spectrometric measurements of CO in irradiated UO 2 kerneled HTR fuel particles containing various oxygen getters are summarized and evaluated. Uranium carbide addition in the 3 to 15% range reduces the CO release by factors between 25 and 80, up to burn-up levels as high as 70% FIMA. Unintentional gettering by SiC in TRISO coated particles with failed inner pyrocarbon layers results in CO reduction factors between 15 and 110. For ZrC, only somewhat ambiguous results have been obtained; most likely, ZrC results in CO reduction by a factor of about 40. Ce 2O 3 and La 2O 3 seem to be somewhat less effective than the three carbides; for Ce 2O 3, reduction factors between 3 and 15 have been found. However, these results are possibly incorrect due to premature oxidation of the getter already during fabrication. Addition of SiO 2 + Al 2O 3 has no influence on CO release at all.

Ferroelectricity emerging in strained (111)-textured ZrO{sub 2} thin films

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

Fan, Zhen, E-mail: a0082709@u.nus.edu, E-mail: msecj@nus.edu.sg; Deng, Jinyu; Liu, Ziyan

2016-01-04

(Anti-)ferroelectricity in complementary metal-oxide-semiconductor (CMOS)-compatible binary oxides have attracted considerable research interest recently. Here, we show that by using substrate-induced strain, the orthorhombic phase and the desired ferroelectricity could be achieved in ZrO{sub 2} thin films. Our theoretical analyses suggest that the strain imposed on the ZrO{sub 2} (111) film by the TiN/MgO (001) substrate would energetically favor the tetragonal (t) and orthorhombic (o) phases over the monoclinic (m) phase of ZrO{sub 2}, and the compressive strain along certain 〈11-2〉 directions may further stabilize the o-phase. Experimentally ZrO{sub 2} thin films are sputtered onto the MgO (001) substrates buffered bymore » epitaxial TiN layers. ZrO{sub 2} thin films exhibit t- and o-phases, which are highly (111)-textured and strained, as evidenced by X-ray diffraction and transmission electron microscopy. Both polarization-electric field (P-E) loops and corresponding current responses to voltage stimulations measured with appropriate applied fields reveal the ferroelectric sub-loop behavior of the ZrO{sub 2} films at certain thicknesses, confirming that the ferroelectric o-phase has been developed in the strained (111)-textured ZrO{sub 2} films. However, further increasing the applied field leads to the disappearance of ferroelectric hysteresis, the possible reasons of which are discussed.« less

Encapsulating Bi2Ti2O7 (BTO) with reduced graphene oxide (RGO): an effective strategy to enhance photocatalytic and photoelectrocatalytic activity of BTO.

PubMed

Gupta, Satyajit; Subramanian, Vaidyanathan Ravi

2014-11-12

Multimetal oxides (AxByOz) offer a higher degree of freedom compared to single metal oxides (AOx) in that these oxides facilitate (i) designing nanomaterials with greater stability, (ii) tuning of the optical bandgap, and (iii) promoting visible light absorption. However, all AxByOz materials such as pyrochlores (A2B2O7)--referred to here as band-gap engineered composite oxide nanomaterials or BECONs--are traditionally prone to severe charge recombination at their surface. To alleviate the charge recombination, an effective strategy is to employ reduced graphene oxide (RGO) as a charge separator. The BECON and the RGO with oppositely charged functional groups attached to them can be integrated at the interface by employing a simple electrostatic self-assembly approach. As a case study, the approach is demonstrated using the Pt-free pyrochlore bismuth titanate (BTO) with RGO, and the application of the composite is investigated for the first time. When tested as a photocatalyst toward hydrogen production, an increase of ∼ 250% using BTO in the presence of RGO was observed. Further, photoelectrochemical measurements indicate an enhancement of ∼ 130% in the photocurrent with RGO inclusion. These two results firmly establish the viability of the electrostatic approach and the inclusion of RGO. The merits of the RGO addition is identified as (i) the RGO-assisted improvement in the separation of the photogenerated charges of BTO, (ii) the enhanced utilization of the charges in a photocatalytic process, and (iii) the maintenance of the BTO/RGO structural integrity after repeated use (established through reusability analysis). The success of the self-assembly strategy presented here lays the foundation for developing other forms of BECONs, belonging to perovskites (ABO3), sillenite (A12BO20), or delafossite (ABO2) groups, hitherto written off due to limited or no photoelectrochemicalactivity.

Using machine learning to identify factors that govern amorphization of irradiated pyrochlores

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

Pilania, Ghanshyam; Whittle, Karl R.; Jiang, Chao

Structure–property relationships are a key materials science concept that enables the design of new materials. In the case of materials for application in radiation environments, correlating radiation tolerance with fundamental structural features of a material enables materials discovery. Here, we use a machine learning model to examine the factors that govern amorphization resistance in the complex oxide pyrochlore (A 2B 2O 7) in a regime in which amorphization occurs as a consequence of defect accumulation. We examine the fidelity of predictions based on cation radii and electronegativities, the oxygen positional parameter, and the energetics of disordering and amorphizing the material.more » No one factor alone adequately predicts amorphization resistance. We find that when multiple families of pyrochlores (with different B cations) are considered, radii and electronegativities provide the best prediction, but when the machine learning model is restricted to only the B = Ti pyrochlores, the energetics of disordering and amorphization are critical factors. We discuss how these static quantities provide insight into an inherently kinetic property such as amorphization resistance at finite temperature. Lastly, this work provides new insight into the factors that govern the amorphization susceptibility and highlights the ability of machine learning approaches to generate that insight.« less

Using machine learning to identify factors that govern amorphization of irradiated pyrochlores

DOE PAGES

Pilania, Ghanshyam; Whittle, Karl R.; Jiang, Chao; ...

2017-02-10

Structure–property relationships are a key materials science concept that enables the design of new materials. In the case of materials for application in radiation environments, correlating radiation tolerance with fundamental structural features of a material enables materials discovery. Here, we use a machine learning model to examine the factors that govern amorphization resistance in the complex oxide pyrochlore (A 2B 2O 7) in a regime in which amorphization occurs as a consequence of defect accumulation. We examine the fidelity of predictions based on cation radii and electronegativities, the oxygen positional parameter, and the energetics of disordering and amorphizing the material.more » No one factor alone adequately predicts amorphization resistance. We find that when multiple families of pyrochlores (with different B cations) are considered, radii and electronegativities provide the best prediction, but when the machine learning model is restricted to only the B = Ti pyrochlores, the energetics of disordering and amorphization are critical factors. We discuss how these static quantities provide insight into an inherently kinetic property such as amorphization resistance at finite temperature. Lastly, this work provides new insight into the factors that govern the amorphization susceptibility and highlights the ability of machine learning approaches to generate that insight.« less

Fracture toughness for copper oxide superconductors

DOEpatents

Goretta, K.C.; Kullberg, M.L.

1993-04-13

An oxide-based strengthening and toughening agent, such as tetragonal ZrO[sub 2] particles, has been added to copper oxide superconductors, such as superconducting YBa[sub 2]Cu[sub 3]O[sub x] (123) to improve its fracture toughness (K[sub IC]). A sol-gel coating which is non-reactive with the superconductor, such as Y[sub 2]BaCuO[sub 5] (211) on the ZrO[sub 2] particles minimized the deleterious reactions between the superconductor and the toughening agent dispersed therethrough. Addition of 20 mole percent ZrO[sub 2] coated with 211 yielded a 123 composite with a K[sub IC] of 4.5 MPa(m)[sup 0.5].

Experimental and theoretical screening of nanoscale oxide reactivity with LiBH4

NASA Astrophysics Data System (ADS)

Opalka, S. M.; Tang, X.; Laube, B. L.; Vanderspurt, T. H.

2009-05-01

Experimentation, thermodynamic modeling, and atomic modeling were combined to screen the reactivity of SiO2, Al2O3, and ZrO2 nanoscale oxides with LiBH4. Equilibrium thermodynamic modeling showed that the reactions of oxides with LiBH4 could lead to formation of stable Li-bearing oxide and metal boride phases. Experimentation was conducted to evaluate the discharge/recharge reaction products of nanoscale oxide-LiBH4 mixtures. Thermal gravimetric analyses-mass spectroscopy and x-ray diffraction revealed significant SiO2 destabilization of LiBH4 dehydrogenation, resulting in the formation of lithium silicate and boric acid. A smaller amount of lithium metaborate and boric acid was formed with Al2O3. No destabilization products were observed with ZrO2. Density functional theory atomic modeling predicted much stronger LiBH4 interfacial adsorption on the SiO2 and Al2O3 surfaces than on the ZrO2 surface, which was consistent with the experimental findings. Following dehydrogenation, interfacial Li atoms were predicted to strongly adsorb on the oxide surfaces effectively competing with LiH formation. The interfacial Li interactions with Al2O3 and ZrO2 were equal in strength in the fully hydrided and dehydrided states, so that their predicted net effect on LiBH4 dehydrogenation was insignificant. Zirconia was selected for nanoframework development based on the combined observations of compatibility and weaker associative interactions with LiBH4.

Possible observation of highly itinerant quantum magnetic monopoles in the frustrated pyrochlore Yb2Ti2O7

PubMed Central

Tokiwa, Y.; Yamashita, T.; Udagawa, M.; Kittaka, S.; Sakakibara, T; Terazawa, D.; Shimoyama, Y.; Terashima, T.; Yasui, Y.; Shibauchi, T.; Matsuda, Y.

2016-01-01

The low-energy elementary excitations in frustrated quantum magnets have fascinated researchers for decades. In frustrated Ising magnets on a pyrochlore lattice possessing macroscopically degenerate spin-ice ground states, the excitations have been discussed in terms of classical magnetic monopoles, which do not contain quantum fluctuations. Here we report unusual behaviours of magneto-thermal conductivity in the disordered spin-liquid regime of pyrochlore Yb2Ti2O7, which hosts frustrated spin-ice correlations with large quantum fluctuations owing to pseudospin-1/2 of Yb ions. The analysis of the temperature and magnetic field dependencies shows the presence of gapped elementary excitations. We find that the gap energy is largely suppressed from that expected in classical monopoles. Moreover, these excitations propagate a long distance without being scattered, in contrast to the diffusive nature of classical monopoles. These results suggests the emergence of highly itinerant quantum magnetic monopole, which is a heavy quasiparticle that propagates coherently in three-dimensional spin liquids. PMID:26912080

Possible observation of highly itinerant quantum magnetic monopoles in the frustrated pyrochlore Yb2Ti2O7.

PubMed

Tokiwa, Y; Yamashita, T; Udagawa, M; Kittaka, S; Sakakibara, T; Terazawa, D; Shimoyama, Y; Terashima, T; Yasui, Y; Shibauchi, T; Matsuda, Y

2016-02-25

The low-energy elementary excitations in frustrated quantum magnets have fascinated researchers for decades. In frustrated Ising magnets on a pyrochlore lattice possessing macroscopically degenerate spin-ice ground states, the excitations have been discussed in terms of classical magnetic monopoles, which do not contain quantum fluctuations. Here we report unusual behaviours of magneto-thermal conductivity in the disordered spin-liquid regime of pyrochlore Yb2Ti2O7, which hosts frustrated spin-ice correlations with large quantum fluctuations owing to pseudospin-1/2 of Yb ions. The analysis of the temperature and magnetic field dependencies shows the presence of gapped elementary excitations. We find that the gap energy is largely suppressed from that expected in classical monopoles. Moreover, these excitations propagate a long distance without being scattered, in contrast to the diffusive nature of classical monopoles. These results suggests the emergence of highly itinerant quantum magnetic monopole, which is a heavy quasiparticle that propagates coherently in three-dimensional spin liquids.

Method of depositing a protective layer over a biaxially textured alloy substrate and composition therefrom

DOEpatents

Goyal, Amit; Kroeger, Donald M.; Paranthaman, Mariappan; Lee, Dominic F.; Feenstra, Roeland; Norton, David P.

2002-01-01

A laminate article consists of a substrate and a biaxially textured protective layer over the substrate. The substrate can be biaxially textured and also have reduced magnetism over the magnetism of Ni. The substrate can be selected from the group consisting of nickel, copper, iron, aluminum, silver and alloys containing any of the foregoing. The protective layer can be selected from the group consisting of gold, silver, platinum, palladium, and nickel and alloys containing any of the foregoing. The protective layer is also non-oxidizable under conditions employed to deposit a desired, subsequent oxide buffer layer. Layers of YBCO, CeO.sub.2, YSZ, LaAlO.sub.3, SrTiO.sub.3, Y.sub.2 O.sub.3, RE.sub.2 O.sub.3, SrRuO.sub.3, LaNiO.sub.3 and La.sub.2 ZrO.sub.3 can be deposited over the protective layer. A method of forming the laminate article is also disclosed.

Low-temperature CO oxidation over Cu/Pt co-doped ZrO2 nanoparticles synthesized by solution combustion.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2017-01-01

Zirconia (ZrO 2 ) nanoparticles co-doped with Cu and Pt were applied as catalysts for carbon monoxide (CO) oxidation. These materials were prepared through solution combustion in order to obtain highly active and stable catalytic nanomaterials. This method allows Pt 2+ and Cu 2+ ions to dissolve into the ZrO 2 lattice and thus creates oxygen vacancies due to lattice distortion and charge imbalance. High-resolution transmission electron microscopy (HRTEM) results showed Cu/Pt co-doped ZrO 2 nanoparticles with a size of ca. 10 nm. X-ray diffraction (XRD) and Raman spectra confirmed cubic structure and larger oxygen vacancies. The nanoparticles showed excellent activity for CO oxidation. The temperature T 50 (the temperature at which 50% of CO are converted) was lowered by 175 °C in comparison to bare ZrO 2 . Further, they exhibited very high stability for CO reaction (time-on-stream ≈ 70 h). This is due to combined effect of smaller particle size, large oxygen vacancies, high specific surface area and better thermal stability of the Cu/Pt co-doped ZrO 2 nanoparticles. The apparent activation energy for CO oxidation is found to be 45.6 kJ·mol -1 . The CO conversion decreases with increase in gas hourly space velocity (GHSV) and initial CO concentration.

ZrO2 film interfaces with Si and SiO2

NASA Astrophysics Data System (ADS)

Lopez, C. M.; Suvorova, N. A.; Irene, E. A.; Suvorova, A. A.; Saunders, M.

2005-08-01

The interface formed by the thermal oxidation of sputter-deposited Zr metal onto Si(100)- and SiO2-coated Si(100) wafers was studied in situ and in real time using spectroscopic ellipsometry (SE) in the 1.5-4.5 photon energy range and mass spectrometry of recoiled ions (MSRI). SE yielded optical properties for the film and interface and MSRI yielded film and interface composition. An optical model was developed and verified using transmission electron microscopy. Interfacial reaction of the ZrO2 was observed for both substrates, with more interaction for Si substrates. Equivalent oxide thicknesses and interface trap levels were determined on capacitors with lower trap levels found on samples with a thicker SiO2 underlayer. In addition to the optical properties for the intermixed interface layer, the optical properties for Zr metal and unreacted ZrO2 are also reported.

Influence of synthesis conditions on the crystal structure of the powder formed in the “HfO2 - CeO2/Ce2O3” system

NASA Astrophysics Data System (ADS)

Popov, V. V.; Menushenkov, A. P.; Khubbutdinov, R. M.; Yastrebtsev, A. A.; Svetogorov, R. D.; Zubavichus, Ya V.; Trigub, A. L.; Sharapov, A. S.; Pisarev, A. A.; Kurilkin, V. V.; Tsarenko, N. A.; Arzhatkina, L. A.

2017-12-01

Influence of synthesis conditions (type of atmosphere: reduction or oxidation, annealing temperature) on the chemical composition and structure of the compounds formed in the “HfO2 - CeO2/Ce2O3” system has been investigated by X-ray absorption fine structure spectroscopy combined with Raman spectroscopy, X-ray diffraction and thermogravimetric analysis. It was revealed that isothermal annealing of precursor at temperatures less than 1000°C in air leads to formation of Ce0.5Hf0.5O2 powders with cubic fluorite-type structure (space group Fm-3m). Further increase of annealing temperatures above 1000°C causes decomposition of formed crystal structure into two phases: cubic and monoclinic. Annealing in reduction hydrogen atmosphere causes formation of Ce4+ 2x Ce3+ 2-2x Hf2O7+x compounds with intermediate oxidation state of cerium, where value of x depends on the reducing conditions and treatment parameters. Annealing in vacuum at 1400°C strongly reduces the content of Ce4+ in a powder samples and leads to formation of pyrochlore structure (space group Fd-3m) with predominant +3 oxidation state of cerium.

A new approach to preparing Bi2Zr2O7 photocatalysts for dye degradation

NASA Astrophysics Data System (ADS)

Luo, Yijia; Cao, Liyun; Huang, Jianfeng; Feng, Liangliang; Yao, Chunyan

2018-01-01

A new synthetic route is presented to prepared pure Bi2Zr2O7 material, in which a NaNO3/KNO3 molten salt is used to obtain the resulting Bi2Zr2O7 at a relatively low temperature of 400 °C under atmospheric pressure. Powder x-ray diffraction confirmed the structure type and purity of the as-prepared sample, and further revealed that a single-source Bi(OH)3 · Zr(OH)4 · nH2O complex precursor plays a crucial role to synthesize Bi2Zr2O7 nanocrystals. Scanning electron microscope and transmission electron microscope show the morphologies and sizes of Bi2Zr2O7 crystal in detail, and UV-vis diffuse reflectance measurements evidenced the wide light absorption range. Furthermore, the as-synthesized Bi2Zr2O7 with smaller particle size and larger specific surface area exhibit superior photocatalytic activities compared with the sample obtained without adding molten salts.

Fast ion conductivity in strained defect-fluorite structure created by ion tracks in Gd 2Ti 2O 7

DOE PAGES

Aidhy, Dilpuneet S.; Sachan, Ritesh; Zarkadoula, Eva; ...

2015-11-10

In this research, the structure and ion-conducting properties of the defect-fluorite ring structure formed around amorphous ion-tracks by swift heavy ion irradiation of Gd 2Ti 2O 7 pyrochlore are investigated. High angle annular dark field imaging complemented with ion-track molecular dynamics simulations show that the atoms in the ring structure are disordered, and have relatively larger cation-cation interspacing than in the bulk pyrochlore, illustrating the presence of tensile strain in the ring region. Density functional theory calculations show that the non-equilibrium defect-fluorite structure can be stabilized by tensile strain. The pyrochlore to defect-fluorite structure transformation in the ring region ismore » predicted to be induced by recrystallization during a melt-quench process and stabilized by tensile strain. Static pair-potential calculations show that planar tensile strain lowers oxygen vacancy migration barriers in pyrochlores, in agreement with recent studies on fluorite and perovskite materials. From these results, it is suggested that strain engineering could be simultaneously used to stabilize the defect-fluorite structure and gain control over its high ion-conducting properties.« less

Formation of metallic clusters in oxide insulators by means of ion beam mixing

NASA Astrophysics Data System (ADS)

Talut, G.; Potzger, K.; Mücklich, A.; Zhou, Shengqiang

2008-04-01

The intermixing and near-interface cluster formation of Pt and FePt thin films deposited on different oxide surfaces by means of Pt+ ion irradiation and subsequent annealing was investigated. Irradiated as well as postannealed samples were investigated using high resolution transmission electron microscopy. In MgO and Y :ZrO2 covered with Pt, crystalline clusters with mean sizes of 2 and 3.5nm were found after the Pt+ irradiations with 8×1015 and 2×1016cm-2 and subsequent annealing, respectively. In MgO samples covered with FePt, clusters with mean sizes of 1 and 2nm were found after the Pt+ irradiations with 8×1015 and 2×1016cm-2 and subsequent annealing, respectively. In Y :ZrO2 samples covered with FePt, clusters up to 5nm in size were found after the Pt+ irradiation with 2×1016cm-2 and subsequent annealing. In LaAlO3 the irradiation was accompanied by a full amorphization of the host matrix and appearance of embedded clusters of different sizes. The determination of the lattice constant and thus the kind of the clusters in samples covered by FePt was hindered due to strong deviation of the electron beam by the ferromagnetic FePt.

A high performance transparent resistive switching memory made from ZrO2/AlON bilayer structure

NASA Astrophysics Data System (ADS)

Tsai, Tsung-Ling; Chang, Hsiang-Yu; Lou, Jesse Jen-Chung; Tseng, Tseung-Yuen

2016-04-01

In this study, the switching properties of an indium tin oxide (ITO)/zirconium oxide (ZrO2)/ITO single layer device and those of a device with an aluminum oxynitride (AlON) layer were investigated. The devices with highly transparent characteristics were fabricated. Compared with the ITO/ZrO2/ITO single layer device, the ITO/ZrO2/AlON/ITO bilayer device exhibited a larger ON/OFF ratio, higher endurance performance, and superior retention properties by using a simple two-step forming process. These substantial improvements in the resistive switching properties were attributed to the minimized influence of oxygen migration through the ITO top electrode (TE), which can be realized by forming an asymmetrical conductive filament with the weakest part at the ZrO2/AlON interface. Therefore, in the ITO/ZrO2/AlON/ITO bilayer device, the regions where conductive filament formation and rupture occur can be effectively moved from the TE interface to the interior of the device.

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

Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C,more » steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.« less

High Temperature Corrosion and Heat Transfer Studies of Zirconium-Silicide Coatings for Light Water Reactor Cladding Applications

NASA Astrophysics Data System (ADS)

Yeom, Hwasung

Experimental results investigating the feasibility of zirconium-silicide coating for accident tolerance of LWR fuel cladding coating was presented. The oxidation resistance of ZrSi2 appeared to be superior to bare Zircaloy-4 in high temperature air. It was shown that micro- and nanostructures consisting of alternating SiO2 and ZrO2 evolved during transient oxidation of ZrSi2, which was explained by spinodal phase decomposition of Zr-Si-O oxide. Coating optimization regarding oxidation resistance was performed mainly using magnetron sputter deposition method. ZrSi 2 coatings ( 3.9 microm) showed improvement of almost two orders of magnitude when compared to bare Zircaloy-4 after air-oxidation at 700 °C for 20-hours. Pre-oxidation of ZrSi2 coating at 700 °C for 5 h significantly mitigated oxygen diffusion in air-oxidation tests at 1000 °C for 1-hour and 1200 °C for 10-minutes. The ZrSi2 coating with the pre-oxidation was found to be the best condition to prevent oxide formation in Zircaloy-4 substrate in the steam condition even if the top surface of the coating was degraded by formation of zirconium-rich oxide layer. Only the ZrSiO4 phase, formed by exposing the ZrSi2 coating at 1400 °C in air, allowed for immobilization of silicon species in the oxide scale in the aqueous environments. A quench test facility was designed and built to study transient boiling heat transfer of modified Zircaloy-4 surfaces (e.g., roughened surfaces, oxidized surfaces, ZrSi2 coated surfaces) at various system conditions (e.g., elevated pressures and water subcooling). The minimum film boiling temperature increased with increasing system pressure and water subcooling, consistent with past literature. Quenching behavior was affected by the types of surface modification regardless of the environmental conditions. Quenching heat transfer was improved by the ZrSi 2 coating, a degree of surface oxidation (deltaox = 3 to 50 microm), and surface roughening (Ra 20 microm). A plausible hypothesis based on transient heat conduction models for liquid-solid contact in quenching process was proposed to explain the enhanced quenching performance. The theoretical model incorporated localized temperature behavior on superheated surface and elucidated bubble dynamics qualitatively, and predicts minimum film boiling temperature of oxidized Zirc-4 surfaces, which were in good agreement with experimental data.

Synthesis and characterization of micro/nanoscopic Pb(Zr0.52Ti0.48)O3 fibers by electrospinning

NASA Astrophysics Data System (ADS)

Wang, Y.; Furlan, R.; Ramos, I.; Santiago-Aviles, J. J.

Micro/nanoscopic Pb(Zr0.52Ti0.48)O3 fibers were synthesized from commercially available zirconium n-pro-poxide, titanium isopropoxide, and lead 2-ethylhexanoate. Using xylene as a solvent, they were mixed to form a precursor solution with a suitable viscosity for electrospinning. The solution was analyzed using thermo-gravimetric and differential thermal methods. Ultra-fine fibers and mats were electrostatically drawn from the precursor solution. The as-deposited materials were sintered for 2 h at 400, 500, 600, 700 and 800 °C, respectively. Sintered mats or fibers were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Auger electron spectroscopy (AES), Raman micro-spectrometry and scanning-probe microscopy (SPM). The SEM results revealed that the fibers had diameters varying from hundreds of nanometers to 10 μm. Using AES, the elements Pb, Zr, Ti and O, as well as residual C, were detected on the surface of the fibers. Raman and XRD spectra indicated that the precursors began to transform into the intermediate pyrochlore phase at 400 °C, followed by the perovskite Pb(Zr0.52Ti0.48)O3 phase above 600 °C. Scanning-probe microscopy (SPM), operated in the piezo-response imaging mode, revealed spontaneous polarization domains in the fibers, with diameters ranging from 100 to 500 nm.

Synthesis of Transparent Aqueous ZrO2 Nanodispersion with a Controllable Crystalline Phase without Modification for a High-Refractive-Index Nanocomposite Film.

PubMed

Xia, Yi; Zhang, Cong; Wang, Jie-Xin; Wang, Dan; Zeng, Xiao-Fei; Chen, Jian-Feng

2018-05-30

The controllable synthesis of metal oxide nanoparticles is of fundamental and technological interest. In this article, highly transparent aqueous nanodispersion of ZrO 2 with controllable crystalline phase, high concentration, and long-term stability was facilely prepared without any modification via the reaction of inexpensive inorganic zirconium salt and sodium hydroxide in water under an acid surrounding, combined with hydrothermal treatment. The as-prepared transparent nanodispersion had an average particle size of 7 nm, a high stability of 18 months, and a high solid content of 35 wt %. ZrO 2 nanocrystals could be readily dispersed in many solvents with high polarity including ethanol, dimethyl sulfoxide, acetic acid, ethylene glycol, and N, N-dimethylformamide, forming stable transparent nanodispersions. Furthermore, highly transparent polyvinyl alcohol/ZrO 2 nanocomposite films with high refractive index were successfully prepared with a simple solution mixing route. The refractive index could be tuned from 1.528 to 1.754 (@ 589 nm) by changing the mass fraction (0-80 wt %) of ZrO 2 in transparent nanocomposite films.

Optimization of pyrochlore catalysts for the dry reforming of methane

NASA Astrophysics Data System (ADS)

Polo Garzon, Felipe

The conversion of methane into syngas (a mixture of CO and H2), which can be further converted into a variety of chemicals and particularly liquid fuels, is of growing importance given recent increases in methane production world-wide. Furthermore, since using CO2 as the co-feed offers many environmental advantages, dry reforming of methane (DRM, CH4 + CO2 [special character omitted] 2CO + 2H 2) has received renewed attention. In recent years, experimentalists have shown that the Rh-substituted lanthanum zirconate pyrochlore (LRhZ) material is catalytically active for DRM, exhibits long-term thermal stability and resists deactivation; however, previous to this doctoral work, a detailed understanding of the reaction mechanism on pyrochlore catalyst surfaces was still scarce, making it difficult to optimize this material. In this work, initial computational efforts employing density functional theory (DFT) showed the plane (111) of the LRhZ crystal structure as the one catalytically active for DRM. In addition, the primary reaction pathway was identified, along with two rate determining steps (RDSs), the CH2 oxygenation step and the CHO dehydrogenation step, which lie on the CH 4 dehydrogenation/oxygenation path. The mechanistic understanding of DRM over LRhZ was further developed using steady-state isotopic transient kinetic analysis (SSITKA). Reversible adsorption of CO2 on the surface was observed, along with short surface residence times (< 0.6 s) at 650 and 800 °C, and increasing turnover frequencies with temperature. Comparisons between isotopic responses supported the DFT-derived reaction mechanism. Furthermore, isotopic transient kinetics confirmed that all metal atoms (Rh, Zr and La) on the surface are involved in the reaction mechanism, as previously pointed by DFT calculations. A DFT-based microkinetic model that predicts the reaction performance at different conditions was built. The model was validated against experimental data, showing remarkable agreement, which further confirmed the reliability of the DFT data. Computational analysis of one of the RDSs (the CHO dehydrogenation step) suggested Pd as an effective co-dopant to reduce the activation barrier of this step. This bimetallic Rh-Pd-substituted lanthanum zirconate pyrochlore (Rh-Pd-LZ) was synthesized, characterized and tested. The Rh-Pd-LZ catalyst successfully increased conversions at high temperatures while providing H 2 to CO ratios close to unity; thus fostering DRM and inhibiting the competing reaction, the reverse water gas shift reaction (RWGS, CO2 + H2 [special character omitted] CO + H2O). The Rh-Pd-LZ catalyst outperformed the initial catalyst, the LRhZ, at high temperatures.

Structural environments of incompatible elements in silicate glass/melt systems: I. Zirconium at trace levels

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Ponader, Carl W.; Brown, Gordon E., Jr.

1991-06-01

The structural environments of trace levels (2˜000 ppm) of Zr 4+ in several silicate glasses were examined as a function of melt composition and polymerization using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Glass compositions investigated were albite (NaAlSi 3O 8: AB) and a peralkaline composition (Na 3.3AlSi 7O 17: PR)- Zirconium was added to the oxide-carbonate mix prior to melting in the form of ZrO 2 (baddeleyite). A second set of Zr-silicate glasses containing 2000 ppm Zr and 1.0 to 2.4 wt% halogens (F as NaF and Cl as NaCl) was also synthesized. These included the Zr-AB and Zr-PR base-glass compositions as well as Zr-sodium trisilicate composition (Na2Si 3O 7: TS). In all glasses studied, Zr is mainly 6-coordinated by oxygen atoms ( d[Zr-O] ˜2.07 ± 0.01 Å). In the most polymerized glass (AB), a small but significant amount of Zr was also found to occur in 8-coordinated sites ( d[Zr-O] ˜2.22 Å). No clear evidence for F or Cl complexes of Zr was observed in any of the halogen-containing glasses. The regularity of the Zr site increases in the series AB < TS ˜PR. We attribute this change to an increase in the number of non-bridging oxygens in the first-coordination sphere of Zr related to the depolymerizing effects of halogens and/or sodium. Minor but significant interactions of Zr with the tetrahedral network were observed ( d[Zr-{Si, Al}] ˜3.65-3.71 Å ± 0.03 Å), which are consistent with Zr-O-{Si, Al} angles close to 160-170°, as in catapleiite (Na 2ZrSi 3O 9 · 2H 2O). Intermediaterange order, as reflected by the presence and number of second-neighbor {Si, Al} around Zr, increases significantly with increasing melt polymerization. The local environment around Zr is more strongly influenced by bonding requirements than by the network topology of the melt. Stabilization of zirconium in 6-coordinated sites in relatively depolymerized melts should act to decrease the crystal-melt partition coefficients of Zr and may explain the normally incompatible character of Zr during magmatic differentiation. The presence of Zr in sites of higher coordination (ZrO 8) in highly polymerized melts could be a precursor to the crystallization of zircon from such melts and thus may explain why Zr becomes a more compatible element, especially in the latest stages of magmatic differentiation.

Chemical solution deposition method of fabricating highly aligned MgO templates

DOEpatents

Paranthaman, Mariappan Parans [Knoxville, TN; Sathyamurthy, Srivatsan [Knoxville, TN; Aytug, Tolga [Knoxville, TN; Arendt, Paul N [Los Alamos, NM; Stan, Liliana [Los Alamos, NM; Foltyn, Stephen R [Los Alamos, NM

2012-01-03

A superconducting article includes a substrate having an untextured metal surface; an untextured barrier layer of La.sub.2Zr.sub.2O.sub.7 or Gd.sub.2Zr.sub.2O.sub.7 supported by and in contact with the surface of the substrate; a biaxially textured buffer layer supported by the untextured barrier layer; and a biaxially textured superconducting layer supported by the biaxially textured buffer layer. Moreover, a method of forming a buffer layer on a metal substrate includes the steps of: providing a substrate having an untextured metal surface; coating the surface of the substrate with a barrier layer precursor; converting the precursor to an untextured barrier layer; and depositing a biaxially textured buffer layer above and supported by the untextured barrier layer.

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

Absence of magnetic long-range order in Y2CrSbO7 : Bond-disorder-induced magnetic frustration in a ferromagnetic pyrochlore

NASA Astrophysics Data System (ADS)

Shen, L.; Greaves, C.; Riyat, R.; Hansen, T. C.; Blackburn, E.

2017-09-01

The consequences of random nonmagnetic-ion dilution for the pyrochlore family Y2(M 1 -xN x)2O7 (M = magnetic ion, N = nonmagnetic ion) have been investigated. As a first step, we experimentally examine the magnetic properties of Y2CrSbO7 (x =0.5 ), in which the magnetic sites (Cr3 +) are percolative. Although the effective Cr-Cr spin exchange is ferromagnetic, as evidenced by a positive Curie-Weiss temperature, ΘCW ≃19.5 K , our high-resolution neutron powder diffraction measurements detect no sign of magnetic long-range order down to 2 K. In order to understand our observations, we construct a lattice model to numerically study the bond disorder introduced by the ionic size mismatch between M and N , which reveals that the bond disorder percolates at xb ≃0.23 , explaining the absence of magnetic long-range order. This model could be applied to a series of frustrated magnets with a pyrochlore sublattice, for example, the spinel compound Zn (Cr1 -xGax )2O4 , wherein a Néel to spin glass phase transition occurs between x =0.2 and 0.25 [Lee et al., Phys. Rev. B 77, 014405 (2008), 10.1103/PhysRevB.77.014405]. Our study stresses the non-negligible role of bond disorder on magnetic frustration, even in ferromagnets.

Salt-assistant combustion synthesis of nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} (0 {<=} x {<=} 1) solid solutions

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

Tong Yuping, E-mail: huabeitong@yahoo.cn; Wang Yanping

2009-11-15

Nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} series solid solutions were prepared by a convenient salt-assisted combustion process using glycine as fuel. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The results showed the Zr ion can be partially replaced by Sn ion. The partial substituted products were still single-phase solid solutions and the crystal form remained unchanged. TEM images reveal that the products are composed of well-dispersed square-shaped nanocrystals. The method provides a convenient and low-cost route for the synthesis of nanostructures of oxide materials.

Effects of Plume Hydrodynamics and Oxidation on the Composition of a Condensing Laser-Induced Plasma

DOE PAGES

Weisz, David G.; Crowhurst, Jonathan C.; Finko, Mikhail S.; ...

2018-02-01

High-temperature chemistry in laser ablation plumes leads to vapor-phase speciation, which can induce chemical fractionation during condensation. In this work, using emission spectroscopy acquired after ablation of a SrZrO 3 target, we have experimentally observed the formation of multiple molecular species (ZrO and SrO) as a function of time as the laser ablation plume evolves. Although the stable oxides SrO and ZrO 2 are both refractory, we observed emission from the ZrO intermediate at earlier times than SrO. We deduced the time-scale of oxygen entrainment into the laser ablation plume using an 18O 2 environment by observing the in-growth ofmore » Zr 18O in the emission spectra relative to Zr 16O, which was formed by reaction of Zr with 16O from the target itself. Using temporally resolved plume-imaging, we determined that ZrO formed more readily at early times, volumetrically in the plume, while SrO formed later in time, around the periphery. Lastly, using a simple temperature-dependent reaction model, we have illustrated that the formation sequence of these oxides subsequent to ablation is predictable to first order.« less

Krypton ion irradiation-induced amorphization and nano-crystal formation in pyrochlore Lu2Ti2O7 at room temperature

NASA Astrophysics Data System (ADS)

Xie, Qiu-Rong; Zhang, Jian; Yin, Dong-Min; Guo, Qi-Xun; Li, Ning

2015-12-01

Polycrystalline pyrochlore Lu2Ti2O7 pellets are irradiated with 600-keV Kr3+ ions up to a fluence of 1.45 × 1016 Kr3+/cm2. Irradiation induced structural modifications are examined by using grazing incidence x-ray diffraction (GIXRD) and cross-sectional transmission electron microscopy (TEM). The GIXRD reveals that amorphous fraction increases with the increase of fluences up to 2 × 1015 Kr3+/cm2, and the results are explained with a direct-impact model. However, when the irradiation fluence is higher than 2 × 1015 Kr3+/cm2, the amorphous fraction reaches a saturation of ∼80%. Further TEM observations imply that nano-crystal is formed with a diameter of ∼10 nm within the irradiation layer at a fluence of 4 × 1015 Kr3+/cm2. No full amorphization is achieved even at the highest fluence of 1.45 × 1016 Kr3+/cm2 (∼36 displacement per atom). The high irradiation resistance of pyrochlore Lu2Ti2O7 at higher fluence is explained on the basis of enhanced radiation tolerance of nano-crystal structure. Project sponsored by the National Natural Science Foundation of China (Grant No. 11205128) and the Fundamental Research Funds for the Central Universities, China (Grant No. 2012121034).

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

DOEpatents

Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

2012-03-13

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

Pyrochlore catalysts for hydrocarbon fuel reforming

DOEpatents

Berry, David A.; Shekhawat, Dushyant; Haynes, Daniel; Smith, Mark; Spivey, James J.

2012-08-14

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A₂B_2-y-zB'_yB"_zO_7-.DELTA., where y>0 and z.gtoreq.0. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H₂+CO) for fuel cells, among other uses.

Evaluation of zirconia, thoria and zirconium diboride for advanced resistojet use

NASA Technical Reports Server (NTRS)

Page, R. J.; Short, R. A.; Halbach, C. R.

1972-01-01

A literature survey was conducted to collect material properties data on all advanced high temperature materials. Three of these, Y2O3-stabilized ZrO2, ThO2, and ZrB2 with additives of C and SiC were selected for further study. Stabilized ZrO2 and ThO2 were found to have higher temperature oxidation resistance than any metal and great potential for use in advanced biowaste resistojets. ZrO2 has a lower electrical resistivity and sublimation and a higher creep endurance strength. ZrO2 and ThO2 tubular heat exchangers, electrically heated indirectly, were evaluated in short tests to about 1900 K in flowing CO2. ZrO2 was subjected to N2, H2, H2O and vacuum as well. X-ray diffraction and fluorescence analyses were made. The metal-to-ceramic seal technology for ZrO2 and ThO2 was developed using chemical vapor deposition of tantalum for metallizing and 82 Au - 18 Ni filler braze.

Influence of Li3BO3 additives on the Li+ conductivity and stability of Ca/Ta-substituted Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 electrolytes

NASA Astrophysics Data System (ADS)

Zhang, L. C.; Yang, J. F.; Gao, Y. X.; Wang, X. P.; Fang, Q. F.; Chen, C. H.

2017-07-01

The cubic Ca/Ta-substituted Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 (LLCZTO) electrolytes were synthesized at 800 °C with Li3BO3 as additives. The optimal amount of Li3BO3 and its influences on the microstructure, crystal structures, Li+ conductivity and the stability of the Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 were studied by SEM, XRD and EIS. Among all the samples, when the molar ratio of Li3BO3 to the Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 is 4:5, the highest Li+ conductivity of 1.33 × 10-4 S cm-1 at 30 °C is obtained. When the LLCZTO samples are exposed in air, the Li+ conductivity is deteriorated possibly owing to the side reactions between the LLCZTO and the H2O or CO2 in the air. The Li3BO3 addition can alleviate such deterioration of the Li+ conductivity.

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

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.

Key parameters governing the densification of cubic-Li7La3Zr2O12 Li+ conductors

NASA Astrophysics Data System (ADS)

Yi, Eongyu; Wang, Weimin; Kieffer, John; Laine, Richard M.

2017-06-01

Cubic-Li7La3Zr2O12 (LLZO) is regarded as one of the most promising solid electrolytes for the construction of inherently safe, next generation all-solid-state Li batteries. Unfortunately, sintering these materials to full density with controlled grain sizes, mechanical and electrochemical properties relies on energy and equipment intensive processes. In this work, we elucidate key parameters dictating LLZO densification by tracing the compositional and structural changes during processing calcined and ball-milled Al3+ doped LLZO powders. We find that the powders undergo ion (Li+/H+) exchange during room temperature processing, such that on heating, the protonated LLZO lattice collapses and crystallizes to its constituent oxides, leading to reaction driven densification at < 1000 °C, prior to sintering of LLZO grains at higher temperatures. It is shown that small particle sizes and protonation cannot be decoupled, and actually aid densification. We conclude that using fully decomposed nanoparticle mixtures, as obtained by liquid-feed flame spray pyrolysis, provides an ideal approach to use high surface and reaction energy to drive densification, resulting in pressureless sintering of Ga3+ doped LLZO thin films (25 μm) at 1130 °C/0.3 h to ideal microstructures (95 ± 1% density, 1.2 ± 0.2 μm average grain size) normally accessible only by pressure-assisted sintering. Such films offer both high ionic conductivity (1.3 ± 0.1 mS cm-1) and record low ionic area specific resistance (2 Ω cm2).

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

Chitosan /Zeolite Y/Nano ZrO2 nanocomposite as an adsorbent for the removal of nitrate from the aqueous solution.

PubMed

Teimouri, Abbas; Nasab, Shima Ghanavati; Vahdatpoor, Niaz; Habibollahi, Saeed; Salavati, Hossein; Chermahini, Alireza Najafi

2016-12-01

In the present study, a series of chitosan/Zeolite Y/Nano Zirconium oxide (CTS/ZY/Nano ZrO 2 ) nanocomposites were made by controlling the molar ratio of chitosan (CTS) to Zeolite Y/Nano Zirconium oxide in order to remove nitrate (NO 3 - ) ions in the aqueous solution. The nanocomposite adsorbents were characterized by XRD, FTIR, BET, SEM and TEM. The influence of different molar ratios of CTS to ZY/Nano ZrO 2 , the initial pH value of the nitrate solution, contact time, temperature, the initial concentration of nitrate and adsorbent dose was studied. The adsorption isotherms and kinetics were also analyzed. It was attempted to describe the sorption processes by the Langmuir equation and the theoretical adsorption capacity (Q 0 ) was found to be 23.58mg nitrate per g of the adsorbent. The optimal conditions for nitrate removal were found to be: molar ratio of CTS/ZY/Nano ZrO 2 : 5:1; pH: 3; 0.02g of adsorbent and temperature: 35°C, for 60min. The adsorption capacities of CTS, ZY, Nano ZrO 2 , CTS/Nano ZrO 2 , CTS/ZY and CTS/ZY/Nano ZrO 2 nanocomposites for nitrate removal were compared, showing that the adsorption ability of CTS/ZY/Nano ZrO 2 nanocomposite was higher than the average values of those of CTS (1.95mg/g for nitrate removal), ZY, Nano ZrO 2 , CTS/Nano ZrO 2, and CTS/ZY. Copyright © 2016. Published by Elsevier B.V.

In-plane orientation and composition dependences of crystal structure and electrical properties of {100}-oriented Pb(Zr,Ti)O3 films grown on (100) Si substrates by metal organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Okamoto, Shoji; Sankara Rama Krishnan, P. S.; Okamoto, Satoshi; Yokoyama, Shintaro; Akiyama, Kensuke; Funakubo, Hiroshi

2017-10-01

In-plane orientation-controlled Pb(Zr x ,Ti1- x )O3 (PZT) films with a thickness of approximately 2 µm and a Zr/(Zr + Ti) ratio of 0.39-0.65 were grown on (100) Si substrates by pulsed metal-organic chemical vapor deposition (MOCVD). In-plane-oriented epitaxial PZT films and in-plane random fiber-textured PZT films with {100} out-of-plane orientation were grown on (100)c SrRuO3//(100)c LaNiO3//(100) CeO2//(100) YSZ//(100) Si and (100)c SrRuO3/(100)c LaNiO3/(111) Pt/TiO2/SiO2/(100) Si substrates, respectively. The effects of Zr/(Zr + Ti) ratio and in-plane orientation on the crystal structure, dielectric, ferroelectric, and piezoelectric properties of the films were systematically investigated. The X-ray diffraction measurement showed that the epitaxial PZT films had a higher volume fraction of (100) orientation than the fiber-textured PZT films in the tetragonal Zr/(Zr + Ti) ratio region. A large difference was not detected between the epitaxial films and the fiber-textured films for Zr/(Zr + Ti) ratio dependence of the dielectric constant, and remanent polarization. However, in the rhombohedral phase region [Zr/(Zr + Ti) = 0.65], coercive field was found to be 1.5-fold different between the epitaxial and fiber-textured PZT films. The maximum field-induced strains measured at 0-100 kV/cm by scanning atomic force microscopy were obtained at approximately Zr/(Zr + Ti) = 0.50 and were about 0.5 and 0.3% for the epitaxial and fiber-textured PZT films, respectively.

Processing - microstructure relationships of chemically vapor deposited zirconia fiber coating for environmentally durable silicon carbide/silicon carbide composites

NASA Astrophysics Data System (ADS)

Lee, Jinil

In SiC/SiC ceramic matrix composites, toughness is obtained by adding a fiber coating which provides a weak interface for crack deflection and debonding between the fiber and the matrix. However, the most commonly used fiber coatings, carbon and boron nitride, are unstable in oxidative environments. In the present study, the feasibility of using a chemically vapor deposited zirconia (CVD-ZrO 2) fiber coating as an oxidation-resistant interphase for SiC/SiC composites was investigated. The feasibility of the CVD-ZrO2 coating as a useful interphase for SiC/SiC composites was investigated with emphasis on developing critical processing-microstructure relationships. A study of morphological evolution in the CVD-ZrO2 coating suggested that a size-controlled displacive phase transformation from tetragonal ZrO2 (t-ZrO2) to monoclinic ZrO2 (m-ZrO2) was the key mechanism responsible for the weak interface behavior exhibited by the ZrO2 coating. The pre-delamination occurred as a result of (i) continuous formation of t-ZrO2 nuclei on the deposition surface; (ii) martensitic transformation of the tetragonal phase to a monoclinic phase upon reaching a critical grain size; and (iii) development of significant compressive hoop stresses due to the volume dilation associated with the transformation. We also discovered that low oxygen partial pressure in the CVD reactor was required for the nucleation of t-ZrO2 and was ultimately responsible for the delamination behavior. The effects of oxygen partial pressure on the nucleation behavior of the CVD-ZrO2 coating was systematically studied by intentionally adding the controlled amount of O2 into the CVD chamber. Characterization results suggested that the number density of t-ZrO2 nuclei apparently decreased with increasing the oxygen partial pressure from 0.004 to 1.6 Pa. Also, the coating layer became more columnar and contained larger m-ZrO2 grains. The observed relationships between the oxygen partial pressure and the morphological characteristics of the ZrO 2 coating were explained in the context of the grain size and oxygen deficiency effects which have been previously reported to cause the stabilization of the t-ZrO2 phase in bulk ZrO2 specimens.

Ceo2 Based Catalysts for the Treatment of Propylene in Motorcycle’s Exhaust Gases

PubMed Central

Pham, Phuong Thi Mai; Le Minh, Thang; Nguyen, Tien The; Van Driessche, Isabel

2014-01-01

In this work, the catalytic activities of several single metallic oxides were studied for the treatment of propylene, a component in motorcycles’ exhaust gases, under oxygen deficient conditions. Amongst them, CeO2 is one of the materials that exhibit the highest activity for the oxidation of C3H6. Therefore, several mixtures of CeO2 with other oxides (SnO2, ZrO2, Co3O4) were tested to investigate the changes in catalytic activity (both propylene conversion and CO2 selectivity). Ce0.9Zr0.1O2, Ce0.8Zr0.2O2 solid solutions and the mixtures of CeO2 and Co3O4 was shown to exhibit the highest propylene conversion and CO2 selectivity. They also exhibited good activities when tested under oxygen sufficient and excess conditions and with the presence of co-existing gases (CO, H2O). PMID:28788253

Microanalysis of an oxidized cobalt oxide: Zirconia eutectic

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

Bentley, J.; McKernan, S.; Carter, C.B.

The compositions of CoO, Co{sub 3}O{sub 4}, and Ca-stabilized cubic ZrO{sub 2} in an oxidized directionally solidified CoO-ZrO{sub 2} eutectic were determined by PEELS and EDS. An oxygen gradient exists across the Co{sub 3}O{sub 4} with highest levels near the ZrO{sub 2} interface. Oxygen ELNES for CoO and Co{sub 3}O{sub 4} are quite different; published oxygen ELNES have been incorrectly attributed to CoO. Normalized Co-L{sub 23} white line intensity (WLI) ratios for CoO and Co{sub 3}O{sub 4} are similar (0.53 {plus_minus} 0.02) but L{sub 3}/L{sub 2} WLI ratios are 3.88 and 2.58, respectively. ELCE data suggest Co{sub 3}O{sub 4} hasmore » the inverse spinel structure.« less

Comparison of the Supercooled Spin Liquid States in the Pyrochlore Magnets Dy2Ti2O7 and Ho2Ti2O7

NASA Astrophysics Data System (ADS)

Eyal, Anna; Eyvazov, Azar B.; Dusad, Ritika; Munsie, Timothy J. S.; Luke, Graeme M.; Davis, J. C. Séamus

Despite a well-ordered crystal structure and strong magnetic interactions between the Dy or Ho ions, no long-range magnetic order has been detected in the pyrochlore titanates Ho2Ti2O7 and Dy2Ti2O7. The low temperature state in these materials is governed by spin-ice rules. These constrain the Ising like spins in the materials, yet does not result in a global broken symmetry state. To explore the actual magnetic phases, we simultaneously measure the time- and frequency-dependent magnetization dynamics of Dy2Ti2O7 and Ho2Ti2O7 using toroidal, boundary-free magnetization transport techniques. We demonstrate a distinctive behavior of the magnetic susceptibility of both compounds, that is indistinguishable in form from the permittivity of supercooled dipolar liquids. Moreover, we show that the microscopic magnetic relaxation times for both materials increase along a super-Arrhenius trajectory also characteristic of supercooled glass-forming liquids. Both materials therefore exhibit characteristics of a supercooled spin liquid. Strongly-correlated dynamics of loops of spins is suggested as a possible mechanism which could account for these findings. Potential connections to many-body spin localization will also be discussed.

Weyl magnons in pyrochlore antiferromagnets with an all-in-all-out order

NASA Astrophysics Data System (ADS)

Jian, Shao-Kai; Nie, Wenxing

2018-03-01

We investigate topological magnon band crossings of pyrochlore antiferromagnets with all-in-all-out (AIAO) magnetic order. By general symmetry analysis and spin-wave theory, we show that pyrochlore materials with AIAO orders can host Weyl magnons under external magnetic fields or uniaxial strains. Under a small magnetic field, the magnon bands of the pyrochlore with AIAO background can feature two opposite-charged Weyl points, which is the minimal number of Weyl points realizable in quantum materials, and has not been experimentally observed so far. We further show that breathing pyrochlores with AIAO orders can exhibit Weyl magnons upon uniaxial strains. These findings apply to any pyrochlore material supporting AIAO orders, irrespective of the forms of interactions. Specifically, we show that the Weyl magnons are robust against direct (positive) Dzyaloshinskii-Moriya interactions. Because of the ubiquitous AIAO orders in pyrochlore magnets including R2Ir2O7 , and experimentally achievable external strain and magnetic field, our predictions provide a promising arena to witness the Weyl magnons in quantum magnets.

Labeling of HeLa cells using ZrO2:Yb3+-Er3+ nanoparticles with upconversion emission

NASA Astrophysics Data System (ADS)

Ceja-Fdez, Andrea; López-Luke, Tzarara; Oliva, Jorge; Vivero-Escoto, Juan; Gonzalez-Yebra, Ana Lilia; Rojas, Ruben A. Rodriguez; Martínez-Pérez, Andrea; de la Rosa, Elder

2015-04-01

This work reports the synthesis, structural characterization, and optical properties of ZrO2:Yb3+-Er3+ (2-1 mol%) nanocrystals. The nanoparticles were coated with 3-aminopropyl triethoxysilane (APTES) and further modified with biomolecules, such as Biotin-Anti-rabbit (mouse IgG) and rabbit antibody-AntiKi-67, through a conjugation method. The conjugation was successfully confirmed by Fourier transform infrared, zeta potential, and dynamic light scattering. The internalization of the conjugated nanoparticles in human cervical cancer (HeLa) cells was followed by two-photon confocal microscopy. The ZrO2:Yb3+-Er3+ nanocrystals exhibited strong red emission under 970-nm excitation. Moreover, the luminescence change due to the addition of APTES molecules and biomolecules on the nanocrystals was also studied. These results demonstrate that ZrO2:Yb3+-Er3+ nanocrystals can be successfully functionalized with biomolecules to develop platforms for biolabeling and bioimaging.

Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

DOE PAGES

Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; ...

2015-12-16

The oxide known as LLZO, with nominal composition Li 7La 3Zr 2O 12, is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte smore » shear modulus increases. In the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.« less

Ceramic oxide reactions with V2O5 and SO3

NASA Technical Reports Server (NTRS)

Jones, R. L.; Williams, C. E.

1985-01-01

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Structure and thermodynamics of uranium-containing iron garnets

NASA Astrophysics Data System (ADS)

Guo, Xiaofeng; Navrotsky, Alexandra; Kukkadapu, Ravi K.; Engelhard, Mark H.; Lanzirotti, Antonio; Newville, Matthew; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu

2016-09-01

Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca3UxZr2-xFe3O12 (x = 0.5-0.7), along with the endmember phase, Ca3(Zr2)SiFe3+2O12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca3UxZr2-xFe3O12 as viable waste form phases for U and other actinides.

Effect of Zirconium Oxide and Zinc Oxide Nanoparticles on Physicochemical Properties and Antibiofilm Activity of a Calcium Silicate-Based Material

PubMed Central

Guerreiro-Tanomaru, Juliane Maria; Trindade-Junior, Adinael; Cesar Costa, Bernardo; da Silva, Guilherme Ferreira; Drullis Cifali, Leonardo; Basso Bernardi, Maria Inês

2014-01-01

The aim of the present study was to evaluate the antibiofilm activity against Enterococcus faecalis, compressive strength. and radiopacity of Portland cement (PC) added to zirconium oxide (ZrO2), as radiopacifier, with or without nanoparticulated zinc oxide (ZnO). The following experimental materials were evaluated: PC, PC + ZrO2, PC + ZrO2 + ZnO (5%), and PC + ZrO2 + ZnO (10%). Antibiofilm activity was analyzed by using direct contact test (DCT) on Enterococcus faecalis biofilm, for 5 h or 15 h. The analysis was conducted by using the number of colony-forming units (CFU/mL). The compressive strength was performed in a mechanical testing machine. For the radiopacity tests, the specimens were radiographed together with an aluminium stepwedge. The results were submitted to ANOVA and Tukey tests, with level of significance at 5%. The results showed that all materials presented similar antibiofilm activity (P > 0.05). The addition of nanoparticulated ZnO decreased the compressive strength of PC. All materials presented higher radiopacity than pure PC. It can be concluded that the addition of ZrO2 and ZnO does not interfere with the antibiofilm activity and provides radiopacity to Portland cement. However, the presence of ZnO (5% or 10%) significantly decreased the compressive strength of the materials. PMID:25431798

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

PubMed

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation of steam corrosion and water quenching behavior of zirconium-silicide coated LWR fuel claddings

NASA Astrophysics Data System (ADS)

Yeom, Hwasung; Lockhart, Cody; Mariani, Robert; Xu, Peng; Corradini, Michael; Sridharan, Kumar

2018-02-01

This study investigates steam corrosion of bulk ZrSi2, pure Si, and zirconium-silicide coatings as well as water quenching behavior of ZrSi2 coatings to evaluate its feasibility as a potential accident-tolerant fuel cladding coating material in light water nuclear reactor. The ZrSi2 coating and Zr2Si-ZrSi2 coating were deposited on Zircaloy-4 flats, SiC flats, and cylindrical Zircaloy-4 rodlets using magnetron sputter deposition. Bulk ZrSi2 and pure Si samples showed weight loss after the corrosion test in pure steam at 400 °C and 10.3 MPa for 72 h. Silicon depletion on the ZrSi2 surface during the steam test was related to the surface recession observed in the silicon samples. ZrSi2 coating (∼3.9 μm) pre-oxidized in 700 °C air prevented substrate oxidation but thin porous ZrO2 formed on the coating. The only condition which achieved complete silicon immobilization in the oxide scale in aqueous environments was the formation of ZrSiO4 via ZrSi2 coating oxidation in 1400 °C air. In addition, ZrSi2 coatings were beneficial in enhancing quenching heat transfer - the minimum film boiling temperature increased by 6-8% in the three different environmental conditions tested. During repeated thermal cycles (water quenching from 700 °C to 85 °C for 20 s) performed as a part of quench tests, no spallation and cracking was observed and the coating prevented oxidation of the underlying Zircaloy-4 substrate.

Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

PubMed

Ai, Na; Li, Na; Rickard, William D A; Cheng, Yi; Chen, Kongfa; Jiang, San Ping

2017-03-09

Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y 2 O 3 -ZrO 2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO 3-δ (LC) and Sm 0.95 CoO 3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm -2 and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm 0.95 Co 0.95 Pd 0.05 O 3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm -2 at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Wang, Yuxing; Yan, Pengfei; Xiao, Jie

It is widely recognized that Al plays a dual role in the fabrication of garnet-type solid electrolytes, i.e., as a dopant that stabilizes the cubic structure and a sintering aid that facilitates the densification. However, the sintering effect of Al2O3 has not been well understood so far because Al is typically “unintentionally” introduced into the sample from the crucible during the fabrication process. In this study, we have investigated the sintering effect of Al on the phase composition, microstructure, and ionic conductivity of Li6.5La3Zr1.5Ta0.5O12 by using an Al-free crucible and intentionally adding various amounts of γ-Al2O3. It was found thatmore » the densification of Li6.5La3Zr1.5Ta0.5O12 occurred via liquid-phase sintering, with evidence of morphology change among different compositions. Among all of the compositions, samples with 0.05 mol of Al per unit formula of garnet oxide (i.e., 0.3 wt% Al2O3) exhibited the optimal microstructure and the highest total ionic conductivity of 5 10-4 S cm-1 at room temperature.« less

Static magnetic susceptibility, crystal field and exchange interactions in rare earth titanate pyrochlores.

PubMed

Malkin, B Z; Lummen, T T A; van Loosdrecht, P H M; Dhalenne, G; Zakirov, A R

2010-07-14

The experimental temperature dependence (T = 2-300 K) of single crystal bulk and site susceptibilities of rare earth titanate pyrochlores R(2)Ti(2)O(7) (R = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) is analyzed in the framework of crystal field theory and a mean field approximation. Analytical expressions for the site and bulk susceptibilities of the pyrochlore lattice are derived taking into account long range dipole-dipole interactions and anisotropic exchange interactions between the nearest neighbor rare earth ions. The sets of crystal field parameters and anisotropic exchange coupling constants have been determined and their variations along the lanthanide series are discussed.

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

Changes in the state of iron atoms in Zr alloys during corrosion tests in an autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.; Kargin, N. I.; Petrov, V. I.

2014-04-01

Mössbauerinvestigations were carried out on oxide films formed on specimens of zirconium alloys Zr-1.0 %wtFe-1.2 %wtSn-0.5 %wtCr subjected to corrosion in steam-water environment at a temperature of 360 °C and at a pressure of 16.8 MPa with lithium and boron additions, and on Zr-1.4 %wtFe-0.7 %wtCr corroded in steam-water environment at 350 °C and 16.8 MPa as well as in steam-water environment at 500 °C and 10 MPa. In the metal part of the samples, under the oxide film, the iron atoms are in form of intermetallic precipitates of Zr(Fe, Cr)2. The corrosion process decomposes the intermetallic precipitates and particles are formed of metallic iron with inclusions of chromium atoms -Fe(Cr), α-Fe2O3 and Fe3O4 compounds. Part of the iron ions are in divalent and part in trivalent paramagnetic states. It is proposed that some part of the iron containing oxide precipitates in the oxide film may be in the form of nanoparticles which pass from the superparamagnetic to the ferromagnetic state with decreasing temperature.

Low temperature solution processed high-κ ZrO2 gate dielectrics for nanoelectonics

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, K. S. R. Koteswara

2016-05-01

The high-κ gate dielectrics, specifically amorphous films offer salient features such as exceptional mechanical flexibility, smooth surfaces and better uniformity associated with low leakage current density. In this work, ∼35 nm thick amorphous ZrO2 films were deposited on silicon substrate at low temperature (300 °C, 1 h) from facile spin-coating method and characterized by various analytical techniques. The X-ray diffraction and X-ray photoelectron spectroscopy reveal the formation of amorphous phase ZrO2, while ellipsometry analysis together with the Atomic Force Microscope suggest the formation of dense film with surface roughness of 1.5 Å, respectively. The fabricated films were integrated in metal-oxide-semiconductor (MOS) structures to check the electrical capabilities. The oxide capacitance (Cox), flat band capacitance (CFB), flat band voltage (VFB), dielectric constant (κ) and oxide trapped charges (Qot) extracted from high frequency (1 MHz) C-V curve are 186 pF, 104 pF, 0.37 V, 15 and 2 × 10-11 C, respectively. The small flat band voltage 0.37 V, narrow hysteresis and very little frequency dispersion between 10 kHz-1 MHz suggest an excellent a-ZrO2/Si interface with very less trapped charges in the oxide. The films exhibit a low leakage current density 4.7 × 10-9 A/cm2 at 1 V. In addition, the charge transport mechanism across the MOSC is analyzed and found to have a strong bias dependence. The space charge limited conduction mechanism is dominant in the high electric field region (1.3-5 V) due to the presence of traps, while the trap-supported tunneling is prevailed in the intermediate region (0.35-1.3 V). Low temperature solution processed ZrO2 thin films obtained are of high quality and find their importance as a potential dielectric layer on Si and polymer based flexible electronics.

The preparation and activity of Cu-Fe-Zr-Ce based catalysts for water gas shift

NASA Astrophysics Data System (ADS)

Wu, H. D.; Liu, T. S.; Liu, H. Z.

2018-01-01

CeO2-ZrO2 composite oxide was synthesized with precipitation method as support and CuaFeb(ZrCe4)8Ox catalysts were prepared by impregnation; X-ray diffraction, H2 temperature program reduction, and scanning electron microscope techniques were jointly used to characterize the crystal phases and reduction properties of catalysts. Then the activity of catalysts in water gas shift was studied, thus investigated how catalyst composition impacted the water gas shift. Conclusions drew from the results can be briefly stated. CuaFeb(ZrCe4)8Ox was provided with stable cubic crystalline framework and Cu and Fe, as the active components, was highly dispersed on the surface of supports in the form of CuO and Fe2O3 respectively. The strong interactions between copper and iron component enhanced the reducing capacity of CuO and Fe2O3. CuaFeb(ZrCe4)8Ox catalysts exhibited high catalytic activity and selectivity while the main active components were Cu and Fe3O4. The CO conversion rate reached 96% when Cu7Fe3(ZrCe4)8Ox catalysts was used in water gas shift at 623K and the only products were H2 and CO2. The activity was still desirable even the catalysts was applied at 723K.

High-Temperature Wettability and Interactions between Y-Containing Ni-Based Alloys and Various Oxide Ceramics

PubMed Central

Li, Jinpeng; Gao, Ming; Li, Qingling; Bian, Weidong; Tao, Tongxiang; Zhang, Hu

2018-01-01

To obtain appropriate crucible materials for vacuum induction melting of MCrAlY alloys, four different oxide ceramics, including MgO, Y2O3, Al2O3, and ZrO2, with various microstructures were designed and characterized. The high-temperature wettability and interactions between Ni-20Co-20Cr-10Al-1.5Y alloys and oxide ceramics were studied by sessile drop experiments under vacuum. The results showed that all the systems exhibited non-wetting behavior. The contact angles were stable during the melting process of alloys and the equilibrium contact angles were 140° (MgO), 148° (Y2O3), 154° (Al2O3), and 157° (ZrO2), respectively. The interfacial reaction between the ceramic substrates and alloys occurred at high temperature. Though the ceramics had different microstructures, similar continuous Y2O3 reaction layer with thicknesses of about 25 μm at the alloy-ceramic interface in MgO, Al2O3, and ZrO2 systems formed. The average area percentage of oxides in the alloy matrices were 0.59% (MgO), 0.11% (Al2O3), 0.09% (ZrO2), and 0.02% (Y2O3), respectively. The alloys, after reacting with MgO ceramic, had the highest inclusion content, while those with the lowest content were in the Y2O3 system. Y2O3 ceramic was the most beneficial for vacuum induction melting of high-purity Y-containing Ni-based alloys. PMID:29735958

BaZr 0.1Ce 0.7Y 0.1Yb 0.1O 3- δ electrolyte-based solid oxide fuel cells with cobalt-free PrBaFe 2O 5+ δ layered perovskite cathode

NASA Astrophysics Data System (ADS)

Ding, Hanping; Xue, Xingjian

A new anode-supported SOFC material system Ni-BZCYYb|BZCYYb|PBFO is investigated, in which a cobalt-free layered perovskite oxide, PrBaFe 2O 5+ δ (PBFO), is synthesized and employed as a novel cathode while the synthesized BZCYYb is used as an electrolyte. The cell is fabricated by a simple dry-pressing/co-sintering process. The cell is tested and characterized under intermediate temperature range from 600 to 700 °C with humified H 2 (∼3% H 2O) as fuel, ambient air as oxidant. The results show that the open-circuit potential of 1.006 V and maximal power density of 452 mW cm -2 are achieved at 700 °C. The polarization resistance of the electrodes is 0.18 Ω cm 2 at 700 °C. Compared to BaZr 0.1Ce 0.7Y 0.1O 3- δ, the conductivity of co-doped barium zirconate-cerate BZCYYb is significantly improved. The ohmic resistance of single cell is 0.37 Ω cm 2 at 700 °C. The results indicate that the developed Ni-BZCYYb|BZCYYb|PBFO cell is a promising functional material system for SOFCs.

Modulation-Doped SrTiO3/SrTi1-xZrxO3 Heterostructures

NASA Astrophysics Data System (ADS)

Kajdos, Adam Paul

Two-dimensional electron gases (2DEGs) in SrTiO3 have attracted considerable attention for exhibiting a variety of interesting physical phenomena, such as superconductivity and magnetism. So far, most of the literature has focused on interfaces between nonpolar SrTiO3 and polar perovskite oxides (e.g. LaAlO3 or rare-earth titanates), where high carrier density 2DEGs (˜3 x 1014 cm-2) are generated by polar discontinuity. Modulation doping is an alternative approach to generating a 2DEG that has been explored extensively in III-V semiconductors but has not heretofore been explored in complex oxides. This approach involves interfacing an undoped semiconductor with a doped semiconductor whose conduction band edge lies at a higher energy, which results in electrons diffusing into the undoped semiconductor transport channel, where scattering from ionized dopants is minimized. Realizing a high-mobility modulation-doped structure with a SrTiO3 transport channel therefore requires both the optimization of the transport channel by minimizing native defects as well as the development of a perovskite oxide which has a suitable band offset with SrTiO3 and can be electron-doped. The growth of high electron mobility SrTiO3 as a suitable transport channel material was previously demonstrated using the hybrid molecular beam epitaxy (MBE) approach, where Sr is delivered via a solid source and Ti is delivered using a metal-organic precursor, titanium (IV) tetra-isopropoxide (TTIP). Expanding on this, in-situ reflection high-energy electron diffraction (RHEED) is used to track the surface and resulting film cation stoichiometry of homoepitaxial SrTiO3 (001) thin films grown by hybrid MBE. It is shown that films with lattice parameters identical to bulk single-crystal substrates within the detection limit of high-resolution X-ray diffraction (XRD) measurements exhibit an evolution in surface reconstruction with increasing TTIP beam-equivalent pressure. The change in the observed surface reconstruction from (1x1) to (2x1) to c(4x4) is correlated with a change from mixed SrO/TiO2 to pure TiO2 surface termination. It is argued that optimal cation stoichiometry is achieved for growth conditions within the XRD-defined growth window that result in a c(4x4) surface lattice. The development of a doped perovskite oxide semiconductor with a suitable conduction band offset is then discussed as the next necessary step towards realizing modulation-doped heterostructures. The SrTixZr1-x O3 solid solution is investigated for this purpose, with a focus on optimizing cation stoichiometry to allow for controlled doping. In particular, the hybrid MBE growth of SrTixZr1-xO3 thin films is explored using a metal-organic precursor for Zr, zirconium tert-butoxide (ZTB). The successful generation of 2DEGs by modulation doping of SrTiO3 is then demonstrated in SrTiO3/La:SrTi0.95Zr0.05O 3 heterostructures, and the electronic structure is studied by Shubnikov-de Haas analysis using multiple-subband models.

A high performance transparent resistive switching memory made from ZrO{sub 2}/AlON bilayer structure

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

Tsai, Tsung-Ling; Chang, Hsiang-Yu; Tseng, Tseung-Yuen, E-mail: tseng@cc.nctu.edu.tw

2016-04-11

In this study, the switching properties of an indium tin oxide (ITO)/zirconium oxide (ZrO{sub 2})/ITO single layer device and those of a device with an aluminum oxynitride (AlON) layer were investigated. The devices with highly transparent characteristics were fabricated. Compared with the ITO/ZrO{sub 2}/ITO single layer device, the ITO/ZrO{sub 2}/AlON/ITO bilayer device exhibited a larger ON/OFF ratio, higher endurance performance, and superior retention properties by using a simple two-step forming process. These substantial improvements in the resistive switching properties were attributed to the minimized influence of oxygen migration through the ITO top electrode (TE), which can be realized by formingmore » an asymmetrical conductive filament with the weakest part at the ZrO{sub 2}/AlON interface. Therefore, in the ITO/ZrO{sub 2}/AlON/ITO bilayer device, the regions where conductive filament formation and rupture occur can be effectively moved from the TE interface to the interior of the device.« less

High temperature oxidation behavior of austenitic stainless steel AISI 304 in steam of nanofluids contain nanoparticle ZrO2

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

Prajitno, Djoko Hadi, E-mail: djokohp@batan.go.id; Syarif, Dani Gustaman, E-mail: djokohp@batan.go.id

2014-03-24

The objective of this study is to evaluate high temperature oxidation behavior of austenitic stainless steel SS 304 in steam of nanofluids contain nanoparticle ZrO{sub 2}. The oxidation was performed at high temperatures ranging from 600 to 800°C. The oxidation time was 60 minutes. After oxidation the surface of the samples was analyzed by different methods including, optical microscope, scanning electron microscope (SEM) and X-ray diffraction (XRD). X-ray diffraction examination show that the oxide scale formed during oxidation of stainless steel AISI 304 alloys is dominated by iron oxide, Fe{sub 2}O{sub 3}. Minor element such as Cr{sub 2}O{sub 3} ismore » also appeared in the diffraction pattern. Characterization by optical microscope showed that cross section microstructure of stainless steel changed after oxidized with the oxide scale on the surface stainless steels. SEM and x-ray diffraction examination show that the oxide of ZrO{sub 2} appeared on the surface of stainless steel. Kinetic rate of oxidation of austenite stainless steel AISI 304 showed that increasing oxidation temperature and time will increase oxidation rate.« less

Investigation of Ce(3+) Dopant in Appropriate Hosts for Blue Green Lasers.

DTIC Science & Technology

1986-11-25

crystal of La(A10 .8Sc 0 .2 )0 3 doped with 0.01% Ce. During one experiment a small amount of the charge was fused in an iridium crucible. The...from ordering was not observed. Similar results were achieved in Experiment #47 with (LaAlO3 ) 0 .5 (SrZrO 3 )0 5 composition. Small additions of...compositions evaluated, enlarged cubic cells could not be formed by ordering. Small additions of less than 5% of BaZrO 3 or SrZrO 3 to LaAIO 3 produced

Benzene selectivity in competitive arene hydrogenation: effects of single-site catalyst···acidic oxide surface binding geometry.

PubMed

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P; Bhattacharyya, Alak; Motta, Alessandro; Gallagher, James R; Zhang, Guanghui; Miller, Jeffrey T; Kobayashi, Takeshi; Pruski, Marek; Delferro, Massimiliano; Marks, Tobin J

2015-06-03

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO2 (ZrS), sulfated Al2O3 (AlS), and ZrO2-WO3 (ZrW). Under mild conditions (25 °C, 1 atm H2), the supported Cp*ZrMe3, Cp*ZrBz3, and Cp*ZrPh3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS ≫ AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures, and selectivities for benzene hydrogenation vary with catalyst as ZrBz3(+)/ZrS(-), 83% > Cp*ZrMe2(+)/ZrS(-), 80% > Cp*ZrBz2(+)/ZrS(-), 67% > Cp*ZrPh2(+)/ZrS(-), 57%. For Cp*ZrBz2(+)/ZrS(-), which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe3 and Cp*ZrBz3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz2(+)/AlS(-) vs Cp*ZrMe2(+)/AlS(-). The combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the "cationic" metal center-anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.

Benzene selectivity in competitive arene hydrogenation: Effects of single-site catalyst···acidic oxide surface binding geometry

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

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P.

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO 2 (ZrS), sulfated Al 2O 3 (AlS), and ZrO 2–WO 3 (ZrW). Under mild conditions (25 °C, 1 atm H 2), the supported Cp*ZrMe 3, Cp*ZrBz 3, and Cp*ZrPh 3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS >> AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures,more » and selectivities for benzene hydrogenation vary with catalyst as ZrBz 3 +/ZrS –, 83% > Cp*ZrMe 2 +/ZrS –, 80% > Cp*ZrBz 2 +/ZrS –, 67% > Cp*ZrPh 2 +/ZrS –, 57%. For Cp*ZrBz 2+/ZrS –, which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe 3 and Cp*ZrBz 3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz 2 +/AlS – vs Cp*ZrMe 2 +/AlS –. Furthermore, the combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the “cationic” metal center–anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.« less

Benzene selectivity in competitive arene hydrogenation: Effects of single-site catalyst···acidic oxide surface binding geometry

DOE PAGES

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P.; ...

2015-04-17

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO 2 (ZrS), sulfated Al 2O 3 (AlS), and ZrO 2–WO 3 (ZrW). Under mild conditions (25 °C, 1 atm H 2), the supported Cp*ZrMe 3, Cp*ZrBz 3, and Cp*ZrPh 3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS >> AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures,more » and selectivities for benzene hydrogenation vary with catalyst as ZrBz 3 +/ZrS –, 83% > Cp*ZrMe 2 +/ZrS –, 80% > Cp*ZrBz 2 +/ZrS –, 67% > Cp*ZrPh 2 +/ZrS –, 57%. For Cp*ZrBz 2+/ZrS –, which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe 3 and Cp*ZrBz 3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz 2 +/AlS – vs Cp*ZrMe 2 +/AlS –. Furthermore, the combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the “cationic” metal center–anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.« less

Ilyukhinite (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 • 3H2O, a New Mineral of the Eudialyte Group

NASA Astrophysics Data System (ADS)

Chukanov, N. V.; Rastsvetaeva, R. K.; Rozenberg, K. A.; Aksenov, S. M.; Pekov, I. V.; Belakovsky, D. I.; Kristiansen, R.; Van, K. V.

2017-12-01

A new eudialyte-group mineral, ilyukhinite, ideally (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 · 3H2O, has been found in peralkaline pegmatite at Mt. Kukisvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. It occurs as brownish orange, with vitreous luster anhedral grains up to 1 mm across in hydrothermally altered peralkaline rock, in association with aegirine, murmanite, albite, microcline, rhabdophane-(Ce), fluorite, sphalerite and molybdenite. The Mohs hardness is 5; cleavage is not observed. D meas 2.67(2), D calc 2.703 g/cm3. Ilyukhinite is optically uniaxial (-): ω = 1.585(2), ɛ = 1.584(2). The IR spectrum is given. The average chemical composition of ilyukhinite (wt %; electron microprobe, ranges given in parentheses; H2O determined by gas chromatography) is as follows: 3.07 (3.63-4.43) Na2O, 0.32 (0.28-0.52) K2O, 10.63 (10.26-10.90) CaO, 3.06 (2.74-3.22) MnO, 1.15 (0.93-1.37) FeO, 0.79 (0.51-0.89) La2O3, 1.21 (0.97-1.44) Ce2O3, 0.41 (0.30-0.56) Nd2O3, 0.90 (0.77-1.12) TiO2, 10.94 (10.15-11.21) ZrO2, 1.40 (0.76-1.68) Nb2O5, 51.24 (49.98-52.28) SiO2, 1.14 (0.89-1.37) SO3, 0.27 (0.19—0.38) Cl, 10.9(5 )H2O,-0.06-O = C1, total is 98.27. The empirical formula is H36.04(Na3.82K0.20)(Ca5.65Ce0.22La0.14Nd0.07)(Mn1.285Fe0.48)(Zr2.645Ti0.34)Nb0.31Si25.41S0.42Cl0.23O86.82. The crystal structure has been solved ( R = 0.046). Ilyukhinite is trigonal, R3 m; a = 14.1695(6) Å, b = 31.026(1) Å, V = 5394.7(7) Å3, Z = 3. The strongest XRD reflections [ d, Å (I, %) ( hkl)] are 11.44 (82) (101), 7.09 (70) (110), 6.02 (44) (021), 4.371 (89) 205), 3.805 (47) (303, 033), 3.376 (41) (131), 2.985 (100) (315, 128), 2.852 (92) (404). Ilyukhinite was named in memory of Vladimir V. Ilyukhin (1934-1982), an outstanding Soviet crystallographer. The type specimen of ilyukhinite has been deposited in the collection of the Natural History Museum, University of Oslo, Norway.

Simultaneous oxidation of Hg0 and NH3-SCR of NO by nanophase Ce x Zr y Mn z O2 at low temperature: the interaction and mechanism.

PubMed

Wu, Wanrong; Zeng, Zheng; Lu, Pei; Xing, Yi; Wei, Jianjun; Yue, Huifang; Li, Rui

2018-03-10

Simultaneous oxidation of Hg 0 and NH 3 -SCR of NO by catalyst is one of the key methods for co-purification of coal-fired flue gas. Till now, the interaction between the oxidation of Hg 0 and NH 3 -SCR of NO and its mechanism have not clarified. In this study, a series of nanophase Ce x Zr y Mn z O 2 was prepared for the simultaneous oxidation of Hg 0 and NH 3 -SCR of NO at low temperature. The catalysts were characterized using surface area analysis, X-ray diffraction, temperature-programmed techniques, and several types of microscopy and spectroscopy. The experimental results indicated that the Ce 0.47 Zr 0.22 Mn 0.31 O 2 exhibited superior Hg 0 removal efficiency (> 99%) and NO conversion efficiency (> 90%) even at 150 °C, and it also exhibited a good durability in the presence of SO 2 and H 2 O. The excellent performance of Ce 0.47 Zr 0.22 Mn 0.31 O 2 on co-purifying Hg 0 and NO was due to the stronger synergistic effects of Ce-Zr-Mn in Ce 0.47 Zr 0.22 Mn 0.31 O 2 than that of the others, which was illustrated by the characterization results of XPS, XRD, and FT-IR. Moreover, it was found that the NO conversion of Ce 0.47 Zr 0.22 Mn 0.31 O 2 could be slightly influenced by Hg 0 and was decreased about 4% to the max, while that of Hg 0 could rarely be affected by the selected catalytic reduction process of NO. It might be due to the co-purification mechanism of NO and Hg 0 . The mechanism of the simultaneous oxidation of Hg 0 and NH 3 -SCR of NO was mainly due to the synergetic effect on the mobility of surface oxygen and the activation of lattice oxygen of Ce 0.47 Zr 0.22 Mn 0.31 O 2 . The effect of the oxidation of Hg 0 on the NH 3 -SCR of NO was mainly due to the absorbed Hg 0 /Hg 2+ on the surface of Ce 0.47 Zr 0.22 Mn 0.31 O 2 , which attenuated the formation of NH 3(ad) , -NH 2(ad) , and NH 4 + on its acid sites. Similarly, the NH 3 -SCR of NO process could hardly influence the oxidation of Hg 0 when NO and Hg 0 were co-purified.

Decomposition of L a 2 – x S r x Cu O 4 into several L a 2 O 3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

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

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet

Here, we report the decomposition of La 2–xSr xCuO 4 into La 2O 3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La 2O 3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La 2O 3 phases are further identified to be derivatives of a fluorite structure—fluorite,more » pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM 4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La 2O 3 phases remain unchanged after cooling to room temperature.« less

Decomposition of L a 2 – x S r x Cu O 4 into several L a 2 O 3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

DOE PAGES

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; ...

2018-05-15

Here, we report the decomposition of La 2–xSr xCuO 4 into La 2O 3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La 2O 3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La 2O 3 phases are further identified to be derivatives of a fluorite structure—fluorite,more » pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM 4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La 2O 3 phases remain unchanged after cooling to room temperature.« less

Zirconia based ceramic coating on a metal with plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Akatsu, T.; Kato, T.; Shinoda, Y.; Wakai, F.

2011-10-01

We challenge to fabricate a thermal barrier coating (TBC) made of ZrO2 based ceramics on a Ni based single crystal superalloy with plasma electrolytic oxidation (PEO) by incorporating metal species from electrolyte into the coating. The PEO process is carried out on the superalloy galvanized with aluminium for 15min in Na4O7P4 solution for an oxygen barrier coating (OBC) and is followed by PEO in K2[Zr(CO3)2(OH)2] solution for TBC. We obtained the following results; (1) Monoclinic-, tetragonal-, cubic-ZrO2 crystals were detected in TBC. (2) High porosity with large pores was observed near the interface between OBC and TBC. The fine grain structure with a grain size of about 300nm was typically observed. (3) The adhesion strength between PEO coatings and substrate was evaluated to be 26.8±6.6MPa. At the adhesion strength test, PEO coatings fractured around the interface between OBC and TBC. The effect of coating structure on adhesion strength is explained through the change in spark discharge during PEO process.

Solubility of metal oxides in molten equimolar KBr-NaBr mixture at 973 K

NASA Astrophysics Data System (ADS)

Cherginets, V. L.; Rebrova, T. P.; Naumenko, V. A.

2014-09-01

Solubility products (p K s,MO, molality) are measured by potentiometric titration with a Pt(O2)|ZrO2(Y2O3) oxygen electrode in the molten KBr-NaBr equimolar mixture at 973 K for the following oxides: CaO (5.00 ± 0.3), MnO (7.85 ± 0.3), NiO (9.72 ± 0.04), PbO (5.20 ± 0.3), and SrO (3.81 ± 0.3). The correlation between p K s,MeO and the polarization of the corresponding cations by Goldschmidt is obtained.

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.

Growth of metal oxide thin films by laser-induced metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Tokita, Koji; Okada, Fumio

1996-12-01

The growth of metal oxide thin films by laser-induced metalorganic chemical vapor deposition was investigated by changing wavelength, power, repetition rate, and irradiation angle of the excimer laser. When O2 was used as an oxidizing gas with 193 or 248 nm irradiation, amorphous TiO2 and crystalline PbO films were obtained in the laser-irradiated area of Si substrates from the parent metalorganic compounds, Ti(O-iC3H7)4 and (C2H5)3PbOCH2C(CH3)3, respectively. In contrast, no ZrO2 film could be formed from Zr(O-tC4H9)4. One-photon formation of TiO2 films was confirmed from laser power dependence measurements. The maximum growth rate of 0.05 Å per laser pulse was compared with that estimated by a simple surface reaction model, according to which the slow growth rate is due to the small absorption cross section of Ti(O-iC3H7)4 and mild fluence of laser irradiation. In experiments of ozone gas excitation by KrF laser, a SiO2 film was obtained by gas-phase reactions of the oxygen radical, O(1D), with Si(O-C2H5)4. The direct patterning of TiO2 and PbO films as well as the possibility of producing patterned PbTiO3 film was demonstrated. The growth of the patterned SiO2 film was prevented by gas-phase diffusion of intermediates.

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

Ikeuchi, Hirotomo; Yano, Kimihiko; Kaji, Naoya

For the decommissioning of the Fukushima-Daiichi Nuclear Power Station (1F), the characterization of fuel-debris in cores of Units 1-3 is necessary. In this study, typical phases of the in-vessel fuel-debris were estimated using a thermodynamic equilibrium (TDE) calculation. The FactSage program and NUCLEA database were applied to estimate the phase equilibria of debris. It was confirmed that the TDE calculation using the database can reproduce the phase separation behavior of debris observed in the Three Mile Island accident. In the TDE calculation of 1F, the oxygen potential [G(O{sub 2})] was assumed to be a variable. At low G(O{sub 2}) wheremore » metallic zirconium remains, (U,Zr)O{sub 2}, UO{sub 2}, and ZrO{sub 2} were found as oxides, and oxygen-dispersed Zr, Fe{sub 2}(Zr,U), and Fe{sub 3}UZr{sub 2} were found as metals. With an increase in zirconium oxidation, the mass of those metals, especially Fe{sub 3}UZr{sub 2}, decreased, but the other phases of metals hardly changed qualitatively. Consequently, (U,Zr)O{sub 2} is suggested as a typical phase of oxide, and Fe{sub 2}(Zr,U) is suggested as that of metal. However, a more detailed estimation is necessary to consider the distribution of Fe in the reactor pressure vessel through core-melt progression. (authors)« less

Superconductivity at 43K in SmFeAsO1-xFx

NASA Astrophysics Data System (ADS)

Chen, X. H.; Wu, T.; Wu, G.; Liu, R. H.; Chen, H.; Fang, D. F.

2008-06-01

Since the discovery of high-transition-temperature (high-Tc) superconductivity in layered copper oxides, extensive effort has been devoted to exploring the origins of this phenomenon. A Tc higher than 40K (about the theoretical maximum predicted from Bardeen-Cooper-Schrieffer theory), however, has been obtained only in the copper oxide superconductors. The highest reported value for non-copper-oxide bulk superconductivity is Tc = 39K in MgB2 (ref. 2). The layered rare-earth metal oxypnictides LnOFeAs (where Ln is La-Nd, Sm and Gd) are now attracting attention following the discovery of superconductivity at 26K in the iron-based LaO1-xFxFeAs (ref. 3). Here we report the discovery of bulk superconductivity in the related compound SmFeAsO1-xFx, which has a ZrCuSiAs-type structure. Resistivity and magnetization measurements reveal a transition temperature as high as 43K. This provides a new material base for studying the origin of high-temperature superconductivity.

Compound ultrarefractory CAI-bearing inclusions from CV3 carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Ivanova, Marina A.; Krot, Alexander N.; Nagashima, Kazuhide; MacPherson, Glenn J.

2012-12-01