On the stabilization of NbV-solutions by ZrIV and HfIV

International Nuclear Information System (INIS)

Soerensen, E.; Bjerre, A.B.

1987-11-01

Niobium cannot be separated from zirconium or hafnium when these elements occur together in solution with common anions such as Cl- and SO 4 --. This is ascribed to the copolymerisation of Nb v and the hydrolyzed ionic species of Zr IV v and Hf IV by which the colloidal particles are masked as Zr- and Hf-compounds. In HCl the particles are positively charged as opposed to when they are in sulphate solution where the Zr- and Hf- sulphate complexes confer a negative charge. The two cases are considered separately. (author)

Highly ordered nanotubular film formation on Ti–25Nb–xZr and Ti–25Ta–xHf

Energy Technology Data Exchange (ETDEWEB)

Kim, Jeong-Jae; Byeon, In-Seop [Department of Dental Materials, Research Center of Nano-Interface Activation for Biomaterials, & Research Center for Oral Disease Regulation of the Aged, College of Dentistry, Chosun University, Gwangju (Korea, Republic of); Brantley, William A. [Division of Restorative Sciences and Prosthodontics, College of Dentistry, The Ohio State University, Columbus, OH (United States); Choe, Han-Cheol, E-mail: hcchoe@chosun.ac.kr [Department of Dental Materials, Research Center of Nano-Interface Activation for Biomaterials, & Research Center for Oral Disease Regulation of the Aged, College of Dentistry, Chosun University, Gwangju (Korea, Republic of)

2015-12-01

The purpose of this study was to investigate the highly ordered nanotubular film formation on Ti–25Nb–xZr and Ti–25Ta–xHf, examining the roles of niobium, zirconium, tantalum and hafnium alloying elements. The Ti–25Nb–xZr and Ti–25Ta–xHf ternary alloys contained 0, 7 and 15 wt.% of these alloying elements and were manufactured using a vacuum arc-melting furnace. Cast ingots of the alloys were homogenized in Ar atmosphere at 1050 °C for 2 h, followed by quenching into ice water. Formation of nanotubular films was achieved by an electrochemical method in 1 M H{sub 3}PO{sub 4} + 0.8 wt.% NaF at 30 V and 1 h for the Ti–25Nb–xZr alloys and 2 h for the Ti–25Ta–xHf alloys. Microstructures of the Ti–25Ta–xHf alloys transformed from α″ phase to β phase, changing from a needle-like structure to an equiaxed structure as the Hf content increased. In a similar manner, the needle-like structure of the Ti–25Nb–xZr alloys transformed to an equiaxed structure as the Zr content increased. Highly ordered nanotubes formed on the Ti–25Ta–15Hf and Ti–25Nb–15Zr alloys compared to the other alloys, and the nanotube layer thickness on Ti–25Ta–15Hf and Ti–25Nb–15Zr was greater than for the other alloys. Nanotubes formed on Ti–25Ta–15Hf and Ti–25Nb–15Zr showed two sizes of highly ordered structures. The diameters of the large nanotubes decreased and the diameters of the small nanotubes increased as Zr and Hf contents increased. It was found that the layer thickness, diameter, surface density and growth rate of nanotubes on the Ti–25Ta–xHf and Ti–25Nb–xZr alloys can be controlled by varying the Hf and Zr contents. X-ray diffraction analyses revealed only weak peaks for crystalline anatase or rutile TiO{sub 2} phases from the nanotubes on the Ti–25Nb–xZr and Ti–25Ta–xHf alloys, indicating a largely amorphous condition. - Highlights: • Nanotubular film formation on anodized Ti-25Nb-xZr and Ti-25Ta-xHf (x = 0, 7 and

A new class of materials with promising thermoelectric properties: MNiSn (M=Ti, Zr, Hf)

Energy Technology Data Exchange (ETDEWEB)

Hohl, H; Ramirez, A P; Kaefer, W; Fess, K; Thurner, Ch; Kloc, Ch; Bucher, E

1997-07-01

TiNiSn, ZrNiSn and HfNiSn are members of a large group of intermetallic compounds which crystallize in the cubic MgAgAs-type structure. Polycrystalline samples of these compounds have been prepared and investigated for their thermoelectric properties. With thermopowers of about {minus}200 {micro}V/K and resistivities of a few m{Omega}cm, power factors S{sup 2}/{rho} as high as 38 {micro}W/K{sup 2}cm were obtained at 700 K. These remarkably high power factors are, however, accompanied by a thermal conductivity, solid solutions Zr{sub 1{minus}x}Hf{sub x}NiSn, Zr{sub 1{minus}x}Ti{sub x}NiSn, and Hf{prime}{sub 1{minus}x}Ti{sub x}NiSn were formed. The figure of merit of Zr{sub 0.5}Hf{sub 0.5}NiSn at 700 K (ZT = 0.41) exceeds the end members ZrNiSn (ZT = 0.26) and HfNiSn (ZT = 0.22).

Constitutive Model for Hot Deformation of the Cu-Zr-Ce Alloy

Science.gov (United States)

Zhang, Yi; Sun, Huili; Volinsky, Alex A.; Wang, Bingjie; Tian, Baohong; Liu, Yong; Song, Kexing

2018-02-01

Hot compressive deformation behavior of the Cu-Zr-Ce alloy has been investigated according to the hot deformation tests in the 550-900 °C temperature range and 0.001-10 s-1 strain rate range. Based on the true stress-true strain curves, the flow stress behavior of the Cu-Zr-Ce alloy was investigated. Microstructure evolution was observed by optical microscopy. Based on the experimental results, a constitutive equation, which reflects the relationships between the stress, strain, strain rate and temperature, has been established. Material constants n, α, Q and ln A were calculated as functions of strain. The equation predicting the flow stress combined with these materials constants has been proposed. The predicted stress is consistent with experimental stress, indicating that developed constitutive equation can adequately predict the flow stress of the Cu-Zr-Ce alloy. Dynamic recrystallization critical strain was determined using the work hardening rate method. According to the dynamic material model, the processing maps for the Cu-Zr and Cu-Zr-Ce alloy were obtained at 0.4 and 0.5 strain. Based on the processing maps and microstructure observations, the optimal processing parameters for the two alloys were determined, and it was found that the addition of Ce can promote the hot workability of the Cu-Zr alloy.

Glass-forming ability and stability of ternary Ni-early transition metal (Ti/Zr/Hf) alloys

Energy Technology Data Exchange (ETDEWEB)

Basu, Joysurya [Department of Metallurgy, Indian Institute of Science, Bangalore 560 012 (India); Ranganathan, S. [Department of Metallurgy, Indian Institute of Science, Bangalore 560 012 (India)]. E-mail: rangu@met.iisc.ernet.in

2006-08-15

Four Ni-bearing Ti, Zr and Hf ternary alloys of nominal composition Zr{sub 41.5}Ti{sub 41.5}Ni{sub 17}, Zr{sub 25}Ti{sub 25}Ni{sub 50}, Zr{sub 41.5}Hf{sub 41.5}Ni{sub 17} and Ti{sub 41.5}Hf{sub 41.5}Ni{sub 17} were rapidly solidified in order to produce ribbons. The Zr-Ti-Ni and Ti-Hf-Ni alloys become amorphous, whereas the Zr-Hf-Ni alloy shows precipitation of a cubic phase. The devitrification of all three alloys was followed and the relative tendency to form nanoquasicrystals and cF96 phases analysed. The relative glass-forming ability of the alloys can be explained by taking into account their atomic size difference. Addition of Ni often leads to quasicrystallisation or quasicrystal-related phases. This can be explained by the atomic radius and heat of mixing of the constituent elements. The phases precipitated at the initial stages of crystallisation indicate the possible presence of Frank-Kasper polyhedral structure in the amorphous alloys. Structural analysis reveals that the Laves and the anti-Laves phases have the same polyhedral structural unit, which is similar to the structural characteristics of glass.

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

Science.gov (United States)

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

2018-04-01

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

Glass forming ability: Miedema approach to (Zr, Ti, Hf)-(Cu, Ni) binary and ternary alloys

Energy Technology Data Exchange (ETDEWEB)

Basu, Joysurya [Department of Chemical, Materials and Biomolecular Engineering, 191 Auditorium Road, University of Connecticut, Storrs 06269, CT (United States)], E-mail: jbasu@engr.uconn.edu; Murty, B.S. [Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036 (India); Ranganathan, S. [Department of Materials Engineering, Indian Institute of Science, Bangalore 560012 (India)

2008-10-06

Miedema's approach has been useful in determining the glass forming composition range for a particular alloy system. The concept of mixing enthalpy and mismatch entropy can be used in order to quantify Inoue's criteria of bulk metallic glass formation. In the present study, glass forming composition range has been determined for different binary and ternary (Zr, Ti, Hf)-(Cu, Ni) alloys based on the mixing enthalpy and mismatch entropy calculations. Though copper and nickel appear next to each other in the periodic table, the glass forming ability of the copper and nickel bearing alloys is different. Thermodynamic analysis reveals that the glass forming behaviour of Zr and Hf is similar, whereas it is different from that of Ti. The smaller atomic size of Ti and the difference in the heat of mixing of Ti, Zr, Hf with Cu and Ni leads to the observed changes in the glass forming behaviour. Enthalpy contour plots can be used to distinguish the glass forming compositions on the basis of the increasing negative enthalpy of the composition. This method reveals the high glass forming ability of binary Zr-Cu, Hf-Cu, Hf-Ni systems over a narrow composition range.

Performance of cubic ZrO{sub 2} doped CeO{sub 2}: First-principles investigation on elastic, electronic and optical properties of Ce{sub 1−x} Zr{sub x}O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Tian, Dong [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Zeng, Chunhua, E-mail: zchh2009@126.com [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Science, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Wang, Hua, E-mail: wanghuaheat@hotmail.com [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Luo, Hongchun [Faculty of Science, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Cheng, Xianming [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Xiang, Chao [College of Mechanical and Electrical Engineering, Yangtze Normal University, Fuling 408100, Chongqing (China); Wei, Yonggang; Li, Kongzhai; Zhu, Xing [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan (China); Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan (China)

2016-06-25

The structural, elastic, electronic and optical properties of Ce{sub 1−x} Zr{sub x}O{sub 2} (x = 0, 0.25, 0.5, 0.75, 1) fluorite type oxides are studied by researchers using the method of density functional theory (DFT) + U method. The calculated equilibrium lattice parameter, cell volume, elastic and optical properties for CeO{sub 2} and ZrO{sub 2} are all in good agreement with the available experimental data and other theoretical results. It is found that Ce substituted by Zr leads to the formation of the pseudo-cubic fluorite-type structure. With doping concentration × increasing, the lattice parameter, cell volume and the bond length of d{sub Ce−O} and d{sub Zr−O} decrease linearly. It is interesting to find that the hardness of materials increase with Zr concentration increasing. For Ce{sub 0.75} Zr{sub 0.25} O{sub 2}, we also find that its ductility is good. Meanwhile, the range of the conduction band energy in the doped system becomes wider than that in the undoped system. The overlapping band phenomenon occur for all substitutions in Ce{sub 1−x} Zr{sub x}O{sub 2} (from x = 0.25 to x = 0.75), especially for the structure of Ce{sub 0.5} Zr{sub 0.5} O{sub 2} and Ce{sub 0.25} Zr{sub 0.75} O{sub 2}, its second band gaps almost disappear. Based on the dielectric functions obtained, it is shown that the static dielectric constant ε{sub 0} and refractive index n{sub 0} obviously decrease with Zr concentration increasing. After discussing, we know that CeO{sub 2} is suitable as a useful high-refractive index film material in single and multilayered optical coatings, whereas ZrO{sub 2} can be used as gate-dielectric materials in metal-oxide semiconductor (MOS) devices, in metallurgy and as a thermal barrier coating in engines. - Highlights: • Structural, and optical properties of fluorite type oxides are studied; • Ce substituted by Zr leads to formation of pseudo-cubic fluorite-type structure; • Hardness of materials are increased with Zr

Study on the adducts formation of Zr and Hf chelates

International Nuclear Information System (INIS)

Ree, Chin Taik; Jung, Young Sam; Park, Jun Kown

1986-01-01

The synergistic effect observed in Zr(IV) and Hf(IV) extraction from strong perchloric acid solutions by the mixtures of 2-Thenoyltri-fluoroacetone(TTA) and Octanols is shown to be caused by the formation of a mixed complex, M(TTA) 3 XS (M=Zr(IV), HF(IV), X=ClO 4 - , S=Octanol). One of the four TTA molecules coordinated at lower HClO 4 concentration to the metal as bidendate ligand seems to be changed to monodendate due to increasing HClO 4 concentration. The monodenate TTA ligand leaves the coordination site, finally, due to the activity of perchlorate at higher concentration and the additional coordination of an Octanol molecule seems to be allowed to the vaccant site which shows the synergistic extraction phenomena. (Author)

Interatomic potential to predict the favored and optimized compositions for ternary Cu-Zr-Hf metallic glasses

International Nuclear Information System (INIS)

Luo, S. Y.; Cui, Y. Y.; Dai, Y.; Li, J. H.; Liu, B. X.

2012-01-01

Under the framework of smoothed and long range second-moment approximation of tight-binding, a realistic interatomic potential was first constructed for the Cu-Zr-Hf ternary metal system. Applying the constructed potential, Monte Carlo simulations were carried out to compare the relative stability of crystalline solid solution versus its disordered counterpart over the entire composition triangle of the system (as a function of alloy composition). Simulations not only reveal that the origin of metallic glass formation but also determine, in the composition triangle, a quadrilateral region, within which metallic glass formation is energetically favored. It is proposed to define the energy differences between the crystalline solid solutions and disordered states as the driving force for amorphization and the corresponding calculations pinpoint an optimized composition locating at an composition of Cu 55 Zr 10 Hf 35 , around which the driving force for metallic glass formation reaches its maximum, suggesting that the ternary Cu-Zr-Hf metallic glasses designed to have the compositions around Cu 55 Zr 10 Hf 35 could be more stable than other alloys in the system. Moreover, for the Cu 55 Zr 10 Hf 35 metallic glass, the Voronoi tessellation calculations reveal some interesting features of its atomic configurations and coordination polyhedra distribution.

Electrochemical characterization of Pt-CeO{sub 2}/C and Pt-Ce{sub x}Zr{sub 1-x}O{sub 2}/C catalysts for ethanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Bai, Yuxia; Qiu, Xinping; Xi, Jingyu; Wang, Jianshe; Li, Jinfeng; Zhu, Wentao; Chen, Liquan [Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China); Wu, Jianjun [Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China); Department of Chemistry, Shijiazhuang College, Shijiazhuang 050801 (China)

2007-04-24

Pt-CeO{sub 2}/C and a series of Pt-Ce{sub x}Zr{sub 1-x}O{sub 2}/C catalyst powders with different Ce/Zr ratio were prepared and evaluated in terms of the electrochemical activity for ethanol electro-oxidation using cyclic voltammetry (CV), steady state polarization experiments and CO-stripping technique at room temperature. XRD results show that Ce{sub x}Zr{sub 1-x}O{sub 2} and Pt coexist in the Pt-Ce{sub x}Zr{sub 1-x}O{sub 2}/C catalyst and Ce{sub x}Zr{sub 1-x}O{sub 2} has no effect on the crystalline lattice of Pt. TEM results show that the Pt and Ce{sub x}Zr{sub 1-x}O{sub 2} particles dispersed uniformly over the surface of the carbon black. Cyclic voltammetry results show that the mass activity and specific activity of Pt-CeO{sub 2}/C for ethanol electro-oxidation is higher than that of Pt/C. The structure and Ce/Zr ratio of Pt-Ce{sub x}Zr{sub 1-x}O{sub 2}/C has effect on the catalytic activity of catalysts. CO-stripping voltammetry showed that the inclusion of CeO{sub 2} and Ce{sub x}Zr{sub 1-x}O{sub 2} favors the CO oxidation at lower potential. (author)

Mechanical, electronic and thermal properties of Cu{sub 5}Zr and Cu{sub 5}Hf by first-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Yi, Guohui [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Zhang, Xinyu, E-mail: xyzhang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Qin, Jiaqian, E-mail: jiaqianqin@gmail.com [Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok 10330 (Thailand); Ning, Jinliang; Zhang, Suhong; Ma, Mingzhen; Liu, Riping [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China)

2015-08-15

Highlights: • The mechanical and fundamental thermal data of Cu{sub 5}Zr and Cu{sub 5}Hf are determined. • The technologically important elastic anisotropy is obtained and discussed according to its industrial applications. • The brittle/ductile and bonding nature of Cu{sub 5}Zr and Cu{sub 5}Hf are analyzed in details. - Abstract: The structural, elastic, electronic and thermodynamic properties of Cu{sub 5}Zr and Cu{sub 5}Hf compounds are investigated by first-principles calculations combined with the quasi-harmonic Debye model. The calculated lattice parameters of cubic AuBe{sub 5}-type Cu{sub 5}Zr and Cu{sub 5}Hf agree well with available experimental and other theoretical results and the formation enthalpy calculations show that AuBe{sub 5}-type Cu{sub 5}Hf is more energetically stable than the competing hexagonal CaCu{sub 5}-type phase. The mechanical properties such as mechanical stabilities, anisotropy character, ductility (estimated from the value of B/G, Poisson’s ratio υ and Cauchy pressures C{sub 12}–C{sub 44}) and thermodynamic properties such as volume change under temperature and pressure (V/V{sub 0}), heat capacity (C{sub v}), Debye temperature (Θ), thermal expansion coefficient (α) of AuBe{sub 5}-type Cu{sub 5}Zr and Cu{sub 5}Hf are calculated together. Cu{sub 5}Hf has better performances than Cu{sub 5}Zr with higher hardness and better resistance to fracture which are rationalized from the calculated electronic structure (including density of states, charge density distributions, Mulliken’s population analysis) and we find that all ionic, covalent and metallic components exist in bonding of Cu{sub 5}Zr and Cu{sub 5}Hf but the covalent bonding in Cu{sub 5}Hf is stronger.

Discovery of ferromagnetism with large magnetic anisotropy in ZrMnP and HfMnP

Energy Technology Data Exchange (ETDEWEB)

Lamichhane, Tej N.; Taufour, Valentin; Kaluarachchi, Udhara S.; Bud' ko, Sergey L.; Canfield, Paul C. [Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011 (United States); The Ames Laboratory, US Department of Energy, Iowa State University, Ames, Iowa 50011 (United States); Masters, Morgan W. [Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011 (United States); Parker, David S. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Thimmaiah, Srinivasa [The Ames Laboratory, US Department of Energy, Iowa State University, Ames, Iowa 50011 (United States)

2016-08-29

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

Discovery of ferromagnetism with large magnetic anisotropy in ZrMnP and HfMnP

International Nuclear Information System (INIS)

Lamichhane, Tej N.; Taufour, Valentin; Kaluarachchi, Udhara S.; Bud'ko, Sergey L.; Canfield, Paul C.; Masters, Morgan W.; Parker, David S.; Thimmaiah, Srinivasa

2016-01-01

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

A new Ti-Zr-Hf-Cu-Ni-Si-Sn bulk amorphous alloy with high glass-forming ability

International Nuclear Information System (INIS)

Huang, Y.J.; Shen, J.; Sun, J.F.; Yu, X.B.

2007-01-01

The effect of Sn substitution for Cu on the glass-forming ability was investigated in Ti 41.5 Zr 2.5 Hf 5 Cu 42.5-x Ni 7.5 Si 1 Sn x (x = 0, 1, 3, 5, 7) alloys by using differential scanning calorimetry (DSC) and X-ray diffractometry. The alloy containing 5% Sn shows the highest glass-forming ability (GFA) among the Ti-Zr-Hf-Cu-Ni-Si-Sn system. Fully amorphous rod sample with diameters up to 6 mm could be successfully fabricated by the copper mold casting Ti 41.5 Zr 2.5 Hf 5 Cu 37.5 Ni 7.5 Si 1 Sn 5 alloy. The activation energies for glass transition and crystallization for Ti 41.5 Zr 2.5 Hf 5 Cu 37.5 Ni 7.5 Si 1 Sn 5 amorphous alloy are both larger than those values for the Sn-free alloy. The enhancement in GFA and thermal stability after the partial replacement of Cu by Sn may be contributed to the strong atomic bonding nature between Ti and Sn and the increasing of atomic packing density. The amorphous Ti 41.5 Zr 2.5 Hf 5 Cu 37.5 Ni 7.5 Si 1 Sn 5 alloy also possesses superior mechanical properties

Electron paramagnetic resonance study of Ce doped partially stabilized ZrO2 crystals

Directory of Open Access Journals (Sweden)

Mikhail А. Borik

2017-09-01

Full Text Available ZrO2 (PSZ solid solutions crystals stabilized with yttrium and cerium oxides have been studied using electron paramagnetic resonance (EPR in the X and Q ranges. Zr3+ have been observed centers in the as-annealed ZrO2 crystals stabilized only by yttrium oxide (2.8 mol% Y2O3. Another type of paramagnetic-O-centers appear as a result of CeO2 addition to ZrO2 crystals along with yttrium oxide. To estimate the concentration of Ce3+ ions in PZS crystals, we recorded the EPR spectra in the presence of a reference at 7 K. Paramagnetic Ce3+ ions have been identified and their relative amount in the PSZ crystals before and after high-temperature heat treatment has been assessed. Annealing in air leads decreases the concentration of Ce3+ ions for all the test compositions and changes the color of the crystals from red to white. After annealing of the sample 2.0Y0.8Ce3Zr, the amount of paramagnetic Ce3+ ions decreased approximately twofold. Paramagnetic centers from Ce3+ have not been detected in the specimen with a low cerium content of 0.1 mol% after annealing which indicates the complete transition of Ce3+ to the Ce4+ state. We show that the forming cerium paramagnetic centers are bound by strong exchange interactions. No angular dependence of the EPR lines of the paramagnetic Ce3+ cations on the applied external magnetic field has been observed. Probable origin of the absence of angular dependence is that the impurity rare-earth ions are located close to one another, forming impurity clusters with an effective spin of Seff=1/2.

Validation of Zr and Hf analysis contained on water phase using k_0-neutron activation analysis method

International Nuclear Information System (INIS)

Wisjachudin Faisa; Sutisna

2010-01-01

At conversion of Zr-sand to Zircon Oxide, the Hf content in product process should not be more than 100 ppm. While Zr and Hf are two elements that have a similar chemical property Hs, they are difficult to analyze by ordinary chemical analysis. One of reliable analytical method that can be used to quantify Zr and Hf is the instrumental neutron activation analysis. Related to this problem, a result of k_0-Instrumental Neutron Activation Analysis (k_0-INAA) on Zr and Hf (in aqueous phase) has been validated. A number of 200 µL SPEX Pure standard solution which have a concentration of 1 g/L pipeted into a cleaned micro vial, then dried at a temperature of 40°C for 24 hours. Samples, together with flux monitors, were irradiated simultaneously at 15 MW power (thermal neutron flux around 4.1 x 10"1"7n. m"-"2.s"-"1) for 30 minutes in the rabbit facility of GA. Siwabessy reactor. Counting of the irradiated sample have been done using a high resolution HPGe detector (FWHM = 1.9 keV at Eγ 1332.5 keV of "6"0Co,Peak to Compton ratio ~ 40). The analytical results showed a relative standard deviation (RSD) of Zr is 6.6 % with average uncertainty of 3.08 % and a detection limit of 0.1 mg, while RSD of Hf = 8.2 %, with average uncertainty of 8.04 % and a detection limit of 0.3 mg. Recovery obtained was 106,0 % and 96,0 % for Zr and Hf respectively. These results are relatively better compared to the previous result using the Standard Reference Material (SRM) 1633b Coal Fly Ash which have RSD Hf was 20.6 %. (author)

CeO2-stabilized tetragonal ZrO2 polycrystals (Ce-TZP ceramics)

International Nuclear Information System (INIS)

Andrade Nono, M.C. de.

1990-12-01

This work presents the development and the characterization of CeO 2 -stabilized tetragonal ZrO 2 polycrystals (Ce-TZP ceramics), since it is considered candidate material for applications as structural high performance ceramics. Sintered ceramics were fabricated from mixtures of powders containing different CeO 2 content prepared by conventional and nonconventional techniques. These powders and their resultant sintered ceramics were specified by chemical and physical characterization, compactation state and mechanical properties. The chemical characteristics were determined by chemical analysis and the physical characteristics were evaluated by phase content, particle and agglomerate size and aspect, and powder porosity. (author)

Electric transport properties of the pentatelluride materials HfTe{sub 5} and ZrTe{sub 5}

Energy Technology Data Exchange (ETDEWEB)

Tritt, T M; Wilson, M L; Littleton, R L [and others

1997-07-01

The authors have measured the resistivity and thermopower of single crystals as well as polycrystalline pressed powders of the low-dimensional pentatelluride materials: HfTe{sub 5} and ZrTe{sub 5}. They have performed these measurements as a function of temperature between 5K and 320K. In the single crystals there is a peak in the resistivity for both materials at a peak temperature, T{sub p} where T{sub p} {approx} 80K for HfTe{sub 5} and T{sub p} {approx} 145K for ZrTe{sub 5}. Both materials exhibit a large p-type thermopower around room temperature which undergoes a change to n-type below the peak. These data are similar to behavior observed previously in these materials. They have also synthesized pressed powders of polycrystalline pentatelluride materials, HfTe{sub 5} and ZrTe{sub 5}. They have measured the resistivity and thermopower of these polycrystalline materials as a function of temperature between 5K and 320K. For the polycrystalline material, the room temperature thermopower for each of these materials is relatively high, +95 {micro}V/K and +65 {micro}V/K for HfTe{sub 5} and ZrTe{sub 5}, respectively. These values compare closely to thermopower values for single crystals of these materials. At 77 K, the thermopower is +55 {micro}V/K for HfTe{sub 5} and +35 {micro}V/K for ZrTe{sub 5}. In fact, the thermopower for the polycrystals decreases monotonically with temperature to T {approx} 5K, thus exhibiting p-type behavior over the entire range of temperature. As expected, the resistivity for the polycrystals is higher than the single crystal material, with values of 430 m{Omega}-cm and 24 m{Omega}-cm for HfTe{sub 5} and ZrTe{sub 5} respectively, compared to single crystal values of 0.35 m{Omega}-cm (HfTe{sub 5}) and 1.0 m{Omega}-cm (ZrTe{sub 5}). The authors have found that the peak in the resistivity evident in both single crystal materials is absent in these polycrystalline materials. They will discuss these materials in relation to their potential as

Lattice Thermal Conductivity from Atomistic Simulations: ZrB2 and HfB2

Science.gov (United States)

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

2012-01-01

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

Mechanical Properties of TiTaHfNbZr High-Entropy Alloy Coatings Deposited on NiTi Shape Memory Alloy Substrates

Science.gov (United States)

Motallebzadeh, A.; Yagci, M. B.; Bedir, E.; Aksoy, C. B.; Canadinc, D.

2018-04-01

TiTaHfNbZr high-entropy alloy (HEA) thin films with thicknesses of about 750 and 1500 nm were deposited on NiTi substrates by RF magnetron sputtering using TiTaHfNbZr equimolar targets. The thorough experimental analysis on microstructure and mechanical properties of deposited films revealed that the TiTaHfNbZr films exhibited amorphous and cauliflower-like structure, where grain size and surface roughness increased concomitant with film thickness. More importantly, the current findings demonstrate that the TiTaHfNbZr HEA films with mechanical properties of the same order as those of the NiTi substrate constitute promising biomedical coatings effective in preventing Ni release.

Mechanical Properties of TiTaHfNbZr High-Entropy Alloy Coatings Deposited on NiTi Shape Memory Alloy Substrates

Science.gov (United States)

Motallebzadeh, A.; Yagci, M. B.; Bedir, E.; Aksoy, C. B.; Canadinc, D.

2018-06-01

TiTaHfNbZr high-entropy alloy (HEA) thin films with thicknesses of about 750 and 1500 nm were deposited on NiTi substrates by RF magnetron sputtering using TiTaHfNbZr equimolar targets. The thorough experimental analysis on microstructure and mechanical properties of deposited films revealed that the TiTaHfNbZr films exhibited amorphous and cauliflower-like structure, where grain size and surface roughness increased concomitant with film thickness. More importantly, the current findings demonstrate that the TiTaHfNbZr HEA films with mechanical properties of the same order as those of the NiTi substrate constitute promising biomedical coatings effective in preventing Ni release.

Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

Directory of Open Access Journals (Sweden)

Véronique Pitchon

2012-02-01

Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

Microstructure and tensile properties of Fe-40 at. pct Al alloys with C, Zr, Hf, and B additions

Science.gov (United States)

Gaydosh, D. J.; Draper, S. L.; Nathal, M. V.

1989-01-01

The influence of small additions of C, Zr, and Hf, alone or in combination with B, on the microstructure and tensile behavior of substoichiometric FeAl was investigated. Tensile properties were determined from 300 to 1100 K on powder which was consolidated by hot extrusion. All materials possessed some ductility at room temperature, although ternary additions generally reduced ductility compared to the binary alloy. Adding B to the C- and Zr-containing alloys changed the fracture mode from intergranular to transgranular and restored the ductility to approximately 5 percent elongation. Additions of Zr and Hf increased strength up to about 900 K. Fe6Al6Zr and Fe6Al6Hf precipitates, both with identical body-centered tetragonal structures, were identified as the principal second phase in these alloys. Strength decreased steadily as temperature increased above 700 K, as diffusion-assisted mechanisms became operative. Although all alloys had similar strengths at 1100 K, Hf additions significantly improved high-temperature ductility by suppressing cavitation.

ZrCu2P2 and HfCu2P2 phosphides and their crystal structure

International Nuclear Information System (INIS)

Lomnitskaya, Ya.F.

1986-01-01

Isostructural ZrCu 2 P 2 and HfCu 2 P 2 compounds are prepared for the first time. X-ray diffraction analysis (of powder, DRON-2.0 diffractometer, FeKsub(α) radiation) was used to study crystal structure of HfCu 2 P 2 phosphide belonging to the CaAl 2 Si 2 structural type (sp. group P anti 3 m 1, R=0.095). Lattice parameters the compounds are as follows: for ZrCu 2 P 2 a=0.3810(1), c=0.6184(5); for HfCu 2 P 2 a=0.3799(1), c=0.6160(2) (nm). Atomic parameters in the HfCu 2 P 2 structure and interatomic distances are determined

Phase and Microstructural Correlation of Spark Plasma Sintered HfB2-ZrB2 Based Ultra-High Temperature Ceramic Composites

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Ambreen Nisar

2017-07-01

Full Text Available The refractory diborides (HfB2 and ZrB2 are considered as promising ultra-high temperature ceramic (UHTCs where low damage tolerance limits their application for the thermal protection system in re-entry vehicles. In this regard, SiC and CNT have been synergistically added as the sintering aids and toughening agents in the spark plasma sintered (SPS HfB2-ZrB2 system. Herein, a novel equimolar composition of HfB2 and ZrB2 has shown to form a solid-solution which then allows compositional tailoring of mechanical properties (such as hardness, elastic modulus, and fracture toughness. The hardness of the processed composite is higher than the individual phase hardness up to 1.5 times, insinuating the synergy of SiC and CNT reinforcement in HfB2-ZrB2 composites. The enhanced fracture toughness of CNT reinforced composite (up to a 196% increment surpassing that of the parent materials (ZrB2/HfB2-SiC is attributed to the synergy of solid solution formation and enhanced densification (~99.5%. In addition, the reduction in the analytically quantified interfacial residual tensile stress with SiC and CNT reinforcements contribute to the enhancement in the fracture toughness of HfB2-ZrB2-SiC-CNT composites, mandatory for aerospace applications.

A new Ti-Zr-Hf-Cu-Ni-Si-Sn bulk amorphous alloy with high glass-forming ability

Energy Technology Data Exchange (ETDEWEB)

Huang, Y.J. [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China); Shen, J. [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China)]. E-mail: junshen@hit.edu.cn; Sun, J.F. [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China); Yu, X.B. [Lab of Energy Science and Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China)]. E-mail: yuxuebin@hotmail.com

2007-01-16

The effect of Sn substitution for Cu on the glass-forming ability was investigated in Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 42.5-x}Ni{sub 7.5}Si{sub 1}Sn {sub x} (x = 0, 1, 3, 5, 7) alloys by using differential scanning calorimetry (DSC) and X-ray diffractometry. The alloy containing 5% Sn shows the highest glass-forming ability (GFA) among the Ti-Zr-Hf-Cu-Ni-Si-Sn system. Fully amorphous rod sample with diameters up to 6 mm could be successfully fabricated by the copper mold casting Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 37.5}Ni{sub 7.5}Si{sub 1}Sn{sub 5} alloy. The activation energies for glass transition and crystallization for Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 37.5}Ni{sub 7.5}Si{sub 1}Sn{sub 5} amorphous alloy are both larger than those values for the Sn-free alloy. The enhancement in GFA and thermal stability after the partial replacement of Cu by Sn may be contributed to the strong atomic bonding nature between Ti and Sn and the increasing of atomic packing density. The amorphous Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 37.5}Ni{sub 7.5}Si{sub 1}Sn{sub 5} alloy also possesses superior mechanical properties.

Effect of Ce and Zr Addition to Ni/SiO2 Catalysts for Hydrogen Production through Ethanol Steam Reforming

Directory of Open Access Journals (Sweden)

Jose Antonio Calles

2015-01-01

Full Text Available A series of Ni/Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\/SiO\\(_{2}\\ catalysts with different Zr/Ce mass ratios were prepared by incipient wetness impregnation. Ni/SiO\\(_{2}\\, Ni/CeO\\(_{2}\\ and Ni/ZrO\\(_{2}\\ were also prepared as reference materials to compare. Catalysts' performances were tested in ethanol steam reforming for hydrogen production and characterized by XRD, H\\(_{2}\\-temperature programmed reduction (TPR, NH\\(_{3}\\-temperature programmed desorption (TPD, TEM, ICP-AES and N\\(_{2}\\-sorption measurements. The Ni/SiO\\(_{2}\\ catalyst led to a higher hydrogen selectivity than Ni/CeO\\(_{2}\\ and Ni/ZrO\\(_{2}\\, but it could not maintain complete ethanol conversion due to deactivation. The incorporation of Ce or Zr prior to Ni on the silica support resulted in catalysts with better performance for steam reforming, keeping complete ethanol conversion over time. When both Zr and Ce were incorporated into the catalyst, Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\ solid solution was formed, as confirmed by XRD analyses. TPR results revealed stronger Ni-support interaction in the Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\-modified catalysts than in Ni/SiO\\(_{2}\\ one, which can be attributed to an increase of the dispersion of Ni species. All of the Ni/Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\/SiO\\(_{2}\\ catalysts exhibited good catalytic activity and stability after 8 h of time on stream at 600°. The best catalytic performance in terms of hydrogen selectivity was achieved when the Zr/Ce mass ratio was three.

Development and reactivity tests of Ce-Zr-based Claus catalysts for coal gas cleanup

Energy Technology Data Exchange (ETDEWEB)

No-Kuk Park; Dong Cheul Han; Gi Bo Han; Si Ok Ryu; Tae Jin Lee; Ki Jun Yoon [Yeungnam University, Gyeongbuk (Republic of Korea). National Research Laboratory, School of Chemical Engineering and Technology

2007-09-15

Claus reaction (2H{sub 2}S + SO{sub 2} {leftrightarrow} 3/nS{sub n} + 2H{sub 2}O) was used to clean the gasified coal gas and the reactivity of several metal oxide-based catalysts on Claus reaction was investigated at various operating conditions. In order to convert H{sub 2}S contained in the gasified coal gas to elemental sulfur during Claus reaction, the catalysts having the high activity under the highly reducing condition with the moisture should be developed. CeO{sub 2}, ZrO{sub 2}, and Ce{sub 1-x}Zr{sub x}O{sub 2} catalysts were prepared for Claus reaction and their reactivity changes due to the existence of the reducing gases and H{sub 2}O in the fuel gas was investigated in this study. The Ce-based catalysts shows that their activity was deteriorated by the reduction of the catalyst due to the reducing gases at higher than 220{sup o}C. Meanwhile, the effect of the reducing gases on the catalytic activity was not considerable at low temperature. The activities of all three catalysts were degraded on the condition that the moisture existed in the test gas. Specifically, the Ce-based catalysts were remarkably deactivated by their sulfation. The Ce-Zr-based catalyst had a high catalytic activity when the reducing gases and the moisture co-existed in the simulated fuel gas. The deactivation of the Ce-Zr-based catalyst was not observed in this study. The lattice oxygen of the Ce-based catalyst was used for the oxidation of H{sub 2}S and the lattice oxygen vacancy on the catalyst was contributed to the reduction of SO{sub 2}. ZrO{sub 2} added to the Ce-Zr-based catalyst improved the redox properties of the catalyst in Claus reaction by increasing the mobility of the lattice oxygen of CeO{sub 2}. 21 refs., 14 figs.

Anion exchange behaviour of Zr, Hf, Nb, Ta and Pa as homologues of RF and Db in fluoride medium

International Nuclear Information System (INIS)

Monroy G, F.; Trubert, D.; Brillard, L.; Hussonnois, M.; Constantinescu, O.; Le Naour, C.

2010-01-01

Studies of the chemical property of trans actinide elements are very difficult due to their short half-lives and extremely small production yields. However it is still possible to obtain considerable information about their chemical properties, such as the most stable oxidation states in aqueous solution, complexing ability, etc., comparing their behaviour with their lighter homologous in the periodic table. In order to obtain a better knowledge of the behaviour of rutherfordium, RF (element 104), dub nium, Db (element 105) in HF medium, the sorption properties of Zr, Hf, Nb, Ta an Pa, homologues of RF and Db, were studied in NH 4 F/HClO 4 medium in this work. Stability constants of the fluoride complexes of these elements were experimentally obtained from K d obtained at different F - and H + concentrations. The anionic complexes: [Zr(Hf)F 5 ] - , [Zr(Hf)F 6 ] 2- , [Zr(Hf)F 7 ] 3- , [Ta(Pa)F 6 ] - , [Ta(Pa)F 7 ] 2- , [Ta(Pa)F 8 ] 3- , [NbOF 4 ] - and [NbOF 5 ] 2- are present as predominant species in the HF range over investigation. (Author)

Separation of zirconium (Zr) and hafnium (Hf) using solvent mixture of TBP-D_2EHPA and amberlite XAD-16

International Nuclear Information System (INIS)

Dwi Biyantoro; I Made Sukarna; Agus Suyanto

2017-01-01

The aims of this research were to determine the composition (ratio of extractant and resin) of the SIR which is effective for the separation of Zr and Hf, knowing adsorption equilibrium models Zr and Hf using the SIR, and knowing the most effective adsorption results from SIR weight ratio. The research was conducted by using the SIR method that is impregnating the extractant into the resin. Extractant used is a mixture of TBP and D_2EHPA (1 : 3), the resin used is XAD-16, and the feed used is ZOC. This research was conducted by varying the composition of the SIR, after the result of effective SIR variation. Adsorption process is then performed using the ZOC with SIR. Then filtered, the filtrate was analyzed by XRF. While solids SIR adsorption product was desorbed using sulfuric acid. Then the desorption results were analyzed using XRF spectrometer. Based on calculations, the results of the most effective SIR composition for the separation of Zr-Hf are comparison extractant and resin = 5:5 either for the dry method and wet method, the equilibrium equations for Zr approaching Langmuir equilibrium models while the equilibrium equation for Hf approaching Freundlich equilibrium models which the most effective adsorption results that bait comparison with the SIR = 10 mL : 5 g with β = 0.1831; η Zr = 26.39 % and η Hf = 66.19 % for dry method and β = 0.1557; η Zr = 25.17 % and η Hf = 68.36 % for wet method. From result desorption process was 2 M H_2SO_4. (author)

H and D implantation transforms Ti, Zr and Hf into good superconductors

International Nuclear Information System (INIS)

Meyer, J.D.; Stritzker, B.

1981-01-01

The elements Ti, Zr, and Hf from group IVB with superconducting transition temperatures of Tsub(c) = 0.4, 0.6 and 0.13 K, respectively, were implanted at liquid helium temperature with hydrogen, deuterium and helium. The He implantations were performed to simulate the Tsub(c) enhancement due to lattice disorder introduced during the implantation. In this case, only Zr showed a Tsub(c) increase above the measuring limit of 1 K. On the other hand, the implantation of H and D will change the electronic properties of the materials in addition to lattice damage. Indeed all H and D implantations lead to a substantial increase of Tsub(c). For example, a transition temperature of 4.65 K was achieved in D implanted Zr at a concentration of D/Zr = 0.13. Whereas a pronounced inverse isotope effects was observed for H(D) implanted Zr and Hf, H and D implanted Ti had essentially the same Tsub(c) of 4.9 K. Based on the similarity of most of these results to the Pd-H(D) system [1], similar mechanisms are proposed to explain the experimental observation, i.e: (1) the electron-phonon coupling is enhanced due to coupling to the protons (deuterons) and/or to the optic phonon modes; (2) anharmonic effects are responsible for the inverse isotope effect. (orig.)

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

Science.gov (United States)

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

2018-05-01

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

Anion exchange behaviour of Zr, Hf, Nb, Ta and Pa as homologues of RF and Db in fluoride medium

Energy Technology Data Exchange (ETDEWEB)

Monroy G, F. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Trubert, D.; Brillard, L.; Hussonnois, M.; Constantinescu, O.; Le Naour, C., E-mail: fabiola.monroy@inin.gob.m [Institut de Physique Nucleaire, F-91406 Orsay, France (France)

2010-07-01

Studies of the chemical property of trans actinide elements are very difficult due to their short half-lives and extremely small production yields. However it is still possible to obtain considerable information about their chemical properties, such as the most stable oxidation states in aqueous solution, complexing ability, etc., comparing their behaviour with their lighter homologous in the periodic table. In order to obtain a better knowledge of the behaviour of rutherfordium, RF (element 104), dub nium, Db (element 105) in HF medium, the sorption properties of Zr, Hf, Nb, Ta an Pa, homologues of RF and Db, were studied in NH{sub 4}F/HClO{sub 4} medium in this work. Stability constants of the fluoride complexes of these elements were experimentally obtained from K{sub d} obtained at different F{sup -} and H{sup +} concentrations. The anionic complexes: [Zr(Hf)F{sub 5}]{sup -}, [Zr(Hf)F{sub 6}]{sup 2-}, [Zr(Hf)F{sub 7}]{sup 3-}, [Ta(Pa)F{sub 6}]{sup -}, [Ta(Pa)F{sub 7}]{sup 2-}, [Ta(Pa)F{sub 8}]{sup 3-}, [NbOF{sub 4}]{sup -} and [NbOF{sub 5}]{sup 2-} are present as predominant species in the HF range over investigation. (Author)

Effects of Ce and Zr addition on microstructure and hardness of Al-Si-Cu-Mg alloy

International Nuclear Information System (INIS)

Bevilaqua, William Lemos; Reguly, Afonso; Froehlich, Andre Ronaldo; Stadtlander, Antonio Ricardo

2016-01-01

The effects of cerium and zirconium contents (0.3%-0.16%Zr; 0.3%-0.27%Zr e 0.3%-0.36%Zr) to aluminum alloy 354.0 was investigated by microstructural analysis and hardness measurements in as-cast and heat-treated conditions. The macrostructure show an excellent grain refinement for all Ce and Zr contents used. Additionally, the Cu-Ce reaction during solidification changes significantly the age hardening process of modified alloys. (author)

Synthesis and physico-chemical characterization of CeO2/ZrO2-SO42- mixed oxides

International Nuclear Information System (INIS)

Hernandez E, J. M.; Silva R, R.; Garcia A, R.; Garcia S, L. A.; Handy, B. E.; Cardenas G, G.; Cueto H, A.

2012-01-01

Environmentally friendly solid-acid catalysts CeO 2 /ZrO 2 -SO 4 2- were prepared by the sol gel method varying CeO 2 content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO 2 and ZrO 2 -SO 4 2- were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO 2 -SO 4 2- was high (160 m 2 /g) compared with the unmodified ZrO 2 (80 m 2 /g), however this area decreased with increasing the CeO 2 content (37-100 m 2 /g). There was no significant effect of CeO 2 on the tetragonal structure of ZrO 2 -SO 4 2- . The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO 2 /ZrO 2 -SO 4 2- catalyst with the highest CeO 2 content was used. (Author)

Mechanoluminescence, photoluminescence and thermoluminescence studies of SrZrO3:Ce phosphor

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Neha Tiwari

2015-01-01

Full Text Available The present paper reports the synthesis and characterization, photoluminescence thermoluminescence and mechanoluminescence studies of Ce3+ doped SrZrO3 phosphors. The effects of variable concentration of Cerium on meachanoluminescence (ML and photoluminescence behavior were studied. The samples were prepared by combustion a synthesis technique which is suitable for less time taking techniques also for large scale production for phosphors. The starting material used for sample preparation are Sr(NO33, Zr(NO33 XH2O and Ce(NO33 6H2O and urea used as a fuel. The prepared sample was characterized by X-ray diffraction technique (XRD with variable concentration of Ce (0.05–0.5 mol%. There is no any phase change found with increase the concentration of Ce. Sample shows orthorhombic structure and the particle size calculated by Scherer's formula. The surface morphology of prepared phosphor was determined by field emission gun scanning electron microscopy (FEGSEM technique. Mechanoluminescence studies on SrZrO3phosphors doped with Ce and underwent an impulsive deformation with an impact of a piston for Mechanoluminescence (ML investigations. Temporal characteristics in order to investigate about the luminescence centre responsible for ML peak, increasing impact velocity causes more number of electrons will be ionized to reach to the conduction band so there will be more number of electrons available to be recombined at recombination or luminescence centre. In photoluminescence study PL emission spectra show the isolated peak position observed at 388 nm near UV region of spectrum due to 5d–4f transition of Ce3+ion.Thermoluminescence study shows doping of Ce3+ ions reduced the TL intensity TL glow curve shows the high fading and less stability when it doped with cerium. The activation energy high for the doped SrZrO3 phosphor means that the trapped electron is highly trapped in trap level. The present study gives the advance application for fracture

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

Science.gov (United States)

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

2018-04-01

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

Mesocrystals luminescent BaZrHfO{sub 3} synthesized via hydrothermal process assisted by microwave

Energy Technology Data Exchange (ETDEWEB)

Fassbender, Rafael Uarth, E-mail: uarth.fisica@gmail.com

2016-07-01

Full text: The Barium Zirconate (BaZrO{sub 3}), is a ceramic oxide belonging to the functional group of perovskites (ABO{sub 3}), this compound can be doped with hafniun (Hf) in solid solution by microwave assisted hydrothermal method (MAH) radioluminescent increases their properties. This method allows to obtain barium zirconate at low temperature as 140 deg C and short times as 160 minutes. The choice of Hafnium (Hf) as a dopant is based on its similarity with Zirconium (Zr), another good reason for this choice is that the Hafnium has intrinsic luminescent characteristics. In general, radioluminescent materials have high density and high atomic mass (atomic number of Hafnium is 72), thereby facilitating the absorption of ionizing radiation to convert it into visible light, this characteristic is strongly dependent on the morphology and especially the electronic structure of (BaZrO{sub 3}). This work consisted in production of barium zirconate powders doped 1-2-4-8-16% (Hf) using (MAH) method. For the characterization of the powders was employed methods : a) X-ray diffraction, b) Raman Spectroscopy, c) Xanes, d) photoluminescence spectroscopy. After the electronic and structural characterization the powders were introduced in a polymeric resin (nylon-BZO), one new characterizations will be performed to validate the results obtained in the production of films to the results already obtained for the powders. We conclude so far, that the powders-doped with 16% Hf has an intense luminescent emission compared to the powders with less concentration of Hf. The small structural change that causes the Hf in (BZO) is considered as a secondary factory. (author)

Luminescence properties of the Mg co–doped Ce:SrHfO_3 ceramics prepared by the Spark Plasma Sintering Method

International Nuclear Information System (INIS)

Chiba, Hiroyuki; Kurosawa, Shunsuke; Harata, Koichi; Murakami, Rikito; Yamaji, Akihiro; Ohashi, Yuji; Pejchal, Jan; Kamada, Kei; Yokota, Yuui; Yoshikawa, Akira

2016-01-01

1300 or 1400 °C pre–sintered Al/Ce/Mg:SrHfO_3 and Al/Ce:SrHfO_3 ceramics were prepared by the Spark Plasma Sintering (SPS) in order to search for a new scintillation material with a high–effective atomic number(Z_e_f_f) and good light output. The SrHfO_3 has a high Z_e_f_f of 60, and high gamma–ray detection efficiency is expected. Meanwhile it has a high melting point of over 2500 °C, and single crystal is hard to be grown. On the other hand, high melting materials can be prepared as ceramics, and the SPS method is a simple process to fabricate the ceramics within a few hours. Thus, we prepared the samples using the SPS method, and their optical and scintillation properties were investigated. We found that Al/Ce/Mg:SrHfO_3 and Al/Ce:SrHfO_3 ceramics had an emission wavelength at around 400 nm originating from 5d–4f transition of Ce"3"+. Moreover, Al/Ce/Mg:SrHfO_3 pre-sintered at a temperature of 1400 °C had a light output of approximately 5,000 ph/MeV. In this paper, the light output of Mg-co-doped samples was improved compared with the Mg-free ones. The light output also depends on the pre-sintering temperature. - Highlights: • Luminescence Properties of Al/Ce/Mg:SrHfO_3 ceramics scintillator was investigated. • These ceramics were prepared by the Spark Plasma Sintering Method. • Light output of the Al/Ce/Mg:SrHfO_3 ceramics was approximately 5,000 ph/MeV.

Effects of Zr4+ codoping on the Lu0.8Sc0.2BO3:Ce scintillation materials

International Nuclear Information System (INIS)

Wu, Yuntao; Ren, Guohao; Ding, Dongzhou; Shang, Shanshan; Sun, Dandan; Zhang, Guoqing; Wang, Jiayu; Pan, Shangke; Yang, Fan

2013-01-01

Both Zr-codoped Lu 0.8 Sc 0.2 BO 3 :Ce polycrystalline powders and single crystals were obtained by solid-state reaction and Czochralski method, respectively. The effects of Zr codoping on the optical absorption, Ce 3+ /Ce 4+ ratio, scintillation efficiency, decay time and point defect in Lu 0.8 Sc 0.2 BO 3 :Ce materials were examined systematically. Our results show that there is no positive contribution of Zr 4+ ion codoping to the scintillation efficiency. And the reasons for the deterioration of scintillation efficiency by codoping Zr 4+ were revealed. - Highlights: ► No positive contribution of the Zr 4+ ions on the scintillation efficiency was found. ► New optical absorption band was in the region from 200 to 225 nm. ► Continuously accelerated decay time indicated that Zr 4+ codoping induced new point defects. ► The induced hole trap located at 1.91 eV below the conduction band.

Catalytic purification of waste gases containing VOC mixtures with Ce/Zr solid solutions

International Nuclear Information System (INIS)

Gutierrez-Ortiz, Jose I.; De Rivas, Beatriz; Lopez-Fonseca, Ruben; Gonzalez-Velasco, Juan R.

2006-01-01

This study has been undertaken to investigate the efficiency of ceria, zirconia, and Ce x Zr 1-x O 2 mixed oxides as catalysts for the vapour-phase destruction in air of single model VOCs (n-hexane, 1,2-dichloroethane and trichloroethylene) and non-chlorinated VOC/chlorinated VOC binary mixtures. Considering all catalyst compositions examined for the individual destruction of these compounds, activity for complete oxidation decreased in the following order: n-hexane 0.5 Zr 0.5 O 2 and Ce 0.15 Zr 0.85 O 2 ) were different than that with the best performance for n-hexane oxidation (CeO 2 ). Concerning chlorinated VOCs conversion, it was observed that notable improvements in catalyst activity of CeO 2 could be achieved through structural doping with Zr ions. Mixed oxides exhibited promoted redox and acid properties, which resulted catalytically relevant for the oxidation of 1,2-dichloroethane and trichloroethylene. In contrast, the combustion of n-hexane was essentially controlled by surface oxygen species, which were more abundant on CeO 2 . Attainment of high n-hexane conversions with CeO 2 was also attributed in part to the hydrophobicity of the support and the reduced interaction with carbon dioxide. Significant 'mixture effects' on both activity and selectivity were noticed when a given chlorinated feed was decomposed in the presence of n-hexane. On one hand, each VOC decreased the reactivity of the other relative to that of the pure compound resulting in higher operating temperatures to achieve adequate destruction. Competitive adsorption played an important role in the reciprocal inhibition effects detected with all catalysts. On the other hand, the selectivity to HCl was noticeably enhanced when n-hexane was co-fed, probably due to the increased presence of water generated as an oxidation product. (author)

Thermoelectric Properties of the XCoSb (X: Ti,Zr,Hf) Half-Heusler Alloys

KAUST Repository

Gandi, Appala; Schwingenschlö gl, Udo

2017-01-01

We investigate the thermoelectric properties of the half-Heusler alloys XCoSb (X: Ti,Zr,Hf) by solving Boltzmann transport equations and discuss them in terms of the electronic band structure. The rigid band approximation is employed to address

Site preference of metal atoms in Gd_5_-_xM_xTt_4 (M = Zr, Hf; Tt = Si, Ge)

International Nuclear Information System (INIS)

Yao, Jinlei; Mozharivskyj, Yurij

2011-01-01

Zirconium and hafnium were incorporated into the Gd_5Ge_4 and Gd_5Si_4 parent compounds in order to study the metal-site occupation in the M_5X_4 magnetocaloric phases (M = metals; X = p elements) family. The Gd_5_-_xZr_xGe_4 phases adopt the orthorhombic Sm_5Ge_4-type (space group Pnma) structure for x ≤ 1.49 and the tetragonal Zr_5Si_4-type (P4_12_12) structure for x ≥ 1.77. The Gd_5_-_xHf_xSi_4 compounds crystallize in the orthorhombic Gd_5Si_4-type (Pnma) structure for x ≤ 0.41 and the Zr_5Si_4-type structure for x ≥ 0.7. In both systems, single-crystal X-ray diffraction reveals that the Zr/Hf atoms preferentially occupy the slab-surface M2 and slab-center M3 sites, both of which have a significantly larger Zr/Hf population than the slab-surface M1 site. The metal-site preference, i.e. the coloring problem on the three metal sites, is discussed considering geometric and electronic effects of the local coordination environments. The analysis of the metal-site occupation in Gd_5_-_xZr_xGe_4 and Gd_5_-_xHf_xSi_4 as well as other metal-substituted M_5X_4 systems suggests that both geometric and electronic effects can be used to explain the metal-site occupation. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Electronic structure and magnetism of new ilmenite compounds for spintronic devices: FeBO{sub 3} (B = Ti, Hf, Zr, Si, Ge, Sn)

Energy Technology Data Exchange (ETDEWEB)

Ribeiro, R.A.P. [Department of Chemistry, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil); Camilo, A. [Department of Physics, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil); Lazaro, S.R. de, E-mail: srlazaro@uepg.br [Department of Chemistry, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil)

2015-11-15

First-principles calculations were performed in the framework of Density Functional Theory (DFT) within hybrid functional (B3LYP) to study the electronic structure and magnetic properties of new ilmenite FeBO{sub 3} (B=Ti, Hf, Zr, Si, Ge, Sn) materials. In particular, the magnetic exchange interaction between Fe{sup 2+} layers is dependent on the interlayer distance and it can be controlled by ionic radius of B-site cation. Thus, Fe(Ti, Si, Ge)O{sub 3} are antiferromagnetic materials, while Fe(Zr, Hf, Sn)O{sub 3} are ferromagnetic. We also argue that antiferromagnetic materials and FeZrO{sub 3} are convectional semiconductors, whereas FeHfO{sub 3} and FeSnO{sub 3} exhibit intrinsic half-metallic behavior, making them promising candidates for spintronic devices. - Highlights: • We study electronic structure and magnetism of new FeBO{sub 3} (B=Ti, Hf, Zr, Si, Ge, Sn) ilmenite materials. • We found that magnetic ordering of Fe-based ilmenite materials can be controlled by size of B-site cation. • Fe(Ti, Zr, Si, Ge)O{sub 3} are convectional semiconductors. • FeHfO{sub 3} and FeSnO{sub 3} exhibit intrinsic half-metallic behavior with potential application for spintronic devices.

Catalytic purification of waste gases containing VOC mixtures with Ce/Zr solid solutions

Energy Technology Data Exchange (ETDEWEB)

Gutierrez-Ortiz, Jose I.; De Rivas, Beatriz; Lopez-Fonseca, Ruben; Gonzalez-Velasco, Juan R. [Chemical Technologies for Environmental Sustainability Group, Department of Chemical Engineering, Faculty of Science and Technology, Universidad del Pais Vasco/EHU, P.O. Box 644, E-48080 Bilbao (Spain)

2006-06-06

This study has been undertaken to investigate the efficiency of ceria, zirconia, and Ce{sub x}Zr{sub 1-x}O{sub 2} mixed oxides as catalysts for the vapour-phase destruction in air of single model VOCs (n-hexane, 1,2-dichloroethane and trichloroethylene) and non-chlorinated VOC/chlorinated VOC binary mixtures. Considering all catalyst compositions examined for the individual destruction of these compounds, activity for complete oxidation decreased in the following order: n-hexane<1,2-dichloroethaneCe{sub 0.5}Zr{sub 0.5}O{sub 2} and Ce{sub 0.15}Zr{sub 0.85}O{sub 2}) were different than that with the best performance for n-hexane oxidation (CeO{sub 2}). Concerning chlorinated VOCs conversion, it was observed that notable improvements in catalyst activity of CeO{sub 2} could be achieved through structural doping with Zr ions. Mixed oxides exhibited promoted redox and acid properties, which resulted catalytically relevant for the oxidation of 1,2-dichloroethane and trichloroethylene. In contrast, the combustion of n-hexane was essentially controlled by surface oxygen species, which were more abundant on CeO{sub 2}. Attainment of high n-hexane conversions with CeO{sub 2} was also attributed in part to the hydrophobicity of the support and the reduced interaction with carbon dioxide. Significant 'mixture effects' on both activity and selectivity were noticed when a given chlorinated feed was decomposed in the presence of n-hexane. On one hand, each VOC decreased the reactivity of the other relative to that of the pure compound resulting in higher operating temperatures to achieve adequate destruction. Competitive adsorption played an important role in the reciprocal inhibition effects detected with all catalysts. On the other hand, the selectivity to HCl was noticeably enhanced when n-hexane was co-fed, probably due to the increased presence of water generated as an

Ln3+ (Ln=Ce, Tb, Dy) and Hf doping of LuI3 powders – A material and spectroscopic study

International Nuclear Information System (INIS)

Wiatrowska, Aneta; Keur, Wilco; Ronda, Cees

2016-01-01

The moisture sensitivity of LuI 3 :Ce,Hf and luminescent properties of undoped LuI 3 and LuI 3 :M (M=Ce 3+ , Tb 3+ , Dy 3+ ) powders were investigated. The possibility of improving the air and moisture stability of LuI 3 :Ce by Hf doping was tested. It was proven that the Hf contribution to the LuI 3 :Ce stability is very limited and is insignificant to render LuI 3 :Ce scintillator powders suitable for applications. Photoluminescence results of LuI 3 without dopants added on purpose showed luminescence due to a plurality of rare-earth elements' impurities. Two types of self-trapped luminescence were found. Energy transfer between host lattice, self-trapped excitons and rare-earth ions was investigated.

Band Alignment and Optical Properties of (ZrO20.66(HfO20.34 Gate Dielectrics Thin Films on p-Si (100

Directory of Open Access Journals (Sweden)

Dahlang Tahir

2011-11-01

Full Text Available (ZrO20.66(HfO20.34 dielectric films on p-Si (100 were grown by atomic layer deposition method, for which the conduction band offsets, valence band offsets and band gaps were obtained by using X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. The band gap, valence and conduction band offset values for (ZrO20.66(HfO20.34 dielectric thin film, grown on Si substrate were about 5.34, 2.35 and 1.87 eV respectively. This band alignment was similar to that of ZrO2. In addition, The dielectric function ε (k, ω, index of refraction n and the extinction coefficient k for the (ZrO20.66(HfO20.34 thin films were obtained from a quantitative analysis of REELS data by comparison to detailed dielectric response model calculations using the QUEELS-ε (k,ω-REELS software package. These optical properties are similar with ZrO2 dielectric thin films.

First-principles study of new quaternary Heusler compounds without 3d transition metal elements: ZrRhHfZ (Z = Al, Ga, In)

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiaotian [School of Material Sciences and Engineering, Hebei University of Technology, Tianjin 300130 (China); Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Cheng, Zhenxiang, E-mail: cheng@uow.edu.au [Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Guo, Ruikang [School of Material Sciences and Engineering, Hebei University of Technology, Tianjin 300130 (China); Wang, Jianli [Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Rozale, Habib [Condensed Matter and Sustainable Development Laboratory, Physics Department, University of Sidi-Bel-Abbès, 22000 Sidi-Bel-Abbès (Algeria); Wang, Liying [Department of Physics, Tianjin University, Tianjin 300350 (China); Yu, Zheyin [Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Liu, Guodong, E-mail: gdliu1978@126.com [School of Material Sciences and Engineering, Hebei University of Technology, Tianjin 300130 (China)

2017-06-01

Plane-wave pseudo-potential methods based on density functional theory are employed to investigate the electronic structures, and the magnetic and half-metallic properties of the newly designed quaternary Heusler compounds ZrRhHfZ (Z = Al, Ga, In) without 3d transition metal elements. The calculated results show that ZrRhHfZ (Z = Al, Ga, In) compounds are half-metallic, with 100% spin polarization around the Fermi level. The structural stability of these compounds has been tested from the aspects of their cohesion energy and formation. The spin-flip/half-metallic gaps of ZrRhHfZ (Z = Al, Ga, In) compounds are quite large, with values of 0.2548 eV, 0.3483 eV, and 0.2866 eV, respectively. These compounds show Slater-Pauling behavior, and the total spin magnetic moment per unit cell (M{sub t}) scales with the total number of valence electrons (Z{sub t}) following the rule: M{sub t} = Z{sub t} - 18. The magnetization of ZrRhHfZ (Z = Al, Ga, In) compounds mainly comes from the 4d electrons of the Zr atoms and the 5d electrons of the Hf atoms. Furthermore, the effects of uniform strain and tetragonal deformation on the half metallicity has been investigated in detail, which is important for practical application. Finally, we reveal that the half-metallicity can be maintained when the Coulomb interactions are considered. - Highlights: • New quaternary compounds without 3d transition metal elements have been designed. • The electronic structures and magnetism of the ZrRhHfZ compounds have been studied. • The effect of strain on the half-metallic behavior has been tested. • The effect of the Coulomb interactions on the half-metallicity has been investigated.

Scintillation properties of Zr co-doped Ce:(Gd, La)_2Si_2O_7 grown by the Czochralski process

International Nuclear Information System (INIS)

Murakami, Rikito; Kurosawa, Shunsuke; Shoji, Yasuhiro; Jary, Vitezslav; Ohashi, Yuji; Pejchal, Jan; Yokota, Yuui; Kamada, Kei; Nikl, Martin; Yoshikawa, Akira

2016-01-01

(Gd_0_._7_5,Ce_0_._0_1_5,La_0_._2_3_5)_2Si_2O_7 (Ce:La-GPS) single crystals co-doped with 0, 100, 200, 500 and 1000 ppm Zr were grown by the Czochralski process, and their scintillation properties were investigated. We investigated the co-doping effect of a stable tetravalent ion in Ce:La-GPS for the first time. The scintillation decay times in the faster component were shortened with increasing the Zr concentration. While the non-co-doped sample showed ∼63 ns day time, the Zr 100, 200, 500 and 1000 ppm co-doped samples showed ∼61, ∼59, ∼57, ∼54 ns, respectively. Additionally, light output, photon nonproportional response (PNR) and other optical properties were investigated. - Highlights: • Czochralski growth of Ce:(Gd,La)_2Si_2O_7 single crystals. • Co-doping effect of a stable tetravalent ion in Ce:(Gd,La)_2Si_2O_7 system. • Photon nonproportional response of Zr co-doped Ce:(Gd,La)_2Si_2O_7.

Novel Ni-Ce-Zr/Al2O3 Cellular Structure for the Oxidative Dehydrogenation of Ethane

Directory of Open Access Journals (Sweden)

Juan Pablo Bortolozzi

2017-11-01

Full Text Available A novel γ-alumina-supported Ni-Ce-Zr catalyst with cellular structure was developed for oxidative dehydrogenation of ethane (ODHE. First, powdered samples were synthesized to study the effect of both the total metal content and the Ce/Zr ratio on the physicochemical properties and performance of these catalysts. All synthesized powdered samples were highly active and selective for ODHE with a maximum ethylene productivity of 6.94 µmolethylene gact cat−1 s−1. According to the results, cerium addition increased the most reducible nickel species population, which would benefit ethane conversion, whereas zirconium incorporation would enhance ethylene selectivity through the generation of higher amounts of the least reducible nickel species. Therefore, the modification of active site properties by addition of both promoters synergistically increases the productivity of the Ni-based catalysts. The most efficient formulation, in terms of ethylene productivity per active phase amount, contained 15 wt% of the mixed oxide with Ni0.85Ce0.075Zr0.075 composition. This formulation was selected to synthesize a Ni-Ce-Zr/Al2O3 structured body by deposition of the active phase onto a homemade γ-alumina monolith. The structured support was manufactured by extrusion of boehmite-containing dough. The main properties of the Ni0.85Ce0.075Zr0.075 powder were successfully preserved after the shaping procedure. In addition, the catalytic performance of the monolithic sample was comparable in terms of ethylene productivity to that of the powdered counterpart.

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

Science.gov (United States)

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

2018-06-01

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

Systems Tl2MoO4-E(MoO4)2, where E=Zr or Hf, and the crystal structure of Tl8Hf(MoO4)6

International Nuclear Information System (INIS)

Bazarov, B.G.; Bazarova, Ts.T.; Fedorov, K.N.; Bazarova, Zh.G.; Chimitova, O.D.; Klevtsova, R.F.; Glinskaya, L.A.

2006-01-01

Systems Tl 2 MoO 4 -E(MoO 4 ) 2 (E=Zr, Hf) were studied by X-ray diffraction, differential thermal analysis and IR spectroscopy. Formation of Tl 8 E(MoO 4 ) 6 and Tl 2 E(MoO 4 ) 2 compounds was established. Phase T-x diagrams of the Tl 2 MoO 4 -Zr(MoO 4 ) 2 system were constructed. Monocrystals were grown, and structure of Tl 8 Hf(MoO 4 ) 6 was studied. The compound is crystallized in monoclinic syngony with elementary cell parameters a=9.9688(6), b=18.830(1), c=7.8488(5) A, β=108.538(1) Deg, Z=2, sp. gr. C2/m. The isolated group [HfMo 6 O 24 ] 8- is responsible for fundamental fragment of the structure. Three varieties of crystallographically independent Tl-polyhedra fill space evenly between fragments [HfMo 6 O 24 ] 8- forming three-dimensional form [ru

Growth and characterization of acentric BaHf(BO{sub 3}){sub 2} and BaZr(BO{sub 3}){sub 2}

Energy Technology Data Exchange (ETDEWEB)

Mączka, Mirosław, E-mail: m.maczka@int.pan.wroc.pl [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2 (Poland); Szymborska-Małek, Katarzyna; Gągor, Anna [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2 (Poland); Majchrowski, Andrzej [Institute of Applied Physics, Military University of Technology, 2 Kaliskiego Str., 00-908 Warszawa (Poland)

2015-05-15

Growth, single crystal X-ray diffraction, polarized Raman and infrared (IR) studies of BaHf(BO{sub 3}){sub 2} are presented. Raman and IR spectra of polycrystalline BaZr(BO{sub 3}){sub 2} are also reported to facilitate assignment of modes. BaHf(BO{sub 3}){sub 2} borate crystallizes in trigonal system, space group R3c, with lattice parameters: a=5.1540(4) Å, c=33.901(3) Å. It accommodates dolomite-like structure doubled in the c direction, which is built of alternating layers of HfO{sub 6} octahedra and BaO{sub 6} distorted trigonal prisms that are connected through borate groups. The obtained structural as well as spectroscopic data show that BaHf(BO{sub 3}){sub 2} is isostructural with BaZr(BO{sub 3}){sub 2} and the deviations from centrosymmetry is small. - Graphical abstract: Arrangement of BO{sub 3} groups in BaHf(BO{sub 3}){sub 2} along the c direction in one unit cell. Dark and light blue denote different borate groups. - Highlights: • BaHf(BO{sub 3}){sub 2} single crystals were grown. • X-ray diffraction showed that this borate crystallizes in the acentric R3c structure. • Raman and IR spectra were measured for BaHf(BO{sub 3}){sub 2} and BaZr(BO{sub 3}){sub 2}, respectively. • Assignment of modes is proposed.

TEM study of structural and microstructural characteristics of a precipitate phase in Ni-rich Ni–Ti–Hf and Ni–Ti–Zr shape memory alloys

International Nuclear Information System (INIS)

Santamarta, R.; Arróyave, R.; Pons, J.; Evirgen, A.; Karaman, I.; Karaca, H.E.; Noebe, R.D.

2013-01-01

The precipitates formed after suitable thermal treatments in seven Ni-rich Ni–Ti–Hf and Ni–Ti–Zr high-temperature shape memory alloys have been investigated by conventional and high-resolution transmission electron microscopy. In both ternary systems, the precipitate coarsening kinetics become faster as the Ni and ternary element contents (Hf or Zr) of the bulk alloy are increased, in agreement with the precipitate composition measured by energy-dispersive X-ray microanalysis. The precipitate structure has been found to be the same in both Hf- and Zr-containing ternary alloys, and determined to be a superstructure of the B2 austenite phase, which arises from a recombination of the Hf/Zr and Ti atoms in their sublattice. Two different structural models for the precipitate phase were optimized using density functional theory methods. These calculations indicate that the energetics of the structure are not very sensitive to the atomic configuration of the Ti–Hf/Zr planes, thus significant configurational disorder due to entropic effects can be envisaged at high temperatures. The precipitates are fully coherent with the austenite B2 matrix; however, upon martensitic transformation, they lose some coherency with the B19′ matrix as a result of the transformation shear process in the surrounding matrix. The strain accommodation around the particles is much easier in the Ni–Ti–Zr-containing alloys than in the Ni–Ti–Hf system, which correlates well with the lower transformation strain and stiffness predicted for the Ni–Ti–Zr alloys. The B19′ martensite twinning modes observed in the studied Ni-rich ternary alloys are not changed by the new precipitated phase, being equivalent to those previously reported in Ni-poor ternary alloys

Fatigue and strain effects in NbTi, Nb3Sn, and V2(Hf, Zr) multifilamentary superconductors

International Nuclear Information System (INIS)

Kuroda, T.; Wada, H.; Tachikawa, K.

1988-01-01

The effects of cyclic strain on critical current were studied in NbTi, bronze processed Nb 3 Sn, and composite diffusion processed V 2 (Hf,Zr) multifilamentary wires. No appreciable changes in critical current were found in NbTi wires until just prior to fatigue-induced fracture. Critical current degradation was also not observed in Nb 3 Sn or V 2 (Hf,Zr) as long as the wires were strained below the reversible limit strain. For strains beyond this limit strain the critical current was first degraded by an increasing number of cycles and then remained constant after a certain cycle number was passed

Influence of the physico-chemical properties of CeO{sub 2}-ZrO{sub 2} mixed oxides on the catalytic oxidation of NO to NO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Atribak, Idriss; Guillen-Hurtado, Noelia; Bueno-Lopez, Agustin [MCMA Group, Department of Inorganic Chemistry, Faculty of Sciences, University of Alicante, Carretera San Vicente del Raspeig s/n - 03690 San Vicente del Raspeig, Alicante (Spain); Garcia-Garcia, Avelina, E-mail: a.garcia@ua.es [MCMA Group, Department of Inorganic Chemistry, Faculty of Sciences, University of Alicante, Carretera San Vicente del Raspeig s/n - 03690 San Vicente del Raspeig, Alicante (Spain)

2010-10-01

Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N{sub 2} adsorption at -196 deg. C and XPS, and were tested for NO oxidation to NO{sub 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 deg. C with regard to 500 deg. 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.

Enhanced photorefractive properties in Hf, Ce and Cu co-doped LiNbO{sub 3} crystals for holographic application

Energy Technology Data Exchange (ETDEWEB)

Zhang, Tao, E-mail: tzhang_hit02@yahoo.com [Key Laboratory of In-fiber Integrated Optics, Ministry of Education of China, Harbin Engineering University, Harbin 150001 (China); College of Science, Harbin Engineering University, Harbin 150001 (China); Postdoctoral Research Station of Mechanical Engineering, College of Mechanical and Electrical Engineering, Harbin Engineering University, Harbin 150001 (China); Wang, Xin; Geng, Tao; Tong, Chengguo [Key Laboratory of In-fiber Integrated Optics, Ministry of Education of China, Harbin Engineering University, Harbin 150001 (China); College of Science, Harbin Engineering University, Harbin 150001 (China); Kang, Chong [Key Laboratory of In-fiber Integrated Optics, Ministry of Education of China, Harbin Engineering University, Harbin 150001 (China); College of Science, Harbin Engineering University, Harbin 150001 (China); Postdoctoral Research Station of Mechanical Engineering, College of Mechanical and Electrical Engineering, Harbin Engineering University, Harbin 150001 (China)

2015-04-25

Graphical abstract: Correlation spots of 200 holograms in a Hf, Ce and Cu co-doped LiNbO{sub 3}. - Highlights: • Several doped LiNbO{sub 3} crystals with various level of Hf doping were grown by Cz method. • IR peak shift is attributed to the complex defect change at different level of Hf. • Enhanced photorefractive properties have been got with higher Hf-doping level. • Reduced defect and increased photoconductivity are responsible for optical properties. • 200 holograms’ experiment is realized in a coherent volume 0.073 cm{sup 3}. - Abstract: Hf, Ce and Cu co-doped LiNbO{sub 3} crystals with various level of Hf doping were grown in air by a conventional Cz method. The infrared spectra were measured to discuss the defect structures and the mechanism of the absorption peak shift in these crystals. The light-induced scattering of the crystals was evaluated by the transmitted light method. The influence of the Hf-doping level on the photorefractive properties of Hf, Ce and Cu co-doped LiNbO{sub 3} crystals was studied via two-beam coupling. It is found that proper doping Hf is an efficient method to enhance the comprehensive photorefractive properties of the LiNbO{sub 3}. Using one of these crystals as medium, 200 holograms storage and correlation experiments based on angle fractal multiplexing have been realized in a coherent volume 0.073 cm{sup 3}. Moreover the diffraction efficiency is uniform and the storage density has reached 2.2 Gb/cm{sup 3}.

(V,Nb)-doped half Heusler alloys based on {Ti,Zr,Hf}NiSn with high ZT

International Nuclear Information System (INIS)

Rogl, G.; Sauerschnig, P.; Rykavets, Z.; Romaka, V.V.; Heinrich, P.; Hinterleitner, B.; Grytsiv, A.; Bauer, E.; Rogl, P.

2017-01-01

Half Heusler alloys are among the most promising materials for thermoelectric generators as they can be used in a wide temperature range and their starting materials are abundant and cheap, the latter as long as no hafnium is involved. For Sb-doped Ti 0.5 Zr 0.25 Hf 0.25 NiSn Sakurada and Shutoh in 2008 have published ZT max  = 1.5 at 690 K, a value that hitherto was never reproduced independently. In this paper we successfully prepared Ti 0.5 Zr 0.25 Hf 0.25 NiSn with ZT max  = 1.5, however, at higher temperature (825 K). As the main goal is to produce hafnium – free half Heusler alloys, we investigated the influence of niobium or vanadium dopants on Ti x Zr 1−x NiSn 0.98 Sb 0.02 , reaching ZTs > 1.2 and thermal-electric conversion efficiencies up to 13.1%. For Hf-free n-type TiNiSn-based half Heusler alloys these values are unsurpassed. In order to further improve our thermoelectric materials our study is completed by electrical resistivity and thermal conductivity data in the low temperature range but also by mechanical properties (elastic moduli, hardness) at room temperature. The electrical properties have been discussed in comparison with DFT calculations.

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

Science.gov (United States)

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

2012-01-01

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

Thermoelectric Performance of the MXenes M2CO2 (M = Ti, Zr, or Hf)

KAUST Repository

Gandi, Appala; Alshareef, Husam N.; Schwingenschlö gl, Udo

2016-01-01

MXenes, M2CO2, where M = Ti, Zr, or Hf, in order to evaluate the effect of the metal M on the thermoelectric performance. The lattice contribution to the thermal conductivity, obtained from the phonon life times, is found to be lowest in Ti2CO2

Tetragonal zirconia ceramics in Zr O2-Ce O2 system (Ce-TZP): preparation, characterization and mechanical properties

International Nuclear Information System (INIS)

Andrade Nono, M.C. de.

1992-01-01

This paper describes and discusses the results achieved in a study about Ce-TZP ceramics prepared from conventional powder mixtures of Zr O 2 and Ce O 2 (with composition in the range of 8 to 16 mol% Ce O 2 ). Physical and chemical characteristics were related with the powder compaction behavior and with the sintering state. The sintered ceramics showed a level of high porosity (≅ 4%), mainly due to the fairly adequate powder characteristics and compaction. The crystalline phases were analysed from X-rays diffraction data and showed that these ceramics can present tetragonal-to-monoclinic stress induced transformation. The bending strength, fracture toughness and Vickers hardness results were influenced by Ce O 2 content microstructure and sintering temperature. These Ce-TZP ceramics showed mechanical strength results comparable to those published in the international literature. (author)

Synthesis of ZrO2-8%CeO2 and ZrO2-8%Y2O3 by polymeric precursors route

International Nuclear Information System (INIS)

Macedo, D.A.; Macedo, M.C.; Melo, D.M.A.; Nascimento, R.M.; Rabelo, A.A.

2006-01-01

The stabilization of zirconia in the cubical and tetragonal structures comes gaining importance because of its excellent thermal stability, chemical resistance, mechanical properties and oxygen conductivity. Its main applications include electrolytes of high temperature fuel cells, sensors of oxygen and electrochemical reactors. In this work the polymeric precursors route was used to synthesize ZrO 2 -8 mol% Y 2 O 3 and ZrO 2 -8 mol%CeO 2 . In this process the dopant concentration, besides making possible the stabilization of distinct structures, influences in the morphologic characteristics of the powders synthesized. The characterization of the powders was carried through X-ray diffraction for existing phases verification and average crystallite size, thermogravimetric analysis, specific surface area measures, particles size distribution by laser scattering and the powder morphology was observed using scanning electronic microscopy. The powder only calcined at 700 deg C had presented of average crystallite size of 6,77 nm for ZrO 2 -8%Y 2 O 3 and 7,14 nm for ZrO 2 -CeO 2 . (author)

The influence of thermal treatment on the phase development in HfO2-Al2O3 and ZrO2-Al2O3 systems

International Nuclear Information System (INIS)

Stefanic, G.; Music, S.; Trojko, R.

2005-01-01

Amorphous precursors of HfO 2 -AlO 1.5 and ZrO 2 -AlO 1.5 systems covering the whole concentration range were co-precipitated from aqueous solutions of the corresponding salts. The thermal behaviour of the amorphous precursors was examined by differential thermal analysis, X-ray powder diffraction (XRD), laser Raman spectroscopy and scanning electron microscopy. The crystallization temperature of both systems increased with increase in the AlO 1.5 content, from 530 to 940 deg. C in the HfO 2 -AlO 1.5 system, and from 405 to 915 deg. C in the ZrO 2 -AlO 1.5 system. The results of phase analysis indicate an extended capability for the incorporation of Al 3+ ions in the metastable HfO 2 - and ZrO 2 -type solid solutions obtained after crystallization of amorphous co-gels. Precise determination of lattice parameters, performed using whole-powder-pattern decomposition method, showed that the axial ratio c f /a f in the ZrO 2 - and HfO 2 -type solid solutions with 10 mol% or more of Al 3+ approach 1. The tetragonal symmetry of these samples, as determined by laser Raman spectroscopy, was attributed to the displacement of the oxygen sublattice from the ideal fluorite positions. It was found that the lattice parameters of the ZrO 2 -type solid solutions decreased with increasing Al 3+ content up to ∼10 mol%, whereas above 10 mol%, further increase of the Al 3+ content has very small influence on the unit-cell volume of both HfO 2 - and ZrO 2 -type solid solutions. The reason for such behaviour was discussed. The solubility of Hf 4+ and Zr 4+ ions in the aluminium oxides lattice appeared to be negligible

Assessment of the structural relations between the bcc and omega phases of Ti, Zr, Hf and other transition metals

International Nuclear Information System (INIS)

Aurelio, G.; Guillermet, A.F.

2000-01-01

The name omega (Ω) phase refers to a high-pressure structural modification of the transition metals (TMs) Ti, Zr, and Hf. In alloys of Ti, Zr and Hf with other TMs, the Ω phase can be formed and retained metastably at room temperature by quenching the bcc structure, which is usually the stable high-temperature phase in these alloy systems. As a part of a systematic investigation of the structural and bonding properties of the bcc and Ω phases, and of the bcc → Ω phase transformation in TMs and alloys, we present in this paper a detailed analysis of the structural relations between these phases in Ti, Zr, Hf and in other TMs. The approach is as follows. First, we establish the most general geometrical relations connecting the lattice parameters and interatomic distances (IDs) of the bcc and Ω structures. Next, we focus on the ratio between the relevant IDs of these phases, which are assessed on the basis of an extensive database with experimental and theoretical information. Both stable and metastable structures are considered, and various remarkable regularities in ID ratios are discussed. Finally, in the light of the systematics of ID ratios established in the present work, a discussion is made of the probable lattice parameters for the Ω phase of Hf, which are not yet accurately known from direct measurements. (orig.)

Synthesis and physico-chemical characterization of CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} mixed oxides

Energy Technology Data Exchange (ETDEWEB)

Hernandez E, J. M.; Silva R, R.; Garcia A, R. [Instituto Tecnologico de Ciudad Madero, Div. de Estudios de Posgrado e Investigacion, Juventino Rosas y Jesus Urueta s/n, Col. Los Mangos, 89440 Ciudad Madero, Tamaulipas (Mexico); Garcia S, L. A. [IPN, Centro Interdisciplinario de Investigaciones y de Estudios sobre Medio Ambiente y Desarrollo, 30 de Junio No. 1520, Barrio La Laguna Ticoman, 07340 Mexico D. F. (Mexico); Handy, B. E.; Cardenas G, G. [Universidad Autonoma de San Luis Potosi, CIEP, Facultad de Ciencias Quimicas, Av. Dr. Manuel Nava No. 6, Zona Universitaria, 78210 SLP, San Luis Potosi (Mexico); Cueto H, A. [Universidad Autonoma Metropolitana, Unidad Azcapotzalco, Av. San Pablo No. 180, Col. Reynosa Tamaulipas, 02200 Mexico D. F. (Mexico)

2012-07-01

Environmentally friendly solid-acid catalysts CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} were prepared by the sol gel method varying CeO{sub 2} content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO{sub 2} and ZrO{sub 2}-SO{sub 4}{sup 2-} were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO{sub 2}-SO{sub 4}{sup 2-} was high (160 m{sup 2}/g) compared with the unmodified ZrO{sub 2} (80 m{sup 2}/g), however this area decreased with increasing the CeO{sub 2} content (37-100 m{sup 2}/g). There was no significant effect of CeO{sub 2} on the tetragonal structure of ZrO{sub 2}-SO{sub 4}{sup 2-}. The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} catalyst with the highest CeO{sub 2} content was used. (Author)

Isoelectronic substitutions and aluminium alloying in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

Science.gov (United States)

von Rohr, Fabian O.; Cava, Robert J.

2018-03-01

High-entropy alloys (HEAs) are a new class of materials constructed from multiple principal elements statistically arranged on simple crystallographic lattices. Due to the large amount of disorder present, they are excellent model systems for investigating the properties of materials intermediate between crystalline and amorphous states. Here we report the effects of systematic isoelectronic replacements, using Mo-Y, Mo-Sc, and Cr-Sc mixtures, for the valence electron count 4 and 5 elements in the body-centered cubic (BCC) Ta-Nb-Zr-Hf-Ti high-entropy alloy (HEA) superconductor. We find that the superconducting transition temperature Tc strongly depends on the elemental makeup of the alloy, and not exclusively its electron count. The replacement of niobium or tantalum by an isoelectronic mixture lowers the transition temperature by more than 60%, while the isoelectronic replacement of hafnium, zirconium, or titanium has a limited impact on Tc. We further explore the alloying of aluminium into the nearly optimal electron count [TaNb] 0.67(ZrHfTi) 0.33 HEA superconductor. The electron count dependence of the superconducting Tc for (HEA)Al x is found to be more crystallinelike than for the [TaNb] 1 -x(ZrHfTi) x HEA solid solution. For an aluminum content of x =0.4 the high-entropy stabilization of the simple BCC lattice breaks down. This material crystallizes in the tetragonal β -uranium structure type and superconductivity is not observed above 1.8 K.

Effects of minor Zr and Sr on as-cast microstructure and mechanical properties of Mg-3Ce-1.2Mn-0.9Sc (wt.%) magnesium alloy

International Nuclear Information System (INIS)

Pan Fusheng; Yang Mingbo; Shen Jia; Wu Lu

2011-01-01

Research highlights: → Minor Zr and/or Sr additions can effectively refine the grains of the Mg-3Ce-1.2Mn-0.9Sc alloy. → Minor Zr and/or Sr additions can improve the tensile properties of the Mg-3Ce-1.2Mn-0.9Sc alloy. → Minor Zr and/or Sr additions can improve the creep properties of the Mg-3Ce-1.2Mn-0.9Sc alloy. - Abstract: The effects of minor Zr and Sr on the as-cast microstructure and mechanical properties of the Mg-3Ce-1.2Mn-0.9Sc (wt.%) alloy were investigated by using optical and electron microscopies, differential scanning calorimetry (DSC) analysis, and tensile and creep tests. The results indicate that adding minor Zr and/or Sr to the Mg-3Ce-1.2Mn-0.9Sc alloy does not cause an obvious change in the morphology and distribution of the Mg 12 Ce phase. However, the grains of the Zr and/or Sr-containing alloys are effectively refined. Among the Zr and/or Sr-containing alloys, the grains of the alloy with the addition of 0.5 wt.%Zr + 0.1 wt.%Sr are the finest, followed by the alloys with the additions of 0.5 wt.%Zr and 0.1 wt.%Sr, respectively. In addition, small additions of Zr and/or Sr can improve the tensile and creep properties of the Mg-3Ce-1.2Mn-0.9Sc alloy. Among the Zr and/or Sr-containing alloys, the alloy with the addition of 0.5 wt.%Zr + 0.1 wt.%Sr obtains the optimum tensile and creep properties.

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

Science.gov (United States)

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

2018-03-01

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

Magnetic susceptibility and electron–phonon (e–p) interaction in some U and Ce based heavy fermion (HF) systems

International Nuclear Information System (INIS)

Sahoo, J.; Shadangi, N.; Nayak, P.

2015-01-01

Here an attempt is made to explore the variation of magnetic susceptibility with temperature for different values of the position of f-level (d) and electron–phonon interaction (EPI) strength (r) in some U and Ce based heavy Fermion (HF) systems within Periodic Anderson Model (PAM) in the presence of a static magnetic field B and interaction of phonons with electrons of hybridization band. Since magnetic susceptibility χ is related to the f-electron occupation n ±σ f , the expression for the latter is analytically derived through f–f correlation function following the Green function technique of Zubarev. The numerical analysis of χ as a function of temperature ‘T’ is done for different values of d and r. The results show a good agreement with the experiments for some U and Ce based HFs. An explanation for the existence of a critical value of d w.r.t. E F for switching of nature of χ∼T from U to Ce based HF systems is provided. Our calculated value of the temperature T χmax corresponding to the peak position of χ for small values of hybridization constant γ=0.002 and 0.0036 coincides with the experimental value of 19 K for UPt 3 and 35 K for UPd 2 Al 3 reported by Frings et al. and Geibel et al. respectively. - Highlights: • Variation of magnetic susceptibility χ with temperature T is studied for some HF systems. • Periodic Anderson Model in presence of magnetic field and electron–phonon interaction is used for numerical evaluation. • The existence of a critical value of the position of f-level(d) is proposed for distinction between χ∼T behavior of U and Ce based HF systems. • Results obtained are in good agreement with the experimental observations for some Ce and U based HF systems. • Theoretically evaluated temperature corresponding to the peak value of χ matches with the experimental results of UPt 3 and UPd 2 Al 3

Enhanced stability of Zr-doped Ba(CeTb)O(3-δ)-Ni cermet membrane for hydrogen separation.

Science.gov (United States)

Wei, Yanying; Xue, Jian; Fang, Wei; Chen, Yan; Wang, Haihui; Caro, Jürgen

2015-07-25

A mixed protonic and electronic conductor material BaCe(0.85)Tb(0.05)Zr(0.1)O(3-δ) (BCTZ) is prepared and a Ni-BCTZ cermet membrane is synthesized for hydrogen separation. Stable hydrogen permeation fluxes can be obtained for over 100 h through the Ni-BCTZ membrane in both dry and humid conditions, which exhibits an excellent stability compared with Ni-BaCe(0.95)Tb(0.05)O(3-δ) membrane due to the Zr doping.

Calcination effects on CeZrOx geometry and styrene production from ethylbenzene

NARCIS (Netherlands)

Kovacevic, M.; Brunet Espinosa, Roger; Lefferts, Leonardus; Mojet, Barbara

2014-01-01

A series of CeZrOx catalysts was prepared by calcination of hydrothermally obtained metal oxide precipitate at increasing temperatures. The samples were characterized by HRSEM, XRD and Raman spectroscopy, showing a change in morphology and particle size as a function of calcination temperature.

Mechanochemical synthesis of magnetically hard anisotropic RFe{sub 10}Si{sub 2} powders with R representing combinations of Sm, Ce and Zr

Energy Technology Data Exchange (ETDEWEB)

Gabay, A.M., E-mail: gabay@udel.edu; Hadjipanayis, G.C.

2017-01-15

Alloy synthesis consisting of mechanical activation followed by annealing was explored as a method of manufacturing medium-grade permanent magnet materials with a reduced content of the critical rare earth elements. Four R{sub x}Fe{sub 10}Si{sub 2} alloys with R=Sm, Sm{sub 0.7}Zr{sub 0.3}, Sm{sub 0.3}Ce{sub 0.3}Zr{sub 0.4} and Ce{sub 0.6}Zr{sub 0.4} (nominal compositions) were prepared from mixtures of Sm{sub 2}O{sub 3}, CeO{sub 2}, ZrO{sub 2}, Fe{sub 2}O{sub 3} and Si powders in the presence of a reducing agent Ca and a CaO dispersant. The collected alloy particles typically consisted of few joined submicron crystals. For R=Sm, X-ray diffraction analysis reveals a significant amount of the unwanted Th{sub 2}Zn{sub 17}-type compound forming alongside the desired ThMn{sub 12}-type 1:12 compound. A more pure 1:12 phase could be obtained for R=Ce{sub 0.6}Zr{sub 0.4}, but it exhibited a room-temperature coercivity of less than 1 kOe. The most pure 1:12 phase and the highest values of the coercivity (10.8 kOe) and calculated maximum energy product (13.8 MGOe) were obtained for R=Sm{sub 0.7}Zr{sub 0.3} processed at 1150 °C. The calculated maximum energy products of the Sm{sub 0.3}Ce{sub 0.3}Zr{sub 0.4}Fe{sub 10}Si{sub 2} particles, with half of their rare earths constituents represented by the relatively abundant Ce, was 10.1 MGOe. - Highlights: • 30% Zr substitution for Sm improves prospects of the alloys as permanent magnets. • Pure ThMn{sub 12}-type structure could only be obtained in the Zr-substituted alloys. • Obtained powders exhibit better properties than nanocrystalline Sm(Fe,M){sub 12} alloys. • If fully dense, alloy containing only 2.3 at% Sm would energy product of 10 MGOe.

Effect of the annealing temperature of thin Hf0.3Zr0.7O2 films on their energy storage behavior

International Nuclear Information System (INIS)

Park, Min Hyuk; Kim, Han Joon; Kim, Yu Jin; Moon, Taehwan; Kim, Keum Do; Hwang, Cheol Seong

2014-01-01

With increasing annealing temperature (T anneal ), the magnitude of the electric fields for the antiferroelectric-to-ferro-electric (E AF ) and ferroelectric-to-antiferroelectric (E FA ) transition of a 9.2 nm thick Hf 0.3 Zr 0.7 O 2 film decreased. The energy storage densities of the Hf 0.3 Zr 0.7 O 2 films crystallized at 400 C, 500 C, and 600 C were as large as 42.2 J/cm 3 , 40.4 J/cm 3 , and 28.3 J/cm 3 , respectively, at the electric field of 4.35 MV/cm. The maximum dielectric constant of the Hf 0.3 Zr 0.7 O 2 film crystallized at 600 C was the largest (∝46) as it had the smallest E AF and E FA , whereas the leakage current density of the film crystallized at 400 C was the smallest. The 400 C of T anneal was the optimum condition for energy storage application. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

Science.gov (United States)

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.

Effects of substrate temperature on the structure and mechanical properties of (TiVCrZrHf)N coatings

Energy Technology Data Exchange (ETDEWEB)

Liang, Shih-Chang [Department of Materials Science and Engineering, National Chung Hsing University, Taichung 402, Taiwan (China); Chang, Zue-Chin [Department of Mechanical Engineering, National Chin-Yi University of Technology, Taichung 411, Taiwan (China); Tsai, Du-Cheng [Department of Materials Science and Engineering, National Chung Hsing University, Taichung 402, Taiwan (China); Lin, Yi-Chen; Sung, Huan-Shin [Department of Mechanical Engineering, National Chin-Yi University of Technology, Taichung 411, Taiwan (China); Deng, Min-Jen [Department of Materials Science and Engineering, National Chung Hsing University, Taichung 402, Taiwan (China); Department of Optometry, Jen-Teh Junior College of Medicine, Nursing and Management, Miaoli County 356, Taiwan (China); Shieu, Fuh-Sheng, E-mail: fsshieu@dragon.nchu.edu.tw [Department of Materials Science and Engineering, National Chung Hsing University, Taichung 402, Taiwan (China)

2011-06-15

The present paper reports the influence of growth conditions on the characteristics of (TiVCrZrHf)N films prepared by rf reactive magnetron sputtering at various substrate temperatures. The nitrogen content is observed to decrease with increasing substrate temperature. The X-ray diffraction results indicate that all (TiVCrZrHf)N films are simple face centered cubic (FCC) structures. Initially, there is an obvious decrease followed by an increase in grain size with the increase in substrate temperature. The lower part of the microstructure has an amorphous structure. A nano grain structure (size {approx}1 nm) with a random orientation is also observed above the amorphous structure. The fully dense columnar structure with an fcc crystal phase then starts to develop. Extreme hardness of around 48 GPa is obtained in the present alloy design.

Effects of substrate temperature on the structure and mechanical properties of (TiVCrZrHf)N coatings

International Nuclear Information System (INIS)

Liang, Shih-Chang; Chang, Zue-Chin; Tsai, Du-Cheng; Lin, Yi-Chen; Sung, Huan-Shin; Deng, Min-Jen; Shieu, Fuh-Sheng

2011-01-01

The present paper reports the influence of growth conditions on the characteristics of (TiVCrZrHf)N films prepared by rf reactive magnetron sputtering at various substrate temperatures. The nitrogen content is observed to decrease with increasing substrate temperature. The X-ray diffraction results indicate that all (TiVCrZrHf)N films are simple face centered cubic (FCC) structures. Initially, there is an obvious decrease followed by an increase in grain size with the increase in substrate temperature. The lower part of the microstructure has an amorphous structure. A nano grain structure (size ∼1 nm) with a random orientation is also observed above the amorphous structure. The fully dense columnar structure with an fcc crystal phase then starts to develop. Extreme hardness of around 48 GPa is obtained in the present alloy design.

Behaviour at the indicator scale of the elements Zr, Hf and 104, Nb,Ta and Pa (105) in very complexation media; Comportement a l`echelle des indicateurs des elements Zr, Hf, et 104, Nb, Ta, et Pa (105) en milieux tres complexants

Energy Technology Data Exchange (ETDEWEB)

Monroy Guzman, F. [Institut de Physique Nucleaire, CNRS - IN2P3 Universite Paris Sud, 91406 Orsay Cedex (France)

1997-12-31

In order to determine the chemical properties of the trans-actinide elements of Z = 104 and 105 in aqueous solutions we studied their behaviour to ion exchange resin in different complex media. Due to the very short lifetimes (some tens of seconds) et to the low yield of these elements (a few atoms per irradiation hour) only very fast radiochemical techniques can be used. These severe constraints impose comparative studies of these elements with their most likely homologues to be carried out. The corresponding homologues were the elements of group 4 (Zr and Hf) for the element 104 and the elements of group 5 (Nb and Ta) and also Pa for the element 105. The complexation properties of the elements at indicator scale were determined in the media of HF, NH{sub 4}/HClO{sub 4}, NH{sub 4}SCN/HClO{sub 4}, NH{sub 4}SCN/HF and HCl/HF by ion exchange chromatography. The studies in fluorides media allowed us to identify the complexes in solution and to explain the shape of the experimentally observed sorption curves. The decrease of sorption for higher acid concentration in case of HF/HCl medium was interpreted by formation of chloro-fluoro-complexes. In case of the mixture NH{sub 4}SCN/HF, the particularly pronounced anti-synergic effects were observed and discussed. At the same time studies of the Hf and Ta short-lived isotopes were carried out by means of the RACHEL facility operating by the Orsay Tandem accelerator. These realistic simulations allowed optimization of different production, transportation and separation stages of the trans-actinide elements. The two experiments of 104 element production showed that this element forms in HF very stable anionic complexes similarly to its homologues Zr and Hf. (authors). 181 refs.

Behaviour at the indicator scale of the elements Zr, Hf and 104, Nb,Ta and Pa (105) in very complexation media; Comportement a l`echelle des indicateurs des elements Zr, Hf, et 104, Nb, Ta, et Pa (105) en milieux tres complexants

Energy Technology Data Exchange (ETDEWEB)

Monroy Guzman, F [Institut de Physique Nucleaire, CNRS - IN2P3 Universite Paris Sud, 91406 Orsay Cedex (France)

1998-12-31

In order to determine the chemical properties of the trans-actinide elements of Z = 104 and 105 in aqueous solutions we studied their behaviour to ion exchange resin in different complex media. Due to the very short lifetimes (some tens of seconds) et to the low yield of these elements (a few atoms per irradiation hour) only very fast radiochemical techniques can be used. These severe constraints impose comparative studies of these elements with their most likely homologues to be carried out. The corresponding homologues were the elements of group 4 (Zr and Hf) for the element 104 and the elements of group 5 (Nb and Ta) and also Pa for the element 105. The complexation properties of the elements at indicator scale were determined in the media of HF, NH{sub 4}/HClO{sub 4}, NH{sub 4}SCN/HClO{sub 4}, NH{sub 4}SCN/HF and HCl/HF by ion exchange chromatography. The studies in fluorides media allowed us to identify the complexes in solution and to explain the shape of the experimentally observed sorption curves. The decrease of sorption for higher acid concentration in case of HF/HCl medium was interpreted by formation of chloro-fluoro-complexes. In case of the mixture NH{sub 4}SCN/HF, the particularly pronounced anti-synergic effects were observed and discussed. At the same time studies of the Hf and Ta short-lived isotopes were carried out by means of the RACHEL facility operating by the Orsay Tandem accelerator. These realistic simulations allowed optimization of different production, transportation and separation stages of the trans-actinide elements. The two experiments of 104 element production showed that this element forms in HF very stable anionic complexes similarly to its homologues Zr and Hf. (authors). 181 refs.

Steam reforming of bio-ethanol over Ni on Ce-ZrO2 support: Influence of redox properties on the catalyst reactivity

Directory of Open Access Journals (Sweden)

Sumittra Charojrochkul

2006-11-01

Full Text Available The steam reforming of ethanol over Ni on Ce-ZrO2 support, (Ni/ Ce-ZrO2 were studied. The catalyst provides significantly higher reforming reactivity and excellent resistance toward carbon deposition compared to Ni/Al2O3 under the same conditions. At the temperature above 800ºC, the main products from the reforming processes over Ni/Ce-ZrO2 were H2, CO, and CO2 with small amount of CH4 depending on the inlet ethanol/steam and oxygen/ethanol ratios, whereas high hydrocarbon compounds i.e., C2H4 and C2H6 were also observed from the reforming of ethanol over Ni/Al2O3 in the range of conditions studied (700- 1000ºC.These excellent ethanol reforming performances of Ni/Ce-ZrO2 in terms of stability, reactivity and product selectivities are due to the high redox property of Ce-ZrO2. During the ethanol reforming process, in addition to the reactions on Ni surface, the gas-solid reactions between the gaseous components presented in the system (C2H5OH, C2H6, C2H4, CH4, CO2, CO, H2O, and H2 and the lattice oxygen (Ox on Ce-ZrO2 surface also take place. Among these redox reactions, the reactions of adsorbed surface hydrocarbons with the lattice oxygen (Ox (CnHm + Ox → nCO + m/2(H2 + Ox-n can eliminate the formation of high hydrocarbons (C2H6 and C2H4, which easily decompose and form carbon species on Ni surface (CnHm→ nC + m/2H2.

The CaO-TiO2-ZrO2 system at 1,200 degree C and the solubilities of Hf and Gd in zirconolite

International Nuclear Information System (INIS)

Swenson, D.; Nieh, T.G.; Fournelle, J.H.

1995-12-01

In recent years, significant technological advancements have been made in the Synroc scheme for the immobilization high-level nuclear waste. However, many basic scientific issues related to Synroc fabrication have yet to be addressed. The CaO-TiO 2 -ZrO 2 system is an integral part of the Synroc formulation. Phase equilibria are established in the CaO-TiO 2 -ZrO 2 system at 1,200 C, using X-ray diffraction and electron probe microanalysis. The existence of two previously reported ternary phases, zirconolite (CaZrTi 2 O 7 ) and calzirtite (Ca 2 Zr 5 Ti 2 O 16 ), is confirmed. Each of these phases exhibits a significant range of homogeneity between TiO 2 and ZrO 2 while maintaining a nearly constant concentration of CaO. The ternary solubilities of the constituent binary phases are found to be negligible, with the exceptions of the perovskites, which display mutual solubility of at least 22 mol.% and may in fact form a series of continuous solid solutions. The solubilities of Hf and Gd in zirconolite are also investigated. While Hf-bearing samples did not reach thermodynamic equilibrium under the experimental conditions employed, the existence of a Hf analog to zirconolite, CaHfTi 2 O 7 , is conclusively demonstrated. The phase is stable at the stoichiometric composition, and its lattice parameters are very close to those reported in the literature for stoichiometric zirconolite. A Gd-bearing sample of the composition Ca 0.88 Zr 0.88 Gd 9.24 Ti 2 O 7 is found to be essentially single phase zirconolite, in agreement with previous investigations at higher temperatures

Uncertainty estimation of analysis of Fe, Ca, Zr, Ba, La, Ti and Ce in sediment sample using XRF method

International Nuclear Information System (INIS)

Sukirno; Agus Taftazani

2010-01-01

An uncertainty of analysis of Fe, Ca, Zr, Ba, La, Ti and Ce in river sediment of Panfuran Wariness sample by X RF method has been done. The result value of testing is meaningless if it isn't completed without uncertainty value. The calculation of Ba metal have been presented for example. The aim of the research is to get accreditation certificate of X-Ray Fluorescence method on laboratory of analytical PTAPB – BATAN as well as ISO guide 17025-2005. The result of calculation uncertainty of Fe, Zr, Ba, La, Ce, Ti and Ca analysis showed that the uncertainty components come from: preparation of sample and standard/comparator, purity of material, counting statistic (sample and standard ) and repeatability. The results showed that metals in river sediment of Pancuran Wonosari were Fe = 7.290%, Zr = 54.5 mg/kg, Ba = 1661.6 mg/kg, La = 22.9 mg/kg, Ce = 161.0 mg/kg, Ti = 3193.2 and Ca = 7.816%, and the result of uncertainty estimate of Fe, Zr, Ba, La, Ce, Ti and Ca were ± 0.60%, ± 4.5 mg/kg, ± 55 mg/kg, ± 1.4 mg/kg, 12.0 mg/kg, ± 208 mg/kg and ± 0.61%. (author)

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

Science.gov (United States)

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

2014-07-01

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

Collapse of the magnetic moment under pressure of AFe{sub 2} (A=Y, Zr, Lu and Hf) in the cubic Laves phase

Energy Technology Data Exchange (ETDEWEB)

Zhang, Wenxu, E-mail: xwzhang@uestc.edu.cn; Zhang, Wanli

2016-04-15

The electronic structures of four Laves phase iron compounds (e.g. YFe{sub 2}, ZrFe{sub 2}, LuFe{sub 2} and HfFe{sub 2}) have been calculated with a state-of-the-art full potential electronic structure code. Our theoretical work predicted that the magnetic moments collapse under hydrostatic pressure. This feature is found to be universal in these materials. Its electronic origin is provided by the sharp peaks in the density of states near the Fermi level. It is shown that a first order quantum phase transition can be expected under pressure in Y(Zr, or Lu)Fe{sub 2}, while a second order one in HfFe{sub 2}. The bonding characteristics are discussed to elucidate the equilibrium lattice constant variation. The large spontaneous volume magnetostriction gives one of the most important characteristics of these compounds. Invar anomalies in these compounds can be partly explained by the current work when the fast continuous magnetic moment decrease with the decrease of the lattice constant was properly considered. This work may be as a first insight into the rich world of quantum phase transition and Invar mechanism in these Laves phase compounds. - Highlights: • Magnetic moment of YFe{sub 2}, ZrFe{sub 2}, LuFe{sub 2} and HfFe{sub 2} collapses under pressure. • The transition in Y(Zr or Lu) Fe{sub 2} under pressure is first order. • The transition in HfFe{sub 2} under pressure is second order. • The Invar effects in the compounds can be put into the magnetostriction model.

Sequential evolution of different phases in metastable Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 (0.0 ≤ x ≤ 2.0) system: crucial role of reaction conditions.

Science.gov (United States)

Shukla, Rakesh; Sayed, Farheen N; Phapale, Suhas; Mishra, Ratikant; Tyagi, Avesh K

2013-07-15

The Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 (0.0 ≤ x ≤ 2.0) series was synthesized by the gel combustion method. This system exhibited the presence of a fluorite-type phase, along with a narrow biphasic region, depending upon the Ce/Gd content in the sample. Thermal stability of these new compounds under oxidizing and reducing conditions has been investigated. The products obtained on decomposition of Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 in oxidizing and reducing conditions were found to be entirely different. It was observed that in air the fluorite-type solid solutions of Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 composition undergo phase separation into perovskite GdAlO3 and fluorite-type solid solutions of Gd-Ce-Zr-O or Ce-Zr-Al-O depending upon the extent of Ce and Al substitution. On the other hand, Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 samples on heating under reducing conditions show a phase separation to CeAlO3 perovskite and a defect-fluorite of Gd2Zr2O7. The extent of metastability for a typical composition of Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O7 (nano), Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O(6.6) (heated under reduced conditions), Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O7 (heated in air at 1200 °C) has been experimentally determined employing a high temperature Calvet calorimeter. On the basis of thermodynamic stability data, it could be inferred that the formation of a more stable compound in the presence of two competing cations (i.e., Gd(3+) and Ce(3+)) is guided by the crystallographic stability.

Catalytic Hydrothermal Liquefaction of Food Waste Using CeZrOx

Directory of Open Access Journals (Sweden)

Alex R. Maag

2018-03-01

Full Text Available Approximately 15 million dry tons of food waste is produced annually in the United States (USA, and 92% of this waste is disposed of in landfills where it decomposes to produce greenhouse gases and water pollution. Hydrothermal liquefaction (HTL is an attractive technology capable of converting a broad range of organic compounds, especially those with substantial water content, into energy products. The HTL process produces a bio-oil precursor that can be further upgraded to transportation fuels and an aqueous phase containing water-soluble organic impurities. Converting small oxygenated compounds that partition into the water phase into larger, hydrophobic compounds can reduce aqueous phase remediation costs and improve energy yields. HTL was investigated at 300 °C and a reaction time of 1 h for conversion of an institutional food waste to bio-oil, using either homogeneous Na2CO3 or heterogeneous CeZrOx to promote in situ conversion of water-soluble organic compounds into less oxygenated, oil-soluble products. Results with food waste indicate that CeZrOx improves both bio-oil higher heating value (HHV and energy recovery when compared both to non-catalytic and Na2CO3-catalyzed HTL. The aqueous phase obtained using CeZrOx as an HTL catalyst contained approximately half the total organic carbon compared to that obtained using Na2CO3—suggesting reduced water treatment costs using the heterogeneous catalyst. Experiments with model compounds indicated that the primary mechanism of action was condensation of aldehydes, a reaction which simultaneously increases molecular weight and oxygen-to-carbon ratio—consistent with the improvements in bio-oil yield and HHV observed with institutional food waste. The catalyst was stable under hydrothermal conditions (≥16 h at 300 °C and could be reused at least three times for conversion of model aldehydes to water insoluble products. Energy and economic analysis suggested favorable performance for the

Ce O2-Zr O2 powder synthesis by alcohol dehydration of aqueous salt solutions

International Nuclear Information System (INIS)

Andrade Nono, M.C. de

1993-01-01

A method for the precipitation of Ce O 2 -Zr O 2 powder is reported. It involves the powder synthesis by precipitation from an aqueous of Y and Zr sulphates in ethanol and isopropanol followed by calcination. The powder characteristics and their relations with the green compaction and densification by sintering are shown and discussed. It is observed that the ethanol gives powders with the best compaction and sintering behavior. (author)

Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces

International Nuclear Information System (INIS)

Pershina, V.; Borschevsky, A.; Iliaš, M.; Türler, A.

2014-01-01

With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl 4 , MOCl 2 , MCl 6 − , and MOCl 4 2 with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl 4 , the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔH sub , of the Zr and Hf tetrachlorides, i.e., Zr < Hf. On the basis of a correlation between these quantities, ΔH sub (RfCl 4 ) was predicted as 104.2 kJ/mol. The energy of physisorption of MOCl 2 on quartz should increase in the group, Zr < Hf < Rf, as defined by increasing dipole moments of these molecules along the series. In the case of adsorption of MCl 4 on quartz by chemical forces, formation of the MOCl 2 or MOCl 4 2− complexes on the surface can take place, so that the sequence in the adsorption energy should be Zr > Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl 4 on a chlorinated quartz surface, formation of the MCl 6 2− surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the “one-atom-at-a-time” gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations

Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces

Energy Technology Data Exchange (ETDEWEB)

Pershina, V., E-mail: V.Pershina@gsi.de [GSI Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, Darmstadt D-64291 (Germany); Borschevsky, A. [Helmholtz Institute Mainz, Mainz D-55128, Germany and Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Private Bag 102904, 0745 North Shore MSC, Auckland (New Zealand); Iliaš, M. [Department of Chemistry, Faculty of Natural Sciences, Matej Bel University, Tajovského 40, SK-974 00 Banská Bystrica (Slovakia); Türler, A. [Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland and Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland)

2014-08-14

With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl{sub 4}, MOCl{sub 2}, MCl{sub 6}{sup −}, and MOCl{sub 4}{sup 2} with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl{sub 4}, the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔH{sub sub}, of the Zr and Hf tetrachlorides, i.e., Zr < Hf. On the basis of a correlation between these quantities, ΔH{sub sub}(RfCl{sub 4}) was predicted as 104.2 kJ/mol. The energy of physisorption of MOCl{sub 2} on quartz should increase in the group, Zr < Hf < Rf, as defined by increasing dipole moments of these molecules along the series. In the case of adsorption of MCl{sub 4} on quartz by chemical forces, formation of the MOCl{sub 2} or MOCl{sub 4}{sup 2−} complexes on the surface can take place, so that the sequence in the adsorption energy should be Zr > Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl{sub 4} on a chlorinated quartz surface, formation of the MCl{sub 6}{sup 2−} surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the “one-atom-at-a-time” gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations.

Ideal solution behaviour of glassy Cu–Ti, Zr, Hf alloys and properties of amorphous copper

International Nuclear Information System (INIS)

Ristić, R.; Cooper, J.R.; Zadro, K.; Pajić, D.; Ivkov, J.; Babić, E.

2015-01-01

Highlights: • Ideal solution behaviour (ISB) is established in all Cu–Ti, Zr, Hf glassy alloys. • ISB enables reliable estimates for various properties of amorphous Cu. • ISB also impacts glass forming ability in these and probably other similar alloys. - Abstract: A comprehensive study of selected properties of amorphous (a) Cu–TE alloys (TE = Ti, Zr and Hf) has been performed. Data for average atomic volumes of a-Cu–Hf, Ti alloys combined with literature data show that ideal solution behaviour (Vegard’s law) extends over the whole glass forming range (GFR) in all a-Cu–TE alloys. This enables one to obtain an insight into some properties and probable atomic arrangements for both, a-TEs (Ristić et al., 2010) and a-Cu by extrapolation of the data for alloys. Indeed the atomic volumes and other properties studied for all a-Cu–TE alloys extrapolate to the same values for a-Cu. Depending on the property, these values are either close to those of crystalline (c) Cu, or are close to those for liquid (L) Cu. In particular, the electronic transport properties of a-Cu seem close to those of L-Cu, whereas the static properties, such as the density of states, and Young’s modulus, converge to those of c-Cu. The possible impact of these results on our understanding of a-Cu–TE alloys, including glass forming ability, is discussed

Composite Fe - BaCe0.2Zr0.6Y0.2O2.9 Anodes for Proton Conductor Fuel Cells

DEFF Research Database (Denmark)

Lapina, Alberto; Chatzichristodoulou, Christodoulos; Holtappels, Peter

2014-01-01

Symmetrical cells with Fe - BaCe0.2Zr0.6Y0.2O2.9 composite electrodes are produced by screen printing and infiltration, using BaCe0.2Zr0.6Y0.2O2.9 as electrolyte. The electrochemical performance of the composite electrode is studied by impedance spectroscopy at 250–500◦C in dry and wet hydrogen/n...

The thermal stability and catalytic performance of Ce-Zr promoted Rh-Pd/γ-Al2O3 automotive catalysts

International Nuclear Information System (INIS)

Wu Xiaodong; Xu Luhua; Weng Duan

2004-01-01

The noble metals (Rh, Pd) supported on alumina promoted with Ce-Zr mixed oxides were investigated as catalysts under diverse oxidants/reductants ratios of simulated automotive exhaust feed gas. Aging test was performed in air at 1000 deg. C for 20 h. Both fresh and aged catalysts, as well as alumina-supported Ce-Zr mixed powders, were characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and X-ray photoelectron spectroscopy (XPS). The results confirmed the oxygen storage capacity of Ce-Zr mixed oxides favored CO, C 3 H 8 and NO conversions in stationary versus dynamic stoichiometric operation. The accelerated aging of the systems produced inconspicuous effect on the phase structure, specific surface area and chemical state of these samples. Accordingly, the aged samples still showed low light-off temperature and broad λ-window, which suggested the relative low relevance of the thermal degradation on the overall catalytic performance of the system

Synthesis of nano-Ce{sub 0.5}Zr{sub 0.5}O{sub 2} by absorption of ammonia into water-in-oil microemulsion in a rotor–stator reactor

Energy Technology Data Exchange (ETDEWEB)

Li, Yingwen; Wang, Hongrun; Arowo, Moses; Sun, Baochang, E-mail: sunbc@mail.buct.edu.cn; Chen, Jianfeng; Shao, Lei, E-mail: shaol@mail.buct.edu.cn [Beijing University of Chemical Technology, State Key Laboratory of Organic–Inorganic Composites (China)

2015-01-15

A gas-microemulsion reaction precipitation method was employed to prepare nano-Ce{sub 0.5}Zr{sub 0.5}O{sub 2} by absorption of NH{sub 3} into water-in-oil (W/O) microemulsion in a rotor–stator reactor . The effects of different operating conditions including final pH of the microemulsion, reaction temperature, initial Ce{sup 3+} and Zr{sup 4+} concentration, rotation speed, and gas–liquid volumetric ratio were investigated. Nano-Ce{sub 0.5}Zr{sub 0.5}O{sub 2} with an average diameter of about 5.5 nm, a specific surface area of 215.6 m{sup 2}/g and a size distribution of 4–8 nm was obtained under the optimum operating conditions. The as-prepared nano-Ce{sub 0.5}Zr{sub 0.5}O{sub 2} was loaded with Au to prepare nano-Au/Ce{sub 0.5}Zr{sub 0.5}O{sub 2} catalyst which was subsequently used for CO oxidation test. CO conversion rate reached 100 % at room temperature, indicating high catalytic activity of the nano-Au/Ce{sub 0.5}Zr{sub 0.5}O{sub 2} catalyst.

Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces

Science.gov (United States)

Pershina, V.; Borschevsky, A.; Iliaš, M.; Türler, A.

2014-08-01

With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl4, MOCl2, MCl6-, and MOCl42 with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl4, the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔHsub, of the Zr and Hf tetrachlorides, i.e., Zr Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl4 on a chlorinated quartz surface, formation of the MCl62- surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the "one-atom-at-a-time" gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations.

Phase transformations in the rapidly solidified Ti{sub 40}Zr{sub 20}Hf{sub 20}Pd{sub 20} alloy

Energy Technology Data Exchange (ETDEWEB)

Chen, N. [Division of Engineering Materials, Department of Mechanical Engineering, Tsinghua University, Beijing 100084 (China); Yao Kefu [Division of Engineering Materials, Department of Mechanical Engineering, Tsinghua University, Beijing 100084 (China)], E-mail: kfyao@tsinghua.edu.cn; Louzguine-Luzgin, D.V. [Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aoba-Ku, Sendai 980-8577 (Japan); Qiu Shengbao [Division of Engineering Materials, Department of Mechanical Engineering, Tsinghua University, Beijing 100084 (China); Ranganathan, S. [Department of Metallurgy, Indian Institute of Science, Bangalore 560 012 (India); Inoue, A. [Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aoba-Ku, Sendai 980-8577 (Japan)

2007-10-15

We report that an approximant phase was initially obtained in amorphous Ti{sub 40}Zr{sub 20}Hf{sub 20}Pd{sub 20} alloy. In the initial stage of the devitrification process, the approximant phase transforms into an icosahedral (I) phase with a high thermal stability while the cF96 Zr{sub 2}Ni-type (space group Fd3-bar m with a=1.25nm and 96 atoms cell{sup -1}) particles precipitate from the amorphous matrix. Eventually the I phase grows to several hundred nanometers when annealed at about 1000K and then transforms into the Zr{sub 2}Ni-type phase with an endothermic reaction.

Thermal Expansion Property of U-Zr Alloys and U-Zr-Ce Alloys as a Surrogate Metallic Fuel for SFR

International Nuclear Information System (INIS)

Kim, Sun Ki; Lee, Jong Tak; Oh, Seok Jin; Ko, Young Mo; Kim, Ki Hwan; Woo, Youn Myung; Lee, Chan Bock

2010-01-01

Metal fuels was selected for fueling many of the first reactors in the US, including the Experimental Breeder Reactor-I (EBR-I) and the Experimental Breeder Reactor-II (EBR-II) in Idaho, the FERMI-I reactor, and the Dounreay Fast Reactor (DFR) in the UK. Metallic U.Pu.Zr alloys were the reference fuel for the US Integral Fast Reactor (IFR) program. An extensive database on the performance of advanced metal fuels was generated as a result of the operation of these reactors and the IFR program. In this study, the U-Zr binary alloys and U-Zr-Ce ternary alloys as surrogate metallic fuel were fabricated in lower pressure Ar environment by gravity casting. The melt temperature was approximately 1,500 .deg. C. Thermal expansion of the fuel during normal operation is related with fuel performance in a reactor. Therefore, it is necessary to investigate the thermal expansion of the fuel in order to warrant a good prediction the fuel performance

Phase evolution and aqueous durability of Zr{sub 1−x−y}Ce{sub x}Nd{sub y}O{sub 2−y/2} ceramics designed to immobilize actinides with multi-valences

Energy Technology Data Exchange (ETDEWEB)

Ding, Yi, E-mail: dingyi2279@126.com [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, Sichuan, 621900 (China); Key Subject Laboratory of National Defense for Radioactive Waste and Environmental Security, Southwest University of Science and Technology, Mianyang 621010 (China); Long, Xinggui, E-mail: xingguil@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, Sichuan, 621900 (China); Peng, Shuming [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, Sichuan, 621900 (China); Zhang, Dong, E-mail: zd0823@sina.com [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, Sichuan, 621900 (China); Tan, Zhaoyi [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, Sichuan, 621900 (China); Lu, Xirui [Key Subject Laboratory of National Defense for Radioactive Waste and Environmental Security, Southwest University of Science and Technology, Mianyang 621010 (China)

2017-04-15

Zr{sub 1−x−y}Ce{sub x}Nd{sub y}O{sub 2−y/2} ceramics, which were designed as waste form materials, were obtained by simultaneous substitution of Ce{sup 4+} and Nd{sup 3+} for Zr{sup 4+} in ZrO{sub 2}. The influences of the simultaneous substitution of Ce and Nd on phase transformation of ZrO{sub 2} were investigated systematically. Also, the aqueous durability of the ceramics was evaluated. The results show that the phase transformation caused by the simultaneous substitution mainly relates to the total content of Ce and Nd. The ZrO{sub 2} ceramics containing Ce + Nd < 30 mol% exhibit both monoclinic and cubic phases, while the ceramics containing Ce + Nd ≥ 30 mol% are cubic phase. And the cubic phase can be stabilized by incorporating 30 mol% Ce + Nd. Moreover, LR{sub i} are modified by the incorporation of Ce and Nd, because of the presence of oxygen vacancies. The Nd and Ce co-doped zirconia waste form exhibit excellent aqueous durability (∼10{sup −5} g m{sup −2} d{sup −1}). - Highlights: •Zr{sub 1−x−y}Ce{sub x}Nd{sub y}O{sub 2−y/2} were obtained by substitution of Ce and Nd for Zr in ZrO{sub 2}. •Phase transformation mainly relates to the total content of Ce and Nd. •Samples with Ce + Nd < 30 mol% show monoclinic and cubic phases, while ≥30 mol% are cubic. •Stabilized cubic zirconia can be obtained by doping with 30 mol% Ce and Nd. •LR{sub Ce} and LR{sub Nd} (42 d) are ∼ 10{sup −5} g m{sup −2} d{sup −1}, exhibiting excellent aqueous durability.

Tunneling current in HfO2 and Hf0.5Zr0.5O2-based ferroelectric tunnel junction

Science.gov (United States)

Dong, Zhipeng; Cao, Xi; Wu, Tong; Guo, Jing

2018-03-01

Ferroelectric tunnel junctions (FTJs) have been intensively explored for future low power data storage and information processing applications. Among various ferroelectric (FE) materials studied, HfO2 and H0.5Zr0.5O2 (HZO) have the advantage of CMOS process compatibility. The validity of the simple effective mass approximation, for describing the tunneling process in these materials, is examined by computing the complex band structure from ab initio simulations. The results show that the simple effective mass approximation is insufficient to describe the tunneling current in HfO2 and HZO materials, and quantitative accurate descriptions of the complex band structures are indispensable for calculation of the tunneling current. A compact k . p Hamiltonian is parameterized to and validated by ab initio complex band structures, which provides a method for efficiently and accurately computing the tunneling current in HfO2 and HZO. The device characteristics of a metal/FE/metal structure and a metal/FE/semiconductor (M-F-S) structure are investigated by using the non-equilibrium Green's function formalism with the parameterized effective Hamiltonian. The result shows that the M-F-S structure offers a larger resistance window due to an extra barrier in the semiconductor region at off-state. A FTJ utilizing M-F-S structure is beneficial for memory design.

Pb, U, Ti, Hf and Zr distributions in zircons determined by proton microprobe and fission track techniques

International Nuclear Information System (INIS)

Clark, G.J.; Gulson, B.L.; Cookson, J.A.

1979-01-01

A proton microprobe has been used to determine Pb, Tl, Hf and Zr distributions across four single zircon crystals separated from a 'rapakivi' granite. The Pb and Zr data are quantitative: Pb and Tl concentrations were below the measurable limits for determinations in situ by most other techniques. The distribution of U in the same crystals was determined by the fission track technique. Limits on precision of U allow only a qualitative correlation of U and Pb, whereas the Tl and Pb correlation is more exactly determined. Zircons with distinct cores and overgrowths exhibited uniform Zr and Hf concentrations across the crystals, whereas the high U rims and 'inclusions' (domains) also had high Tl and Pb contents. Since almost all the Pb in these zircons is derived by radioactive decay of U, the Tl substitution has paralleled that of U. The results indicate that the high U domains are 'hot spots' rather than a separate mineral phase. The strong positive correlation of U and Pb indicates that there is little U daughter product migration relative to U, within the crystal. However, for the zircon population investigated here, the data are equivocal on the question of whether U addition to zircon crystals is associated with new zircon growth or not. In either case, the heterogeneous U and Pb distributions complicate any interpretations of U-Pb isotopic analysis for such zircon populations. (author)

Optimization of CeO2-ZrO2 mixed oxide catalysts for ethyl acetate combustion

Czech Academy of Sciences Publication Activity Database

Dimitrov, M.; Ivanova, R.; Štengl, Václav; Henych, Jiří; Kovacheva, D.; Tsoncheva, T.

2015-01-01

Roč. 47, č. 1 (2015), s. 323-329 ISSN 0324-1130 Institutional support: RVO:61388980 Keywords : nanosized CeO2-ZrO2 * mixed oxide phase * ethyl acetate combustion Subject RIV: CA - Inorganic Chemistry Impact factor: 0.229, year: 2015

TiNiSn and Zr{sub 0.5}Hf{sub 0.5}NiSn superlattices for thermoelectrics

Energy Technology Data Exchange (ETDEWEB)

Jaeger, Tino; Jakob, Gerhard [Institut fuer Physik, Universitaet Mainz, 55099 Mainz (Germany); Schwall, Michael; Kozina, Xeniya; Balke, Benjamin; Felser, Claudia [Institut fuer Analytische und Anorganische Chemie, Universitaet Mainz, 55099 Mainz (Germany); Populoh, Sascha; Weidenkaff, Anke [EMPA, Ueberlandstrasse 129, 8600 Duebendorf (Switzerland)

2012-07-01

In order to increase the attractiveness of thermoelectric devices, their efficiency must be increased. Beside others, the properties of the thermoelectric material can be improved. That can be achieved by either increasing Seebeck coefficient or conductivity or by a depressed thermal conductivity along the thermal gradient. For thin films, superlattices or multilayers can be used to lower the cross plane thermal conductivity. As a bottom up approach, artificially layered films with a periodicity of about 5-6 nm are assumed to generate the most phonon scattering at the interfaces. If electrical properties remain unchanged or less effected, the thermoelectric efficiency is enhanced. Semiconducting Half-Heuslers are well studied thermoelectric bulk materials. Among others, TiNiSn and Zr{sub 0.5}Hf{sub 0.5}NiSn are potential candidates. Essentially, their similar lattice constants enable epitaxial layers on top of each other. Furthermore, varied atomic masses of Ti, Zr and Hf generate the aspired alternating mass distribution. By rotating the substrate in between simultaneously burning cathodes, significant film thicknesses can be achieved by sputter deposition.

Experimental charge density determination in iso-structural Tellurides: Hf0.85GeTe4 and ZrGeTe4

International Nuclear Information System (INIS)

Israel, S.; Saravana Kumar, S.; Sheeba, R.A.J.R.; Saravanan, R.

2012-01-01

Hf 0.85 GeTe 4 is isostructural with stoichiometric ZrGeTe 4 and their crystal structure adopts a two-dimensional layered structure, each layer being composed of two unique one-dimensional chains of face sharing Hf/Zr-centered bicapped trigonal prisms and corner sharing Ge- centered tetrahedra. These layers stack on top of each other to complete the three-dimensional structure with undulating van der Waals gaps. Single crystal XRD is used for the refinement of the structural parameters. The space group Cmc2 1 was considered and the structure was the refined using the harmonic model by the software called JANA2006. The refined structure factors were then subsequently used in MEM (Maximum Entropy Method) technique for the construction of the charge density in the unit cell using software called PRIMA and then visualized with the help of visualization software called VESTA

Thermoelectric and Structural Properties of Zr-/Hf-Based Half-Heusler Compounds Produced at a Large Scale

Science.gov (United States)

Zillmann, D.; Waag, A.; Peiner, E.; Feyand, M.-H.; Wolyniec, A.

2018-02-01

The half-Heusler (HH) systems are promising candidates for thermoelectric (TE) applications since they have shown high figures of merit ( zT) of ˜ 1, which are directly related to the energy conversion efficiency. To use HH compounds for TE devices, the materials must be phase-stable at operating temperatures up to 600°C. Currently, only a few HH compositions are available in large quantities. Hence, we focus on the TE and structural properties of three commercially available Zr-/Hf-based HH compounds in this publication. In particular, we evaluate the thermal conductivities and the figures of merit and critically discuss uncertainties and propagation error in the measurements. We find thermal conductivities of less than 6.0 W K^{-1}m^{-1} for all investigated materials and notably high figures of merit of 0.93 and 0.60 for n- and p-type compounds, respectively, at 600°C. Additionally, our investigations reveal that the grain structures of all materials also contain secondary phases like HfO2, Sn-Ni and Ti-Zr-Sn rich phases while an additional SnO_2 phase was found following several hours of harsh heat treatment at 800°C.

Enhanced arsenic removal from water by hierarchically porous CeO₂-ZrO₂ nanospheres: role of surface- and structure-dependent properties.

Science.gov (United States)

Xu, Weihong; Wang, Jing; Wang, Lei; Sheng, Guoping; Liu, Jinhuai; Yu, Hanqing; Huang, Xing-Jiu

2013-09-15

Arsenic contaminated natural water is commonly used as drinking water source in some districts of Asia. To meet the increasingly strict drinking water standards, exploration of efficient arsenic removal methods is highly desired. In this study, hierarchically porous CeO₂-ZrO₂ nanospheres were synthesized, and their suitability as arsenic sorbents was examined. The CeO₂-ZrO₂ hollow nanospheres showed an adsorption capacity of 27.1 and 9.2 mg g(-1) for As(V) and As(III), respectively, at an equilibrium arsenic concentration of 0.01 mg L(-1) (the standard for drinking water) under neutral conditions, indicating a high arsenic removal performance of the adsorbent at low arsenic concentrations. Such a great arsenic adsorption capacity was attributed to the high surface hydroxyl density and presence of hierarchically porous network in the hollow nanospheres. The analysis of Fourier transformed infrared spectra and X-ray photoelectron spectroscopy demonstrated that the adsorption of arsenic on the CeO₂-ZrO₂ nanospheres was completed through the formation of a surface complex by substituting hydroxyl with arsenic species. In addition, the CeO₂-ZrO₂ nanospheres were able to remove over 97% arsenic in real underground water with initial arsenic concentration of 0.376 mg L(-1) to meet the guideline limit of arsenic in drinking water regulated by the World Health Organization without any pre-treatment and/or pH adjustment. Copyright © 2013 Elsevier B.V. All rights reserved.

Thermoelectric Performance of the MXenes M2CO2 (M = Ti, Zr, or Hf)

KAUST Repository

Gandi, Appala

2016-02-21

We present the first report in which the thermoelectric properties of two-dimensional MXenes are calculated by considering both the electron and phonon transport. Specifically, we solve the transport equations of the electrons and phonons for three MXenes, M2CO2, where M = Ti, Zr, or Hf, in order to evaluate the effect of the metal M on the thermoelectric performance. The lattice contribution to the thermal conductivity, obtained from the phonon life times, is found to be lowest in Ti2CO2 and highest in Hf2CO2 in the temperature range from 300 K to 700 K. The highest figure of merit is predicted for Ti2CO2 . The heavy mass of the electrons due to flat conduction bands results in a larger thermopower in the case of n-doping in these compounds.

Influence of Zr and Ce doping on electromagnetic properties of (Gd,Y)-Ba-Cu-O superconducting tapes fabricated by metal organic chemical vapor deposition

International Nuclear Information System (INIS)

Selvamanickam, V.; Chen, Y.; Xie, J.; Zhang, Y.; Guevara, A.; Kesgin, I.; Majkic, G.; Martchevsky, M.

2009-01-01

(Gd,Y)Ba 2 Cu 3 O x tapes have been fabricated by metal organic chemical vapor deposition (MOCVD) with Zr-doping levels of 0-15 mol.% and Ce doping levels of 0-10 mol.% in 0.4 μm thick films. The critical current density (J c ) of Zr-doped samples at 77 K, 1 T applied in the orientation of H -parallel c is found to increase with Zr content and shows a maximum at 7.5% Zr doping. The 7.5% Zr-doped sample exhibits a critical current density (J c ) of 0.95 MA/cm 2 at H -parallel c which is more than 70% higher than the J c of the undoped sample. The peak in J c at H -parallel c is 83% of that at H -parallel a-b in the 7.5% Zr-doped sample which is more than twice as that in the undoped sample. Superconducting transition temperature (T c ) values as high as about 89 K have been achieved in samples even with 15% Zr and 10% Ce. Ce-doped samples with and without Ba compensation are found to exhibit substantially different J c values as well as angular dependence characteristics.

Influence of Zr and Ce doping on electromagnetic properties of (Gd,Y)-Ba-Cu-O superconducting tapes fabricated by metal organic chemical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Selvamanickam, V., E-mail: selva@uh.ed [Department of Mechanical Engineering and Texas Center for Superconductivity, University of Houston, 4800 Calhoun Rd., Houston, TX 77204-4006 (United States); Chen, Y.; Xie, J. [SuperPower Inc., 450 Duane Ave., Schenectady, NY 12304 (United States); Zhang, Y.; Guevara, A.; Kesgin, I.; Majkic, G. [Department of Mechanical Engineering and Texas Center for Superconductivity, University of Houston, 4800 Calhoun Rd., Houston, TX 77204-4006 (United States); Martchevsky, M. [SuperPower Inc., 450 Duane Ave., Schenectady, NY 12304 (United States)

2009-12-01

(Gd,Y)Ba{sub 2}Cu{sub 3}O{sub x} tapes have been fabricated by metal organic chemical vapor deposition (MOCVD) with Zr-doping levels of 0-15 mol.% and Ce doping levels of 0-10 mol.% in 0.4 mum thick films. The critical current density (J{sub c}) of Zr-doped samples at 77 K, 1 T applied in the orientation of H -parallel c is found to increase with Zr content and shows a maximum at 7.5% Zr doping. The 7.5% Zr-doped sample exhibits a critical current density (J{sub c}) of 0.95 MA/cm{sup 2} at H -parallel c which is more than 70% higher than the J{sub c} of the undoped sample. The peak in J{sub c} at H -parallel c is 83% of that at H -parallel a-b in the 7.5% Zr-doped sample which is more than twice as that in the undoped sample. Superconducting transition temperature (T{sub c}) values as high as about 89 K have been achieved in samples even with 15% Zr and 10% Ce. Ce-doped samples with and without Ba compensation are found to exhibit substantially different J{sub c} values as well as angular dependence characteristics.

A new type of Nb (Ta)-Zr(Hf)-REE-Ga polymetallic deposit in the late Permian coal-bearing strata, eastern Yunnan, southwestern China: Possible economic significance and genetic implications

Energy Technology Data Exchange (ETDEWEB)

Dai, Shifeng; Wang, Xibo; Luo, Yangbing; Song, Zhentao; Ren, Deyi [State Key Laboratory of Coal Resources and Safe Mining, China University of Mining and Technology, Beijing 100083 (China); Zhou, Yiping; Zhang, Mingquan; Wang, Jumin; Song, Xiaolin; Yang, Zong [Yunnan Institute of Coal Geology Prospection, Kunming 650218 (China); Jiang, Yaofa [Xuzhou Institute of Architectural Technology, Xuzhou 221116 (China)

2010-07-01

This paper describes a new type of Nb(Ta)-Zr(Hf)-REE-Ga polymetallic deposit of volcanic origin in the late Permian coal-bearing strata of eastern Yunnan, southwestern China. Well logging data (especially natural gamma-ray), geochemical data (high concentrations of Nb, Ta, Zr, Hf, REE, and Ga) and mineralogical compositions (Nb(Ta)-, Zr(Hf)-, or REE-bearing minerals rarely observed), together with the volcanic lithological characteristics indicate that there are thick (1-10 m, mostly 2-5 m) ore beds in the lower Xuanwei Formation (late Permian) in eastern Yunann of southwestern China. The ore beds are highly enriched in (Nb,Ta){sub 2}O{sub 5} (302-627 ppm), (Zr,Hf)O{sub 2} (3805-8468 ppm), REE (oxides of La-Lu + Y) (1216-1358 ppm), and Ga (52.4-81.3 ppm). The ore beds are mainly composed of quartz, mixed-layer illite-smectite, kaolinite, berthierine, and albite. Four types of ore beds in the study area were identified, namely, clay altered volcanic ash, tuffaceous clay, tuff, and volcanic breccia. Preliminary studies suggest that the high concentrations of otherwise rare metals were mainly derived from the alkalic pyroclastic rocks. The modes of occurrence, spatial distribution, and enrichment mechanism of the rare metals, however, require further study. (author)

Structure and oxygen storage capacity of Pr-doped Ce0.26Zr0.74O2 mixed oxides

Institute of Scientific and Technical Information of China (English)

RAN Rui; WENG Duan; WU Xiaodong; FAN Jun; WANG Lei; WU Xiaodi

2011-01-01

Binary Ce-Zr (CZ),Pr-Zr (PZ) and ternary Ce-Zr-Pr (CZP) mixed oxides were prepared by an ammonia-aided co-precipitation method,and were aged in a steam/air flow at 1050 ℃.X-my diffraction (XRD),Raman spectra,X-photon spectra (XPS) and CO temperature programmed reduction (TPR) were carried out to characterize the micro-structure and reducibility of catalysts.The oxygen storage capacity (OSC) was evaluated with CO serving as probe gas.The results showed that a pseudo cubic structure was formed for the Zr-rich ceria-zirconia mixed oxides with Pr doping.The insertion of Pr prevented the phase segregation of the mixed oxides during the hydrothermal ageing.The Pr doped samples showed better redox performances in comparison with CZ,and the sample doped with 5 wt.％ Pr showed the most remarkably promoted dynamic oxygen storage capacity.This phenomenon was closely related to both the reducibility and oxygen mobility of the mixed oxides.The introduction of praseodymium into ceria-zirconia could accelerate the oxygen migration by increasing the amount of oxygen vacancies,although it was difficult for Pr3+ ions themselves to participate in the oxygen exchange process.

Influence of Ce 0.68 Zr 0.32 O 2 solid solution on depositing ...

Indian Academy of Sciences (India)

Home; Journals; Bulletin of Materials Science; Volume 29; Issue 1. Influence of Ce0.68Zr0.32O2 solid solution on depositing -alumina washcoat on FeCrAl foils. Mei-Qing Shen Li-Wei Jia Wen-Long Zhou Jun Wang Ying Huang. Composites Volume 29 Issue 1 February 2006 pp 73-76 ...

Half-Heusler (TiZrHf)NiSn Unileg Module with High Powder Density.

Science.gov (United States)

Populoh, Sascha; Brunko, Oliver C; Gałązka, Krzysztof; Xie, Wenjie; Weidenkaff, Anke

2013-03-27

(TiZrHf)NiSn half-Heusler compounds were prepared by arc melting and their thermoelectric properties characterized in the temperature range between 325 K and 857 K, resulting in a Figure of Merit ZT ≈ 0.45. Furthermore, the prepared samples were used to construct a unileg module. This module was characterized in a homemade thermoelectric module measurement stand and yielded 275 mW/cm² and a maximum volumetric power density of 700 mW/cm³. This was reached using normal silver paint as a contacting material; from an improved contacting, much higher power yields are to be expected.

Catalyst Deactivation and Regeneration in Low Temperature Ethanol Steam Reforming with Rh/CeO2-ZrO2 Catalysts

Energy Technology Data Exchange (ETDEWEB)

Roh, Hyun-Seog; Platon, Alex; Wang, Yong; King, David L.

2006-08-01

Rh/CeO2-ZrO2 catalysts with various CeO2/ZrO2 ratios have been applied to H2 production from ethanol steam reforming at low temperatures. The catalysts all deactivated with time on stream (TOS) at 350 C. The addition of 0.5% K has a beneficial effect on catalyst stability, while 5% K has a negative effect on catalytic activity. The catalyst could be regenerated considerably even at ambient temperature and could recover its initial activity after regeneration above 200 C with 1% O2. The results are most consistent with catalyst deactivation due to carbonaceous deposition on the catalyst.

A comparison of the microstructure and high temperature tensile properties of a novel P/M Mo-Hf-Zr-Ta-C alloy and TZM

International Nuclear Information System (INIS)

Warren, J.; Reznikov, G.

2001-01-01

The microstructure and elevated temperature quasi-static tensile yield and ultimate strength observed in a novel, forged Mo-based alloy (Mo-0.25 Hf-0.25 Zr-0.25 Ta-0.025 C) has been analyzed and compared to a standard forged TZM composition (Mo-0.50 Ti-0.08 Zr-0.02 C). The novel material exhibits the desirable forging characteristics typical of the widely used TZM composition yet possess a higher ultimate strength and 0.2 % offset yield strength in both the stress-relieved and recrystallized conditions over a 400 o -1200 o C temperature range. The greater strength measured in the novel composition has been attributed to the combined effects of precipitation of Hf, Zr and Mo-(carbide) precipitates that strengthen the matrix in the classical Orowan fashion and improved resistance to recrystallization after high temperature exposure. Elevated temperature creep behavior, not addressed in the study presented here, will be reported on in a subsequent analysis. (author)

Photocatalytic performance of TiO2 catalysts modified by H3PW12O40, ZrO2 and CeO2

Institute of Scientific and Technical Information of China (English)

CAI Tiejun; LIAO Yuchao; PENG Zhenshan; LONG Yunfei; WEI Zongyuan; DENG Qian

2009-01-01

The binary composite photo-catalysts CeO2/TiO2, ZrO2/TiO2 and the ternary composite photo-catalysts H3PW12O40-CeO2/TiO2,H2PW12O40-ZrO2/TiO2 were prepared by sol-gel method. The catalysts were characterized by thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photocatalyfic elimination of methanol was used as model reaction to evaluate the photocatalytic activity of the composite catalysts under ultraviolet light irradiation. The effects of doped content, activation temperature, time, initial concentration of methanol and gas flow rate on the catalytic activity were investigated. The results showed that after doping a certain amount of CeO2 and ZrO2, crystaniTation process of TiO2 was restrained, particles of catalysts are smaller and more uniform. Doping ZrO2 not only significantly improved the catalytic activity, but also increased thermal stability. Doping H3PW12O40 also enhanced the catalytic activity. The catalytic activities of binary and ternary composite photocatalysts were significantly higher than tin-doped TiO2. The dynamics law of photocatalytic reaction over the binary CeO2/TiO2 and ZrO2/TiO2 catalysts has been studied. The activation energy 15.627 and 15.631 kJ/mol and pre-exponential factors 0.5176 and 0.9899 s-1 over each corresponding catalyst were obtained. This reaction accords to the first order dynamics law.

Hf Isotope Evidence for Subducted Basalt and Sediment Contributions to the Eastern Trans-Mexican Volcanic Belt

Science.gov (United States)

Cai, Y.; Tuena, A. G.; Capra, L.; Straub, S. M.; Goldstein, S. L.; Langmuir, C. H.

2005-12-01

Magmas generated at thick crust continental arcs often have enriched continental crust-like trace element patterns and Pb-Sr-Nd isotope ratios that are intermediate to both upper mantle and crustal compositions. Thus it is difficult to distinguish between contributions from (a) the subducted basalt and the upper mantle wedge, and (b) subducted sediment and the continental crust. These issues have been the focus of major controversy. Here we show evidence for subduction contributions to lavas in a classic thick crust environment. In Eastern Trans-Mexican Volcanic Belt, the upper continental crust is 30 km to 45 km thick. However, primitive mafic lavas erupt on many sites across the arc. We have analyzed the subducting sediments as represented by DSDP 487, located seaward of the trench, where the lower third of the sediment column has strongly hydrothermal pelagic features and the upper two-thirds is composed of terrigenous sediments. The pelagic sediments have distinctive features that could be used to identify a subduction component in the volcanics, including high REE/Hf, negative Ce anomalies, and Nd-Hf isotopes that lie on the "seawater array" and offset from the "mantle-crust" array. We have focused on a unique series of lavas from volcano Nevado de Toluca, located southwest of Mexico City. These lavas show negative Ce anomalies coupled with low REE/Hf and Zr/Nd ratios. Hf-Nd isotope ratios show a shallow trend compared to the mantle-crust array, consistent with a pelagic component. In addition, Hf isotopes show a striking positive correlation with Ce anomalies that trend toward the pelagic sediment compositions. These and other observations provide clear evidence for a component from subducted sediment in the lavas. In addition, there is a negative correlation of Lu/Hf and Hf isotopes that requires a mixing endmember with MORB-like Hf isotope ratios but with lower than MORB Lu/Hf. This indicates a melt from eclogitic subducted basalt. Compared to other

Measurement of formation cross sections producing short-lived nuclei by 14 MeV neutrons. Pr, Ba, Ce, Sm, W, Sn, Hf

International Nuclear Information System (INIS)

Murahira, S.; Satoh, Y.; Honda, N.; Shibata, M.; Yamamoto, H.; Kawade, K.; Takahashi, A.; Iida, T.

1996-01-01

Thirteen neutron activation cross sections for (n,2n), (n,p), (n,np) and (n,α) reactions producing short-lived nuclei with half-lives between 56 s and 24 min were measured in the energy range from 13.4 MeV to 14.9 MeV for Pr, Ba, Ce, Sm, W, Sn and Hf. The cross sections of 179 Hf(n,np) 178m Lu and 180 Hf(n,p) 180 Lu were measured for the first time. (author)

Partial oxidation of methane to syngas on Rh/Al{sub 2}O{sub 3} and Rh/Ce-ZrO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Raquel L.; Bitencourt, Isabela G.; Passos, Fabio B., E-mail: fbpassos@vm.uff.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e Petroleo

2013-01-15

The partial oxidation of methane with {gamma}-Al{sub 2}O{sub 3}-, CeO{sub 2}-, ZrO{sub 2}- and Ce-ZrO{sub 2}-supported rhodium catalysts was investigated. DRIFTS (diffuse reflectance infrared spectroscopy) measurements of adsorbed CO showed the formation of different rhodium species on different supports, which influenced the dispersion of the metal. The effects of the metal dispersion, oxygen storage capacity on the activity of these catalysts for the partial oxidation of methane are discussed. (author)

Electron dominated thermoelectric response in MNiSn (M: Ti, Zr, Hf) half-Heusler alloys

KAUST Repository

Gandi, Appala

2016-05-09

We solve the transport equations of the electrons and phonons to understand the thermoelectric behaviour of the technologically important half-Heusler alloys MNiSn (M: Ti, Zr, Hf). Doping is simulated within the rigid band approximation. We clarify the origin of the electron dominated thermoelectric response and determine the carrier concentrations with maximal figures of merit. The phonon mean free path is studied to calculate the grain size below which grain refinement methods can enforce ballistic heat conduction to enhance the figure of merit. © The Owner Societies 2016.

Electron dominated thermoelectric response in MNiSn (M: Ti, Zr, Hf) half-Heusler alloys

KAUST Repository

Gandi, Appala; Schwingenschlö gl, Udo

2016-01-01

We solve the transport equations of the electrons and phonons to understand the thermoelectric behaviour of the technologically important half-Heusler alloys MNiSn (M: Ti, Zr, Hf). Doping is simulated within the rigid band approximation. We clarify the origin of the electron dominated thermoelectric response and determine the carrier concentrations with maximal figures of merit. The phonon mean free path is studied to calculate the grain size below which grain refinement methods can enforce ballistic heat conduction to enhance the figure of merit. © The Owner Societies 2016.

Phase diagrams for pseudo-binary carbide systems TiC-NbC, TiC-TaC, ZrC-NbC, ZrC-TaC and HfC-TaC

International Nuclear Information System (INIS)

Gusev, A.I.

1985-01-01

Parameters of interaction and energy of mutual exchange in the liquid and solid phases of pseudobinary TiC-NbC, TiC-TaC, ZrC-NbC, ZrC-TaC, HfC-TaC systems are calculated with account of dependence on composition and temperature. Positions of liquidus-solidus phase boundaries on the phase diagrams of the mentioned systems are calculated on the basis of the determined mutual exchange energies in approximati.on of subregular solutions. The existance of latent decomposition ranges in the solid phase on the phase diagrams of the investgated systems is established

Low temperature plasma-enhanced ALD TiN ultrathin films for Hf{sub 0.5}Zr{sub 0.5}O{sub 2}-based ferroelectric MIM structures

Energy Technology Data Exchange (ETDEWEB)

Kozodaev, M.G.; Chernikova, A.G.; Markeev, A.M. [Moscow Institute of Physics and Technology, Institutsky Lane 9, Dolgoprudny, Moscow Region 141700 (Russian Federation); Lebedinskii, Y.Y. [Moscow Institute of Physics and Technology, Institutsky Lane 9, Dolgoprudny, Moscow Region 141700 (Russian Federation); National Research Nuclear University MEPhI, Moscow Engineering Physics Institute, Kashirskoye Shosse 31, 115409 Moscow (Russian Federation); Polyakov, S.N. [Technological Institute for Superhard and Novel Carbon Materials, Tsentral' naya str. 7a, 142190, Troitsk, Moscow (Russian Federation)

2017-06-15

In this work chemical and electrical properties of TiN films, grown by low temperature plasma-enhanced atomic layer deposition (PE-ALD) process from TiCl{sub 4} and NH{sub 3}, were investigated. Electrical resistivity as low as 250 μOhm x cm, as well as the lowest Cl impurity content, was achieved at 320 C. Full-ALD Hf{sub 0.5}Zr{sub 0.5}O{sub 2}-based metal-ferroelectric-metal capacitor with TiN electrodes was fabricated and its electrical properties were investigated. It was also shown that the proposed PE-ALD process provides an early film continuity, which was confirmed by ultrathin fully continuous film growth. Such ultrathin (3 nm) and fully continuous TiN film was also successfully implemented as the top electrode to Hf{sub 0.5}Zr{sub 0.5}O{sub 2}-based ferroelectric capacitor. Angle-resolved X-ray photoelectron spectroscopy (AR-XPS) was used for its thickness determination and a visible wake-up effect in underlying Hf{sub 0.5}Zr{sub 0.5}O{sub 2} layer was clearly observed. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Some observations on the synthesis and electrolytic properties of (Ba1-xCax (M0.9Y0.1O3, M = Ce, Zr-based samples modified with calcium

Directory of Open Access Journals (Sweden)

Dudek Magdalena

2016-03-01

Full Text Available In this paper, the impact of partial substitution of calcium for barium in (Ba1-xCax (M0.9Y0.1 O3, M = Ce, Zr on physicochemical properties of the powders and sintered samples was investigated. The powders, with various contents of calcium (x = 0, 0.02, 0.05, 0.1, were prepared by means of thermal decomposition of organometallic precursors containing EDTA. All of the BaCeO3-based powders synthesised at 1100 °C were monophasic with a rhombohedral structure, however, completely cubic BaZrO3-based solid solutions were obtained at 1200 °C. A study of the sinterability of BaZr0.9Y0.1O3 and BaCe0.9Y0.1O3-based pellets was performed under non-isothermal conditions within a temperature range of 25 to 1200 °C. The partial substitution of barium for calcium in the (Ba1-xCax (M0.9Y0.1 O3, M = Ce, Zr solid solution improved the sinterability of the samples in comparison to the initial BaCe0.9Y0.1O3 or BaZr0.9Y0.1O3. The relative density of calcium-modified BaCe0.9Y0.1O3-based samples reached approximately 95 to 97 % after sintering at 1500 °C for 2 h in air. The same level of relative density was achieved after sintering calcium-modified BaZr0.9Y0.1O3 at 1600 °C for 2 h. Analysis of the electrical conductivity from both series of investigated materials showed that the highest ionic conductivity, in air and wet 5 % H2 in Ar, was attained for the compositions of x = 0.02 to 0.05 (Ba1-xCax(M0.9Y0.1O3, M = Zr, Ce. The oxygen reduction reaction on the interface Pt│BaM0.9Y0.1O3, M = Ce, Zr was investigated using Pt microelectrodes. Selected samples of (Ba1-xCax (M0.9Y0.1O3, M = Zr, Ce were tested as ceramic electrolytes in hydrogen-oxygen solid oxide fuel cells operating at temperatures of 700 to 850 °C.

Methanol reformer with water vapor and oxygen in catalysts of Cu/CeO2-ZrO2 to generate H2

International Nuclear Information System (INIS)

Aguila M, M.M.

2007-01-01

The environmental pollution is one of the problems more important to solve in the present time because its affect the quality of the alive beings' life. For such a reason alternatives have been looked for to diminish the percentage of air pollution (NO x , CO x , SO x , etc.), for they have been developed it the well-known catalytic converters. Another possibility is the energy use through fuel cells in vehicles using H 2 as fuel free of CO (smaller concentration to 10 ppm). Processes exist for the production of H 2 starting from the methanol and in this work the one was used reformed of methanol with water vapor and oxygen (OSRM) as the main reaction of this work. The primordial objective of this work consists on studying the catalytic properties of the copper (Cu) supported in mixed oxides (ZrO 2 -CeO 2 ) in the reaction of having reformed of methanol with water vapor and oxygen for the production of H 2 . Zirconia is synthesized (ZrO 2 ) and mixed oxides ZrO 2 -CeO 2 (with different relationship Zr/Ce) for the sol-gel method and the one cerium oxide (CeO 2 ) by direct combustion of the cerium nitrate. The oxides were stabilized thermally at 600 C by 5h. The catalysts were prepared by classic impregnation using copper acetate, the nominal concentration was of 3% in weight. The catalysts were roasted at 350 C and later on reduced in flow from H 2 to 350 C for 1h. The characterization of the catalytic materials is carried out through different techniques as: adsorption-desorption of nitrogen to determine the surface area BET, scanning electron microscopy (SEM) to determine the final morphology of the catalysts, X-ray diffraction (XRD) to identify the crystalline phases of the catalytic materials and reduction to programmed temperature (TPR) to evidence the interaction metal-support. The catalytic properties of the catalysts were studied in the reaction CH 3 OH + H 2 O + O 2 , to determine the activity and selectivity. The surface area of the mixed oxides was

Thermoluminescence induced by UV radiation in ZrO2-La2O3 and ZrO2-CeO2 mixed systems

International Nuclear Information System (INIS)

Estrada G, R.; Salas C, P.; Mendoza A, D.; Gonzalez, P.R.

2002-01-01

Nowadays, the development of catalytic materials by means of pure or mixed oxides mainly as TiO 2 , Al 2 O 3 , ZrO 2 , La 2 O 3 and CeO 2 used as support or active phases, are widely used in oxidation-reduction reactions in the chemical industry and in petroleum refining processes. the cerium and lanthanum oxides in zircon, have been studied recently in processes for reduction of pollutant gases (SO x , NO x , etc.). They result very interesting for resolving the problems of environmental pollution. Moreover, it has been observed that some of these materials are highly sensitive to ultraviolet radiation (UV), characteristic that can be took in advantage for detecting this type of radiation. In this work the preliminary obtained results on the thermoluminescent response (Tl) induced by the UV radiation in ZrO 2 -La 2 O 3 and ZrO 2 -CeO 2 mixed systems obtained by the sol-gel method are presented. The results show that the first system has a high sensitivity to UV radiation with a Tl curve composed by three peaks, two ones of greater intensity located in 70 and 140 Centigrade degrees. Likewise it was observed that for both materials, the peak located at low temperature is fadeout in few minutes after irradiation, while that the second one peak presented very good stability, resulting promising for dosimetric applications in UV radiation fields. (Author)

The Effect of Acidic and Redox Properties of V2O5/CeO2-ZrO2 Catalysts in Selective Catalytic Reduction of NO by NH3

DEFF Research Database (Denmark)

Putluru, Siva Sankar Reddy; Riisager, Anders; Fehrmann, Rasmus

2009-01-01

V2O5 supported ZrO2 and CeO2–ZrO2 catalysts were prepared and characterized by N2 physisorption, XRPD, TPR, and NH3-TPD methods. The influence of calcination temperature from 400 to 600 °C on crystallinity, acidic and redox properties were studied and compared with the catalytic activity...... in the selective catalytic reduction (SCR) of NO with ammonia. The surface area of the catalysts decreased gradually with increasing calcination temperature. The SCR activity of V2O5/ZrO2 catalysts was found to be related with the support crystallinity, whereas V2O5/CeO2–ZrO2 catalysts were also dependent...... on acidic and redox properties of the catalyst. The V2O5/CeO2–ZrO2 catalysts showed high activity and selectivity for reduction of NO with NH3....

Electrical and structural properties of group-4 transition-metal nitride (TiN, ZrN, and HfN) contacts on Ge

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Keisuke; Nakashima, Hiroshi, E-mail: nakasima@astec.kyushu-u.ac.jp [Art, Science and Technology Center for Cooperative Research, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580 (Japan); Noguchi, Ryutaro; Wang, Dong [Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580 (Japan); Mitsuhara, Masatoshi; Nishida, Minoru [Department of Engineering Sciences for Electronics and Materials, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580 (Japan); Hara, Toru [National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)

2015-09-21

Electrical and structural properties were investigated for group-4 transition-metal nitride contacts on Ge (TiN/Ge, ZrN/Ge, and HfN/Ge), which were prepared by direct sputter depositions using nitride targets. These contacts could alleviate the intrinsic Fermi-level pinning (FLP) position toward the conduction band edge. It was revealed that this phenomenon is induced by an amorphous interlayer (a-IL) containing nitrogen atoms at the nitride/Ge interfaces. The strength of FLP alleviation positively depended on the thickness of a-IL. TiN/Ge and ZrN/Ge contacts with ∼2 nm-thick a-ILs showed strong FLP alleviations with hole barrier heights (Φ{sub BP}) in the range of 0.52–56 eV, and a HfN/Ge contact with an ∼1 nm-thick a-IL showed a weaker one with a Φ{sub BP} of 0.39 eV. However, TaN/Ge contact without a-IL did not show such FLP alleviation. Based on the results of depth distributions for respective elements, we discussed the formation kinetics of a-ILs at TiN/Ge and ZrN/Ge interfaces. Finally, we proposed an interfacial dipole model to explain the FLP alleviation.

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

Science.gov (United States)

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.

Thermoelectric Properties of the XCoSb (X: Ti,Zr,Hf) Half-Heusler Alloys

KAUST Repository

Gandi, Appala

2017-09-18

We investigate the thermoelectric properties of the half-Heusler alloys XCoSb (X: Ti,Zr,Hf) by solving Boltzmann transport equations and discuss them in terms of the electronic band structure. The rigid band approximation is employed to address the effects of doping. While many half-Heuser alloys show excellent thermoelectric performance, the materials under study are special by supporting both n- and p-doping. We identify the reasons for this balanced thermoelectric transport and explain why experimentally p-doping is superior to n-doping. We also determine the spectrum of phonon mean free paths to guide grain refinement methods to enhance the thermoelectric figure of merit.

Thermal and electric conductivity of Cu50Zr35Ti8Hf5Nb2 volume amorphous alloy

International Nuclear Information System (INIS)

Gavrenko, O.A.; Merisov, B.A.; Mikhajlova, T.N.; Molokanov, V.V.; Sologubenko, A.V.; Khadzhaj, G.Ya.

1996-01-01

The temperature dependences of thermal conductivity and electric resistance of the Cu 50 Zr 35 Ti 8 Hf 5 Nb 2 volume amorphous alloy experimentally studied within the temperature range of 1.8-240 K. The temperature dependence of electrical resistance is well described by the ratio, taking into account the electron scattering on the phonons and in the two-level systems

First principles study the stability and mechanical properties of MC (M = Ti, V, Zr, Nb, Hf and Ta) compounds

International Nuclear Information System (INIS)

Liu, YangZhen; Jiang, YeHua; Zhou, Rong; Feng, Jing

2014-01-01

Highlights: • The stability and elastic constants of carbides are studied by first principles. • The rules of modulus of MC compounds are discussed by their group. • The hardness of carbides is estimated in this paper at the first time. -- Abstract: The first principles calculations based on density functional theory (DFT) were adopted to investigate the stability, elastic constants, chemical bonding, Debye temperature and hardness of MC (M = Ti, V, Zr, Nb, Hf and Ta) compounds. The cohesive energy and formation enthalpy of these carbides indicate that they are thermodynamically stable structures. The population analysis was used to discuss the chemical bonding of these carbides. The elastic constants and moduli of these compounds were calculated. The results show that the bulk moduli of the carbides of transition metals from the fourth group (TiC, ZrC, HfC) are lower than the fifth group (VC, NbC, TaC). However, the Young’s moduli of the carbides from fourth group are higher than the fifth group. The hardness of compounds was estimated using a semi empirical hardness theory

Radiation induced colour centers and damage in YALO.sub.3./sub.:Ce and YAlO.sub.3./sub.:Ce, Zr scintillators

Czech Academy of Sciences Publication Activity Database

Mareš, Jiří A.; Nikl, Martin; Mihóková, Eva; Solovieva, Natalia; Blažek, K.; Nejezchleb, K.; Malý, P.; Pejchal, J.; Mucka, V.; Pospíšil, M.; Vedda, A.; Martini, M.; Baccaro, S.

2002-01-01

Roč. 157, - (2002), s. 677-681 ISSN 1042-0150 R&D Projects: GA ČR GA202/01/0753 Grant - others:NATO(XX) SfP973510 Institutional research plan: CEZ:AV0Z1010914 Keywords : YAlO 3 :Ce scintillator * Zr 4+ co-doping * gamma-ray irradiation * defect states * colour centers * electron and hole Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.290, year: 2002

Titrimetric determination of Zr, Hf, Sn, Ta and rare earths in binary oxide systems

International Nuclear Information System (INIS)

Flyantikova, G.V.; Chekirda, T.N.; Lasovskaya, O.N.; Migun, N.P.

1989-01-01

Proximate method of titrimetric determination of oxides of Zr(4), Hf(4), Sn(4), Ta(5) and rare earths (La, Lu, Nd, Eu, Yb, Y) in binary systems (BS) with high accuracy was developed. A study was made on conditions of decomposition and dissolution of BS by means of their treatment by the mixture of solutions of concentrated sulfuric acid and ammonium sulfate during 2h boiling eith successive complexonometric determination of their components by direct EDTA titration in the presence of xylenol orange. The relative standard deviation when titrating 0.3-9.7mg oxides in BS does not exceed 0.02

A comparative study of charge trapping in HfO{sub 2}/Al{sub 2}O{sub 3} and ZrO{sub 2}/Al{sub 2}O{sub 3} based multilayered metal/high-k/oxide/Si structures

Energy Technology Data Exchange (ETDEWEB)

Spassov, D., E-mail: d_spassov@abv.bg [Institute of Solid State Physics, Bulgarian Academy of Sciences, Tzarigradsko Chaussee 72, Sofia 1784 (Bulgaria); Skeparovski, A. [Institute of Physics, Faculty of Natural Sciences and Mathematics, University “Ss. Cyril and Methodius”, Arhimedova 3, 1000 Skopje (Macedonia, The Former Yugoslav Republic of); Paskaleva, A. [Institute of Solid State Physics, Bulgarian Academy of Sciences, Tzarigradsko Chaussee 72, Sofia 1784 (Bulgaria); Novkovski, N. [Institute of Physics, Faculty of Natural Sciences and Mathematics, University “Ss. Cyril and Methodius”, Arhimedova 3, 1000 Skopje (Macedonia, The Former Yugoslav Republic of)

2016-09-01

The electrical properties of multilayered HfO{sub 2}/Al{sub 2}O{sub 3}/HfO{sub 2}/SiO{sub 2} and ZrO{sub 2}/Al{sub 2}O{sub 3}/ZrO{sub 2}/SiO{sub 2} metal-oxide semiconductor capacitors were investigated in order to evaluate the possibility of their application in charge-trapping non-volatile memory devices. The stacks were deposited by reactive radiofrequency magnetron sputtering on Si substrates with thermal SiO{sub 2} with a thickness ranging from 2 to 5 nm. Both types of stacks show negative initial oxide charge and its density is higher for HfO{sub 2}-based structures. Memory window up to 6V at sweeping voltage range of ± 16V was obtained for HfO{sub 2}-based stacks. The hysteresis in these structures is mainly due to a trapping of electrons injected from the Si substrate. The charge-trapping properties of ZrO{sub 2}-based samples are compromised by the high leakage currents and the dielectric breakdown. The conduction through the capacitors at low applied voltages results from hopping of thermally excited electrons from one isolated state to another. The energy depth of the traps participating in the hopping conduction was determined as ~ 0.7 eV for the HfO{sub 2}-based layers and ~ 0.6 eV for ZrO{sub 2}-based ones, originating from negatively charged oxygen vacancies. At high electric fields, the current voltage characteristics were interpreted in terms of space charge limited currents, Fowler–Nordheim tunneling, Schottky emission, and Poole–Frenkel mechanism. The charge retention characteristics do not depend on the thickness of the tunnel SiO{sub 2}. - Highlights: • Sputtered HfO{sub 2}/Al{sub 2}O{sub 3}/HfO{sub 2} and ZrO{sub 2}/Al{sub 2}O{sub 3}/ZrO{sub 2} charge-trapping layers were studied. • HfO{sub 2}/Al{sub 2}O{sub 3}/HfO{sub 2} stacks show memory window up to 6 V and good retention times. • Negatively charged oxygen vacancies were identified as main defects in the stacks. • Electrical breakdown compromise the charge-trapping properties

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

Science.gov (United States)

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

2011-01-01

Atomistic Green-Kubo simulations are performed to evaluate the lattice thermal conductivity for single crystals of the ultra high temperature ceramics ZrB2 and HfB2 for a range of temperatures. Recently developed interatomic potentials are used for these simulations. Heat current correlation functions show rapid oscillations which can be identified with mixed metal-Boron optical phonon modes. Agreement with available experimental data is good.

Application of Ce{sub x}Zr{sub 1-x}O{sub 2} catalysts for the synthesis of diethyl carbonate from ethanol and carbon dioxide

Energy Technology Data Exchange (ETDEWEB)

Prymak, I.; Kalevaru, V.N.; Kollmorgen, P.; Wohlrab, S. [Leibniz-Institut fuer Katalyse e.V. an der Universitaet Rostock (Germany); Martin, A.

2013-11-01

The direct synthesis of diethyl carbonate (DEC) from ethanol and CO{sub 2} is indeed an attractive approach from both academic and commercial points of view. In the present study, we report on the synthesis, characterization and catalytic evaluation of Ce-Zr-O solids with varying Ce/Zr ratios. The catalysts were prepared by citrate complexation method, and characterized by various techniques such as N{sub 2} adsorption (BET-SA), XRD, H{sub 2}-TPR, NH{sub 3}-TPD etc. The catalytic performance of these catalysts was evaluated towards the synthesis of DEC from ethanol and CO{sub 2} under suitable reaction conditions. According to thermodynamic data, the reaction is favorable at low reaction temperatures and high reaction pressures. Thus, the catalytic experiments were carried out in a continuous mode using a plug-flow reactor that was operated up to 200 bar and ca. 200 C. The effect of the reaction temperature (30-180 C) and pressure (80-180 bar) on the yield of DEC was investigated. Among various catalysts tested, Ce-Zr-O catalyst with 80 mol% Ce content has exhibited a relatively better performance compared to all other Ce-Zr-O catalysts. DEC yield increased with increasing reaction temperature up to 140 C. The highest yield of DEC obtained from the best case was 0.7 % at 140 C and at 140 bars. Further increase in temperature to 180 C caused a decrease in the DEC formation due to thermodynamic reasons as mentioned above. The ceria proportion has shown a considerable influence on the BET surface areas and thereby catalytic activity as well. The results revealed that the redox properties as well as acidity characteristics of the solids are strongly influenced by the content of Ce in the catalysts, which in turn showed a clear impact on the catalytic performance. (orig.)

Effects of Rh on the thermoelectric performance of the p-type Zr0.5Hf0.5Co1-xRhxSb0.99Sn0.01 half-Heusler alloys

International Nuclear Information System (INIS)

Maji, Pramathesh; Takas, Nathan J.; Misra, Dinesh K.; Gabrisch, Heike; Stokes, Kevin; Poudeu, Pierre F.P.

2010-01-01

We show that Rh substitution at the Co site in Zr 0.5 Hf 0.5 Co 1-x Rh x Sb 0.99 Sn 0.01 (0≤x≤1) half-Heusler alloys strongly reduces the thermal conductivity with a simultaneous, significant improvement of the power factor of the materials. Thermoelectric properties of hot-pressed pellets of several compositions with various Rh concentrations were investigated in the temperature range from 300 to 775 K. The Rh 'free' composition shows n-type conduction, while Rh substitution at the Co site drives the system to p-type semiconducting behavior. The lattice thermal conductivity of Zr 0.5 Hf 0.5 Co 1-x Rh x Sb 0.99 Sn 0.01 alloys rapidly decreased with increasing Rh concentration and lattice thermal conductivity as low as 3.7 W/m*K was obtained at 300 K for Zr 0.5 Hf 0.5 RhSb 0.99 Sn 0.01 . The drastic reduction of the lattice thermal conductivity is attributed to mass fluctuation induced by the Rh substitution at the Co site, as well as enhanced phonon scattering at grain boundaries due to the small grain size of the synthesized materials. - Graphical abstract: Significant reduction of the lattice thermal conductivity with increasing Rh concentration in the p-type Zr 0.5 Hf 0.5 Co 1-x Rh x Sb 0.99 Sn 0.01 half-Heusler materials prepared by solid state reaction at 1173 K.

Efficient UV-emitting X-ray phosphors: octahedral Zr(PO4)6 luminescence centers in potassium hafnium-zirconium phosphates K2Hf1-xZrx(PO4)2 and KHf2(1-x)Zr2x(PO4)3

International Nuclear Information System (INIS)

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

2003-01-01

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

Analysis of sodium metal by X-ray fluorescence spectrometry (I). Determination of Hf, Mo, Nb, Ta, Ti, V and Zr; Analisis de sodio metal por espectrometria de fluorescencia de rayos X. Determinacion de Hf, Mo, Nb, Ta, Ti, V y Zr

Energy Technology Data Exchange (ETDEWEB)

Diaz-Guerra, J P

1981-07-01

A method allowing the determination of trace quantities of Hf, Mo, Nb, Ta, Ti, Vi and Zr in sodium metal previous transformation into Na{sub 2}S0{sub 4} is described. The enrichment of the impurities is performed through a coprecipitation technique in sulfuric medium by using Fe{sup 3}+ as a collector and cupferron or phenyfluorone as the precipitating reagent. The matrix influence and the best concentration of the collector (10/{mu}/ml), adequate pH (1,3 or 4, respectively) and optimum filter type (Millipore BSWP02500 or BDWP04700, respectively) have been studied, as well as the precipitation recoveries corresponding to the reagent above. It has been demonstrated the batter efficiency of the cupferron for determining all the Impurities. Detection limits range from 0.01 to 0.2 ppm., depending on the element, for samples 4 g in weight. An automatic spectrometer attached to a 16 K minicomputer and X-ray tube with a gold anode (2250-2700 W) are used. The Interferences between the lines ZrK{alpha} (2{sup n}d order) - HfL{alpha} and TiK{beta} - VK {alpha} have been studied and the respective correction coefficients have been deduced. (Author) 8 refs.

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

Science.gov (United States)

Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

2014-01-01

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values

Asymmetric diffusion of Zr, Sc and Ce, Gd at the interface between zirconia electrolyte and ceria interlayer for solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Liang, Bo, E-mail: Liangbo@gdut.edu.cn; Tao, Tao; Zhang, Silong; Huang, Yongan; Cai, Zhihong; Lu, Shenguo, E-mail: sglu@gdut.edu.cn

2016-09-15

The microstructures of cathode interlayer and elemental diffusion behaviors across the interfacial region (electrolyte/interlayer) have been characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and scanning TEM combined with energy dispersive X-ray spectroscopy (STEM-EDS). A densified film about 100 nm is locally formed at the interface of electrolyte/interlayer as the interlayer using dip-coating method and being sintered at 1200 °C. It is observed that the compositional distribution curves across the interface are asymmetric. More amount of the Zr, Sc component is detected in gadolinium-doped ceria (GDC) than that of the Ce, Gd component is detected in scandia-stabilized-zirconia (SSZ). XRD and EDS results show that the densified layer might consist of (Zr, Ce)O{sub 2}-based solid solution. The high open circuit voltage of the cell is related to the dense structure of electrolyte, while the increased activation energy in overpotential resistance is attributed to the porous structure of interlayer as well as the high resistance phases locally formed at its interface. - Highlights: • The (Ce−Zr)O{sub 2} based solid solution was locally formed at 1200 °C. • More Zr, Sc elements were detected in GDC than Ce, Gd elements in SSZ. • Zirconia nanodomain was embedded in GDC beside grain boundary. • High OCVs were achieved due to the highly dense electrolyte layer.

Enhanced arsenic removal from water by hierarchically porous CeO{sub 2}–ZrO{sub 2} nanospheres: Role of surface- and structure-dependent properties

Energy Technology Data Exchange (ETDEWEB)

Xu, Weihong; Wang, Jing; Wang, Lei [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Sheng, Guoping [Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China); Liu, Jinhuai [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Yu, Hanqing [Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China); Huang, Xing-Jiu, E-mail: xingjiuhuang@iim.ac.cn [Research Center for Biomimetic Functional Materials and Sensing Devices, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China)

2013-09-15

Highlights: • The CeO{sub 2}–ZrO{sub 2} hollow nanospheres had strong affinity and selectivity to arsenic. •The adsorbent showed excellent ability to remove arsenic at low concentrations. • The adsorption mechanism was investigated by FTIR and XPS. • The adsorbent showed potential application for drinking water treatment. -- Abstract: Arsenic contaminated natural water is commonly used as drinking water source in some districts of Asia. To meet the increasingly strict drinking water standards, exploration of efficient arsenic removal methods is highly desired. In this study, hierarchically porous CeO{sub 2}–ZrO{sub 2} nanospheres were synthesized, and their suitability as arsenic sorbents was examined. The CeO{sub 2}–ZrO{sub 2} hollow nanospheres showed an adsorption capacity of 27.1 and 9.2 mg g{sup −1} for As(V) and As(III), respectively, at an equilibrium arsenic concentration of 0.01 mg L{sup −1} (the standard for drinking water) under neutral conditions, indicating a high arsenic removal performance of the adsorbent at low arsenic concentrations. Such a great arsenic adsorption capacity was attributed to the high surface hydroxyl density and presence of hierarchically porous network in the hollow nanospheres. The analysis of Fourier transformed infrared spectra and X-ray photoelectron spectroscopy demonstrated that the adsorption of arsenic on the CeO{sub 2}–ZrO{sub 2} nanospheres was completed through the formation of a surface complex by substituting hydroxyl with arsenic species. In addition, the CeO{sub 2}–ZrO{sub 2} nanospheres were able to remove over 97% arsenic in real underground water with initial arsenic concentration of 0.376 mg L{sup −1} to meet the guideline limit of arsenic in drinking water regulated by the World Health Organization without any pre-treatment and/or pH adjustment.

Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I)

Energy Technology Data Exchange (ETDEWEB)

Schurz, Christian M.; Shlyk, Larysa; Schleid, Thomas; Niewa, Rainer [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

2011-07-01

Two different polymorphs of the metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) are known to crystallize in layered structures. The two crystal structures differ in the way {sub {infinity}}{sup 2}{l_brace}X[M{sub 2}N{sub 2}]X{r_brace} slabs are stacked along the c-axes. Metal atoms and/or organic molecules can be intercalated into the van-der-Waals gap between these layers. After such an electron-doping via intercalation the prototypic band insulators change into superconductors with moderate high critical temperatures T{sub c} up to 25.5 K. This review gathers information on synthesis routes, structural characteristics and properties of the prototypic nitride halides and the derivatives after electron-doping with a focus on superconductivity. (orig.)

Valence electron structure and properties of stabilized ZrO2

Institute of Scientific and Technical Information of China (English)

LI JinPing; HAN JieOai; MENG SongHe; ZHANG XingHong

2008-01-01

To reveal the properties of stabilizers in ZrO2 on nanoscopic levels,the valence elec-tron structures of four stable ZrO2 phases and c-ZrO2 were analyzed on the basis of the empirical electron theory of solids and molecules.The results showed that the hybridization levels of Zr atoms in c-ZrO2 doped with Ca and Mg dropped from B17 to B13,the hybridization levels of Zr atoms in c-ZrO2 doped with Y and Ce dropped from B17 to B15,and that the four stabilizing atoms all made the hybridization levels of O atoms drop from level 4 to level 2.The numbers of covalent electrons in the strongest covalent bond in the descending order are c-ZrO2>ZrCeO2>ZrYOZrMgO>ZrCaO.The bond energies of the strongest covalent bond and the melting points of the solid solutions in the descending order are ZrCeO2>c-ZrO2>ZrYO>ZrMgO>ZrCaO.The percent-ages of the total number of covalent electrons in the descending order arec-ZrO2>ZrYO> ZrCeO2>ZrMgO> ZrCaO.From the above analysis,it can be concluded that the stabilizing degrees of the four stabilizers in the descending order are CaO> MgO>Y2O3>CeO2.

Hydrothermal mobilization of pegmatite-hosted REE and Zr at Strange Lake, Canada: A reaction path model

Science.gov (United States)

Gysi, Alexander P.; Williams-Jones, Anthony E.

2013-12-01

Petrological and geochemical observations of pegmatites in the Strange Lake pluton, Canada, have been combined with numerical simulations to improve our understanding of fluid-rock interaction in peralkaline granitic systems. In particular, they have made it possible to evaluate reaction paths responsible for hydrothermal mobilization and mineralization of rare earth elements (REE) and Zr. The focus of the study was the B-Zone in the northwest of the pluton, which contains a pegmatite swarm and is the target of exploration for an economically exploitable REE deposit. Many of the pegmatites are mineralogically zoned into a border consisting of variably altered primary K-feldspar, arfvedsonite, quartz, and zirconosilicates, and a core rich in quartz, fluorite and exotic REE minerals. Textural relationships indicate that the primary silicate minerals in the pegmatites were leached and/or replaced during acidic alteration by K-, Fe- and Al-phyllosilicates, aegirine, hematite, fluorite and/or quartz, and that primary zirconosilicates (e.g., elpidite) were replaced by gittinsite and/or zircon. Reaction textures recording coupled dissolution of silicate minerals and crystallization of secondary REE-silicates indicate hydrothermal mobilization of the REE. The mobility of the light (L)REE was limited by the stability of REE-F-(CO2)-minerals (basnäsite-(Ce) and fluocerite-(Ce)), whereas zirconosilicates and secondary gadolinite-group minerals controlled the mobility of Zr and the heavy (H)REE. Hydrothermal fluorite and fluorite-fluocerite-(Ce) solid solutions are interpreted to indicate the former presence of F-bearing saline fluids in the pegmatites. Numerical simulations show that the mobilization of REE and Zr in saline HCl-HF-bearing fluids is controlled by pH, ligand activity and temperature. Mobilization of Zr is significant in both saline HF- and HCl-HF-bearing fluids at low temperature (250 °C). In contrast, the REE are mobilized by saline HCl-bearing fluids

Thermal and electronic charge transport in bulk nanostructured Zr0.25Hf0.75NiSn composites with full-Heusler inclusions

International Nuclear Information System (INIS)

Makongo, Julien P.A.; Misra, Dinesh K.; Salvador, James R.; Takas, Nathan J.; Wang, Guoyu; Shabetai, Michael R.; Pant, Aditya; Paudel, Pravin; Uher, Ctirad; Stokes, Kevin L.; Poudeu, Pierre F.P.

2011-01-01

Bulk Zr 0.25 Hf 075 NiSn half-Heusler (HH) nanocomposites containing various mole fractions of full-Heusler (FH) inclusions were prepared by solid state reaction of pre-synthesized HH alloy with elemental Ni at 1073 K. The microstructures of spark plasma sintered specimens of the HH/FH nanocomposites were investigated using transmission electron microscopy and their thermoelectric properties were measured from 300 K to 775 K. The formation of coherent FH inclusions into the HH matrix arises from solid-state Ni diffusion into vacant sites of the HH structure. HH(1-y)/FH(y) composites with mole fraction of FH inclusions below the percolation threshold, y∼0.2, show increased electrical conductivity, reduced Seebeck coefficient and increased total thermal conductivity arising from gradual increase in the carrier concentration for composites. A drastic reduction (∼55%) in κ l was observed for the composite with y=0.6 and is attributed to enhanced phonon scattering due to mass fluctuations between FH and HH, and high density of HH/FH interfaces. - Graphical abstract: Large reduction in the lattice thermal conductivity of bulk nanostructured half-Heusler/full-Heusler (Zr 0.25 Hf 075 NiSn/ Zr 0.25 Hf 075 Ni 2 Sn) composites, obtained by solid-state diffusion at 1073 K of elemental Ni into vacant sites of the half-Heusler structure, arising from the formation of regions of spinodally decomposed HH and FH phases with a spatial composition modulation of ∼2 nm. Highlights: → Bulk composites from solid state transformation of half-Heusler matrix through Ni diffusion. → Formation of coherent phase boundaries between half-Heusler matrix and full-Heusler inclusion. → Alteration of thermal and electronic transports with increasing full-Heusler inclusion. → Enhanced phonon scattering at half-Heusler/ full-Heusler phase boundaries.

Determination of Nb and Zr in U-Nb-Zr alloys by ICP-AES

International Nuclear Information System (INIS)

Wang Cuiping; Dong Shizhe; Li Lin; He Meiying

2003-01-01

The U-Nb-Zr alloy sample is dissolved by HNO 3 , H 2 O 2 and HF, and the contents of Nb and Zr in the sample are determined on the JY-70 II type ICP-AES by using the internal standard synchronous dilution method. The range of determination is 1%-10% and 0.33%-3.33%, respectively for Nb and Zr. The relative standard deviation is better than 3.2% for Nb, and 2.5% for Zr. The method is rapid and convenient for determining Nb and Zr in U-Nb-Zr alloy sample

The Role of Neodymium in the Optimization of a Ni/CeO2 and Ni/CeZrO2 Methane Dry Reforming Catalyst

Directory of Open Access Journals (Sweden)

Alfonsina Pappacena

2018-04-01

Full Text Available The development of a sustainable economy based on the use of renewable resources and the reduction of greenhouse gases emissions is an important mandate in modern societies to minimize the global warming. The CO2-reforming of methane through a conversion of CO2 and CH4 to syngas is a suitable process for this purpose and there is growing interest in the development of new catalysts for this process’ application at an industrial scale. This study is the first to investigate methane dry reforming activity of nickel supported on CeO2 and CeO2–ZrO2 solid solutions doped with neodymium. The supports were synthesized using a surfactant-assisted co-precipitation method and characterized through several analytical techniques to understand the role of synthesis parameters in the distribution of the dopant as well as in the properties of the supports. Co-doping with Zr and Nd resulted in an enhancement of dry reforming activity of ceria due to a higher dispersion of Ni and changes in the strength of basic sites. It was also shown that the addition of Nd helped to mitigate coking issues by increasing the mobility of surface oxygen in ceria and ceria–zirconia oxides and, accordingly, the rate of oxidation of carbonaceous deposits.

Quaternary chalcogenides of the IVa metals with layered structures: preparation and crystal structures of TlCuTIVQ3 (T=Zr, Hf; Q=S, Se) and their relation to the Re3B structure type

International Nuclear Information System (INIS)

Klepp, K.O.; Gurtner, D.

1996-01-01

The new compounds TlCuT IV Q 3 (T = Zr, Hf; Q = S, Se) were prepared by reacting intimate mixtures of Tl 2 S or TlSe with stoichiometric amounts of the corresponding Group IV metal, Cu and the corresponding chalcogen at 870 . The four compounds are isostructural and crystallize in Cmcm, Z = 4 with a 3.726(4) A, b = 13.987(9) A, c = 9.783(4) A for TlCuZrS 3 ; a = 3.847(1) A, b 14.381(6) A, c = 10.150(1) A for TlCuZrSe 3 ; a = 3.694(1) A, b = 14.030(3) A, c = 9.750(3) A for TlCuHfS 3 ; and a = 3.831(1) A, b = 14.409(9) A, c = 10.124(2) A for TlCuHfSe 3 . Their crystal structures were determined from single crystal diffractometer data (Mo Kα radiation, ambient temperature) and refined to conventional R values of 0.016, 0.040, 0.019 and 0.031 respectively. An outstanding feature of their crystal structures is the formation of infinite anionic layers, 2 ∞ -[CuT IV Q 3 ] - parallel to (010), which are separated by Tl + cations. These layers are built up by edge sharing TQ 6 octahedra and distorted CuQ 4 tetrahedra. Average T-Q distances are anti d(Zr-S) = 2.586(1) A, anti d(Zr-Se) = 2.707(1) A, anti d(Hf-S) = 2.569(2) A and anti d(Hf-Se) = 2.694(1) A. Cu-chalcogen distances are anti d(Cu-S) = 2.318(2) A and anti d(Cu-Se) = 2.432(3) A respectively. The thallium ions are in bicapped trigonal prismatic chalcogen coordinations. The atomic arrangement corresponds to that of KCuZrS 3 ; based on the thallium-chalcogen partial structure it can be regarded as a filled variant of an anti-Re 3 B structure type. (orig.)

Analysis of sodium metal by X-ray fluorescence spectrometry (I). Determination of Hf, Mo, Nb, Ta, Ti, V and Zr

International Nuclear Information System (INIS)

Diaz-Guerra, J. P.

1981-01-01

A method allowing the determination of trace quantities of Hf, Mo, Nb, Ta, Ti, Vi and Zr in sodium metal previous transformation into Na 2 S0 4 is described. The enrichment of the impurities is performed through a coprecipitation technique in sulfuric medium by using Fe 3 + as a collector and cupferron or phenyfluorone as the precipitating reagent. The matrix influence and the best concentration of the collector (10/μ/ml), adequate pH (1,3 or 4, respectively) and optimum filter type (Millipore BSWP02500 or BDWP04700, respectively) have been studied, as well as the precipitation recoveries corresponding to the reagent above. It has been demonstrated the batter efficiency of the cupferron for determining all the Impurities. Detection limits range from 0.01 to 0.2 ppm., depending on the element, for samples 4 g in weight. An automatic spectrometer attached to a 16 K minicomputer and X-ray tube with a gold anode (2250-2700 W) are used. The Interferences between the lines ZrKα (2 n d order) - HfLα and TiKβ - VK α have been studied and the respective correction coefficients have been deduced. (Author) 8 refs

Effect on Al:MO{sub 2}/In{sub 0.53}Ga{sub 0.47}As interface (M = Hf, Zr) of trimethyl-aluminum pre-treatment during atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Lamperti, A., E-mail: alessio.lamperti@mdm.imm.cnr.it [Laboratorio MDM, IMM-CNR, via C. Olivetti 2, 20864 Agrate Brianza, MB (Italy); Molle, A.; Cianci, E.; Wiemer, C.; Spiga, S. [Laboratorio MDM, IMM-CNR, via C. Olivetti 2, 20864 Agrate Brianza, MB (Italy); Fanciulli, M. [Laboratorio MDM, IMM-CNR, via C. Olivetti 2, 20864 Agrate Brianza, MB (Italy); Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, Milano (Italy)

2014-07-31

For the fabrication of n-type metal–oxide–semiconductor field-effect transistor based on high mobility III–V compound semiconductors as channel materials, a major requirement is the integration of high quality gate oxides on top of the III–V substrates. A detailed knowledge of the interface between the oxide layer and the substrate is mandatory to assess the relevance of interdiffusion and related defects, which are detrimental. Here we grow high dielectric constant (k) Al:MO{sub 2} (M = Hf, Zr) gate materials on In{sub 0.53}Ga{sub 0.47}As substrates by atomic layer deposition, after an Al{sub 2}O{sub 3} pre-treatment based on trimethylaluminum is performed to properly passivate the substrate surface. Time of flight secondary ion mass spectrometry depth profiles reveal not only the film integrity and the chemical composition of the high-k oxide but also well elucidate the effect of the Al{sub 2}O{sub 3} pre-treatment on Al:MO{sub 2}/In{sub 0.53}Ga{sub 0.47}As interface. Even though the chemical profile is well defined in both cases, a broader interface is detected for Al:ZrO{sub 2}. X-ray photoemission spectroscopy evidenced the presence of As{sup 3+} states in Al:ZrO{sub 2} only. Accordingly, preliminary capacitance–voltage measurements point out to a better field effect modulation in the capacitor incorporating Al:HfO{sub 2}. Based on the above considerations Al:HfO{sub 2} looks as a preferred candidate with respect to Al:ZrO{sub 2} for the integration on top of In{sub 0.53}Ga{sub 0.47}As substrates. - Highlights: • Al:MO{sub 2} (M = Hf, Zr) thin films are grown on In{sub 0.53}Ga{sub 0.47}As substrates. • Trimethylaluminum (TMA) pre-treatment properly passivates the substrate surface. • ToF-SIMS depth profiles reveal the chemical composition of the high-k films. • Depth profiles well elucidate the effect of TMA on Al:MO{sub 2}/In{sub 0.53}Ga{sub 0.47}As substrates. • XPS evidences the presence of As{sup 3+} state in Al:ZrO{sub 2}/In{sub 0

The role of Ti, Zr and Ce in shaping of the Cr-Ni-Nb cast steel resistance to carburising

Directory of Open Access Journals (Sweden)

G. Tęcza

2008-08-01

Full Text Available From the centrifugally cast Cr-Ni-Nb steel pipes, specimens were cut out and subjected to carburising for 100 hours in a mixture of charcoal (90% and Na2CO3 (10% at the temperatures of 950 and 1150°C. The specimens were cut in direction normal to the pipe axis and were examined by optical and scanning microscopy. As a parameter describing the resistance of the examined alloy to the carburising effect, the thickness of a carburised layer was accepted. It has been observed that additions of Ti and Zr, and of Ti+Zr+Ce introduced jointly, increase the thickness of the carburised layer, while the addition of Ce improves the alloy resistance to carburising. On the alloy surface, a layer composed of oxides, mainly of chromium, silicon and iron, has been formed. Changes in the chemical composition of the surface layer were examined by scanning microscopy.

Hybrid HF-DFT comparative study of SrZrO{sub 3} and SrTiO{sub 3}(001) surface properties

Energy Technology Data Exchange (ETDEWEB)

Evarestov, R.A.; Bandura, A.V.; Alexandrov, V.E. [Department of Quantum Chemistry, St. Petersburg State University, 26 Universitetskii Prospekt, Stary Petergof, 198504 St. Petersburg (Russian Federation)

2006-10-15

Hybrid HF-DFT LCAO simulations of SrZrO{sub 3} and SrTiO{sub 3}(001) surface properties are performed in a single-slab model framework. The SrZrO{sub 3}(001) surface was studied by an ab initio method for the first time. Three slab models with different surface terminations including up to 8 atomic planes were used for calculation of the various surface characteristics (surface energies, atomic charges, density of electronic states). The dependence of the results on the chosen model and on the kind of d-element is analyzed. The dissimilarity in the surface oxygen atom contributions to the total density of states of two crystals is attributed to the more ionic nature of Zr-O bonds compared to Ti-O bonds. It is found that in the case of SrZrO{sub 3} the electronic density is biased towards the SrO-terminated surface and this surface should be more basic in nature than the SrO surface of SrTiO{sub 3} crystal. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Valence electron structure and properties of stabilized ZrO2

Institute of Scientific and Technical Information of China (English)

2008-01-01

To reveal the properties of stabilizers in ZrO2 on nanoscopic levels, the valence electron structures of four stable ZrO2 phases and c-ZrO2 were analyzed on the basis of the empirical electron theory of solids and molecules. The results showed that the hybridization levels of Zr atoms in c-ZrO2 doped with Ca and Mg dropped from B17 to B13, the hybridization levels of Zr atoms in c-ZrO2 doped with Y and Ce dropped from B17 to B15, and that the four stabilizing atoms all made the hybridization levels of O atoms drop from level 4 to level 2. The numbers of covalent electrons in the strongest covalent bond in the descending order are c-ZrO2>Zr0.82Ce0.18O2> Zr0.82Y0.18O1.91>Zr0.82Mg0.18O1.82>Zr0.82Ca0.18O1.82. The bond energies of the strongest covalent bond and the melting points of the solid solutions in the descending order are Zr0.82Ce0.18O2> c-ZrO2>Zr0.82Y0.18O1.91>Zr0.82Mg0.18O1.82>Zr0.82Ca0.18O1.82. The percent-ages of the total number of covalent electrons in the descending order are c-ZrO2>Zr0.82Y0.18O1.91> Zr0.82Ce0.18O2>Zr0.82Mg0.18O1.82> Zr0.82Ca0.18O1.82. From the above analysis, it can be concluded that the stabilizing degrees of the four stabilizers in the descending order are CaO> MgO>Y2O3>CeO2.

Influence of Co or Ce addition on the NOx storage and sulfur-resistance performance of the lean-burn NOx trap catalyst Pt/K/TiO{sub 2}-ZrO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Zou Zhiqiang [Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Meng, Ming, E-mail: mengm@tju.edu.cn [Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Tsubaki, Noritatsu [Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama city, Toyama 930 8555 (Japan); He Junjun; Wang Gang; Li Xingang; Zhou Xiaoyan [Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

2009-10-15

The Pt/K/TiO{sub 2}-ZrO{sub 2} catalysts promoted by Co or Ce were prepared by successive impregnation or mechanically mixing method. The influence of Co or Ce addition on the NOx storage and sulfur-resistance performance of the catalyst was investigated carefully. The techniques of XRD, FT-IR, in-situ DRIFTS, H{sub 2}-TPR and XPS were employed for catalyst characterization. The Co or Ce addition can greatly improve the NOx storage capacity of Pt/K/TiO{sub 2}-ZrO{sub 2} due to the enhanced oxidation ability and the release of more K sites. Ce addition induces higher K/Ti atomic ratio and larger NOx storage capacity as compared with Co addition. After sulfation and regeneration, the promoted catalysts shows more or less decreased NSC than Pt/K/TiO{sub 2}-ZrO{sub 2} due to the formation of more sulfates, especially for the Co-promoted catalysts, which possess better oxidation ability and facilitate the formation of large sulfates. The effect of Ce addition on Pt/K/TiO{sub 2}-ZrO{sub 2} largely depends on the addition mode. The high oxidation ability and the high K/Ti ratio of the mechanically prepared Ce-promoted catalyst make it still possess considerable NOx storage capacity (NSC) of 142 {mu}mol/g after sulfation and regeneration. With the decrease of sulfur content in fuels, the Co- and Ce-promoted catalysts possessing large NOx storage capacity, will be applicable to the purification of lean-burn NOx.

Effect of Co addition on the performance and structure of V/ZrCe catalyst for simultaneous removal of NO and Hg0 in simulated flue gas

Science.gov (United States)

Zhao, Lingkui; Li, Caiting; Du, Xueyu; Zeng, Guangming; Gao, Lei; Zhai, Yunbo; Wang, Teng; Zhang, Junyi

2018-04-01

The effect of CoOx addition on the performance and structure of V2O5/ZrO2-CeO2 catalyst for simultaneous removal of NO and Hg0 in simulated flue gas was investigated by various methods including SEM, BET, XRD, XPS, H2-TPR and FT-IR. It was found that the introduction of CoOx not only greatly enhanced the redox properties of catalysts, but also increased the catalytic performance for simultaneous removal of NO and Hg0. The CoOx-modified V2O5/ZrO2-CeO2 catalyst displayed excellent catalytic activity for NO conversion (89.6%) and Hg0 oxidation (88.9%) at 250 °C under SCR atmosphere. The synergistic effect among vanadium, cobalt, and the ZrCe support could induce oxygen vacancies formation and promote oxygen mobility via charge transfer. Besides, CoOx could assist vanadium species in rapidly changing the valence by the redox cycle of V5+ + Co2+ ↔ V4+ + Co3+. All the above features contribute to the excellent catalytic performance through CoOx addition.

Zircon and whole-rock Zr/Hf ratios as markers of the evolution of granitic magmas: Examples from the Teplice caldera (Czech Republic/Germany)

Czech Academy of Sciences Publication Activity Database

Breiter, Karel; Škoda, R.

2017-01-01

Roč. 111, č. 4 (2017), s. 435-457 ISSN 0930-0708 R&D Projects: GA ČR GA14-13600S Institutional support: RVO:67985831 Keywords : Zr/Hf value * zircon * Teplice caldera * rhyolite * rare-metal granite * Cínovec deposit Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Mineralogy Impact factor: 1.236, year: 2016

Photophysical and energy transfer processes in Ce{sup 3+} co-doped ZrO{sub 2}: Eu{sup 3+} nanorods

Energy Technology Data Exchange (ETDEWEB)

Ahemen, I.; Dejene, F.B. [University of the Free State-Qwaqwa Campus, Department of Physics, Phuthaditjhaba (South Africa)

2017-02-15

Cerium (III) ion co-doped ZrO{sub 2}: Eu{sup 3+} nanorods at varying Ce{sup 3+} ion concentrations were synthesized by a simple chemical dehydration route. Their structural, morphological and optical properties were investigated. Structural studies revealed a tetragonal phase with CeO{sub 2} phase grafted onto its surface. Field emission scanning electron microscopy images show nanorods of different dimensions. Diffraction peaks shifted towards smaller angles indicating the incorporation of the rare earth ions. Both Ce{sup 3+} (donor) and Eu{sup 3+} (activator) emission peaks were obtained when the samples were excited via the Ce{sup 3+} excitation band indicating energy transfer from the donor to activator. The process of energy transfer is both multipolar and exchange interactions. However, no significant enhancement of the activator's emission intensity, because concentration quenching process dominated the energy transfer process. The internal quantum efficiency, though low (20-25%), increased with increasing Ce{sup 3+} concentration. (orig.)

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

International Nuclear Information System (INIS)

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

2013-01-01

CeO 2 –ZrO 2 –M x O y (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 H 2 -temperature-programmed reduction (H 2 -TPR) and O 2 -temperature-programmed desorption (O 2 -TPD). The results showed that the prepared CeO 2 –ZrO 2 –M x O y oxides have a face-centered cubic fluorite structure and are nanosize. La 3+ ions can significantly improve thermal stability and efficiently retard CeO 2 –ZrO 2 crystal sintering and growth. Doped CeO 2 –ZrO 2 with Y 3+ and La 3+ has 105 and 60 m 2 /g surface area and 460 and 390 μmol/g OSC before and after aging. The T 50 of fresh Pt–Rh/CZYL/LA is 170 °C for CO, 222 °C for C 3 H 8 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 O 2 on the surface of catalysts are closely related to the catalytic activities.

Luminescence and scintillation properties of Rb2HfCl6 crystals

International Nuclear Information System (INIS)

Saeki, Keiichiro; Wakai, Yuki; Fujimoto, Yutaka; Koshimizu, Masanori; Asai, Keisuke; Yanagida, Takayuki; Nakauchi, Daisuke

2016-01-01

We developed a scintillator based on a Rb 2 HfCl 6 crystal as a ternary halide crystal with intrinsic luminescence. In the photoluminescence spectra, two emission bands are observed at 383 and 434 nm. The 434 nm emission band for Rb 2 HfCl 6 may be attributed to [HfCl 6 ] 2- complex ion or [ZrCl 6 ] 2- impurity, since the Rb 2 HfCl 6 contained Zr as impurity at 0.62 mol %. The radioluminescence band is observed at 420 nm and can be attributed to the same origin as the photoluminescence band at 434 nm. The scintillation decay-time constants were 0.84 and 5.4 μs. The light yield was estimated to be 24,100 photons/MeV. (author)

Isothermal cross-sections of Hf-Sc-Ga(800 deg C) and Hf-Ti-Ga (750 deg C) phase diagrams

International Nuclear Information System (INIS)

Markiv, V.Ya.; Belyavina, N.N.

1981-01-01

Isothermal cross sections of Hf-Sc-Ga (800 deg C) and Hf-Ti-Ga (750 deg C) state diagrams are plotted. The existence of two ternary Hfsub(0.1-0.8)Scsub(0.9)-sub(0.2)Ga and Hfsub(0.8)Scsub(0.2)Gasub(3) phases is stated in the Hf-Sc-Ga system. The crystal structure of these compounds investigated by the powder method belongs to the structural α-MoB and ZrAl 3 types respectively. Continuous rows of (Hf, Sc 5 Ga 5 , (Hf, Ti)Ga 3 and (Hf, Ti)Ga 2 solid solutions are formed in the investigated systems. Essential quantity of the third component dissolve binary Sc 5 Ga 4 , Sc 2 Ga 3 (15 and 30 at % Hf respectively), Hf 5 Ga 4 , HfGa 2 (20, 10 at. % Sc), Hf 5 Ga 4 , HfGa, Hf 5 Ga 3 , Hf 2 Ga 3 (48, 30, 46, 20 at. % Ti) gallides [ru

Crystal structure and thermal expansion of the low- and high-temperature forms of Ba MIV(PO 4) 2 compounds ( M=Ti, Zr, Hf and Sn)

Science.gov (United States)

Bregiroux, D.; Popa, K.; Jardin, R.; Raison, P. E.; Wallez, G.; Quarton, M.; Brunelli, M.; Ferrero, C.; Caciuffo, R.

2009-05-01

The crystal structure of β-BaZr(PO 4) 2, archetype of the high-temperature forms of Ba M(PO 4) 2 phosphates (with M=Ti, Zr, Hf and Sn), has been solved ab initio by Rietveld analysis from synchrotron X-ray powder diffraction data. The phase transition appears as a topotactic modification of the monoclinic (S.G. C2/m) lamellar α-structure into a trigonal one (S.G. P3¯m1) through a simple mechanism involving the unfolding of the [Zr)]n2- layers. The thermal expansion is very anisotropic (e.g., -4.1< α i<34.0×10 -6 K -1 in the case of α-BaZr(PO 4) 2) and quite different in the two forms, as a consequence of symmetry. It stems from a complex combination of several mechanisms, involving bridging oxygen rocking in M-O-P linkages, and "bond thermal expansion".

Nd{sup 3+}-substituted (Zr{sub 1−x}Ce{sub x})O{sub 2} (0.0 ≤ x ≤ 1.0) system: Synthesis, structural and thermophysical investigations

Energy Technology Data Exchange (ETDEWEB)

Nandi, Chiranjit [Radiometallurgy Division, Bhabha Atomic Research Centre, HBNI, Mumbai 400085 (India); Grover, V., E-mail: Vinita@barc.gov.in [Chemistry Division, Bhabha Atomic Research Centre, HBNI, Mumbai 400085 (India); Sahu, M. [Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Krishnan, K. [Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Guleria, A. [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Kaity, Santu; Prakash, Amrit [Radiometallurgy Division, Bhabha Atomic Research Centre, HBNI, Mumbai 400085 (India); Tyagi, A.K. [Chemistry Division, Bhabha Atomic Research Centre, HBNI, Mumbai 400085 (India)

2016-10-15

In order to mimic co-loading of Pu and Am in zirconia, Nd{sub 0.20}[Zr{sub 1−x}Ce{sub x}]{sub 0.80}O{sub 1.90} (0.0 ≤ x ≤ 1.0) system was synthesized and thoroughly characterized by X-ray diffraction (XRD) and Raman spectroscopy. The entire system was found to be single-phasic fluorite-type and most interesting result is stabilization of multi-phasic ceria-zirconia system in a single-phasic system by substituting Nd{sup 3+}. Raman spectroscopy revealed entirely different nature of defects prevalent in the solid solutions possessing F-type structure across the composition range. The heat capacity of representative compositions was measured by heat flux-type differential scanning calorimeter. Specific heat capacity of the solid solutions was found to increase with decreasing CeO{sub 2} content. Different thermodynamic functions such as enthalpy increment, entropy and Gibbs energy functions were determined using heat capacity values. The lattice thermal expansion (298–1273 K) behaviour of the few selected compositions revealed a gradual increase in thermal expansion coefficient with increasing CeO{sub 2} content. - Highlights: • Single-phasic fluorite-type solid solution obtained across the composition range. • Multi-phasic CeO{sub 2}-ZrO{sub 2} system converted into single-phasic by Nd{sup 3+} substitution. • Different local structures and defects in Ce-rich and Zr-rich regions. • Lattice thermal expansion coefficient increases with increasing CeO{sub 2} content. • Thermal expansion behaviour is a manifestation of decreasing melting point.

Microstructure and fatigue behaviors of a biomedical Ti–Nb–Ta–Zr alloy with trace CeO2 additions

International Nuclear Information System (INIS)

Song, Xiu; Wang, Lei; Niinomi, Mitsuo; Nakai, Masaaki; Liu, Yang; Zhu, Miaoyong

2014-01-01

The new β-type Ti–29Nb–13Ta–4.6Zr (TNTZ) alloy containing trace amounts of CeO 2 additions has been designed as a biomedical implant with improved fatigue properties achieved by keeping Young's modulus to a low value. The results show that the microstructure is refined by the addition of CeO 2 ; the β grain size becomes a little larger when Ce content increases from 0.05% to 0.10%. This occurs because dispersed CeO 2 particles can act as nucleation sites for β grains; thus, the effect of rare earth oxides on microstructure refinement mainly depends on the size and dispersion of the rare earth oxides. Young's moduli of TNTZ with CeO 2 additions are maintained as low as those of TNTZ without CeO 2 , while the fatigue limit is highly improved. The 0.10% Ce alloy exhibits the best fatigue strength among the experimental alloys; its fatigue strength is increased by 66.7% compared to that of pure TNTZ. The mechanism by which rare earth oxides affect fatigue performance is dominated by dispersion strengthening. The stiff rare earth oxides can hinder the movement of dislocations, resulting in resistance to the formation of fatigue cracks. Rare earth oxides also change the crack propagation direction and the crack propagation route, effectively decreasing the crack propagation rate

Characterization of catalysts Rh and Ni/Ce{sub x}Zr{sub 1-x}O{sub 2} for hydrogen production by ethanol steam reforming; Caracterisation de catalyseurs Rhodium et Nickel/ Ce{sub x}Zr{sub 1-x}O{sub 2} pour la production d'hydrogene par vaporeformage de l'ethanol

Energy Technology Data Exchange (ETDEWEB)

Birot, A

2005-07-01

This work concerned a study on catalytic behaviour of metallic catalysts (Rh or Ni) supported on earth rare oxides Ce{sub x}Zr{sub 1-x}O{sub 2} in ethanol steam reforming in order to produce hydrogen. Catalyst 1%Rh/Ce0,50Zr0,50O{sub 2} showed a good activity with a good hydrogen yield. We turned a study onto understanding inter-conversion reaction between H{sub 2}, CO and CO{sub 2} which lead to CH{sub 4} formation. We also studied intrinsic properties of catalysts. We confirmed basic character of catalysts and a good hydrogenation activity. A good activity in CO hydrogenation allowed to evidence a necessity to use a catalyst which is less active in hydrogenation reaction and with a basic character in order to improve hydrogen yield. (author)

The new insight into the structure-activity relation of Pd/CeO2-ZrO2-Nd2O3 catalysts by Raman, in situ DRIFTS and XRD Rietveld analysis.

Science.gov (United States)

Yang, X; Yang, L; Lin, J; Zhou, R

2016-01-28

Pd/CeO2-ZrO2-Nd2O3 (CZN) catalysts with different CeO2/ZrO2 molar ratios were synthesized and have been characterized by multiple techniques, e.g. XRD in combination with Rietveld refinement, UV-Raman, XPS and in situ DRIFTS. The XRD pattern of CZN with CeO2/ZrO2 molar ratios ≥1/2 can be indexed satisfactorily to the fluorite structure with a space group Fm3̄m, while the XRD patterns of CZ12 only display diffraction peaks of the tetragonal phase (S.G. P42/nmc). Nd addition can effectively stabilize the cubic structure of the CZN support and increase the enrichment of defect sites on the surface, which may be related to the better catalytic activity of Pd/CZN12 catalysts compared with Pd/CZ12. The presence of moderate ZrO2 can increase the concentration of O* active species, leading to accelerate the formation of nitrate species and thus enhance the catalytic activity of NOx and HC elimination. The Pd-dispersion decreases with the increasing Zr content, leading to the decreased CO catalytic activity, especially for the aged catalysts. The change regularity of the OSC value is almost the same with the in situ dynamic operational window, demonstrating that the in situ dynamic operational window is basically affected by the OSC value.

Very large phase shift of microwave signals in a 6 nm Hf x Zr1-x O2 ferroelectric at ±3 V

Science.gov (United States)

Dragoman, Mircea; Modreanu, Mircea; Povey, Ian M.; Iordanescu, Sergiu; Aldrigo, Martino; Romanitan, Cosmin; Vasilache, Dan; Dinescu, Adrian; Dragoman, Daniela

2017-09-01

In this letter, we report for the first time very large phase shifts of microwaves in the 1-10 GHz range, in a 1 mm long gold coplanar interdigitated structure deposited over a 6 nm Hf x Zr1-x O2 ferroelectric grown directly on a high resistivity silicon substrate. The phase shift is larger than 60° at 1 GHz and 13° at 10 GHz at maximum applied DC voltages of ±3 V, which can be supplied by a simple commercial battery. In this way, we demonstrate experimentally that the new ferroelectrics based on HfO2 could play an important role in the future development of wireless communication systems for very low power applications.

Crystal structure and thermal expansion of the low- and high-temperature forms of BaMIV(PO4)2 compounds (M=Ti, Zr, Hf and Sn)

International Nuclear Information System (INIS)

Bregiroux, D.; Popa, K.; Jardin, R.; Raison, P.E.; Wallez, G.; Quarton, M.; Brunelli, M.; Ferrero, C.; Caciuffo, R.

2009-01-01

The crystal structure of β-BaZr(PO 4 ) 2 , archetype of the high-temperature forms of BaM(PO 4 ) 2 phosphates (with M=Ti, Zr, Hf and Sn), has been solved ab initio by Rietveld analysis from synchrotron X-ray powder diffraction data. The phase transition appears as a topotactic modification of the monoclinic (S.G. C2/m) lamellar α-structure into a trigonal one (S.G. P3-barm1) through a simple mechanism involving the unfolding of the [Zr(PO 4 ) 2 ] n 2- layers. The thermal expansion is very anisotropic (e.g., -4.1 i -6 K -1 in the case of α-BaZr(PO 4 ) 2 ) and quite different in the two forms, as a consequence of symmetry. It stems from a complex combination of several mechanisms, involving bridging oxygen rocking in M-O-P linkages, and 'bond thermal expansion'. - Graphical abstract: The layered high-temperature form of BaM(PO 4 ) 2 , only expands along the c-axis.

Frictional properties of CeO$_{2}$-Al$_{2}$O$_{3}$-ZrO$_{2}$ plasma-sprayed film under mixed and boundary lubricating conditions

CERN Document Server

Kita, H; Osumi, K; 10.2109/jcersj.112.615

2004-01-01

In order to find a counterpart for reducing the frictional coefficient of Al/sub 2/O/sub 3/-ZrO/sub 2/-CeO/sub 2/ plasma-sprayed film, the sliding properties in mixed and boundary lubricating conditions was investigated. It was found that combination of a CrN- coated cast iron pin and an Al/sub 2/O/sub 3/-ZrO/sub 2/-CeO/sub 2/ plasma sprayed plate provided the lowest frictional coefficient among several combinations chosen from practical materials. The coefficient of friction was much lower than that of the materials combination widely used for piston ring and cylinder liner. It was inferred that the combination of a pin made of hard materials with high density, a smooth surface such as CrN-coated cast iron and a porous plate can reduce the frictional coefficient because less sliding resistance is implemented and porosity retains oil.

Design of Rh/Ce0.2Zr0.8O2-Al2O3 nanocomposite for ethanol steam reforming

International Nuclear Information System (INIS)

De Rogatis, Loredana; Montini, Tiziano; Casula, Maria F.; Fornasiero, Paolo

2008-01-01

Rh(1 wt.%)/Ce 0.2 Zr 0.8 O 2 (10 wt.%)-Al 2 O 3 nanocomposite has been investigated as active and thermally stable catalyst for ethanol steam reforming. Rh nanoparticles were synthesised by surfactant assisted route, using N-hexadecyl-N-(2-hydroxyethyl)-N,N-dimethyl ammonium bromide (HEAC16Br). Metal particles with average diameter of 2.1 nm were obtained at 0.53 Rh/HEAC16Br molar ratio, while increasing the amount of surfactant lead to formation of larger particles. The preformed Rh nanoparticles have been effectively embedded into a porous layer of nanocomposite oxides. Low temperature H 2 chemisorption experiments and activity data confirm that most of the Rh atoms are accessible to the reaction mixture. The Ce 0.2 Zr 0.8 O 2 mixed oxide inhibits the dehydration of ethanol to ethylene and favours the water gas shift reaction. The alumina ensures good thermal stability and high surface area of the catalyst. No significant deactivation is observed after repeated run-up and run-down experiments

First-principles calculations of the structural and thermodynamic properties of bcc, fcc and hcp solid solutions in the Al-TM (TM = Ti, Zr and Hf) systems: A comparison of cluster expansion and supercell methods

International Nuclear Information System (INIS)

Ghosh, G.; Walle, A. van de; Asta, M.

2008-01-01

The thermodynamic properties of solid solutions with body-centered cubic (bcc), face-centered cubic (fcc) and hexagonal close-packed (hcp) structures in the Al-TM (TM = Ti, Zr and Hf) systems are calculated from first-principles using cluster expansion (CE), Monte-Carlo simulation and supercell methods. The 32-atom special quasirandom structure (SQS) supercells are employed to compute properties at 25, 50 and 75 at.% TM compositions, and 64-atom supercells have been employed to compute properties of alloys in the dilute concentration limit (one solute and 63 solvent atoms). In general, the energy of mixing (Δ m E) calculated by CE and dilute supercells agree very well. In the concentrated region, the Δ m E values calculated by CE and SQS methods also agree well in many cases; however, noteworthy discrepancies are found in some cases, which we argue originate from inherent elastic and dynamic instabilities of the relevant parent lattice structures. The importance of short-range order on the calculated values of Δ m E for hcp Al-Ti alloys is demonstrated. We also present calculated results for the composition dependence of the atomic volumes in random solid solutions with bcc, fcc and hcp structures. The properties of solid solutions reported here may be integrated within the CALPHAD formalism to develop reliable thermodynamic databases in order to facilitate: (i) calculations of stable and metastable phase diagrams of binary and multicomponent systems, (ii) alloy design, and (iii) processing of Al-TM-based alloys

Phase stability predictions of Cr1−x, Mx)2(Al1−y, Ay)(C1−z, Xz) (M = Ti, Hf, Zr; A = Si, X = B)

International Nuclear Information System (INIS)

Shang, Lin; Music, Denis; Baben, Moritz to; Schneider, Jochen M

2014-01-01

The phase stability of (Cr 1−x , M x ) 2 (Al 1−y , A y )(C 1−z , X z ) (M = Ti, Hf, Zr; A = Si, X = B, space group P6 3 /mmc, prototype Cr 2 AlC) was studied using ab initio calculations. Based on the energy of mixing data as well as the density of states (DOS) analysis, (Cr 1−x , Zr x ) 2 AlC and (Cr 1−x , Hf x ) 2 AlC are predicted to be unstable, whereas (Cr 1−x , Ti x ) 2 AlC, Cr 2 (Al 1−y , Si y )C and Cr 2 Al(C 1−z , B z ) are predicted to be stable or metastable. The density of states analysis reveals that small differences in the position of the Fermi level alters the phase stability: (Cr 1−x , Zr x ) 2 AlC and (Cr 1−x , Hf x ) 2 AlC are predicted to be unstable or metastable as the Fermi level lies at a peak position. While the Cr dominated DOS for (Cr 1−x , Ti x ) 2 AlC plateaus at the Fermi level indicating stability. Implications of these results for the vapour phase condensation of self-healing Cr 2 AlC based materials are discussed. (paper)

Distribution of impurity states and charge transport in Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Liu, Yuanfeng; Makongo, Julien P.A. [Laboratory for Emerging Energy and Electronic Materials, Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Page, Alexander [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Sahoo, Pranati [Laboratory for Emerging Energy and Electronic Materials, Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Uher, Ctirad [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Stokes, Kevin [The Advanced Materials Research Institute, Department of Physics, University of New Orleans, New Orleans, LA 70148 (United States); Poudeu, Pierre F.P., E-mail: ppoudeup@umich.edu [Laboratory for Emerging Energy and Electronic Materials, Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (United States)

2016-02-15

Energy filtering of charge carriers in a semiconducting matrix using atomically coherent nanostructures can lead to a significant improvement of the thermoelectric figure of merit of the resulting composite. In this work, several half-Heusler/full-Heusler (HH/FH) nanocomposites with general compositions Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} (0≤x≤0.15 and y=0.005, 0.01 and 0.025) were synthesized in order to investigate the behavior of extrinsic carriers at the HH/FH interfaces. Electronic transport data showed that energy filtering of carriers at the HH/FH interfaces in Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} samples strongly depends on the doping level (y value) as well as the energy levels occupied by impurity states in the samples. For example, it was found that carrier filtering at HH/FH interfaces is negligible in Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} (y=0.01 and 0.025) composites where donor states originating from Sb dopant dominate electronic conduction. However, we observed a drastic decrease in the effective carrier density upon introduction of HH/FH interfaces for the mechanically alloyed Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 0.995}Sb{sub 0.005} samples where donor states from unintentional Fe impurities contribute the largest fraction of conduction electrons. This work demonstrates the ability to synergistically integrate the concepts of doping and energy filtering through nanostructuring for the optimization of electronic transport in semiconductors. - Graphical abstract: Electronic transport in semiconducting half-Heusler (HH) matrices containing full-Heusler (FH) nanoinclusions strongly depends on the energy distribution of impurity states within the HH matrix with respect to the magnitude of the potential energy barrier at the HH/FH interfaces. - Highlights: • Coherent nanostructures enhanced thermoelectric behavior of half-Heusler alloys. • Nanostructures act as energy filter of

A study on H{sub 2}-TPR of Pt/Ce{sub 0.27}Zr{sub 0.73}O{sub 2} and Pt/Ce{sub 0.27}Zr{sub 0.70}La{sub 0.03}O{sub x} for soot oxidation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hailong [College of Chemical Engineering, Sichuan University, Chengdu 610064 (China); Wang, Jianli; Zhang, Yanhua [College of Chemistry, Sichuan University, Chengdu 610064 (China); Jiao, Yi [Xi’an Modern Chemistry Research Institute, Xi’an 710065 (China); Ren, Chengjun; Gong, Maochu [College of Chemistry, Sichuan University, Chengdu 610064 (China); Chen, Yaoqiang, E-mail: nic7501@scu.edu.cn [College of Chemical Engineering, Sichuan University, Chengdu 610064 (China); College of Chemistry, Sichuan University, Chengdu 610064 (China); Sichuan Provincial Vehicular Exhaust Gases Abatement Engineering Technology Center, Chengdu 610064 (China); Sichuan Provincial Environmental Catalytic Material Engineering Technology Center, Chengdu 610064 (China)

2016-07-30

Highlights: • The H{sub 2} consumption of the catalyst increases after aging. • The availability of surface lattice oxygen could be improved after aging. • Sintering and encapsulation of Pt weaken H{sub 2} spillover mechanism. • Soot oxidation activity is closely related to reduction temperature. - Abstract: Pt/Ce{sub 0.27}Zr{sub 0.73}O{sub 2} and Pt/Ce{sub 0.27}Zr{sub 0.70}La{sub 0.03}O{sub x} catalysts, prepared by co-precipitation and impregnation methods, were thermally treated at different temperatures for 10 h and then characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), H{sub 2} temperature-programmed reduction (H{sub 2}-TPR), thermogravimetric analysis (TGA) and soot temperature-programmed oxidation (soot-TPO). Due to thermal effect on the structural and textural properties, the aged catalysts show increased reduction temperatures. But, interestingly, more H{sub 2} consumption is detected, which would be ascribed to the increased mobility of bulk oxygen and surface lattice oxygen. The promoting and synergistic roles of Pt in H{sub 2}-TPR are discussed and it reveals that the sintering and encapsulation of Pt would weaken the H{sub 2} spillover mechanism and the addition of La is beneficial to stabilize the synergistic effect between Pt and Ce. On the other hand, a humble role of Pt on promoting soot oxidation activity is found in this study. Not all oxygen species available in H{sub 2}-TPR can be used for soot oxidation. The deactivation of the aged catalysts is closely related to the reduction temperature.

Zr, Hf, Mo and W-containing oxide phases as pinning additives in Bi-2212 superconductor

International Nuclear Information System (INIS)

Makarova, M.V.; Kazin, P.E.; Tretyakov, Yu.D.; Jansen, M.; Reissner, M.; Steiner, W.

2005-01-01

Phase formation was investigated in Bi-Sr-Ca-Cu-M-O (M = Mo, W) systems at 850-900 deg C. It was found that Sr 2 CaMO 6 phases were chemically compatible with Bi-2212. The composites Bi-2212-Sr 2 CaMO 6 and Bi-2212-SrAO 3 (A = Zr, Hf) were obtained from a sol-gel precursor using crystallisation from the melt. The materials consisted of Bi-2212 matrix and submicron or micron grains of the corresponding dispersed phase. T c was equal or exceeded that for undoped Bi-2212, reaching T c = 97 K in the Mo-containing composite. The composites exhibited enhanced pinning in comparison with similar prepared pure Bi-2212, especially at T = 60 K. The best pinning parameters were observed for the Bi-2212-Sr 2 CaWO 6 composite

Deactivation Studies of Rh/Ce0.8Zr0.2O2 Catalysts in Low Temperature Ethanol Steam Reforming

Energy Technology Data Exchange (ETDEWEB)

Platon, Alex; Roh, Hyun-Seog; King, David L.; Wang, Yong

2007-10-30

Rapid deactivation of Rh/Ce0.8Zr0.2O2 catalysts in low temperature ethanol steam reforming was studied. A significant build-up of carbonaceous intermediate, instead of carbon deposit, was observed at a lower reaction temperature which was attributed to the rapid catalyst deactivation. Co-feed experiments indicated that acetone and ethylene caused more severe catalyst deactivation than other oxygenates such as acidic acid and acetaldehyde.

A comparative UV-vis-diffuse reflectance study on the location and interaction of cerium ions in Al- and Zr-pillared montmorillonite clays

International Nuclear Information System (INIS)

Rao, G. Ranga; Mishra, Braja Gopal

2005-01-01

The environment, location and interaction of the Ce 3+ ions in the micropores of Al- and Zr-pillared clays have been studied by UV-vis-diffuse reflectance spectroscopy (UV-vis-DRS). The DRS spectra show that the chemical environment of the Ce 3+ ions in cerium exchanged clay is different from that of the Al- and Zr-pillared clays. The Al-Ce pillared clays (Al-Ce-PM) show four distinct absorption bands at 224, 263, 294 and 342 nm in the UV region which are attributed to 4f → 5d interconfigurational transitions of Ce 3+ ions associated with alumina pillars. The O 2- → Ce 3+ charge transfer band observed at 263 nm for Ce-exchanged and Al-Ce-PM clays is blue shifted by 10 nm for Ce-Zr-pillared clays (Ce-Zr-PM) due to fully hydrated Ce 3+ ions. The Ce 3+ ions are incorporated in the Al- and Zr-pillars possibly as AlCeO 3 and Ce x Zr 1-x O 2 particles upon heat treatment

Large Magnetic Anisotropy in HfMnP

Science.gov (United States)

Parker, David; Lamichhane, Tej; Taufour, Valentin; Masters, Morgan; Thimmaiah, Srinivasa; Bud'Ko, Ser'gey; Canfield, Paul

We present a theoretical and experimental study of two little-studied manganese phosphide ferromagnets, HfMnP and ZrMnP, with Curie temperatures above room temperature. We find an anisotropy field in HfMnP approaching 10 T - larger than that of the permanent magnet workhorse NdFeB magnets. From theory we determine the source of this anisotropy. Our results show the potential of 3d-element-based magnetic materials for magnetic applications.

The water adsorption on the surfaces of SrMO3 (M= Ti, Zr, and Hf) crystalline oxides: quantum and classical modelling

International Nuclear Information System (INIS)

Evarestov, R A; Bandura, A V; Blokhin, E N

2007-01-01

Hybrid HF-DFT LCAO simulations of (001) surface properties and water adsorption on cubic SrTiO 3 , SrZrO 3 , and SrHfO 3 perovskites are performed in a single-slab model framework. The optimized atomic structures and water adsorption energies have been calculated for a single water molecule per the surface unit cell. The possibility of the water molecular dissociation was investigated. Basing on the experimental data and results of the ab initio calculations the new interatomic potentials have been developed to describe the bulk and surface properties of the binary and ternary titanium and zirconium oxides. The proposed force-field takes into account the polarization effects via the shell model. The force-field suggested was used in the molecular mechanics calculations with the extended unit cells to study the possible surface reconstruction upon relaxation and hydroxylation of cubic perovskites

Thermoelectric properties of TiNiSn and Zr0.5Hf0.5NiSn thin films and superlattices with reduced thermal conductivities

International Nuclear Information System (INIS)

Jaeger, Tino

2013-01-01

Rising energy costs and enhanced CO 2 emission have moved research about thermoelectric (TE) materials into focus. The suitability of a material for usage in TE devices depends on the figure of merit ZT and is equal to α 2 σTκ -1 including Seebeck coefficient α, conductivity σ, temperature T and thermal conductivity κ. Without affecting the power factor α 2 σ, using nanostructuring, ZT should here be increased by a depressed thermal conductivity. As half-Heusler (HH) bulk materials, the TE properties of TiNiSn and Zr 0.5 Hf 0.5 NiSn have been extensively studied. Here, semiconducting TiNiSn and Zr 0.5 Hf 0.5 NiSn thin films were fabricated for the first time by dc magnetron sputtering. On MgO (100) substrates, strongly textured polycrystalline films were obtained at substrate temperatures of about 450 C. The film consisted of grains with an elongation perpendicular to the surface of 55 nm. These generated rocking curves with FWHMs of less than 1 . Structural analyses were performed by X ray diffraction (XRD). Having deposition rates of about 1 nms -1 within shortest time also films in the order of microns were fabricated. For TiNiSn the highest in-plane power factor of about 0.4 mWK -2 m -1 was measured at about 550 K. In addition, at room temperature a cross-plane thermal conductivity of 2.8 Wm -1 K -1 was observed by the differential 3ω method. Because the reduction of thermal conductivity by mass fluctuation is well-known and interface scattering of phonons is expected, superlattices (SL) were fabricated. Therefore, TiNiSn and Zr 0.5 Hf 0.5 NiSn were successively deposited. While the sputter cathodes were continuously running, for fabrication of SLs the substrates were moved from one to another. The high crystal quality of the SLs and the sharp interfaces were proven by satellite peaks (XRD) and Scanning Transmission Electron Microscopy (STEM). For a SL with a periodicity of 21 nm (TiNiSn and Zr 0.5 Hf 0.5 NiSn each 15 nm) at a temperature of 550 K an

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

Science.gov (United States)

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.

Bio diesel synthesis from pongamia pinnata oil over modified CeO2 catalysts

International Nuclear Information System (INIS)

Venkatesh; Sathgatta Z, M. S.; Manjunatha, S.; Thammannigowda V, V.

2014-01-01

This study investigates the use of CeO 2 , ZrO 2 , Mg O and CeO 2 -ZrO 2 , CeO 2 -Mg O, CeO 2 -ZrO 2 -Mg O mixed oxides as solid base catalysts for the transesterification of Pongamia pinnata oil with methanol to produce bio diesel. SO 4 2- /CeO 2 and SO 4 2- /CeO 2 -ZrO 2 were also prepared and used as solid acid catalysts for esterification of Pongamia pinnata oil (P-oil) to reduce the % of free fatty acid (FFA) in P-oil. The oxide catalysts were prepared by an incipient wetness impregnation method and characterized by techniques such as NH 3 -Tpd for surface acidity, CO 2 -Tpd for surface basicity and powder X-ray diffraction for crystallinity. The effect of nature of the catalyst, methanol to P-oil molar ratio and reaction time in esterification as well as in transesterification was investigated. The catalytic materials were reactive d and reused for five reaction cycles and the results showed that the ceria based catalysts have reasonably good reusability both in esterification and transesterification reaction. The test results also revealed that the CeO 2 -ZrO 2 modified with Mg O could have potential for use in the large scale bio diesel production. (Author)

Influence of boron vacancies on phase stability, bonding and structure of MB2 (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W) with AlB2 type structure

International Nuclear Information System (INIS)

Dahlqvist, Martin; Rosen, Johanna; Jansson, Ulf

2015-01-01

Transition metal diborides in hexagonal AlB 2 type structure typically form stable MB 2 phases for group IV elements (M  =  Ti, Zr, Hf). For group V (M  =  V, Nb, Ta) and group VI (M  =  Cr, Mo, W) the stability is reduced and an alternative hexagonal rhombohedral MB 2 structure becomes more stable. In this work we investigate the effect of vacancies on the B-site in hexagonal MB 2 and its influence on the phase stability and the structure for TiB 2 , ZrB 2 , HfB 2 , VB 2 , NbB 2 , TaB 2 , CrB 2 , MoB 2 , and WB 2 using first-principles calculations. Selected phases are also analyzed with respect to electronic and bonding properties. We identify trends showing that MB 2 with M from group V and IV are stabilized when introducing B-vacancies, consistent with a decrease in the number of states at the Fermi level and by strengthening of the B–M interaction. The stabilization upon vacancy formation also increases when going from M in period 4 to period 6. For TiB 2 , ZrB 2 , and HfB 2 , introduction of B-vacancies have a destabilizing effect due to occupation of B–B antibonding orbitals close to the Fermi level and an increase in states at the Fermi level. (paper)

Analysis of Fe, Ca, Ti, Ba, Ce, Zr and La element in the Sea sediment at Muria peninsula by X RF method

International Nuclear Information System (INIS)

Sukirno and Sri Murniasih

2009-01-01

he analysis of metals (Fe, Ca, Ti, Ba, Ce, Zr and La) in the sea sediment environmental samples at Muria peninsula has been carried out with X-Ray Fluorescence (XRF) method. The aim of this analysis is to know the distribution metals which accommodate the recent environmental data in supporting the license of site and Environmental Impact Assessment (EIA) for the Nuclear Power Plants (NPP). Samples taken preparation and analysis based on the procedures of environmental analysis. The result analysis that contents of mayor elements in 7 sea sediment location of sampling were Ca, Ti and Fe with concentration are (6.74 – 11.69 ) %; (0.74 – 6.89 ) % and (0.45 -1.94 ) % successively; while minor elements were Ba, Ce, Zr and La with concentration are 451.4 – 1331.6 ) mg/kg; (201.8 – 427.3) mg/kg; (192.3 – 338.5) mg/kg dan (171.7 – 298.4) mg/kg. The statistic test result shows that sampling location there is a significant difference all of element with the level significant of 95 %. (author)

Comparative study on cubic and tetragonal CexZr1-xO2 supported MoO3-catalysts for sulfur-resistant methanation

Science.gov (United States)

Liu, Zhaopeng; Xu, Yan; Cheng, Jiaming; Wang, Weihan; Wang, Baowei; Li, Zhenhua; Ma, Xinbin

2018-03-01

In this paper, two kinds of CexZr1-xO2 solid solution carriers with different Ce/Zr ratio were prepared by one-step co-precipitation method: the cubic Ce0.8Zr0.2O2 and the tetragonal Ce0.2Zr0.8O2 support. The MoO3/Ce0.8Zr0.2O2 and MoO3/Ce0.2Zr0.8O2 catalysts were prepared by incipient wetness impregnation method for comparative study on sulfur-resistant methanation reaction. The N2 adsorption/desorption, X-ray diffraction (XRD), Raman spectroscopy (RS), X-ray photoelectron (XPS), transmission electron microscopy (TEM), temperature-programmed reduction by hydrogen (H2-TPR) were undertaken to characterize the physico-chemical properties of the samples. The results indicated that the prepared MoO3/CexZr1-xO2 catalysts have a mesoporous structure with high surface area and uniform pore size distribution, achieving good MoO3 dispersion on CexZr1-xO2 supports. As for the catalytic performance of sulfur-resistant methanation, the cubic MoO3/Ce0.8Zr0.2O2 exhibited better than the tetragonal MoO3/Ce0.2Zr0.8O2 catalyst at reaction temperature 400 °C and 450 °C. CO conversion on the cubic MoO3/Ce0.8Zr0.2O2 catalyst was 50.1% at 400 °C and 75.5% at 450 °C, which is respectively 7% and 20% higher than that on the tetragonal MoO3/Ce0.2Zr0.8O2 catalyst. These were mainly attributed to higher content of active MoS2 on the surface of catalyst, the enhanced oxygen mobility, increased Mo-species dispersion as well as the excellent reducibility resulted from the increased amount of the reducible Ce3+ on the cubic MoO3/Ce0.8Zr0.2O2 catalyst.

The water adsorption on the surfaces of SrMO{sub 3} (M= Ti, Zr, and Hf) crystalline oxides: quantum and classical modelling

Energy Technology Data Exchange (ETDEWEB)

Evarestov, R A; Bandura, A V; Blokhin, E N [Department of Quantum Chemistry, St. Petersburg State University 26 University Ave., Petergoff, St. Petersburg, 198504 (Russian Federation)

2007-12-15

Hybrid HF-DFT LCAO simulations of (001) surface properties and water adsorption on cubic SrTiO{sub 3}, SrZrO{sub 3}, and SrHfO{sub 3} perovskites are performed in a single-slab model framework. The optimized atomic structures and water adsorption energies have been calculated for a single water molecule per the surface unit cell. The possibility of the water molecular dissociation was investigated. Basing on the experimental data and results of the ab initio calculations the new interatomic potentials have been developed to describe the bulk and surface properties of the binary and ternary titanium and zirconium oxides. The proposed force-field takes into account the polarization effects via the shell model. The force-field suggested was used in the molecular mechanics calculations with the extended unit cells to study the possible surface reconstruction upon relaxation and hydroxylation of cubic perovskites.

Remote plasma-assisted nitridation (RPN): applications to Zr and Hf silicate alloys and Al2O3

International Nuclear Information System (INIS)

Hinkle, Chris; Lucovsky, Gerry

2003-01-01

Remote plasma-assisted nitridation or RPN is demonstrated to be a processing pathway for nitridation of Zr and Hf silicate alloys, and for Al 2 O 3 , as well. The dependence of nitrogen incorporation on the process pressure is qualitatively similar to what has been reported for the plasma-assisted nitridation of SiO 2 , the lower the process pressure the greater the nitrogen incorporation in the film. The increased incorporation of nitrogen has been correlated with the penetration of the plasma-glow into the process chamber, and the accompanying increase in the concentration of N 2 + ions that participate in the reactions leading to bulk incorporation. The nitrogen incorporation as been studied by Auger electron spectroscopy (AES), secondary ion mass spectrometry (SIMS) and X-ray absorption spectroscopy (XAS)

Synthesis, spectral, DFT modeling, cytotoxicity and microbial studies of novel Zr(IV), Ce(IV) and U(VI) piroxicam complexes

Science.gov (United States)

El-Shwiniy, Walaa H.; Zordok, Wael A.

2018-06-01

The Zr(IV), Ce(IV) and U(VI) piroxicam anti-inflammatory drug complexes were prepared and characterized using elemental analyses, conductance, IR, UV-Vis, magnetic moment, IHNMR and thermal analysis. The ratio of metal: Pir is found to be 1:2 in all complexes estimated by using molar ratio method. The conductance data reveal that Zr(IV) and U(VI) chelates are non-electrolytes except Ce(IV) complex is electrolyte. Infrared spectroscopic confirm that the Pir behaves as a bidentate ligand co-ordinated to the metal ions via the oxygen and nitrogen atoms of ν(Cdbnd O)carbonyl and ν(Cdbnd N)pyridyl, respectively. The kinetic parameters of thermogravimetric and its differential, such as activation energy, entropy of activation, enthalpy of activation, and Gibbs free energy evaluated using Coats-Redfern and Horowitz-Metzger equations for Pir and complexes. The geometry of the piroxicam drug in the Free State differs significantly from that in the metal complex. In the time of metal ion-drug bond formation the drug switches-on from the closed structure (equilibrium geometry) to the open one. The antimicrobial tests were assessed towards some types of bacteria and fungi. The in vitro cell cytotoxicity of the complexes in comparison with Pir against colon carcinoma (HCT-116) cell line was measured. Optimized geometrical structure of piroxicam ligand by using DFT calculations.

Beta decomposition processes in Hf-rich Hf--Nb alloys

International Nuclear Information System (INIS)

Jones, W.B.; Taggart, R.; Polonis, D.H.

1978-01-01

The decomposition of the bcc β-phase by both athermal and isothermal processes has been investigated in Hf-rich Hf--Nb alloys. An all β-phase structure is retained in chill-cast alloys containing 30 to 50 at.% Nb (Cb), although electron diffraction streaking effects and the behavior of the temperature coefficient of electrical resistivity indicate the presence of a bcc lattice instability similar to that reported in solute lean Ti and Zr alloys. Aging a Hf 0 . 65 Nb 0 . 35 alloy at 400 and 600 0 C resulted in the direct precipitation of a fine dispersion of α-phase needles; this morphology differs from the discs of transition α (α/sub t/) which Carpenter et al observed in Nb-rich Nb 0 . 68 Hf 0 . 32 . During continued aging, the needles grow selectively to form colonies or groups of needles in which both the individual needles and the groups of needles have major axes aligned along (110)/sub β/ type directions. The initial α-phase particles exhibit the Burgers orientation relationship with the parent matrix; continued aging changes the electron diffraction patterns in a way that is similar to that observed in aged Ti--Mo and Ti--Mo--Al alloys where they were attributed to the α-phase having a different crystallographic relationship to the β-phase (Type 2 α-phase). The observed changes in the electron diffraction patterns of aged Hf 0 . 65 Nb 0 . 35 cannot be described as resulting from strained Burgers α-phase

Multielement (P-Yb-Zr-Ce-Al-Ca) fiber for moderate-power laser application with enhanced photodarkening resistivity

Energy Technology Data Exchange (ETDEWEB)

Dhar, Anirban; Paul, Mukul Chandra [CSIR-Central Glass and Ceramic Research Institute, 196 Raja S. C. Mullick Road, Jadavpur, Kolkata 700 032 (India); Das, Shyamal; Reddy, Pinninty Harshavardhan; Siddiki, Salim H.; Dutta, Debjit; Pal, Mrinmay [Academy of Scientific and Innovative Research (AcSIR), CSIR-CGCRI Campus, Kolkata 700 032 (India); Kir' yanov, Alexander V. [Centro de Investigaciones en Optica, Loma del Bosque 115, Col. Lomas del Campestre, Leon 37150, Guanajuato (Mexico)

2017-06-15

Multielement (ME) (P-Yb-Zr-Ce-Al-Ca) nanophase separated silica-glass-based optical fiber is fabricated through a conventional-modified chemical vapor deposition (MCVD) process, coupled with solution doping technique. The lasing and photodarkening behaviors of this ME fiber have been demonstrated and compared, in terms of its photodarkening (PD) performance at moderate pump powers (tens of Watts), with standard Yb-doped fiber with phospho-alumino-silicate (PAS) glass composition, which clearly reveals that the ME-Yb doped fiber is a promising candidate for laser applications with enhanced PD resistivity. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Microstructure and mechanical properties of a single crystal NiAl alloy with Zr or Hf rich G-phase precipitates

Science.gov (United States)

Locci, I. E.; Noebe, R. D.; Bowman, R. R.; Miner, R. V.; Nathal, M. V.; Darolia, R.

1991-01-01

The possibility of producing NiAl reinforced with the G-phase (Ni16X6Si7), where X is Zr or Hf, has been investigated. The microstructure of these NiAl alloys have been characterized in the as-cast and annealed conditions. The G-phases are present as fine cuboidal precipitates (10 to 40 nm) and have lattice parameters almost four times that of NiAl. They are coherent with the matrix and fairly resistant to coarsening during annealing heat treatments. Segregation and nonuniform precipitate distribution observed in as-cast materials were eliminated by homogenization at temperatures near 1600 K. Slow cooling from these temperatures resulted in large plate shaped precipitates, denuded zones, and a loss of coherency in some of the large particles. Faster cooling produced a homogeneous fine distribution of cuboidal G-phase particles in the matrix. Preliminary mechanical properties for the Zr-doped alloy are presented and compared to binary single crystal NiAl. The presence of these precipitates appears to have an important strengthening effect at temperatures not less than 1000 K compared to binary NiAl single crystals.

Microstructure and mechanical properties of a single crystal NiAl alloy with Zr or Hf rich G-phase precipitates

International Nuclear Information System (INIS)

Locci, I.E.; Noebe, R.D.; Bowman, R.R.; Miner, R.V.; Nathal, M.V.

1991-01-01

In this paper the possibility of producing NiAl reinforced with the G-phase (Ni 16 X 6 Si 7 ), where X is Zr or Hf, has been investigated. The microstructures of these NiAl alloys have been characterized in the as-cast and annealed conditions. The G-phases are present as fine cuboidal precipitates (10 to 40 nm) and have lattice parameters almost four times that of NiAl. They are coherent with the matrix and fairly resistant to coarsening during annealing heat treatments. Segregation and non-uniform precipitate distribution observed in as-cast materials were eliminated by homogenization at temperatures near 1600 K. Slow cooling from these temperatures resulted in large plate shaped precipitates, denuded zones, and a loss of coherency in some of the large particles. Faster cooling produced a homogeneous fine distribution of cuboidal G-phase particles (≤10 nm) in the matrix. Preliminary mechanical properties for the Zr-doped alloy are presented and compared to binary single crystal NiAl. The presence of these precipitates appears to have an important strengthening effect at temperatures ≥1000 K compared to binary NiAl single crystals

Bio diesel synthesis from pongamia pinnata oil over modified CeO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Venkatesh; Sathgatta Z, M. S.; Manjunatha, S.; Thammannigowda V, V., E-mail: mohamed.shamshuddin@gmail.com [HMS Institute of Technology, Chemistry Research Laboratory, NH4, Kyathsandra, Tumkur, 572104 Karnataka (India)

2014-07-01

This study investigates the use of CeO{sub 2}, ZrO{sub 2}, Mg O and CeO{sub 2}-ZrO{sub 2}, CeO{sub 2}-Mg O, CeO{sub 2}-ZrO{sub 2}-Mg O mixed oxides as solid base catalysts for the transesterification of Pongamia pinnata oil with methanol to produce bio diesel. SO{sub 4}{sup 2-}/CeO{sub 2} and SO{sub 4}{sup 2-}/CeO{sub 2}-ZrO{sub 2} were also prepared and used as solid acid catalysts for esterification of Pongamia pinnata oil (P-oil) to reduce the % of free fatty acid (FFA) in P-oil. The oxide catalysts were prepared by an incipient wetness impregnation method and characterized by techniques such as NH{sub 3}-Tpd for surface acidity, CO{sub 2}-Tpd for surface basicity and powder X-ray diffraction for crystallinity. The effect of nature of the catalyst, methanol to P-oil molar ratio and reaction time in esterification as well as in transesterification was investigated. The catalytic materials were reactive d and reused for five reaction cycles and the results showed that the ceria based catalysts have reasonably good reusability both in esterification and transesterification reaction. The test results also revealed that the CeO{sub 2}-ZrO{sub 2} modified with Mg O could have potential for use in the large scale bio diesel production. (Author)

Oxidative mobilization of cerium and uranium and enhanced release of "immobile" high field strength elements from igneous rocks in the presence of the biogenic siderophore desferrioxamine B

Science.gov (United States)

Kraemer, Dennis; Kopf, Sebastian; Bau, Michael

2015-09-01

Polyvalent trace elements such as the high field strength elements (HFSE) are commonly considered rather immobile during low-temperature water-rock interaction. Hence, they have become diagnostic tools that are widely applied in geochemical studies. We present results of batch leaching experiments focused on the mobilization of certain HFSE (Y, Zr, Hf, Th, U and rare earth elements) from mafic, intermediate and felsic igneous rocks in the presence and absence, respectively, of the siderophore desferrioxamine B (DFOB). Our data show that DFOB strongly enhances the mobility of these trace elements during low-temperature water-rock interaction. The presence of DFOB produces two distinct features in the Rare Earths and Yttrium (REY) patterns of leaching solutions, regardless of the mineralogical and chemical composition or the texture of the rock type studied. Bulk rock-normalized REY patterns of leaching solutions with DFOB show (i) a very distinct positive Ce anomaly and (ii) depletion of La and other light REY relative to the middle REY, with a concave downward pattern between La and Sm. These features are not observed in experiments with hydrochloric acid, acetic acid or deionized water. In DFOB-bearing leaching solutions Ce and U are decoupled from and selectively enriched relative to light REY and Th, respectively, due to oxidation to Ce(IV) and U(VI). Oxidation of Ce3+ and U4+ is promoted by the significantly higher stability of the Ce(IV) and U(VI) DFOB complexes as compared to the Ce(III) and U(IV) DFOB complexes. This is similar to the relationship between the Ce(IV)- and Ce(III)-pentacarbonate complexes that cause positive Ce anomalies in alkaline lakes. However, while formation of Ce(IV) carbonate complexes is confined to alkaline environments, Ce(IV) DFOB complexes may produce positive Ce anomalies even in mildly acidic and near-neutral natural waters. Siderophore-promoted dissolution processes also significantly enhance mobility of other 'immobile' HFSE

Oxidation behaviour of Zr-Ce alloys. Kinetic and microstructure aspects

International Nuclear Information System (INIS)

Rouillon, Ludovic

1996-01-01

As Zircaloy alloys are used for fuel rods in pressurized water nuclear reactors, this research thesis aims at studying and improving corrosion resistance of zirconium alloys while maintaining their mechanical properties. It more precisely deals with the kinetic and microstructure aspects of the external corrosion of the cladding by the coolant. In the case of Zircaloys, this corrosion is characterized by a kinetic transition from an initially parabolic to a linear regime. This research aims at intervening on this transition by elaborating zirconium alloys containing an element which stabilizes zirconia, in this case cerium. After having reported a bibliographical study on sheath oxidation, on parameters which influence sheath oxidation kinetics, on zirconia stabilization by doping elements, on the interest of lanthanide oxides, the author reports a feasibility study on the use of cerium (choice and preparation, sintered ceramic characterization, annealing of stabilized zirconia), reports a metallurgical study of Zr-Ce alloys, reports the study of the oxidation behaviour of these alloys (in autoclave, in presence of oxygen, under oxygen and then water) and the characterization of the microstructures of the oxide layers. He finally discusses the relationship between microstructure and oxidation kinetics, the role of cerium in the oxidation process, and the role of water in the oxidation process [fr

In situ screen-printed BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} electrolyte-based protonic ceramic membrane fuel cells with layered SmBaCo{sub 2}O{sub 5+x} cathode

Energy Technology Data Exchange (ETDEWEB)

Lin, Bin; Dong, Yingchao; Zhang, Shangquan; Hu, Mingjun; Zhou, Yang; Meng, Guangyao [Department of Materials Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China); Yan, Ruiqiang [Department of Materials Engineering, Taizhou University, Linhai, Zhejiang 317000 (China)

2009-01-15

In order to develop a simple and cost-effective route to fabricate protonic ceramic membrane fuel cells (PCMFCs) with layered SmBaCo{sub 2}O{sub 5+x} (SBCO) cathode, a dense BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} (BZCY) electrolyte was fabricated on a porous anode by in situ screen printing. The porous NiO-BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} (NiO-BZCY) anode was directly prepared from metal oxide (NiO, BaCO{sub 3}, ZrO{sub 2}, CeO{sub 2} and Y{sub 2}O{sub 3}) by a simple gel-casting process. An ink of metal oxide (BaCO{sub 3}, ZrO{sub 2}, CeO{sub 2} and Y{sub 2}O{sub 3}) powders was then employed to deposit BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} (BZCY) thin layer by an in situ reaction-sintering screen printing process on NiO-BZCY anode. The bi-layer with 25 {mu}m dense BZCY electrolyte was obtained by co-sintering at 1400 C for 5 h. With layered SBCO cathode synthesized by gel-casting on the bi-layer, single cells were assembled and tested with H{sub 2} as fuel and the static air as oxidant. A high open-circuit potential of 1.01 V, a maximum power density of 382 mW cm{sup -2}, and a low polarization resistance of the electrodes of 0.15 {omega} cm{sup 2} was achieved at 700 C. (author)

Pressure-induced phase transformation of HfO2

International Nuclear Information System (INIS)

Arashi, H.

1992-01-01

This paper reports on the pressure dependence of the Raman spectra of HfO 2 that was measured by a micro-Raman technique using a single-crystal specimen in the pressure range from 0 to 10 GPa at room temperature. The symmetry assignment of Raman bands of the monoclinic phase was experimentally accomplished from the polarization measurements for the single crystal. With increased pressure, a phase transformation for the monoclinic phase took place at 4.3 ± 0.3 GPa. Nineteen Raman bands were observed for the high-pressure phase. The spectral structure of the Raman bands for the high-pressure phase was similar with those reported previously for ZrO 2 . The space group for the high pressure phase of HfO 2 was determined as Pbcm, which was the same as that of the high-pressure phase for ZrO 2 on the basis of the number and the spectral structure of the Raman bands

The study on catalytic performance of CuO/CexZr1-xO2 catalyst in carbon monoxide oxidation

Directory of Open Access Journals (Sweden)

Huang Jinhua

2017-12-01

Full Text Available A series of CuO/CexZr1-xO2 samples were prepared by incipient-wetness impregnation method with CexZr1-xO2 used as the catalyst carrier which was synthesized by co-precipitation method.The influences of the mass ratio of CeO2:ZrO2 and CuO loading were investigated using catalytic activity test,XRD,BET,H2-TPR,and CO-TPR techniques.The results revealed that with a CeO2:ZrO2 mass ratio of 4:1 and 10% CuO loading,10%CuO/Ce0.815Zr0.185O2 catalyst showed a larger surface area and pore volume,a higher dispersity of CuO particles,better reduction property and CO oxidation property.Thus,10% CuO/Ce0.815Zr0.185O2 catalyst exhibited a high catalytic activity in the carbon monoxide oxidation with 100% CO conversion at the temperature as low as 80℃ under atmospheric pressure.

First results on the sorption behaviour of Rutherfordium from HCl/HF containing aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Schumann, D.; Nitsche, H. [Technische Univ. Dresden (Germany); Taut, S. [Forschungszentrum Rossendorf e.V. (FZR), Dresden (Germany); Jost, D.T.; Gaeggeler, H.W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Yakushev, A.B.; Buklanov, G.V.; Domanov, V.P.; Lien Din Thi [Joint Inst. for Nuclear Research, Dubna (Russian Federation); Kubica, B.; Misiak, R.; Szeglowski, Z. [NINP Cracow (Poland)

1997-09-01

Rutherfordium shows strong sorption on the cation exchanger DOWEX 50x8 at a concentration of 0.1 M HCl/10{sup -2} M HF. This shows that Rf behaves under these conditions differently from Hf and Zr and more like Th under these conditions. (author) 1 fig., 5 refs.

Anodic Fabrication of Ti-Nb-Zr-O Nanotube Arrays

Directory of Open Access Journals (Sweden)

Qiang Liu

2014-01-01

Full Text Available Highly ordered Ti-Nb-Zr-O nanotube arrays were fabricated through pulse anodic oxidation of Ti-Nb-Zr alloy in 1 M NaH2PO4 containing 0.5 wt% HF electrolytes. The effect of anodization parameters and Zr content on the microstructure and composition of Ti-Nb-Zr-O nanotubes was investigated using a scanning electron microscope equipped with energy dispersive X-ray analysis. It was found that length of the Ti-Nb-Zr-O nanotubes increased with increase of Zr contents. The diameter and the length of Ti-Nb-Zr-O nanotubes could be controlled by pulse voltage. XRD analysis of Ti-Nb-Zr-O samples annealed at 500°C in air indicated that the (101 diffraction peaks shifted from 25.78° to 25.05° for annealed Ti-Nb-Zr-O samples with different Zr contents because of larger lattice parameter of Ti-Nb-Zr-O compared to that of undoped TiO2.

Development and characterization of nickel catalysts supported in CeO2-ZrO2-Al2O3, CeO2-La2O3-Al2O3 e ZrO2-La2O3-Al2O3 matrixes evaluated for methane reforming reactions

International Nuclear Information System (INIS)

Abreu, Amanda Jordão de

2012-01-01

Nowadays, the methane reforming is large interest industrial for the take advantage of these gas in production the hydrogen and synthesis gas (syngas). Among in the reactions of methane stand of the reactions steam reforming and carbon dioxide reforming of methane. The main catalysts uses in the methane reforming is Ni/Al 2 O 3 . However, the supported-nickel catalyst is susceptible to the deactivation or the destruction by coke deposition. The carbon dissolves in the nickel crystallite and its diffuses through the nickel, leading for formation of the carbon whiskers, which results in fragmentation of the catalyst. Modification of such catalysts, like incorporation of suitable promoters, is desirable to achieve reduction of the methane hydrogenolysis and/or promotion of the carbon gasification. Catalysts 5%Ni/Al 2 O 3 supported on solid solutions formed by ZrO 2 -CeO 2 , La 2 O 3 and CeO 2 -ZrO 2 -La 2 O 3 were prepared, characterized and evaluated in reactions steam and carbon dioxide reforming and partial oxidation of methane with objective the value effect loading solution solid in support. The supports were prepared by co-precipitation method and catalysts were prepared by impregnation method and calcined at 500 deg C. The supports and catalysts were characterized by Nitrogen Adsorption, method -rays diffraction (XRD), X-rays dispersive spectroscopy (XDS), spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR) to and temperature programmed reduction (TPR), Raman Spectroscopy, X-ray absorption spectroscopy and Thermogravimetric Analysis. After all the catalytic reactions check which the addition of solid solution is beneficial for Ni/Al 2 O 3 catalysts and the best catalysts are Ni/CeO 2 -La 2 O 3 -Al 2 O 3 . (author)

Effect of synthesis conditions on the nanopowder properties of Ce{sub 0.9}Zr{sub 0.1}O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Zimicz, M.G.; Fabregas, I.O.; Lamas, D.G. [CINSO (Centro de Investigaciones en Solidos) CONICET-CITEFA J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Larrondo, S.A., E-mail: susana@di.fcen.uba.ar [Laboratorio de Procesos Cataliticos, Departamento de Ingenieria Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Pabellon de Industrias, Ciudad Universitaria, 1428 Buenos Aires (Argentina)

2011-06-15

Graphical abstract: . The synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{sub 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. Research highlights: {yields} All samples exhibited the fluorite-type crystal structure, nanometric average crystallite size and negligible carbon content. {yields} Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. {yields} Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties. -- Abstract: In this work, the synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{sub 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. The objective is to evaluate the effect of synthesis conditions on the textural and morphological properties, and the crystal structure of the synthesized materials. The solids were characterized by nitrogen physisorption, Scanning Electron Microscopy (SEM), X-ray powder diffraction (XPD), and Carbon-Hydrogen-Nitrogen Elemental Analysis (CHN). All the powders exhibited nanometric crystallite size, fluorite-type structure and negligible carbon content. Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties.

Phase relations in crystalline ceramic nuclear waste forms the system UO/sub 2 + x/-CeO2-ZrO2-ThO2 at 12000C in air

International Nuclear Information System (INIS)

Pepin, J.G.; McCarthy, G.J.

1981-01-01

Steady-state phase relations in the system UO/sub 2 + x/-CeO 2 -ZrO 2 -ThO 2 were determined for application to phase relations in the high-level crystalline ceramic nuclear waste form Supercalcine-Ceramics. Samples were treated at 1200 0 C at an oxygen partial pressure of 0.21 atm and a total pressure of 1 atm. Phase assemblages were found to be composed of cubic solid solutions of the flourite structure type, solid solutions based on ZrO 2 , and orthorhombic solid solutions based on U 3 O 8

Emission and Performance Analysis of ZrO2 And CeO2 Coated Piston Using Refined Vegetable Oils

Science.gov (United States)

Hemanandh, J.; Narayanan, K. V.; Manoj, Vemuri

2017-05-01

Increase in global warming and pollution leads to look for an alternative fuel. The aim of this paper to improve the performance and to reduce the emissions in DI diesel engine. The 80% of ZrO2 and 20% of CeO2 were mixed and coated on the piston head using plasma spray method. The B10 fuel of various refined vegetable oil methyl esters were used as fuel. The test was conducted in the 4-stroke DI diesel engine at a constant speed of 1500 rpm. The results show that the brake thermal efficiency, NOx and BSFC was increased. The CO and HC were decreased.

A high performance BaZr0.1Ce0.7Y0.2O3-δ-based solid oxide fuel cell with a cobalt-free Ba0.5Sr0.5FeO3-δ–Ce0.8Sm0.2O2-δ composite cathode

NARCIS (Netherlands)

Sun, Wenping; Shi, Zhen; Fang, S.; Yan, Litao; Zhu, Zhiwen; Liu, Wei

2010-01-01

A cobalt-free Ba0.5Sr0.5FeO3-δ–Ce0.8Sm0.2O2-δ (BSF–SDC) composite is employed as a cathode for an anode-supported proton-conducting solid oxide fuel cells (H-SOFCs) using BaZr0.1Ce0.7Y0.2O3-δ (BZCY) as the electrolyte. The chemical compatibility between BSF and SDC is evaluated. The XRD results show

PAC study in the HfO2-SiO2 system

International Nuclear Information System (INIS)

Chain, C.Y.; Damonte, L.C.; Ferrari, S.; Munoz, E.; Torres, C. Rodriguez; Pasquevich, A.F.

2010-01-01

A high-k HfO 2 /SiO 2 gate stack is taking the place of SiO 2 as a gate dielectric in field effect transistors. This fact makes the study of the solid-state reaction between these oxides very important. Nanostructure characterization of a high-energy ball milled and post-annealed equimolar HfO 2 and amorphous SiO 2 powder mixture has been carried out by perturbed angular correlations (PAC) technique. The study was complemented with X-ray diffraction and positron annihilation lifetime spectroscopy (PALS). The experimental results revealed that the ball milling of equimolar mixtures increases the defects concentration in hafnium oxide. No solid-state reaction occurred even after 8 h of milling. The formation of HfSiO 4 (hafnon) was observed in the milled blends annealed at high temperatures.The PAC results of the milled samples are compared with those obtained for pure m-ZrO 2 subjected to high-energy ball milling and with reported microstructure data for the system ZrO 2 -SiO 2 .

Lifetime of the first excited 2{sup +} state in {sup 172}Hf and {sup 174}Hf

Energy Technology Data Exchange (ETDEWEB)

Gerst, Rosa-Belle; Stegemann, Simon; Jolie, Jan; Regis, Jean-Marc; Rudigier, Matthias; Saed-Samii, Nima; Zell, Karl Oskar [Institut fuer Kernphysik, Universitaet zu Koeln, Zuelpicher Str. 77, 50937 Koeln (Germany)

2014-07-01

Using the {sup 170}Yb(α,2n) and {sup 172}Yb(α,2n) reactions the lifetimes of the first excited 2{sup +} state in {sup 172}Hf and {sup 174}Hf have been measured in fast-timing experiments using the Cologne Orange-Spectrometer and 6 LaBr{sub 3}(Ce)-Detectors. The lifetimes were obtained analyzing e{sup -}-γ-coincidence time-spectra with the slope method. The new and more precise lifetimes correct existing, outdated lifetimes in nuclear databases. Additionally, the systematics of the B(E2,2{sub 1}{sup +}→0{sub 1}{sup +}) is studied.

Hydrogen Production by Steam Reforming of Ethanol on Rh-Pt Catalysts: Influence of CeO2, ZrO2, and La2O3 as Supports

Directory of Open Access Journals (Sweden)

Bernay Cifuentes

2015-11-01

Full Text Available CeO2-, ZrO2-, and La2O3-supported Rh-Pt catalysts were tested to assess their ability to catalyze the steam reforming of ethanol (SRE for H2 production. SRE activity tests were performed using EtOH:H2O:N2 (molar ratio 1:3:51 at a gaseous space velocity of 70,600 h−1 between 400 and 700 °C at atmospheric pressure. The SRE stability of the catalysts was tested at 700 °C for 27 h time on stream under the same conditions. RhPt/CeO2, which showed the best performance in the stability test, also produced the highest H2 yield above 600 °C, followed by RhPt/La2O3 and RhPt/ZrO2. The fresh and aged catalysts were characterized by TEM, XPS, and TGA. The higher H2 selectivity of RhPt/CeO2 was ascribed to the formation of small (~5 nm and stable particles probably consistent of Rh-Pt alloys with a Pt surface enrichment. Both metals were oxidized and acted as an almost constant active phase during the stability test owing to strong metal-support interactions, as well as the superior oxygen mobility of the support. The TGA results confirmed the absence of carbonaceous residues in all the aged catalysts.

Double-ceramic-layer thermal barrier coatings based on La{sub 2}(Zr{sub 0.7}Ce{sub 0.3}){sub 2}O{sub 7}/La{sub 2}Ce{sub 2}O{sub 7} deposited by electron beam-physical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Xu, Z.H. [Beijing Institute of Aeronautical Materials, Department 5, P.O. Box 81-5, Beijing 100095 (China); State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); He, L.M., E-mail: he_limin@yahoo.com [Beijing Institute of Aeronautical Materials, Department 5, P.O. Box 81-5, Beijing 100095 (China); Mu, R.D.; He, S.M.; Huang, G.H. [Beijing Institute of Aeronautical Materials, Department 5, P.O. Box 81-5, Beijing 100095 (China); Cao, X.Q., E-mail: xcao@ciac.jl.cn [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

2010-03-15

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La{sub 2}(Zr{sub 0.7}Ce{sub 0.3}){sub 2}O{sub 7} (LZ7C3) and La{sub 2}Ce{sub 2}O{sub 7} (LC) were deposited by electron beam-physical vapor deposition (EB-PVD). The composition, interdiffusion, surface and cross-sectional morphologies, cyclic oxidation behavior of DCL coating were studied. Energy dispersive spectroscopy and X-ray diffraction analyses indicate that both LZ7C3 and LC coatings are effectively fabricated by a single LZ7C3 ingot with properly controlling the deposition energy. The chemical compatibility of LC coating and thermally grown oxide (TGO) layer is unstable. LaAlO{sub 3} is formed due to the chemical reaction between LC and Al{sub 2}O{sub 3} which is the main composition of TGO layer. Additionally, the thermal cycling behavior of DCL coating is influenced by the interdiffusion of Zr and Ce between LZ7C3 and LC coatings. The failure of DCL coating is a result of the sintering of LZ7C3 coating surface, the chemical incompatibility of LC coating and TGO layer and the abnormal oxidation of bond coat. Since no single material that has been studied so far satisfies all the requirements for high temperature applications, DCL coating is an important development direction of TBCs.

Multiple excitation modes in ¹⁶³Hf

DEFF Research Database (Denmark)

Yadav, Rachita; Ma, J.C.; Marsh, J.C.

2014-01-01

Excited states of Hf163 were populated using the Zr94(Ge74,5n) reaction and the decay γ rays were measured with the Gammasphere spectrometer. Two previously known bands were extended to higher spins, and nine new bands were identified. In addition to bands associated with three- and five-quasiparticle...

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

Science.gov (United States)

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

2018-05-01

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

Production of hydrogen with methane decomposition using Ni-Mn/Ce-ZrO{sub 2} catalysts; Produccion de hidrogeno via descomposicion de metano mediante catalizadores de Ni-Mn/Ce-ZrO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Diaz, C; Hernandez-Pichardo, M L; Valenzuela, M A [Instituto Politecnico Nacional-ESIQIE, Mexico, D.F. (Mexico); Del Angel, P; Montoya de la Fuente, J.A. [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico)

2009-09-15

The catalytic decomposition of methane makes it possible to obtain CO and CO{sub 2} free hydrogen, which is a desirable characteristic for fuel cell applications. In addition, this method simultaneously obtains diverse carbon nanostructures with a large variety of applications. This work prepared catalysts with different Ni contents supported by Ce-Zr mixed oxides and doped with manganese to promote activity. The supports were synthesized with surfactant-assisted coprecipitation. The Ni and Mn deposits were performed using conventional impregnation for evaluation in the methane decomposition catalyst at 500 degrees Celsius. It was observed that with the incorporation of 1% of Mn into the Ni0 active phase, the conversion of methane into hydrogen and carbon nanostructures increased. The results of reduction at the programmed temperature indicate that the addition of Mn enables the formation of different NiO{sub x} species, increasing dispersion and the degree of reduction to Ni0. Analyses with electron and transmission microscopy show the formation of distinct species of carbon, including nanotubes, nanofibers and concentric onion-like structures, as well as a significant formation of encapsulated Ni0 particles. [Spanish] La descomposicion catalitica de metano permite la obtencion de hidrogeno libre de CO y CO{sub 2}, lo cual es una caracteristica deseable para su aplicacion en celdas de combustible. Ademas, por esta ruta, simultaneamente se obtienen diversas nanoestructuras de carbono con una gran variedad de aplicaciones. En este trabajo se prepararon catalizadores con diferentes contenidos de Ni soportados en oxidos mixtos Ce-Zr y se doparon con manganeso como promotor de actividad. Los soportes se sintetizaron por coprecipitacion asistida por surfactante y el deposito del Ni y del Mn se efectuo por impregnacion convencional para su evaluacion en la descomposicion catalitica de metano a 500 grados centigrados. Se observo que mediante la incorporacion de 1% de Mn a

Surfactant-controlled synthesis of Pd/Ce0.6Zr0.4O2 catalyst for NO reduction by CO with excess oxygen

International Nuclear Information System (INIS)

Chen, L.F.; Gonzalez, G.; Wang, J.A.; Norena, L.E.; Toledo, A.; Castillo, S.; Moran-Pineda, M.

2005-01-01

For the first time, this work reports a surfactant-controlled synthetic method to obtain a nanophase of mesoporous ceria-zirconia solid solution containing cationic defects in the crystalline structure. The incorporation of a cationic surfactant (myristyltrimethylammonium bromide) into the ceria-zirconia solid network not only controlled the pore diameter distribution but also induced creation of the lattice defect. Ceria-zirconia solid solution showed crystal microstrain and structural distortion that varied with the calcination temperature. Compared to pure ceria, the addition of zirconium to the ceria promoted the bulk oxygen reducibility and enhanced the thermal stability of the solid. Hydrogen could be stored into or released from the PdO/Ce 0.6 Zr 0.4 O 2 catalyst during the TPR procedure, which is associated to the formation/decomposition of a PdH x phase, due to the hydrogen dissociation catalyzed by metallic Pd. At cool start of reaction, NO reduction by CO with excess oxygen over the Pd/Ce 0.6 Zr 0.4 O 2 catalyst showed selectivity around 100% to N 2 . A competition between NO reduction by CO and CO oxidation by O 2 was observed: at reaction temperatures below 200 deg. C, NO inhibited CO oxidation activity; however, at reaction temperatures above 200 deg. C, high activity of CO oxidation resulted in an inhibition effect on NO reduction

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

Science.gov (United States)

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

Dopant concentration dependence of radiation-induced positive hysteresis of Ce:GSO and Ce:GSOZ

International Nuclear Information System (INIS)

Yanagida, Takayuki; Fujimoto, Yutaka; Watanabe, Kenichi

2014-01-01

Positive hysteresis and radiation tolerance to high-dose radiation exposure were investigated for Ce 0.5, 1, and 1.5%-doped Gd 2 SiO 5 (GSO) and for Zr co-doped GSO with the same Ce concentrations (GSOZ). When they were irradiated by 200–800 Gy 60 Co in 200 Gy steps, all Ce-doped GSO samples exhibited light yield enhancement (positive hysteresis). On the other hand, the light yield of GSOZ decreased greatly. Ce 0.5%-doped GSO showed the highest positive hysteresis, with ∼20% light yield enhancement. When the Ce concentration was increased, the positive hysteresis became weaker. - Highlights: • Positive hysteresis Ce 0.5, 1, and 1.5% doped GSO and GSOZ are studied. • Ce 0.5, 1, and 1.5% doped GSO show the positive hysteresis by 2–8 M rad 60 Co irradiation. • Ce 0.5, 1, and 1.5% doped GSOZ do not show the positive hysteresis. • By Zn co-doping, radiation tolerance of GSO becomes weaker. • By dense Ce doping, radiation tolerance of GSO and GSOZ are improved

Investigation of the stability of glass-ceramic composites containing CeTi2O6 and CaZrTi2O7 after ion implantation

Science.gov (United States)

Paknahad, Elham; Grosvenor, Andrew P.

2017-12-01

Glass-ceramic composite materials have been investigated for nuclear waste sequestration applications due to their ability to incorporate large amounts of radioactive waste elements. A key property that needs to be understood when developing nuclear waste sequestration materials is how the structure of the material responds to radioactive decay of nuclear waste elements, which can be simulated by high energy ion implantation. Borosilicate glass-ceramic composites containing brannerite-type (CeTi2O6) or zirconolite-type (CaZrTi2O7) oxides were synthesized at different annealing temperatures and investigated after being implanted with high-energy Au ions to mimic radiation induced structural damage. Backscattered electron (BSE) images were collected to investigate the interaction of the brannerite crystallites with the glass matrix before and after implantation and showed that the morphology of the crystallites in the composite materials were not affected by radiation damage. Surface sensitive Ti K-edge glancing angle XANES spectra collected from the implanted composite materials showed that the structures of the CeTi2O6 and CaZrTi2O7 ceramics were damaged as a result of implantation; however, analysis of Si L2,3-edge XANES spectra indicated that the glass matrix was not affected by ion implantation.

Investigation of the stability of glass-ceramic composites containing CeTi 2 O 6 and CaZrTi 2 O 7 after ion implantation

Energy Technology Data Exchange (ETDEWEB)

Paknahad, Elham; Grosvenor, Andrew P.

2017-12-01

Glass-ceramic composite materials have been investigated for nuclear waste sequestration applications due to their ability to incorporate large amounts of radioactive waste elements. A key property that needs to be understood when developing nuclear waste sequestration materials is how the structure of the material responds to radioactive decay of nuclear waste elements, which can be simulated by high energy ion implantation. Borosilicate glass-ceramic composites containing brannerite-type (CeTi2O6) or zirconolite-type (CaZrTi2O7) oxides were synthesized at different annealing temperatures and investigated after being implanted with high-energy Au ions to mimic radiation induced structural damage. Backscattered electron (BSE) images were collected to investigate the interaction of the brannerite crystallites with the glass matrix before and after implantation and showed that the morphology of the crystallites in the composite materials were not affected by radiation damage. Surface sensitive Ti K-edge glancing angle XANES spectra collected from the implanted composite materials showed that the structures of the CeTi2O6 and CaZrTi2O7 ceramics were damaged as a result of implantation; however, analysis of Si L2,3-edge XANES spectra indicated that the glass matrix was not affected by ion implantation.

An insight into the dopant selection for CeO2-based resistive-switching memory system: a DFT and experimental study

Science.gov (United States)

Hussain, Fayyaz; Imran, Muhammad; Rana, Anwar Manzoor; Khalil, R. M. Arif; Khera, Ejaz Ahmad; Kiran, Saira; Javid, M. Arshad; Sattar, M. Atif; Ismail, Muhammad

2018-03-01

The aim of this study is to figure out better metal dopants for CeO2 for designing highly efficient non-volatile memory (NVM) devices. The present DFT work involves four different metals doped interstitially and substitutionally in CeO2 thin films. First principle calculations involve electron density of states (DOS) and partial density of states (PDOS), and isosurface charge densities are carried out within the plane-wave density functional theory using GGA and GGA + U approach by employing the Vienna ab initio simulation package VASP. Isosurface charge density plots confirmed that interstitial doping of Zr and Ti metals truly assists in generating conduction filaments (CFs), while substitutional doping of these metals cannot do so. Substitutional doping of W may contribute in generating CFs in CeO2 directly, but its interstitial doping improves conductivity of CeO2. However, Ni-dopant is capable of directly generating CFs both as substitutional and interstitial dopants in ceria. Such a capability of Ni appears acting as top electrode in Ni/CeO2/Pt memory devices, but its RS behavior is not so good. On inserting Zr layer to make Ni/Zr:CeO2/Pt memory stacks, Ni does not contribute in RS characteristics, but Zr plays a vital role in forming CFs by creating oxygen vacancies and forming ZrO2 interfacial layer. Therefore, Zr-doped devices exhibit high-resistance ratio of 104 and good endurance as compared to undoped devices suitable for RRAM applications.

Raman spectroscopy used for structural investigations of anodically formed ZrO2

International Nuclear Information System (INIS)

Koneska, Zagorka; Arsova, Irena

2003-01-01

The structure of the oxide formed on Zr(99% + Hf) with anodic oxidation at different potentials in 1 mol/dm 3 H 3 PO 4 and 2 mol/dm 3 KOH solutions were investigated using Raman spectroscopy. Normally the anodic oxides of Zr form only crystals. Under certain circumstances, amorphous anodic ZrO 2 can be observed. Amorphous phase is observed for the anodically formed zirconium oxides in H 3 PO 4 . The oxide formed in KOH at potential of 80 V, where sparks appears on the Zr electrode showed crystalline structure. (Original)

Lu-Hf isotope systematics of fossil biogenic apatite and their effects on geochronology

Science.gov (United States)

Herwartz, Daniel; Münker, Carsten; Tütken, Thomas; Hoffmann, J. Elis; Wittke, Andreas; Barbier, Bruno

2013-01-01

Reliable methods for direct dating of biogenic apatite from pre-Pleistocene fossils are currently not available, and recent attempts using the Lu-Hf decay system yielded highly inaccurate ages for both bones and teeth. The geological processes accounting for this poor accuracy of Lu-Hf chronometry are not yet understood. Here we explore Lu-Hf systematics in fossil bones and teeth in detail, by applying five different sample digestion techniques that are tested on bones and composites of bone and sediment. Our current dataset implies that dissolution methods only slightly affect the resulting Lu-Hf ages, while clear differences between the individual digestion techniques became apparent for element concentrations. By analysing the insoluble leftovers from incomplete sample dissolution, four main reservoirs of Hf in fossil bones were identified: (1) a radiogenic end-member associated with apatite; (2) an unradiogenic end-member represented by the authigenic minerals or the embedding sediment; (3) a highly unradiogenic end-member that can be attributed to detrital zircon; and (4) a moderately soluble phase (probably a Zr(Hf)-phosphate) that yielded very low Lu/Hf but a highly radiogenic Hf isotope composition at the same time. This Zr(Hf)-phase must have been precipitated within the fossil bone sample at a late stage of burial history, thereby incorporating radiogenic 176Hf released from apatite surfaces over geological timescales. A second focus of our study is the effect of different sediment matrices and of crystal size on the preservation of pristine Lu-Hf isotope compositions in bioapatite. Because near-depositional Lu-Hf ages of phosphate fossils have previously been reported for the London Clay (England) and a calcareous marl from Tendaguru (Tanzania), we herein investigate specimens fossilised in carbonate matrices (calcareous marl from Oker, Germany; carbonate concretions from the Santana Formation, Brazil; carbonate from the Eifel, Germany) and argillaceous

Precise simultaneous determination of zirconium and hafnium in silicate rocks, meteorites and lunar samples. [Neutron reactions

Energy Technology Data Exchange (ETDEWEB)

Kumar, P A; Garg, A N; Ehmann, W D [Kentucky Univ., Lexington (USA). Dept. of Chemistry

1977-01-01

A precise, sensitive and rapid analytical technique has been developed for the simultaneous determination of Zr and Hf in natural silicate matrices. The technique is based on radiochemical neutron activation analysis and employs a rapid fusion dissolution of the sample and simultaneous precipitation of the Zr-Hf pair with p-hydroxybenzene arsenic acid in an acidic medium. The indicator radionuclides, /sup 95/Zr and /sup 181/Hf, are counted and the /sup 95/Zr activity is corrected for the contribution from U fission. The chemical yields of the radiochemical separation are based on Hf carrier. The yield is determined by reactivation of the processed samples and standards with a /sup 252/Cf isotopic neutron source and by counting the 18.6 sec half-life sup(179m)Hf. The RNAA procedure for Zr and Hf has been shown to be precise and accurate for natural silicate samples, based on replicate analyses of samples containing Zr in the range of 1 ..mu..g/g to over 600 ..mu..g/g. The procedure is relatively rapid with a total chemical processing time of approximately 3 hours. At least 4 samples are processed simultaneously. Ten additional elements (Fe, Cr, Co, Sc, Eu, La, Lu, Ce, Th and Tb) can be determined by direct Ge(Li) spectrometry (INAA) on the samples prior to dissolution for the RNAA determination of Zr and Hf. Corrections for the U fission contribution can be made on the basis of the known U content or from the INAA Th content, based on the relatively constant natural Th/U ratio.

Indirect phase transition of TiC, ZrC, and HfC crystal structures

Energy Technology Data Exchange (ETDEWEB)

Abavare, Eric K.K.; Dodoo, Samuel N.A. [Department of Physics, Kwame Nkrumah University of Science and Technology, Kumasi (Ghana); Uchida, Kazuyuki; Oshiyama, Atsushi [Department of Applied Physics, The University of Tokyo, Hongo, Tokyo (Japan); Nkurumah-Buandoh, George K.; Yaya, Abu [Department of Physics, University of Ghana, Legon (Ghana)

2016-06-15

We have performed first-principles calculations to analyze the electronic structures, static, and dynamical structural stabilities of the pressure-induced phase transformation of refractory compounds (transition-metal carbides) from NaCl-type (B1) to CsCl-type (B2) via zinc-blende phase using the plane-wave pseudopotential approach in the framework of the generalized gradient approximation (GGA) for the exchange and correlation functional. The ground-state properties, equilibrium lattice constant, bulk moduli, and band structures are determined for the stoichiometry of the compounds and compared with known experimental and theoretical values. We find that the phase-transition pressure for the indirect phase transition from B1→B2 via zinc-blende structure is about 17-fold for TiC, 12-fold for both ZrC and HfC, respectively, when compared with the direct phase transition. Calculated phonon instability exists for the CsCl-B2 phase, which can prevent the structures from forming and contrary to the zinc-blende and the NaCl-B1 phases. The band dispersion and electronic density of states for B1 and B2 crystal phases were explored and found to indicate metallic character in contrast with the zinc-blende phase, which has a pseudogap opening in the bandgap region suggesting a semiconducting property and also a frequency gap in the phonon spectrum. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

A comparative study of SrO and BaO doping to CeO2-ZrO2: Characteristic and its catalytic performance for three-way catalysts

International Nuclear Information System (INIS)

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

2013-01-01

Graphical abstract: Display Omitted Highlights: ► The prepared materials have a face-centered cubic structure and nanosize particles. ►Comparing to CZB, aged CZS has 494 μmol/g of OSC and 30 m 2 /g of surface area. ► CZS and CZB have similar NO sorption and reductive properties and different H 2 uptake. ► T 50 of Pt-Rh/CZS/LA is as low as 199 °C for CO, 228 °C for NO, and 252 °C for C 3 H 8 . ► Pt-Rh/CZS/LA has wider working-window at 320 °C under different λ value. -- Abstract: Ceria-zirconia-strontia (Ce 0.35 Zr 0.55 Sr 0.10 O 1.9 ) and ceria-zirconia-baria (Ce 0.35 Zr 0.55 Ba 0.10 O 1.9 ) were synthesized using an oxidation-co-precipitation method with hydrogen peroxide (H 2 O 2 ) as oxidant. The physical and chemical properties of the prepared materials were investigated using Brunauer–Emmett–Teller surface area characterization, transmission electron microscopy, X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, and oxygen pulse reaction. The prepared materials were used in preparing three-way catalysts with low Pt and Rh content. Moreover, catalytic activities were evaluated at a fixed bed under a simulated gaseous mixture. The results are as follows: (1) the prepared materials have a face-centered cubic structure and are nano-sized; (2) aged Ce 0.35 Zr 0.55 Sr 0.10 O 1.9 has higher oxygen storage capacity (494 μmol/g), better thermal stability (30 m 2 /g), good low-temperature reducibility, and high hydrogen uptake after TPR-redox cycles; (3) the light-off temperature (T 50 ) of Pt-Rh/CZS/LA can be as low as 199 °C for CO, 228 °C for NO, and 252 °C for C 3 H 8 ; and (4) Pt-Rh/CZS/LA has a fairly wide working-window.

Catalytic Oxidation of CO and Soot over Ce-Zr-Pr Mixed Oxides Synthesized in a Multi-Inlet Vortex Reactor: Effect of Structural Defects on the Catalytic Activity.

Science.gov (United States)

Bensaid, Samir; Piumetti, Marco; Novara, Chiara; Giorgis, Fabrizio; Chiodoni, Angelica; Russo, Nunzio; Fino, Debora

2016-12-01

In the present work, ceria, ceria-zirconia (Ce = 80 at.%, Zr = 20 at.%), ceria praseodymia (Ce = 80 at.%, Pr = 20 at.%) and ceria-zirconia-praseodymia catalysts (Ce = 80 at.%, Zr = 10 at.% and Pr = 10 at.%) have been prepared by the multi-inlet vortex reactor (MIVR). For each set of samples, two inlet flow rates have been used during the synthesis (namely, 2 ml min -1 , and 20 ml min -1 ) in order to obtain different particle sizes. Catalytic activity of the prepared materials has been investigated for CO and soot oxidation reactions. As a result, when the catalysts exhibit similar crystallite sizes (in the 7.7-8.8 nm range), it is possible to observe a direct correlation between the O v /F 2g vibrational band intensity ratios and the catalytic performance for the CO oxidation. This means that structural (superficial) defects play a key role for this process. The incorporation of Zr and Pr species into the ceria lattice increases the population of structural defects, as measured by Raman spectroscopy, according to the order: CeO 2  oxidation activity for these catalysts, in contrast with nanostructured ones (e.g., Ce-Zr-O nanopolyhedra, Ce-Pr-O nanocubes) described elsewhere (Andana et al. Appl. Catal. B 197: 125-137, 2016; Piumetti et al., Appl Catal B 180: 271-282, 2016).

High catalytic activity and stability of Ni/CexZr1-xO2/MSU-H for CH4/CO2 reforming reaction

Science.gov (United States)

Chang, Xiaoqian; Liu, Bingsi; Xia, Hong; Amin, Roohul

2018-06-01

How to reduce emission of CO2 as greenhouse gases, which resulted in global warming, is of very important significance. A series of Ni/CexZr1-xO2/MSU-H catalysts was prepared by means of hexagonally ordered mesoporous MSU-H with thermal and hydrothermal stabilities, which is cheap and can be synthesized in the large scale. The 10%Ni/Ce0.75Zr0.25O2/MSU-H catalyst presents high catalytic activity, stability and the ability of coke-resistance for CH4/CO2 reforming reaction due to high SBET (428 m2/g) and smaller Nio nanoparticle size (3.14 nm). The high dispersed Nio nanoparticles over MSU-H promoted the decomposition of CH4 and the carbon species accumulated on active Nio sites reacting with crystal lattice oxygen in Ce0.75Zr0.25O2 to form CO molecules. In the meantime, the remained oxygen vacancies on the interface between Nio and Ce0.75Zr0.25O2 could be supplemented via CO2. HRTEM images and XRD results of Ni/Ce0.75Zr0.25O2/MSU-H verified that high dispersion of Ni nanoparticles over Ni/Ce0.75Zr0.25O2/MSU-H correlated closely with the synergistic action between Ce0.75Zr0.25O2 and MSU-H as well as hexagonally ordered structure of MSU-H, which can provide effectively the oxygen storage capacity and inhibit the formation of coke.

Cube textured CeO2, BaZrO3 and LaAlO3 buffer layers on Ni based Substrates

International Nuclear Information System (INIS)

Deinhofer, C; Gritzner, G

2006-01-01

CeO 2 , BaZrO 3 as well as LaAlO 3 buffer layers were deposited on {100} Ni + 5 weight-% W substrates by a wet chemical technique. The solutions were prepared by dissolving the metal nitrates or acetates and zirconiumacetylacetonate, respectively, in mixtures of acetic acid, methanol and water. The solutions were applied by dip- or spincoating, dried at 135 deg. C and annealed at temperatures between 900 and 1 400 deg. C depending on the buffer layer for 15 min. under Ar-5% H 2 gas flow. Pole-figure measurements proved the exact texture of each buffer layer. Electron microscopy showed dense and smooth buffer layers

OMS, OM(η2-SO), and OM(η2-SO)(η2-SO2) molecules (M = Ti, Zr, Hf): infrared spectra and density functional calculations.

Science.gov (United States)

Liu, Xing; Wang, Xuefeng; Wang, Qiang; Andrews, Lester

2012-07-02

Infrared spectra of the matrix isolated OMS, OM(η(2)-SO), and OM(η(2)-SO)(η(2)-SO(2)) (M = Ti, Zr, Hf) molecules were observed following laser-ablated metal atom reactions with SO(2) during condensation in solid argon and neon. The assignments for the major vibrational modes were confirmed by appropriate S(18)O(2) and (34)SO(2) isotopic shifts, and density functional vibrational frequency calculations (B3LYP and BPW91). Bonding in the initial OM(η(2)-SO) reaction products and in the OM(η(2)-SO)(η(2)-SO(2)) adduct molecules with unusual chiral structures is discussed.

Energy transfer phenomena in GdF sub 3 :Mn co-doped with Ce sup 3 sup + , Pr sup 3 sup + or Zr sup 4 sup +

CERN Document Server

Kobayashi, M; Ishii, M; Solovieva, N; Nikl, M

2003-01-01

We studied the effects of Mn sup 2 sup + doping and Ce sup 3 sup + or Pr sup 3 sup + or Zr sup 4 sup + co-doping on the scintillation characteristics of GdF sub 3 powder crystals including excitation-emission spectra and decay time for UV excitation, light yield (LY) and luminescence spectra for X-rays. In GdF sub 3 :Mn sup 2 sup + , the dominant Mn sup 2 sup + emission occurred at 515 nm with a decay constant tau - 24 ms for excitation at 275 nm. The LY increased monotonically as the Mn sup 2 sup + concentration decreased from 1 at.% down to 20 at.ppm, indicating very efficient Gd sup 3 sup + -> Mn sup 2 sup + energy transfer and possible concentration quenching at large Mn sup 2 sup + concentrations. The maximum LY for X-rays was about 19% of Gd sub 2 O sub 2 S:Pr sup 3 sup + , Ce sup 3 sup + , one of the brightest ceramics scintillators employed in X-ray computed tomography. While efficient energy transfers of Ce sup 3 sup + -> Gd sup 3 sup + and Ce sup 3 sup + -> (Gd sup 3 sup +) sub n -> Mn sup 2 sup + w...

Preparation of HfC single crystals by a floating zone technique

International Nuclear Information System (INIS)

Otani, S.; Tanaka, T.

1981-01-01

HfC single crystals have been prepared using a floating zone technique by controlling the compositions of the initial molten zone and the feed rod. The obtained crystal rods were 6 cm long and 0.9 cm in diameter. The various parts of the crystal rods have nearly constant compositions (C/Hf(ZR) = 0.956-0.977), and do not contain any free carbon. The impurities in the crystal, evaporation product, and starting material were examined by fluorescence X-ray spectroscopy. The refining effect due to evaporation was discussed. (orig.)

Structural, mechanical and electronic properties of OsTM and TMOs{sub 2} (TM = Ti, Zr and Hf): First-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Liu, Qi-Jun, E-mail: qijunliu@home.swjtu.edu.cn [Bond and Band Engineering Group, Institute of High Temperature and High Pressure Physics, School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhang, Ning-Chao; Liu, Fu-Sheng [Bond and Band Engineering Group, Institute of High Temperature and High Pressure Physics, School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Liu, Zheng-Tang [State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China)

2014-03-15

Highlights: • OsTM and TMOs{sub 2} compounds have no superhard character. • These compounds are mechanically stable and behave in ductile manner. • OsTM has a mixture of covalent-ionic and metallic character. -- Abstract: The first-principles calculations have been performed to study the structural, elastic, mechanical and electronic properties of cubic OsTM (TM = Ti, Zr, and Hf) and hexagonal TMOs{sub 2} compounds. The calculated structural parameters are in good agreement with the available experimental data. To the best of our knowledge, the elastic constants of OsTM and TMOs{sub 2} compounds have been obtained for the first time. The calculated elastic and mechanical properties show that these compounds have no superhard character. These compounds are mechanically stable and behave in ductile manner. The electronic band structures and densities of states of OsTM and TMOs{sub 2} compounds have been analysed. OsTM has a mixture of covalent-ionic and metallic character, and TMOs{sub 2} has strong metallic nature.

Analysis of local regions near the interfaces in nanostructured multicomponent cathodic – arc – vapor – deposition (CAVD) coatings (Ti-Zr-Hf-V-Nb)N

International Nuclear Information System (INIS)

Kraus-Rekhberg, R.; Pogrebnyak, A. D.; Borisyuk, V. N.; Kaverin, M. V.; Belokur, M.A.; Ponomarev, G.; Ojoshi, K.; Takeda, J.; Beresnev, V. M.; Sobol', O. V.

2013-01-01

Multicomponent, nanostructure (Ti- Zr-Hf-V-Nb)N coatings derived using cathodic – Arc – Vapor – Deposition method, were characterized by applying SPB, (μ-PIXE), EDS and SEM-analysis), XRD methods, including ''a-sin 2 φ'' procedure. It was found that through the creation of high elastic strains of compression in coating it is possible to a significant extent enhance its oxidation resistance under high-temperature annealing. During the characterization of coatings the elements and defects’ redistribution was discovered, its segregation through thermally-stimulated diffusion and the spinoidal segregation process end, in the neighborhood of the interfaces, around grains and subgrains, without substantial change of the average nanograin dimension. (authors)

Dopant induced variations in microstructure and optical properties of CeO2 nanoparticles

International Nuclear Information System (INIS)

Mohanty, Bhaskar Chandra; Lee, Jong Won; Yeon, Deuk-Ho; Jo, Yeon-Hwa; Kim, Jong Hak; Cho, Yong Soo

2011-01-01

Research highlights: → Dopant (Zr 4+ , La 3+ , and Ca 2+ ) induced phase stability, and changes in microstructure and optical properties of CeO 2 nanoparticles have been studied. → The nanoparticles were prepared by hydrothermal synthesis of nitrate solutions. → The results show modification of the unit cell parameter by -0.39, +0.83 and +0.16% for doping of 20% Zr 4+ , La 3+ , and Ca 2+ , respectively. → For each batch prepared, nanoparticles with a narrow size distribution of 5-15 nm have been obtained. These particles are single crystals mostly having polygonal two-dimensional projections. → UV-visible spectra of doped particles exhibit shift of the absorption edge and absorption peak with respect to those of the undoped ones and has been attributed to compensation of Ce 3+ and decreasing crystallite size as result of doping. -- Abstract: Nanocrystalline CeO 2 particles doped in the range of 0-20% of Ca 2+ , La 3+ , and Zr 4+ have been prepared from hydrothermal synthesis of nitrate solutions at 200 o C and the influences of the dopants on microstructure and optical properties of the nanoparticles have been investigated. The unit cell parameter is found to be modified by -0.39, +0.83 and +0.16% for doping of 20% Zr 4+ , La 3+ , and Ca 2+ , respectively. For each batch prepared, nanoparticles with a narrow size distribution of 5-15 nm have been obtained. A high-resolution transmission electron microscopy investigation reveals that these particles are single crystals mostly having hexagonal, square or circular two-dimensional projections. UV-visible spectra of doped powders exhibit shift of the absorption edge and absorption peak with respect to those of the undoped CeO 2 particles and has been attributed to compensation of Ce 3+ and decreasing crystallite size as result of doping.

Low-temperature carbon monoxide oxidation over zirconia-supported CuO–CeO{sub 2} catalysts: Effect of zirconia support properties

Energy Technology Data Exchange (ETDEWEB)

Moretti, Elisa, E-mail: elisa.moretti@unive.it [Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, INSTM Venice Research Unit, Via Torino 155/B, 30172 Mestre Venezia (Italy); Molina, Antonia Infantes [Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos, 29071 Málaga (Spain); Sponchia, Gabriele; Talon, Aldo; Frattini, Romana [Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, INSTM Venice Research Unit, Via Torino 155/B, 30172 Mestre Venezia (Italy); Rodriguez-Castellon, Enrique [Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos, 29071 Málaga (Spain); Storaro, Loretta [Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, INSTM Venice Research Unit, Via Torino 155/B, 30172 Mestre Venezia (Italy)

2017-05-01

Highlights: • CuO-CeO{sub 2}/ZrO{sub 2} materials were investigated in the low temperature CO oxidation. • High surface area ZrO{sub 2} synthetized by sol-gel method. • Low ZrO{sub 2} surface area synthetized by fast precipitation. • Sol-gel samples showed, after impregnation, a severe decrease of surface area. • CuO-CeO{sub 2}/ZrO{sub 2} with precipitated ZrO{sub 2} led to a very active catalyst. - Abstract: A study was conducted to investigate the effect of the preparation route of ZrO{sub 2} in CuO–CeO{sub 2}/ZrO{sub 2} catalysts for the oxidation of carbon monoxide at low temperature (COX). Four ZrO{sub 2} supports were synthetized via either type sol-gel methodology or precipitation. The final Cu-Ce-Zr oxide catalysts were prepared by incipient wetness co-impregnation with copper and cerium solutions (with a loading of 6 wt% of CuO and 20 wt% of CeO{sub 2}). The catalyst crystalline phases, texture and active species reducibility were determined by XRD, N{sub 2} physisorption at −196 °C and H{sub 2}-TPR, respectively; meanwhile the surface composition and copper-cerium electronic states were studied by XPS. The catalytic activity was evaluated in the oxidation of CO to CO{sub 2}, in the 40–215 °C temperature range. Catalytic results evidenced that the samples prepared by a sol-gel methodology showed, after the impregnation, a severe decrease of specific surface area and pore volume attributable to a wide degree of pore blockage caused by the presence of metal oxide particles and a collapse of the structure partially burying the active sites. A simple co-impregnation of a zirconia support, obtained through facile and fast precipitation, provided instead a catalyst with very good redox properties and high dispersion of the active phases, which completely oxidizes CO in the range 115–215 °C with T{sub 50} of 65 °C. This higher observed activity was ascribed to the formation of a larger fraction of highly dispersed and easily reducible Cu

6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion: [M6(O2)6(OH)6(gamma-SiW10O36)3]18- (M = Zr, Hf).

Science.gov (United States)

Bassil, Bassem S; Mal, Sib Sankar; Dickman, Michael H; Kortz, Ulrich; Oelrich, Holger; Walder, Lorenz

2008-05-28

We have synthesized and structurally characterized the unprecedented peroxo-zirconium(IV) containing [Zr6(O2)6(OH)6(gamma-SiW10O36)3]18- (1). Polyanion 1 comprises a cyclic 6-peroxo-6-zirconium core stabilized by three decatungstosilicate units. We have also prepared the isostructural hafnium(IV) analogue [Hf6(O2)6(OH)6(gamma-SiW10O36)3]18- (2). We investigated the acid/base and redox properties of 1 by UV-vis spectroscopy and electrochemistry studies. Polyanion 1 represents the first structurally characterized Zr-peroxo POM with side-on, bridging peroxo units. The simple, one-pot synthesis of 1 and 2 involving dropwise addition of aqueous hydrogen peroxide could represent a general procedure for incorporating peroxo groups into a large variety of transition metal and lanthanide containing POMs.

Thermochemical and thermophysical properties of alkaline-earth perovskites

International Nuclear Information System (INIS)

Yamanaka, Shinsuke; Kurosaki, Ken; Maekawa, Takuji; Matsuda, Tetsushi; Kobayashi, Shin-ichi; Uno, Masayoshi

2005-01-01

In order to contribute to safety evaluation of high burnup oxide fuels, we studied the thermochemical and thermophysical properties of alkaline-earth perovskites known as oxide inclusions. Polycrystalline samples of alkaline-earth perovskites, BaUO 3 , BaZrO 3 , BaCeO 3 , BaMoO 3 , SrTiO 3 , SrZrO 3 , SrCeO 3 , SrMoO 3 , SrHfO 3 and SrRuO 3 , were prepared and the thermal expansion coefficient, melting temperature, elastic moduli, Debye temperature, microhardness, heat capacity, and thermal conductivity were measured. The relationship between some physical properties was studied

LaCoO3: Promising cathode material for protonic ceramic fuel cells based on a BaCe0.2Zr0.7Y0.1O3−δ electrolyte

DEFF Research Database (Denmark)

Ricote, Sandrine; Bonanos, Nikolaos; Lenrick, Filip

2012-01-01

Symmetric cells (cathode/electrolyte/cathode) were prepared using BaCe0.2Zr0.7Y0.1O3−δ (BCZY27) as proton conducting electrolyte and LaCoO3 (LC) infiltrated into a porous BCZY27 backbone as cathode. Single phased LC was formed after annealing in air at 600 °C for 2 h. Scanning electron micrograph...... that the presence of oxide ion conduction in the cathode material is not necessary for good performance.......Symmetric cells (cathode/electrolyte/cathode) were prepared using BaCe0.2Zr0.7Y0.1O3−δ (BCZY27) as proton conducting electrolyte and LaCoO3 (LC) infiltrated into a porous BCZY27 backbone as cathode. Single phased LC was formed after annealing in air at 600 °C for 2 h. Scanning electron micrographs...... showed the presence of the infiltrated LC in the full cathode depth. Transmission electron micrographs revealed LC grains (60–80 nm) covering partly the BCZY27 grains (200 nm–1 μm). Impedance spectra were recorded at 500 °C and 600 °C, varying the oxygen partial pressure and the water vapour pressure...

Surfactant-controlled synthesis of Pd/Ce{sub 0.6}Zr{sub 0.4}O{sub 2} catalyst for NO reduction by CO with excess oxygen

Energy Technology Data Exchange (ETDEWEB)

Chen, L.F. [Laboratorio de Catalisis y Materiales, SEPI-ESIQIE, Instituto Politecnico Nacional, Av. Politecnico S/N, Col. Zacatenco, 07738 Mexico D.F. (Mexico); Departamento de Ingenieria Quimica, Universidad Autonoma Metropolitana-A, Av. San Pablo 180, Col. Reynosa-Tamaulipas, 02200 Mexico D.F. (Mexico); Gonzalez, G. [Laboratorio de Catalisis y Materiales, SEPI-ESIQIE, Instituto Politecnico Nacional, Av. Politecnico S/N, Col. Zacatenco, 07738 Mexico D.F. (Mexico); Wang, J.A. [Laboratorio de Catalisis y Materiales, SEPI-ESIQIE, Instituto Politecnico Nacional, Av. Politecnico S/N, Col. Zacatenco, 07738 Mexico D.F. (Mexico)]. E-mail: jwang@ipn.mx; Norena, L.E. [Departamento de Ingenieria Quimica, Universidad Autonoma Metropolitana-A, Av. San Pablo 180, Col. Reynosa-Tamaulipas, 02200 Mexico D.F. (Mexico); Toledo, A. [Grupo de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico); Castillo, S. [Grupo de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico); Moran-Pineda, M. [Grupo de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)

2005-04-30

For the first time, this work reports a surfactant-controlled synthetic method to obtain a nanophase of mesoporous ceria-zirconia solid solution containing cationic defects in the crystalline structure. The incorporation of a cationic surfactant (myristyltrimethylammonium bromide) into the ceria-zirconia solid network not only controlled the pore diameter distribution but also induced creation of the lattice defect. Ceria-zirconia solid solution showed crystal microstrain and structural distortion that varied with the calcination temperature. Compared to pure ceria, the addition of zirconium to the ceria promoted the bulk oxygen reducibility and enhanced the thermal stability of the solid. Hydrogen could be stored into or released from the PdO/Ce{sub 0.6}Zr{sub 0.4}O{sub 2} catalyst during the TPR procedure, which is associated to the formation/decomposition of a PdH{sub x} phase, due to the hydrogen dissociation catalyzed by metallic Pd. At cool start of reaction, NO reduction by CO with excess oxygen over the Pd/Ce{sub 0.6}Zr{sub 0.4}O{sub 2} catalyst showed selectivity around 100% to N{sub 2}. A competition between NO reduction by CO and CO oxidation by O{sub 2} was observed: at reaction temperatures below 200 deg. C, NO inhibited CO oxidation activity; however, at reaction temperatures above 200 deg. C, high activity of CO oxidation resulted in an inhibition effect on NO reduction.

Structural and thermodynamic aspects of the dissociation of cyclopentadienyl rings from homoleptic cyclopentadienyl early transition metal, cerium, and thorium derivatives

International Nuclear Information System (INIS)

Peng Bin; Cheng Feng; Li Qianshu; Xie Yaoming; King, R. Bruce; Schaefer, Henry F.

2011-01-01

Graphical abstract: Density functional theory indicates that for Cp 4 M the S 4 structures are saddle points and the minima have C 1 symmetry with all η 5 -Cp rings for M = Ce and Th, three η 5 -Cp rings and one η 5 -Cp ring for M = Zr, and two η 5 -Cp rings and two η 5 -Cp rings for M = Ti and Hf. The dissociation energies for Cp 4 M → Cp 3 M + Cp · increase in the sequence Ti 3h structures with all η 5 -Cp rings are genuine minima for most of the Cp 3 M compounds except for Cp 3 Ti, which has a Cs symmetry minimum with two η 5 -Cp rings and one η 2 -Cp ring. The dissociation energies for Cp 3 M → Cp 2 M + Cp · increase in the sequence V 4 M the S 4 structures are saddle points. → The minima for Cp 4 M have all η 5 -Cp rings for M = Ce and Th, three η 5 -Cp rings and one η 1 -Cp ring for M = Zr, and two η 5 -Cp rings and two η 5 -Cp rings for M = Ti and Hf. → The dissociation energies for Cp 4 M → Cp 3 M + Cp · increase in the sequence Ti 3h structures with all η 5 -Cp rings are genuine minima for all of the Cp 3 M compounds except for Cp 3 Ti. → The dissociation energies for Cp 3 M → Cp 2 M + Cp · increase in the sequence V 4 M (M = Ti, Zr, Ce, Hf, Th), Cp 3 M (M = Sc, Y, most lanthanides, Ti, Zr, Hf, Th), and Cp 2 M (M = Ti, V). Density functional theory shows that the Cp 4 M structures with unusual S 4 symmetry are saddle points for the d-block metals Ti, Zr, Hf but genuine minima for the f-block metals Ce and Th. The true equilibrium Cp 4 M geometries have C 1 symmetry with two η 5 -Cp rings and two η 1 -Cp rings for M = Ti and Hf but three η 5 -Cp rings and one η 1 -Cp ring for M = Zr. The dissociation energies for Cp 4 M → Cp 3 M + Cp · are substantial and in the order Ti 3h structures with all η 5 -Cp rings are genuine minima for most of the Cp 3 M compounds except for Cp 3 Ti, which has a C s symmetry minimum with two η 5 -Cp rings and one η 2 -Cp ring, and Cp 3 V, which has two η 5 -Cp rings and one η 1 -Cp ring

Anomalous structural evolution and liquid fragility signatures in Cu–Zr and Cu–Hf liquids and glasses

International Nuclear Information System (INIS)

Mauro, N.A.; Vogt, Adam J.; Johnson, Mark L.; Bendert, James C.; Soklaski, Ryan; Yang, Li; Kelton, K.F.

2013-01-01

The results of high energy X-ray scattering studies of equilibrium and supercooled Cu 100−x Zr x (x = 46 and 54) and Cu x Hf 100−x (x = 55 and 60.8) liquids and the corresponding glasses are presented. The liquid data were obtained in a containerless environment using the beamline electrostatic levitation (BESL) technique. The total structure factor and total pair correlation functions were measured as a function of temperature for the liquids, and for the glasses at room temperature. A developing asymmetry in the peak of the first coordination shell in the total pair correlation function suggests chemical ordering in the liquids with cooling. This asymmetry takes the form of two prominent peaks, suggesting two prominent ordering length scales. When the magnitudes of these peaks are extrapolated to the glass transition temperature a discontinuity is observed, indicating that an abrupt increase in the magnitude is required to match the observed peak heights in the glass. This suggests that the structure of the supercooled liquid orders more rapidly near the glass transition temperature, a conclusion that is supported by molecular dynamics simulations. This observed structural evolution of the liquid indicates that the concept of fragility, typically defined from the behavior of viscosity with temperature, has a measurable structural signature as well, which can be observed in X-ray diffraction studies

Superconductivity of Ta{sub 34}Nb{sub 33}Hf{sub 8}Zr{sub 14}Ti{sub 11} high entropy alloy from first principles calculations

Energy Technology Data Exchange (ETDEWEB)

Jasiewicz, K.; Wiendlocha, B.; Korben, P.; Kaprzyk, S.; Tobola, J. [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, Al. Mickiewicza 30, 30-059, Krakow (Poland)

2016-05-15

The Korringa-Kohn-Rostoker method with the coherent potential approximation (KKR-CPA) is applied to study the first superconducting high entropy alloy (HEA) Ta{sub 34}Nb{sub 33}Hf{sub 8}Zr{sub 14}Ti{sub 11} (discovered in 2014 with T{sub c}=7.3 K), focusing on estimations of the electron-phonon coupling constant λ. The electronic part of λ has been calculated using the rigid muffin-tin approximation (RMTA), while the phonon part has been approximated using average atomic mass and experimental Debye temperature. The estimated λ=1.16 is close to the value determined from specific heat measurements, λ=0.98, and suggests rather strong electron-phonon coupling in this material. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

In situ DRIFTs investigation of the reaction mechanism over MnO{sub x}-MO{sub y}/Ce{sub 0.75}Zr{sub 0.25}O{sub 2} (M = Fe, Co, Ni, Cu) for the selective catalytic reduction of NO{sub x} with NH{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Hu, Hang; Zha, Kaiwen; Li, Hongrui; Shi, Liyi; Zhang, Dengsong, E-mail: dszhang@shu.edu.cn

2016-11-30

Highlights: • MnO{sub x}-FeO{sub y}/Ce{sub 0.75}Zr{sub 0.25}O{sub 2} catalyst has a strong NO oxidation ability. • A high dispersion of active components is achieved on catalyst surface. • At high temperatures, bidentate nitrate is the common active species. • The addition of Fe can improve the reactivity of gaseous NO{sub 2} and bridged nitrates. - Abstract: A series of MnO{sub x}-MO{sub y}/Ce{sub 0.75}Zr{sub 0.25}O{sub 2} (M = Fe, Co, Ni, Cu) catalysts were synthesized by an impregnation method and used for selective catalytic reduction (SCR) of NO{sub x} with NH{sub 3}. The catalytic performances of various MnO{sub x}-MO{sub y}/Ce{sub 0.75}Zr{sub 0.25}O{sub 2} catalysts were studied. It was found that MnO{sub x}-FeO{sub y}/Ce{sub 0.75}Zr{sub 0.25}O{sub 2} catalyst showed excellent low-temperature activity and a broad temperature window. The catalysts were characterized by N{sub 2} adsorption/desorption, X-ray diffraction, X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared transform spectroscopy (DRIFTS). Characterization of the catalyst confirmed the addition of iron oxide can enhance the NO oxidation ability of the catalyst which results in the outstanding low-temperature SCR activity. Meanwhile, iron oxides were well dispersed on catalyst surface which could avoid the agglomeration of active species, contributing to the strong interaction between active species and the support. More importantly, in situ DRIFTS results confirmed that bidentate nitrates are general active species on these catalysts, whereas the reactivity of gaseous NO{sub 2} and bridged nitrates got improved because of the addition of Fe.

Preparation and characterization of Ce/Zr mixed oxides and their use as catalysts for the direct oxidation of dry CH{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Larrondo, Susana; Vidal, Maria Adelina; Irigoyen, Beatriz; Amadeo, Norma [Lab. de Procesos Cataliticos, Depto. de Ing. Quimica, Facultad de Ingenieria, University de Buenos Aires, Pab. de Industrias, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Craievich, Aldo F. [Instituto de Fisica, USP, Travessa R da Rua do Matao, no.187, Cidade Universitaria, 05508-900, Sao Paulo, SP (Brazil); Lamas, Diego G.; Fabregas, Ismael O.; Lascalea, Gustavo E.; Reca, Noemi E. Walsoee de [Centro de Investigaciones en Solidos CINSO, CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Buenos Aires (Argentina)

2005-10-30

Solid oxide fuel cells have a promissory future in the direct combustion of fuels but, their main drawbacks are the high operation temperature and the rapid performance degradation due to carbon deposition in the anode. The development of ceria-based anodes with good electronic conductivity at lower temperatures seems to be a promising way to solve those problems. In this work, preparation of compositionally homogeneous Ce/Zr oxides by a gel-combustion process and their characterization are reported. A detailed crystallographic study performed by synchrotron radiation X-ray diffraction has been carried out, in order to analyze the correlation between crystal structure and catalytic properties. The oxides presented specific area values, porous size distribution and carbon content values desirable for solid catalysts. Likewise, increasing the content of ZrO{sub 2} facilitates the reducibility of both surface and bulk sites in the solid. The oxides have been active in the combustion of methane. Their performances were stable during a typical work period of 8h, with no evidence of formation of carbonaceous deposits. The experiments that were carried out confirm the promising features of these oxides as anodic materials in solid oxide fuel cells.

A comparative study of the effects of CuO, NiO, ZrO{sub 2} and CeO{sub 2} coupling on the photocatalytic activity and characteristics of ZnO

Energy Technology Data Exchange (ETDEWEB)

Sherly, Eluvathingal Devassy; Vijaya, John Judith [Loyola College, Chennai (India); Kennedy, Lourdusamy John [Vellore Institute of Technology (VIT) University, Chennai (India); Meenakshisundaram, Arunachalam; Lavanya, Melcureraj [Chennai Petroleum Corporation Limited, Manali (India)

2016-04-15

ZnO nanoparticles were coupled with CuO, NiO, ZrO{sub 2} and CeO{sub 2} in 2 : 1 molar ratio by a microwave assisted one pot solution combustion synthesis. Structural, morphological and optical properties of ZnO and coupled oxides were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), UV-Vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), Fourier transform infrared (FTIR) spectroscopy and Brunauer- Emmett-Teller (BET) surface area analysis. XRD data revealed the presence of two phases in the coupled oxides. Photocatalytic activity of pure ZnO and ZnO coupled oxides was compared for the degradation of 2,4-dichlorophenol (2,4- DCP) under near UV light (365 nm) irradiation and the rate constant (k) values were calculated from the kinetic studies. The coupled oxide, Zn{sub 2}Ce with ZnO and CeO{sub 2} in 2 : 1 molar ratio showed maximum degradation efficiency due to the efficient interparticle electron transfer between ZnO and CeO{sub 2}.

Effect of Preparation Methods on Al2O3 Supported CuO-CeO2-ZrO2 Catalysts for CO Oxidation

Directory of Open Access Journals (Sweden)

Gaurav Rattan

2012-12-01

Full Text Available To examine the effect of preparation methods, four catalyst samples having same composition (CuCe5.17Zr3.83Ox/g-Al2O3 (15wt% were prepared by four different methods for CO oxidation. The catalysts were prepared by co-impregnation, citric acid sol-gel, urea nitrate combustion and urea gelation co-precipitation methods, and characterized by BET, XRD, TGA/DSC and SEM. The The air oxidation of CO was carried out in a tubular fixed bed reactor under the following operating conditions: catalyst weight - 100 mg, temperature - ambient to 250 oC, pressure - atmospheric, 2.5% CO in air, total feed rate - 60 ml/min.  It was observed that the catalytic activity greatly influenced by the preparation methods. The highest activity of the catalyst prepared by the sol gel method appeared to be associated with its largest BET surface area. All the four catalysts were active for CO oxidation and did not show deactivation of catalytic activity for 50 hours of continuous runs. The ranking order of the preparation methods of the catalyst is as follows: sol-gel > co-impregnation > urea gelation > urea nitrate combustion. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 14th June 2012, Revised: 8th September 2012, Accepted: 19th September 2012[How to Cite: G. Rattan, R. Prasad, R.C.Katyal. (2012. Effect of Preparation Methods on Al2O3 Supported CuO-CeO2-ZrO2 Catalysts for CO Oxidation. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 112-123. doi:10.9767/bcrec.7.2.3646.112-123] [How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.3646.112-123 ] | View in 

Synthesis, structural and electrical studies of Ba1-xSrxCe0.65Zr0.25Pr0.1O3-δ electrolyte materials for solid oxide fuel cells

Science.gov (United States)

Madhuri Sailaja, J.; Murali, N.; Margarette, S. J.; Mammo, Tulu Wegayehu; Veeraiah, V.

2018-03-01

This paper is discussed Sr doping effect on the microstructure, chemical stability and conductivity of Ba1-xSrxCe0.65Zr0.25Pr0.1O3-δ (0 ≤ x ≤ 0.2) electrolyte prepared by sol-gel method. The lattice constants and unit cell volumes are found to decrease as Sr atomic percentage increased in accordance with the Vegard law, confirming the formation of solid solution with orthorhombic structure. Among them all the synthesized samples are showed a conductivity with different atmosphere values at 500 °C. Ba0.92Sr0.08Ce0.65Zr0.25Pr0.1O3-δ recorded highest conductivity with a value of 3.3 × 10-6 S/cm (dry air) & 3.41 × 10-6 S/cm (wet air with 3% relative humidity) at 500 °C due to its smaller lattice volume, larger grain size and lower activation energy that led to excessive increase in conductivity. All pellets exhibited good chemical stability when exposed to air and H2O atmospheres. This study elucidates that the composition will be a promising electrolyte material for use as SOFC at intermediate temperatures if Sr doping is limited to small amounts.

Multiscale Modeling of Ultra High Temperature Ceramics (UHTC) ZrB2 and HfB2: Application to Lattice Thermal Conductivity

Science.gov (United States)

Lawson, John W.; Daw, Murray S.; Squire, Thomas H.; Bauschlicher, Charles W.

2012-01-01

We are developing a multiscale framework in computational modeling for the ultra high temperature ceramics (UHTC) ZrB2 and HfB2. These materials are characterized by high melting point, good strength, and reasonable oxidation resistance. They are candidate materials for a number of applications in extreme environments including sharp leading edges of hypersonic aircraft. In particular, we used a combination of ab initio methods, atomistic simulations and continuum computations to obtain insights into fundamental properties of these materials. Ab initio methods were used to compute basic structural, mechanical and thermal properties. From these results, a database was constructed to fit a Tersoff style interatomic potential suitable for atomistic simulations. These potentials were used to evaluate the lattice thermal conductivity of single crystals and the thermal resistance of simple grain boundaries. Finite element method (FEM) computations using atomistic results as inputs were performed with meshes constructed on SEM images thereby modeling the realistic microstructure. These continuum computations showed the reduction in thermal conductivity due to the grain boundary network.

Theoretical prediction of ion conductivity in solid state HfO2

Science.gov (United States)

Zhang, Wei; Chen, Wen-Zhou; Sun, Jiu-Yu; Jiang, Zhen-Yi

2013-01-01

A theoretical prediction of ion conductivity for solid state HfO2 is carried out in analogy to ZrO2 based on the density functional calculation. Geometric and electronic structures of pure bulks exhibit similarity for the two materials. Negative formation enthalpy and negative vacancy formation energy are found for YSH (yttria-stabilized hafnia) and YSZ (yttria-stabilized zirconia), suggesting the stability of both materials. Low activation energies (below 0.7 eV) of diffusion are found in both materials, and YSH's is a little higher than that of YSZ. In addition, for both HfO2 and ZrO2, the supercells with native oxygen vacancies are also studied. The so-called defect states are observed in the supercells with neutral and +1 charge native vacancy but not in the +2 charge one. It can give an explanation to the relatively lower activation energies of yttria-doped oxides and +2 charge vacancy supercells. A brief discussion is presented to explain the different YSH ion conductivities in the experiment and obtained by us, and we attribute this to the different ion vibrations at different temperatures.

Intermediate-to-low temperature protonic ceramic membrane fuel cells with Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}}-BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} composite cathode

Energy Technology Data Exchange (ETDEWEB)

Lin, Bin; Ding, Hanping; Dong, Yingchao; Wang, Songlin; Zhang, Xiaozhen; Fang, Daru; Meng, Guangyao [Department of Materials Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)

2009-01-01

The perovskite-type Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}}-BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} (BSCF-BZCY) composite oxides were synthesized by a modified Pechini method and examined as a novel composite cathode for intermediate-to-low temperature protonic ceramic membrane fuel cells (ILT-PCMFCs). Thin proton-conducting BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} (BZCY) electrolyte and NiO-BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} (NiO-BZCY) anode functional layer were prepared over porous anode substrates composed of NiO-BaZr{sub 0.1}Ce{sub 0.7}Y{sub 0.2}O{sub 3-{delta}} by a one-step dry-pressing/co-firing process. A laboratory-sized quad-layer cell of NiO-BZCY/NiO-BZCY({proportional_to}50 {mu}m)/BZCY({proportional_to}20 {mu}m)/BSCF-BZCY({proportional_to}50 {mu}m) was operated from 550 to 700 C with humidified hydrogen ({proportional_to}3% H{sub 2}O) as fuel and the static air as oxidant. A high open-circuit potential of 1.009 V, a maximum power density of 418 mW cm{sup -2}, and a low polarization resistance of the electrodes of 0.10 {omega} cm{sup 2} was achieved at 700 C. These investigations have indicated that proton-conducting BZCY electrolyte with BSCF perovskite cathode is a promising material system for the next generation solid oxide fuel cells (SOFCs). (author)

Effect of Nb aggregates on Zr2Fe

International Nuclear Information System (INIS)

Ramos, Cinthia P.

2001-01-01

The binary Zr-Fe phase diagram revision, performed by Arias et al., accepted the intermetallic Zr 2 Fe crystalline structure as tetragonal and determined that the presence of a third element like oxygen, nitrogen or carbon, stabilizes a cubic phase. Nevitt et al. studying Ti, Zr and Hf alloys with transition metals as second or third element and ternary systems with oxygen as third element, systematized the occurrence of phases with a cubic Ti 2 Ni type crystalline structure. From previous studies in the Zr-Nb-Fe system, it is an agreed fact that Nb presence in the Zr 2 Fe intermetallic stabilizes a cubic Ti 2 Ni type phase. The purpose of the present work is to determine the stability range of the Zr 2 Fe intermetallic with Nb contents, the existence range of the ternary cubic Ti 2 Ni type phase (designated Λ) and the corresponding two-phase region. We analyze as cast and heat treated (800 C degrees) Zr-Nb-Fe alloys with 35 atomic % Fe and Nb contents between 0.5 and 15 atomic %. The determination and characterization of the phases is made by optical and scanning electron microscopy, X-ray diffraction microprobe analysis and Moessbauer Spectroscopy. Joining these techniques together it is found, among many other things, that the Zr 2 Fe phase would accept up to around 0.5 atomic % Nb in solution and that the two-phase region Zr 2 Fe+Λ would be stable in the (0.5 - 3.5) Nb atomic % range. It is proposed as well a 800 C degrees section of the ternary (Zr-Nb-Fe) in the studied region. (author) [es

Nanostructured multielement (TiHfZrNbVTa)N coatings before and after implantation of N+ ions (10{sup 18} cm{sup −2}): Their structure and mechanical properties

Energy Technology Data Exchange (ETDEWEB)

Pogrebnjak, A.D., E-mail: alexp@i.ua [Sumy State University, Department of Nanoelectronics, 40007, R.-Korsakova 2, Sumy (Ukraine); Bondar, O.V., E-mail: oleksandr.v.bondar@gmail.com [Sumy State University, Department of Nanoelectronics, 40007, R.-Korsakova 2, Sumy (Ukraine); Borba, S.O. [Sumy State University, Department of Nanoelectronics, 40007, R.-Korsakova 2, Sumy (Ukraine); Abadias, G. [Institut Pprime, CNRS, Université de Poitiers, ISAE-ENSMA, F86962 Futuroscope Chasseneuil (France); Konarski, P. [Tele and Radio Research Institute, Ratuszowa 11, 03-450 Warsaw (Poland); Plotnikov, S.V. [D. Serikbaev East-Kazakhstan State Technical University, 070004, Ust-Kamenogorsk, 69 Protozanov St. (Kazakhstan); Beresnev, V.M. [V.N. Karazin Kharkiv National University, 61022, Svobody Sq. 4, Kharkiv (Ukraine); Kassenova, L.G. [Kazakh University of Economics, Finance and International Trade, St. Zhubanov 7, 010005 Astana (Kazakhstan); Drodziel, P. [Lublin University of Technology, Nadbystrzycka 36, 20-618 Lublin (Poland)

2016-10-15

Highlights: • (TiZrHfVNbTa)N coatings were deposited by vacuum–arc evaporation of a cathode. • Nanostructured coatings were investigated experimentally and by MD simulations. • Good correlation between experimental data and simulation results is observed. • Ion implantation formed amorphous, nanocrystalline and nanostructured layers. • Hardness changed from 12 GPa in the implanted layer to 38 GPa with the depth. - Abstract: Multielement high entropy alloy (HEA) nitride (TiHfZrNbVTa)N coatings were deposited by vacuum arc and their structural and mechanical stability after implantation of high doses of N{sup +} ions, 10{sup 18} cm{sup −2}, were investigated. The crystal structure and phase composition were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy, while depth-resolved nanoindentation tests were used to determine the evolution of hardness and elastic modulus along the implantation depth. XRD patterns show that coatings exhibit a main phase with fcc structure, which preferred orientation varies from (1 1 1) to (2 0 0), depending on the deposition conditions. First-principles calculations reveal that the presence of Nb atoms could favor the formation of solid solution with fcc structure in multielement HEA nitride. TEM results showed that amorphous and nanostructured phases were formed in the implanted coating sub-surface layer (∼100 nm depth). Concentration of nitrogen reached 90 at% in the near-surface layer after implantation, and decreased at higher depth. Nanohardness of the as-deposited coatings varied from 27 to 38 GPa depending on the deposition conditions. Ion implantation led to a significant decrease of the nanohardness to 12 GPa in the implanted region, while it reaches 24 GPa at larger depths. However, the H/E ratio is ⩾0.1 in the sub-surface layer due to N{sup +} implantation, which is expected to have beneficial effect on the wear properties.

Loading clusters composed of nanoparticles on ZrO{sub 2} support via a perovskite-type oxide of La{sub 0.95}Ce{sub 0.05}Co{sub 0.7}Cu{sub 0.3}O{sub 3} for ethanol synthesis from syngas and its structure variation with reaction time

Energy Technology Data Exchange (ETDEWEB)

Song, Zhaoyu [Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering, Tianjin University, Tianjin 300354 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300354 (China); Shi, Xiangpeng [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300354 (China); Key Laboratory of Green Chemical Technology of Ministry of Education, School of Chemical Engineering, Tianjin University, Tianjin 300354 (China); Ning, Hongyan; Liu, Guilong; Zhong, Huixian [Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering, Tianjin University, Tianjin 300354 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300354 (China); Liu, Yuan, E-mail: yuanliu@tju.edu.cn [Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering, Tianjin University, Tianjin 300354 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300354 (China)

2017-05-31

Highlights: • La{sub 0.95}Ce{sub 0.05}Co{sub 0.7}Cu{sub 0.3}O{sub 3}/ZrO{sub 2} catalyst has showed good activity and high selectivity to ethanol. • After reaction for 1000 h, the catalyst was covered by a membrane-like coating. • Carbon deposition is the main reason for the deactivation of the catalyst. - Abstract: A new scheme was proposed to intensify interactions between copper with cobalt and between Cu−Co with the promoters, namely, the ions of copper, cobalt, lanthanum and cerium were confined into La{sub 0.95}Ce{sub 0.05}Co{sub 0.7}Cu{sub 0.3}O{sub 3} with perovskite structure and were supported on zirconia. The catalyst was prepared by impregnation method and used for ethanol synthesis (ES) from syngas and was characterized by using XRD, TG, BET, XPS, ICP-MS and TEM techniques. La{sub 0.95}Ce{sub 0.05}Co{sub 0.7}Cu{sub 0.3}O{sub 3}/ZrO{sub 2} showed very good catalytic performance with selectivity to total alcohols higher than 60% and selectivity to ethanol about 50% in the total alcohols. After reduction, clusters composed of Cu−Co alloy nanoparticles, ceria and lanthanum oxide was formed and loaded on zirconia. Investigation on the variation of the catalyst structure with reaction time showed that with the reaction going on, the clusters spread over the surface of ZrO{sub 2} and at last, all the clusters fused together to form a membrane loaded on the ZrO{sub 2} and the whole catalyst was covered by a membrane-like coating formed by Co{sub 2}C. The characterization results showed that the carbon deposition was the main reason for the deactivation of La{sub 0.95}Ce{sub 0.05}Co{sub 0.7}Cu{sub 0.3}O{sub 3}/ZrO{sub 2} catalyst. This catalyst design scheme could be extended for preparing a lot of catalyst for many reactions.

The Influence of Deposition Methods of Support Layer on Cordierite Substrate on the Characteristics of a MnO2–NiO–Co3O4/Ce0.2Zr0.8O2/Cordierite Three Way Catalyst

Directory of Open Access Journals (Sweden)

Phuong Thi Mai Pham

2014-09-01

Full Text Available This paper compares different coating methods (in situ solid combustion, hybrid deposition, secondary growth on seed, suspension, double deposition of wet impregnation and suspension to deposit Ce0.2Zr0.8O2 mixed oxides on cordierite substrates, for use as a three way catalyst. Among them, the double deposition was proven to be the most efficient one. The coated sample shows a BET (Brunauer–Emmett–Teller surface area of 25 m2/g, combined with a dense and crack free surface. The catalyst with a layer of MnO2–NiO–Co3O4 mixed oxides on top of the Ce0.2Zr0.8O2/cordierite substrate prepared by this method exhibits good activity for the treatment of CO, NO and C3H6 in exhaust gases (CO conversion of 100% at 250 °C, C3H6 conversion of 100% at 400 °C and NO conversion of 40% at 400 °C.

Electrical conductivity and chemical stability of BaCe0· 8− xAxGd0 ...

Indian Academy of Sciences (India)

... K. BaCe0.7In0.1Gd0.2O3− and BaCe0.7Zr0.1Gd0.2O3− ceramics exhibit an excellent chemical stability against boiling water. Indium is a suitable doping element to promote the sintering densification and to enhance both electrical conductivity and chemical stability of Gd-doped BaCeO3 at operating temperatures.

Development and characterization of nickel catalysts supported in CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} matrixes evaluated for methane reforming reactions; Desenvolvimento e caracterização de catalisadores de níquel suportados em matrizes CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} avaliados para as reações de reforma do metano

Energy Technology Data Exchange (ETDEWEB)

Abreu, Amanda Jordão de

2012-07-01

Nowadays, the methane reforming is large interest industrial for the take advantage of these gas in production the hydrogen and synthesis gas (syngas). Among in the reactions of methane stand of the reactions steam reforming and carbon dioxide reforming of methane. The main catalysts uses in the methane reforming is Ni/Al{sub 2}O{sub 3}. However, the supported-nickel catalyst is susceptible to the deactivation or the destruction by coke deposition. The carbon dissolves in the nickel crystallite and its diffuses through the nickel, leading for formation of the carbon whiskers, which results in fragmentation of the catalyst. Modification of such catalysts, like incorporation of suitable promoters, is desirable to achieve reduction of the methane hydrogenolysis and/or promotion of the carbon gasification. Catalysts 5%Ni/Al{sub 2}O{sub 3} supported on solid solutions formed by ZrO{sub 2}-CeO{sub 2}, La{sub 2}O{sub 3} and CeO{sub 2}-ZrO{sub 2}-La{sub 2}O{sub 3} were prepared, characterized and evaluated in reactions steam and carbon dioxide reforming and partial oxidation of methane with objective the value effect loading solution solid in support. The supports were prepared by co-precipitation method and catalysts were prepared by impregnation method and calcined at 500 deg C. The supports and catalysts were characterized by Nitrogen Adsorption, method -rays diffraction (XRD), X-rays dispersive spectroscopy (XDS), spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR) to and temperature programmed reduction (TPR), Raman Spectroscopy, X-ray absorption spectroscopy and Thermogravimetric Analysis. After all the catalytic reactions check which the addition of solid solution is beneficial for Ni/Al{sub 2}O{sub 3} catalysts and the best catalysts are Ni/CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3}. (author)

Steam Electrolysis by Proton-Conducting Solid Oxide Electrolysis Cells (SOECs) with Chemically Stable BaZrO3-Based Electrolytes

KAUST Repository

Bi, Lei

2015-07-17

BaZrO3-based material was applied as the electrolyte for proton-conducting solid oxide fuel cells (SOECs). Compared with the instability of BaCeO3-based proton-conductors, BaZrO3-based material could be a more promising candidate for proton-conducting SOECs due to its excellent chemical stability under H2O conditions, but few reports on this aspect has been made due to the processing difficulty for BaZrO3. Our recent pioneering work has demonstrated the feasibility of using BaZrO3-based electrolyte for SOECs and the fabricated cell achieves relatively high cell performance, which is comparable or even higher than that for BaCeO3-based SOECs and offers better chemical stability. Cell performance can be further improved by tailoring the electrolyte and electrode. © The Electrochemical Society.

Development of all chemical solution derived Ce_0.9La_0.1O_{2 − y}/Gd₂Zr₂O₇ buffer layer stack for coated conductors: influence of the post-annealing process on surface crystallinity

DEFF Research Database (Denmark)

Yue, Zhao; Li, Xiaofen; Khoryushin, Alexey

2012-01-01

Preparation and characterization of a biaxially textured Gd2Zr2O7 and Ce0.9La0.1O2 − y (CLO, cap)/Gd2Zr2O7 (GZO, barrier) buffer layer stack by the metal–organic deposition route are reported. YBa2Cu3O7 − d (YBCO) superconductor films were deposited by the pulsed-laser deposition (PLD) technique ...

The hazard assessment of nanostructured CeO{sub 2}-based mixed oxides on the zebrafish Danio rerio under environmentally relevant UV-A exposure

Energy Technology Data Exchange (ETDEWEB)

Jemec, Anita, E-mail: anita.jemec@bf.uni-lj.si [National Institute of Chemistry, Laboratory for Environmental Sciences and Engineering, Hajdrihova 19, SI-1001 Ljubljana (Slovenia); University of Ljubljana, Biotechnical Faculty, Department of Biology, Večna pot 111, SI-1000 Ljubljana (Slovenia); Djinović, Petar; Črnivec, Ilja Gasan Osojnik; Pintar, Albin [National Institute of Chemistry, Laboratory for Environmental Sciences and Engineering, Hajdrihova 19, SI-1001 Ljubljana (Slovenia)

2015-02-15

The effect of nanomaterials on biota under realistic environmental conditions is an important question. However, there is still a lack of knowledge on how different illumination conditions alter the toxicity of some photocatalytic nanomaterials. We have investigated how environmentally relevant UV-A exposure (intensity 8.50 ± 0.61 W/m{sup 2}, exposure dose 9.0 J/cm{sup 2}) affected the toxicity of cerium oxide (CeO{sub 2})-based nanostructured materials to the early-life stages of zebrafish Danio rerio. Pure cerium oxide (CeO{sub 2}), copper–cerium (CuO–CeO{sub 2}) (with a nominal 10, 15 and 20 mol.% CuO content), cerium–zirconium (CeO{sub 2}–ZrO{sub 2}) and nickel and cobalt (Ni–Co) deposited over CeO{sub 2}–ZrO{sub 2} were tested. It was found that under both illumination regimes, none of the tested materials affected the normal development or induced mortality of zebrafish early-life stages up to 100 mg/L. Only in the case of CuO–CeO{sub 2}, the growth of larvae was decreased (96 h LOEC values for CuCe10, CuCe15 and CuCe20 were 50, 50 and 10 mg/L, respectively). To conclude, CeO{sub 2}-based nanostructured materials are not severely toxic to zebrafish and environmentally relevant UV-A exposure does not enhance their toxicity. - Highlights: • CeO{sub 2}–ZrO{sub 2} nanomaterials and pure CeO{sub 2} (up to 100 mg/L) were not harmful to zebrafish. • Only CuO modified CeO{sub 2} affected the growth of zebrafish larvae. • UV-A radiation did not enhance the toxicity of tested nanomaterials.

Lattice vibrational properties of transition metal carbides (TiC, ZrC

Indian Academy of Sciences (India)

Lattice vibrational properties of transition metal carbides (TiC, ZrC and HfC) have been presented by including the effects of free-carrier doping and three-body interactions in the rigid shell model. The short-range overlap repulsion is operative up to the second neighbour ions. An excellent agreement has been obtained ...

The equiatomic intermetallics REPtCd (RE = La, Ce, Pr, Nd, Eu) and magnetic properties of CeAuCd

Energy Technology Data Exchange (ETDEWEB)

Johnscher, Michael; Niehaus, Oliver; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Tappe, Frank [Hochschule Hamm-Lippstadt, Hamm (Germany)

2015-06-01

The cadmium intermetallics REPtCd (RE = La, Ce, Pr, Nd, Eu) and CeAuCd were synthesized by induction-melting of the elements in sealed niobium ampoules followed by annealing in muffle furnaces. The samples were characterized by powder X-ray diffraction. The structures of CePtCd (ZrNiAl type, P anti 62m, a = 763.8(6), c = 409.1(4) pm, wR2 = 0.0195, 298 F{sup 2} values, 14 variables) and EuPtCd (TiNiSi type, Pnma, a = 741.3(2), b = 436.4(1), c = 858.0(4) pm, wR2 = 0.0385, 440 F{sup 2} values, 20 variables) were refined from single-crystal data. The REPtCd structures exhibit three-dimensional networks of corner- and edge-sharing Cd rate at Pt{sub 2/6}Pt{sub 2/3} and Cd rate at Pt{sub 4/4} tetrahedra, which leave cages for the rare earth atoms. Temperature-dependent magnetic susceptibility data of CeAuCd reveal a paramagnetic to antiferromagnetic phase transition at T{sub N} = 3.7(5) K.

The equiatomic intermetallics REPtCd (RE = La, Ce, Pr, Nd, Eu) and magnetic properties of CeAuCd

International Nuclear Information System (INIS)

Johnscher, Michael; Niehaus, Oliver; Poettgen, Rainer

2015-01-01

The cadmium intermetallics REPtCd (RE = La, Ce, Pr, Nd, Eu) and CeAuCd were synthesized by induction-melting of the elements in sealed niobium ampoules followed by annealing in muffle furnaces. The samples were characterized by powder X-ray diffraction. The structures of CePtCd (ZrNiAl type, P anti 62m, a = 763.8(6), c = 409.1(4) pm, wR2 = 0.0195, 298 F 2 values, 14 variables) and EuPtCd (TiNiSi type, Pnma, a = 741.3(2), b = 436.4(1), c = 858.0(4) pm, wR2 = 0.0385, 440 F 2 values, 20 variables) were refined from single-crystal data. The REPtCd structures exhibit three-dimensional networks of corner- and edge-sharing Cd rate at Pt 2/6 Pt 2/3 and Cd rate at Pt 4/4 tetrahedra, which leave cages for the rare earth atoms. Temperature-dependent magnetic susceptibility data of CeAuCd reveal a paramagnetic to antiferromagnetic phase transition at T N = 3.7(5) K.

On the determination of Zr(IV), Ce((III), Th(IV) and U(VI) in organic phase using arsenazo-I and arsenazo-III

International Nuclear Information System (INIS)

El-Sweify, F.H.; Kamel, M.M.; Shabana, R.

1997-01-01

Some organic extractants of different types, namely tridodecylamine (TDA), tricapryl methyl ammonium chloride (TCMA), di(2-ethylhexyl) phosphoric acid (HDEHP) and 1-[thenoyl-(2)]-3,3,3-trifluoroacetone (HTTA) in xylene have been used to study the extraction behaviour of coloured complexes of Zr(IV), Ce(III), Th(IV) and U(VI) from slightly acidic aqueous solutions of arsenazo-III. Spectrophotometric study for the determination of the aforementioned elements, as well as the colouring agents arsenazo-I and arsenazo-III in the organic phase has been carried out. Some factors affecting the spectrophotometric determination of these elements were studied. These factors were hydrogen ion concentration, concentration of the colouring agents in the aqueous phase and diluent type. Absorption spectra and standard curves are given. The molar extinction coefficients have been calculated. 10 figs

Bipolar resistive switching properties of Hf{sub 0.5}Zr{sub 0.5}O{sub 2} thin film for flexible memory applications

Energy Technology Data Exchange (ETDEWEB)

Wu, Zhipeng; Zhu, Jun; Zhou, Yunxia; Liu, Xingpeng [State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronics Science and Technology of China, Chengdu (China)

2018-01-15

An Au/Ni/Hf{sub 0.5}Zr{sub 0.5}O{sub 2}/Au flexible memory device fabricated on a polyethylene terephthalate substrate was studied for flexible resistive random access memory applications. A typical bipolar resistive switching behavior was revealed with an OFF/ON ratio of approximately 15. The reproducibility and uniformity were investigated using 100 repetitive write/erase cycles. The retention property did not degrade for up to 5 x 10{sup 4} s, and the resistive switching properties did not degrade even under bending conditions, which indicated good mechanical flexibility. The current-voltage characteristics of the memory device show a Poole-Frenkel emission conduction mechanism in the high-voltage region in the high-resistance state, while in the low-voltage region, the Ohmic contact and space charge limit current responded to the low-resistance state and high-resistance state, respectively. Combined with the conductance mechanism, the resistive switching behavior is attributed to conductive filaments forming and rupturing due to oxygen vacancies migrating under the external driving electric field. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Fabrication of Metal Nanoparticle Arrays in the ZrO2(Y, HfO2(Y, and GeOx Films by Magnetron Sputtering

Directory of Open Access Journals (Sweden)

Oleg Gorshkov

2017-01-01

Full Text Available The single sheet arrays of Au nanoparticles (NPs embedded into the ZrO2(Y, HfO2(Y, and GeOx (x≈2 films have been fabricated by the alternating deposition of the nanometer-thick dielectric and metal films using Magnetron Sputtering followed by annealing. The structure and optical properties of the NP arrays have been studied, subject to the fabrication technology parameters. The possibility of fabricating dense single sheet Au NP arrays in the matrices listed above with controlled NP sizes (within 1 to 3 nm and surface density has been demonstrated. A red shift of the plasmonic optical absorption peak in the optical transmission spectra of the nanocomposite films (in the wavelength band of 500 to 650 nm has been observed. The effect was attributed to the excitation of the collective surface plasmon-polaritons in the dense Au NP arrays. The nanocomposite films fabricated in the present study can find various applications in nanoelectronics (e.g., single electronics, nonvolatile memory devices, integrated optics, and plasmonics.

Steam Electrolysis by Proton-Conducting Solid Oxide Electrolysis Cells (SOECs) with Chemically Stable BaZrO3-Based Electrolytes

KAUST Repository

Bi, Lei; Traversa, Enrico

2015-01-01

BaZrO3-based material was applied as the electrolyte for proton-conducting solid oxide fuel cells (SOECs). Compared with the instability of BaCeO3-based proton-conductors, BaZrO3-based material could be a more promising candidate for proton

Electric field gradient at the Nb3M(M = Al, In, Si, Ge, Sn) and T3Al (T = Ti, Zr, Hf, V, Nb, Ta) alloys by perturbed angular correlation method

International Nuclear Information System (INIS)

Junqueira, Astrogildo de Carvalho

1999-01-01

The electric field gradient (efg) at the Nb site in the intermetallic compounds Nb 3 M (M = Al, Si, Ge, Sn) and at the T site in the intermetallic compounds T 3 Al (T = Ti, Zr, Hf, V, Nb, Ta) was measured by Perturbed Angular Correlation (PAC) method using the well known gamma-gamma cascade of 133-482 keV in 181 Ta from the β - decay of 181 Hf. The compounds were prepared by arc melting the constituent elements under argon atmosphere along with radioactive 181 Hf substituting approximately 0.1 atomic percent of Nb and T elements. The PAC measurements were carried out at 295 K for all compounds and the efg was obtained for each alloy. The results for the efg in the T 3 Al compounds showed a strong correlation with the number of conduction electrons, while for the Nbs M compounds the efg behavior is influenced mainly by the p electrons of the M elements. The so-called universal correlation between the electronic and lattice contribution for the efg in metals was not verified in this work for all studied compounds. Measurements of the quadrupole frequency in the range of 100 to 1210 K for the Nb 3 Al compound showed a linear behaviour with the temperature. Superconducting properties of this alloys may probably be related with this observed behaviour. The efg results are compared to those reported for other binary alloys and discussed with the help of ab-initio methods. (author)

Quaternary sulphides Cu2Zn(Ti, Zr, Hf)S4, the new type of photovoltaic materials%四元硫化物Cu2Zn（Ti，Zr，Hf）S4：一类新颖光伏材料∗

Institute of Scientific and Technical Information of China (English)

范巍; 曾雉

2016-01-01

采用第一性原理电子结构方法研究了四价过渡金属Ti, Zr和Hf替代Cu2ZnSnS4(CZTS)中Sn原子以及Se替代S原子所得到的四元硫族化合物的电子结构、光学性质和晶体结构的稳定性。实验上用Se替代CZTS中部分S得到的Cu2ZnSnS4−xSex(CZTSSe)作为光吸收材料,可以进一步提高光伏效率。我们计算表明用Se替代S后, CZTSe的价带顶明显下移,并接近Cu(In, Ga) Se2(CIGS)价带顶位置。与CZTSe的电子结构特征一样, Cu2Zn(Ti, Zr, Hf)S4四元硫化物的价带顶与母体材料CZTS相比也向低能移动,并接近CIGS价带顶位置。由于高光伏效率要求窗口材料ZnO、缓冲层材料和光吸收材料的价带顶和带隙满足一定的渐进的变化关系,因此可以预见用Cu2Zn(Ti, Zr, Hf)S4作光吸收材料可以有效地提高甚至接近CIGS的光伏效率。通过计算弹性常数和声子谱,以及有限温度下第一性原理分子动力学模拟,发现Cu2Zn(Ti, Zr, Hf)S4的结构稳定性与CZTS相近。进一步计算Cu2Zn(Ti, Zr, Hf)S4与不同缓冲层间和窗口材料与缓冲层间的反射系数,并讨论了ZnSe, In2S3, ZnS作为缓冲层材料和TiO2作为窗口材料对光伏效率可能的影响。%Based on the first-principles electronic-structure method, we study the electronic structures, optical properties, and the structural stabilities of the quaternary sulphides Cu2Zn(Ti, Zr, Hf) S4, which are obtained via substituting Ti, Zr, and Hf elements for Sn elements in Cu2ZnSnS4 (CTZS). It is well known that the photovoltaic efficiency of CZTS(Se) will be improved if the Se atoms partially substitute S atoms in CZTS. Our results show that the valence-band top of CZTSe shifts to lower energy and accesses to the valence-band top of Cu(InGa) Se2 (CIGS). Similar to CZTSe, the valence-band tops of Cu2Zn(Ti, Zr, Hf)S4 also shift to lower energies and access to the top of valence-band of CIGS. The high photovoltaic efficiency requires the smooth changes of the

Cerium intermetallics CeTX. Review III

Energy Technology Data Exchange (ETDEWEB)

Poettgen, Rainer; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Chevalier, Bernard [Bordeaux Univ., Pessac (France). Inst. de Chimie de la Matiere Condensee de Bordeaux

2016-05-01

The structure-property relationships of CeTX intermetallics with structures other than the ZrNiAl and TiNiSi type are systematically reviewed. These CeTX phases form with electron-poor and electron-rich transition metals (T) and X = Mg, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, and Bi. The review focusses on the crystal chemistry, the chemical bonding peculiarities, and the magnetic and transport properties. Furthermore {sup 119}Sn Moessbauer spectroscopic data, high-pressure studies, hydrogenation reactions and the formation of solid solutions are reviewed. This paper is the third of a series of four reviews on equiatomic intermetallic cerium compound [Part I: R. Poettgen, B. Chevalier, Z. Naturforsch. 2015, 70b, 289; Part II: R. Poettgen, B. Chevalier, Z. Naturforsch. 2015, 70b, 695].

Low electron density of states at the boron site of TMB{sub 2} (TM = Ti, Zr, Hf, and Nb): a {sup 11}B NMR study

Energy Technology Data Exchange (ETDEWEB)

Paluch, S.; Zogal, O.J.; Peshev, P

2004-11-30

The local density of states at the boron site in TMB{sub 2} (TM=Ti, Zr, Hf, and Nb) has been examined using the solid-state {sup 11}B NMR technique. The magic angle spinning (MAS) NMR spectra at room temperature and the spin-lattice relaxation rates have been measured as functions of temperature (30-293 K). The resonance line shifts are small and become more negative in the direction from 3d- to 5d-elements. The relaxation rates follow a linear law characteristic of hyperfine magnetic interaction with conduction electrons. With borides of IV group metals the data can be understood in terms of a very low s-electron density of states and absence of a p-character of the conduction electron wave function at the Fermi level while in the case of NbB{sub 2} a small partial p-electron density of states is assumed. Then, the results are in good agreement with the earlier theoretical prediction.

Stable, easily sintered BaCe0.5Zr0.3Y0.16Zn0.04O3-δ electrolyte-based proton-conducting solid oxide fuel cells by gel-casting and suspension spray

International Nuclear Information System (INIS)

Lin Bin; Dong Yingchao; Wang Songlin; Fang Daru; Ding Hanping; Zhang Xiaozhen; Liu Xingqin; Meng Guangyao

2009-01-01

Protonic ceramic membrane fuel cells (PCMFCs) based on oxide proton conductors exhibit more advantages than traditional solid oxide fuel cells (SOFCs) based on oxygen-ion conducting electrolytes, such as low activation energy and high energy efficiency. In order to develop a simple and cost-effective route to fabricate PCMFCs with SrCo 0.9 Sb 0.1 O 3-δ (SCS) cubic perovskite cathode, a dense BaCe 0.5 Zr 0.3 Y 0.16 Zn 0.04 O 3-δ (BCZYZn) electrolyte was fabricated in situ metal oxide on a porous anode support by gel-casting and suspension spray, which is cost-effective, easy to realize, and suitable for mass-production. The key part of this process is to directly spray well-mixed suspension of BaCO 3 , CeO 2 , ZrO 2 , Y 2 O 3 and ZnO instead of pre-synthesized BCZYZn ceramic powder on the anode substrate. With SCS cubic perovskite cathode synthesized by gel-casting on the bi-layer, single cells were assembled and tested with H 2 as fuel and the static air as oxidant. An open-circuit potential of 0.987 V, a maximum power density of 364 mW cm -2 , and a low polarization resistance of the electrodes of 0.07 Ω cm 2 was achieved at 700 deg. C.

Thermal evolution of CaO-doped HfO{sub 2} films and powders

Energy Technology Data Exchange (ETDEWEB)

Barolin, S A; Sanctis, O A de [Lab. Materiales Ceramicos, FCEIyA, Universidad Nacional de Rosario, IFIR-CONICET (Argentina); Caracoche, M C; Martinez, J A; Taylor, M A; Pasquevich, A F [Departamento de Fisica, FCE, Universidad Nacional de La Plata, IFLP-CONICET (Argentina); Rivas, P C, E-mail: oski@fceia.unr.edu.a [Facultad de Ciencias Agronomicas y Forestales, Universidad Nacional de La Plata, IFLP (Argentina)

2009-05-01

Solid solutions of ZrO2 and HfO2 are potential electrolyte materials for intermediate-temperature SOFC because both are oxygen-ion conductors. The main challenge for these compounds is to reduce the relatively high value of the activation energies vacancies diffusion, which is influenced by several factors. In this work the thermal evolution of CaO-HfO{sub 2} materials have been investigated. (CaO)y-Hf(1-y)O(2-y) (y = 0.06, 0.14 y 0.2) coatings and powders were synthesized by chemical solution deposition (CSD). Films were deposited onto alumina substrates by Dip Coating technique, the burning of organic waste was carried out at 500 deg. C under normal atmosphere and then the films were thermally treated at intervals of temperature rising to a maximum temperature of 1250 deg. C. By means Glazing Incidence X-ray Diffraction (rho-2theta configuration) the phases were studied in the annealed films. On the other hand, the thermal evolution and crystallization process of powders were analyzed in-situ by HT-XRD. The phenomena crystallization occurred in films and powders were analyzed. The activation energies of diffusion of oxygen vacancies of HfO2-14 mole% CaO and HfO2-20 mole% CaO films were measured from the thermal evolution of the relaxation constant measured by Perturbed Angular Correlation Technique.

Zr-92(d,p)Zr-93 and Zr-92(d,t)Zr-91

Science.gov (United States)

Baron, N.; Fink, C. L.; Christensen, P. R.; Nickels, J.; Torsteinsen, T.

1972-01-01

The structures of Zr-93 and Zr-91 were studied by the stripping reaction Zr-92(d,p)Zr-93 and the pick-up reaction Zr-92(d,t)Zr-91 using 13 MeV incident deuterons. The reaction product particles were detected by counter telescope. Typical spectra from the reactions were analyzed by a nonlinear least squares peak fitting program which included a background search. Spin and parity assignments to observed excited levels were made by comparing experimental angular distributions with distorted wave Born approximation calculations.

Quantum oscillation evidence for a topological semimetal phase in ZrSnTe

Science.gov (United States)

Hu, Jin; Zhu, Yanglin; Gui, Xin; Graf, David; Tang, Zhijie; Xie, Weiwei; Mao, Zhiqiang

2018-04-01

The layered WHM-type (W =Zr /Hf /La , H =Si /Ge /Sn /Sb , M =S /Se /Te ) materials represent a large family of topological semimetals, which provides an excellent platform to study the evolution of topological semimetal state with the fine tuning of spin-orbit coupling and structural dimensionality for various combinations of W , H , and M elements. In this work, through high field de Haas-van Alphen (dHvA) quantum oscillation studies, we have found evidence for the predicted topological nontrivial bands in ZrSnTe. Furthermore, from the angular dependence of quantum oscillation frequency, we have revealed the three-dimensional Fermi surface topologies of this layered material owing to strong interlayer coupling.

Electrical conductivity and chemical stability of BaCe0·8−xAxGd0 ...

Indian Academy of Sciences (India)

−1 in air at 1073 K. BaCe0·7In0·1Gd0·2O3−δ and BaCe0·7Zr0·1Gd0·2O3−δ ceramics exhibit an ... cells convert chemical energy directly into electrical energy and their ... peratures in the presence of CO2 and water vapour (Haile. 2003 ...

Prospects for designing structural cast eutectic alloys on Al-Ce-Ni system base

International Nuclear Information System (INIS)

Belov, N.A.; Naumova, E.S.

1996-01-01

The phase diagram of Al-Ce-Ni system is built for an aluminium corner at component concentration up to 16 mass %Ce and 8 mass%Ni. A ternary eutectic reaction is established at 12%Ce, 5%Ni and 626 deg C. The ternary eutectic alloy is similar in structure to rapidly cooled Al base alloys with transition metals. The possibility to design new cast alloys based on three-phase (Al)+NiAl 3 +CeAl 4 eutectics is under consideration. Al-Zn-Mg-Cu, Al-Sc and Al-Zr base alloys can be used as (Al) constituent of the eutectics. The new alloys may be considered as heat resistant ones due to the fact that no structural changes are observed in castings on heating up to 350 deg C. 18 refs.; 4 figs.; 2 tabs

Systematic study on the electronic structure and mechanical properties of X2BC (X = Mo, Ti, V, Zr, Nb, Hf, Ta and W)

International Nuclear Information System (INIS)

Bolvardi, H; Emmerlich, J; To Baben, M; Music, D; Schneider, J M; Von Appen, J; Dronskowski, R

2013-01-01

In this work the electronic structure and mechanical properties of the phases X 2 BC with X =Ti, V, Zr, Nb, Mo, Hf, Ta, W (Mo 2 BC-prototype) were studied using ab initio calculations. As the valence electron concentration (VEC) per atom is increased by substitution of the transition metal X, the six very strong bonds between the transition metal and the carbon shift to lower energies relative to the Fermi level, thereby increasing the bulk modulus to values of up to 350 GPa, which corresponds to 93% of the value reported for c-BN. Systems with higher VEC appear to be ductile as inferred from both the more positive Cauchy pressure and the larger value of the bulk to shear modulus ratio (B/G). The more ductile behavior is a result of the more delocalized interatomic interactions due to larger orbital overlap in smaller unit cells. The calculated phase stabilities show an increasing trend as the VEC is decreased. This rather unusual combination of high stiffness and moderate ductility renders X 2 BC compounds with X = Ta, Mo and W as promising candidates for protection of cutting and forming tools.

Influence of some metal substitutions on the superconducting behaviour of molybdenum borocarbide. [Mo/sub 2-x/M/sub x/BC; M = Zr, Nb, Rh, Hf, Ta, or W

Energy Technology Data Exchange (ETDEWEB)

Lejay, P.; Chevalier, B.; Etourneau, J.; Hagenmuller, P. [Bordeaux-1 Univ., 33 - Talence (France)

1981-11-15

The superconducting properties of the Mosub(2-x)Msub(x)BC borocarbides (M equivalent to Zr, Nb, Rh, Hf, Ta, W) are reported. They have an Mo/sub 2/BC-type structure with orthorhombic symmetry and the space group Cmcm. Stoichiometric powder samples were prepared by arc melting. A large single crystal of Mo/sub 2/BC was obtained by a Czochralski-type method. The upper limit of x depends mainly on the size of the M atoms. A study of the magnetization as a function of field at different temperatures shows that all borocarbides are type II superconductors. Resistivity measurements give generally a critical temperature Tsub(cr) above 4.2 K. Tsub(cr) and the critical fields Hsub(c2) increase for rhodium substitution but decrease in other cases. For comparison the superconducting properties are discussed in terms of the valence electron concentration and the molar volume.

Re-Os and Lu-Hf isotopic constraints on the formation and age of mantle pyroxenites from the Bohemian Massif

Czech Academy of Sciences Publication Activity Database

Ackerman, Lukáš; Bizimis, M.; Haluzová, Eva; Sláma, Jiří; Svojtka, Martin; Hirajima, T.; Erban, V.

256/257, July (2016), s. 197-210 ISSN 0024-4937 Grant - others:Rada Programu interní podpory projektů mezinárodní spolupráce AV ČR(CZ) M100131203 Program:Program interní podpory projektů mezinárodní spolupráce AV ČR Institutional support: RVO:67985831 Keywords : Bohemian Massif * Lu-Hf * mantle * pyroxenite * Re-Os Subject RIV: DB - Geology ; Mineralogy Impact factor: 3.677, year: 2016

Constraining Mantle Differentiation Processes with La-Ce and Sm-Nd Isotope Systematics

Science.gov (United States)

Willig, M.; Stracke, A.

2016-12-01

Cerium (Ce) and Neodymium (Nd) isotopic ratios in oceanic basalts reflect the time integrated La-Ce and Sm-Nd ratios, and hence the extent of light rare earth element element (LREE) depletion or enrichment of their mantle sources. New high precision Ce-Nd isotope data from several ocean islands define a tight array in ԑCe-ԑNd space with ԑNd = -8.2±0.4 ԑCe + 1.3±0.9 (S.D.), in good agreement with previous data [1, 2]. The slope of the ԑCe-ԑNd array and the overall isotopic range are sensitive indicators of the processes that govern the evolution of the mantle's LREE composition. A Monte Carlo approach is employed to simulate continuous mantle-crust differentiation by partial melting and recycling of crustal materials. Partial melting of mantle peridotites produces variably depleted mantle and oceanic crust, which evolve for different time periods, before the oceanic crust is recycled back into the mantle including small amounts of continental crust (GLOSS [3]). Subsequently, depleted mantle and recycled materials of variable age and composition melt, and the respective melts mix in different proportions. Mixing lines strongly curve towards depleted mantle, and tend to be offset from the data for increasingly older and more depleted mantle. Observed ԑCe-ԑNd in ridge [1] and ocean island basalts and the slope of the ԑCe-ԑNd array therefore define upper limits for the extent and age of LREE depletion preserved in mantle peridotites. Very old average mantle depletion ages (> ca. 1-2 Ga) for the bulk of the mantle are difficult to reconcile with the existing ԑCe-ԑNd data, consistent with the range of Nd-Hf-Os model ages in abyssal peridotites [4-6]. Moreover, unless small amounts of continental crust are included in the recycled material, it is difficult to reproduce the relatively shallow slope of the ԑCe-ԑNd array, consistent with constraints from the ԑNd - ԑHf mantle array [7]. [1] Makishima and Masuda, 1994 Chem. Geol. 118, 1-8. [2] Doucelance et al

Hf-Nd isotope decoupling in the oceanic lithosphere: constraints from spinel peridotites from Oahu, Hawaii

Science.gov (United States)

Bizimis, Michael; Sen, Gautam; Salters, Vincent J. M.

2004-01-01

We present a detailed geochemical investigation on the Hf, Nd and Sr isotope compositions and trace and major element contents of clinopyroxene mineral separates from spinel lherzolite xenoliths from the island of Oahu, Hawaii. These peridotites are believed to represent the depleted oceanic lithosphere beneath Oahu, which is a residue of a MORB-related melting event some 80-100 Ma ago at a mid-ocean ridge. Clinopyroxenes from peridotites from the Salt Lake Crater (SLC) show a large range of Hf isotopic compositions, from ɛHf=12.2 (similar to the Honolulu volcanics series) to extremely radiogenic, ɛHf=65, at nearly constant 143Nd/ 144Nd ratios ( ɛNd=7-8). None of these samples show any isotopic evidence for interaction with Koolau-type melts. A single xenolith from the Pali vent is the only sample with Hf and Nd isotopic compositions that falls within the MORB field. The Hf isotopes correlate positively with the degree of depletion in the clinopyroxene (e.g. increasing Mg#, Cr#, decreasing Ti and heavy REE contents), but also with increasing Zr and Hf depletions relative to the adjacent REE in a compatibility diagram. The Lu/Hf isotope systematics of the SLC clinopyroxenes define apparent ages of 500 Ma or older and these compositions cannot be explained by mixing between any type of Hawaiian melts and the depleted Pacific lithosphere. Metasomatism of an ancient (e.g. 1 Ga or older) depleted peridotite protolith can, in principle, explain these apparent ages and the Nd-Hf isotope decoupling, but requires that the most depleted samples were subject to the least amount of metasomatism. Alternatively, the combined isotope, trace and major element compositions of these clinopyroxenes are best described by metasomatism of the 80-100 Ma depleted oceanic lithosphere by melts products of extensive mantle-melt interaction between Honolulu Volcanics-type melts and the depleted lithosphere.

Epitaxial YBa2Cu3O7-x nanocomposite films and coated conductors from BaMO3 (M = Zr, Hf) colloidal solutions

Science.gov (United States)

Obradors, X.; Puig, T.; Li, Z.; Pop, C.; Mundet, B.; Chamorro, N.; Vallés, F.; Coll, M.; Ricart, S.; Vallejo, B.; Pino, F.; Palau, A.; Gázquez, J.; Ros, J.; Usoskin, A.

2018-04-01

Superconducting nanocomposites are the best material choice to address the performance required in power applications and magnets working under high magnetic fields. However, it is still challenging to sort out how to achieve the highest superconducting performance using attractive and competitive manufacturing processes. Colloidal solutions have been recently developed as a novel and very promising low cost route to manufacture nanocomposite coated conductors. Well dispersed and stabilized preformance nanoparticle solutions are first prepared with high concentrations and then mixed with the YBa2Cu3O7 metalorganic precursor solutions to generate colloidal solutions to grow the nanocomposite films. Here we demonstrate, for the first time, that non-reactive BaZrO3 and BaHfO3 perovskite preformed nanoparticles are suitable for growing high quality thin and thick films, and coated conductors with a homogeneous distribution and controlled particle size using this fabrication method. Additionally, we extend the nanoparticle content of the nanocomposites up to 20%-25% mol without any degradation of the superconducting properties. Thick nanocomposite films, up to 0.8 μm, have been prepared with a single deposition of low-fluorine solutions using an ink jet printing dispenser and we demonstrate that the preformed nanoparticles display only a very limited coarsening during the growth process and so high critical current densities J c (B) under high magnetic fields. These films show the highest critical currents achieved so far based on the colloidal solution approach, I c = 220 A/cm-w at 77 K and self-field, and they still have a high potential for further increase in the film thickness. Finally, we also show that nanocomposite YBa2Cu3O7-BaZrO3 coated conductors based on an alternating beam assisted deposited YSZ buffer layer on stainless steel metallic substrates can be developed based on these novel colloidal solutions. Non-reactive preformed oxide perovskite

Luminescence of Ce doped oxygen crystalline compounds based on Hf and Ba

CERN Document Server

Borisevich, A E; Lecoq, P

2003-01-01

The luminescence properties of the Ce-doped hafnium and barium compounds have been investigated to determine their potential as heavy scintillation materials. Compounds have been prepared by solid state synthesis. All of them have shown a bright luminescence attributed to trivalent cerium. Emission bands are peaked in the 425-475nm spectral region at room temperature.

Magnetoresistance in CePtSn under high hydrostatic pressures

International Nuclear Information System (INIS)

Misek, M.; Prokleska, J.; Javorsky, P.; Sechovsky, V.

2009-01-01

We report the evolution of magnetic-history dependent antiferromagnetic phases in CePtSn. We concentrate on the magnetoresistance in magnetic fields up to 14 T applied along the crystallographic b-axis, measured on a CePtSn single crystal subjected to hydrostatic pressure (p ≤ 2.2 GPa) generated in a double-layered CuBe/NiCrAl piston cylinder cell. We observe a gradual increase of the critical field B c LF of the low field (LF) transition up to ∼1.2 GPa where only one transition is observed at ∼11.5 T. For pressures above 1.2 GPa we observe two transitions again and B c LF decreases with further increasing pressure to reach B c LF ∼7.5T at 2.5 GPa. The position of the high field (HF) transition remains almost unaffected by applied pressure. A scenario considering the spin-slip AF structure in CePtSn is briefly discussed.

Interfacial and Electrical Properties of Ge MOS Capacitor by ZrLaON Passivation Layer and Fluorine Incorporation

Science.gov (United States)

Huang, Yong; Xu, Jing-Ping; Liu, Lu; Cheng, Zhi-Xiang; Lai, Pui-To; Tang, Wing-Man

2017-09-01

Ge Metal-Oxide-Semiconductor (MOS) capacitor with HfTiON/ZrLaON stacked gate dielectric and fluorine-plasma treatment is fabricated, and its interfacial and electrical properties are compared with its counterparts without the ZrLaON passivation layer or the fluorine-plasma treatment. Experimental results show that the sample exhibits excellent performances: low interface-state density (3.7×1011 cm-2eV-1), small flatband voltage (0.21 V), good capacitance-voltage behavior, small frequency dispersion and low gate leakage current (4.41×10-5 A/cm2 at Vg = Vfb + 1V). These should be attributed to the suppressed growth of unstable Ge oxides on the Ge surface during gate-dielectric annealing by the ZrLaON interlayer and fluorine incorporation, thus greatly reducing the defective states at/near the ZrLaON/Ge interface and improving the electrical properties of the device.

Report on the Fracture Analysis of HfB(sub 2)-SiC and ZrB(sub 2)-SiC Composites; TOPICAL

International Nuclear Information System (INIS)

MECHOLSKY, JR. JOHN J.

2001-01-01

Hafnium diboride-silicon carbide (HS) and zirconium diboride-silicon carbide (ZS) composites are potential materials for high temperature, thermal shock applications such as for components on re-entry vehicles. In order to establish material constants necessary for evaluation of in situ fracture, bars fractured in four-point flexure were examined using fractographic principles. The fracture toughness was determined from measurements of the critical crack sizes and the strength values and the crack branching constants were established to use in forensic fractography for future in-flight tests. The fracture toughnesses range from about 13 MPam(sup 1/2) at room temperature to about 6 MPam(sup 1/2) at 1400 C for ZrB(sub 2)-Sic composites and from about 13 MPam(sup 1/2) at room temperature to about 4 MPam(sup 1/2) at 1400 C for HfB(sub 2)-SiC composites. Thus, the toughnesses of either the HS or ZS composites have the potential for use in thermal shock applications. Processing and manufacturing defects limited the strength of the test bars. However, examination of the microstructure on the fracture surfaces shows that the processing of these composites can be improved. There is potential for high toughness composites with high strength to be used in thermal shock conditions if the processing and handling are controlled

Microstructural and magnetic studies on BaMg{sub x}Zn{sub x}X{sub 2x}Fe{sub 12−4x}O{sub 19} (X=Zr,Ce,Sn) prepared via mechanical activation method to act as a microwave absorber in X-band

Energy Technology Data Exchange (ETDEWEB)

Afghahi, Seyyed Salman Seyyed [Department of Engineering, Imam Hossein University, Tehran (Iran, Islamic Republic of); Jafarian, Mojtaba, E-mail: m.jafarian@iau-shahrood.ac.ir [Department of Material Engineering, South Tehran Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Atassi, Yomen [Department of Applied Physics, Higher Institute for Applied Sciences and Technology, Damascus (Syrian Arab Republic)

2016-05-15

In this study, doped barium hexaferrite with the composition of BaMg{sub x}Zn{sub x}X{sub 2x}Fe{sub 12−4x}O{sub 19} (where x= 0.3, 0.5, 0.7, 0.9 and X= Zr, Ce, Sn) was prepared via mechanical activation. X-ray diffractometer (XRD), FTIR spectrophotometer, Field emission scanning electron microscope (FE-SEM), vibrating sample magnetometer (VSM) and vector network analyzer (VNA) were used to analyze its phases, structure, electromagnetic and microwave absorption properties respectively. Based on the results, single phase barium hexaferrite was obtained in all cases after milling the mixed powders for 20 h plus calcination at 1000 °C for 5 h. Morphology of the particles in all of the doped samples was completely hexagonal shape and they had an appropriate distribution. It was found that the sample of BaMg{sub 0.9}Zn{sub 0.9}Zr{sub 1.8}Fe{sub 8.4}O{sub 19} with saturation magnetization and coercive force of 37.3 emu/g and 94 Oe respectively possessed the maximum reflection loss of −19.3 dB at 12.3 GHz with 1.7 GHz bandwidth. - Highlights: • The mechanical activation method was used to prepare: BaMg{sub x}Zn{sub x}X{sub 2x}Fe{sub 12−4x}O{sub 19}(X=Zr, Ce, and Sn) with values of xequal to 0.3, 0.5, 0.7, and 0.9. • Morphology of the particles in all of the doped samples was completely hexagonal shape and they had an appropriate distribution. • BaMg{sub 0.9}Zn{sub 0.9}Zr{sub 1.8}Fe{sub 8.4}O{sub 19} possesses the maximum reflection loss of −19.3 dB at 12.3 GHz with 1.7 GHz bandwidth.

Contamination of foods by radioactive rains

Energy Technology Data Exchange (ETDEWEB)

Obo, F; Wakamatsu, C; Nakae, Y; Higasayama, S

1955-01-01

The radioactivities of various vegetable foods contaminated by radioactive rains in May, 1954, in the Kagoshima Area were detected. Tea showed especially high radioactivities which could be extracted with hot water. Radioactive Nb, Zr, Hf, Ce, Y, Pr, and La were detected in the hot water extractions of tea by ion-exchange chromatography. The partial contribution of /sup 40/K in these radioactive vegetables was critically examined.

Chlorination of UO2, PuO2, and rare-earth oxides using ZrCl4

International Nuclear Information System (INIS)

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

2001-01-01

A new chlorination method using ZrCl 4 , which has a high reactivity with oxygen, has been investigated for more efficient oxide treatment. After actinide oxides are chlorinated and dissolved in a molten salt bath, actinide metals can be selectively collected using the electrorefining process. This process is well suited for pyrochemical reprocessing of metallic fuels. In LiCl-KCI eutectic melts, rare-earth oxides (Y 2 O 3 , La 2 O 3 , CeO 2 , and Nd 2 O 3 ) and actinide oxides (UO 2 and PuO 2 ) were chlorinated by adding ZrCl 4 . As a result, rare-earth and actinide elements were dissolved into the salt as trivalent ions and ZrO 2 was precipitated. When an excess of ZrCI 4 was added, oxides in powder form were completely chlorinated in five hours. It was demonstrated that the ZrCI 4 chlorination method, free from corrosive gas such as chlorine, was very simple and useful. (author)

Cerium luminescence in nd0 perovskites

International Nuclear Information System (INIS)

Setlur, A.A.; Happek, U.

2010-01-01

The luminescence of Ce 3+ in perovskite (ABO 3 ) hosts with nd 0 B-site cations, specifically Ca(Hf,Zr)O 3 and (La,Gd)ScO 3 , is investigated in this report. The energy position of the Ce 3+ excitation and emission bands in these perovskites is compared to those of typical Al 3+ perovskites; we find a Ce 3+ 5d 1 centroid shift and Stokes shift that are larger versus the corresponding values for the Al 3+ perovskites. It is also shown that Ce 3+ luminescence quenching is due to Ce 3+ photoionization. The comparison between these perovskites shows reasonable correlations between Ce 3+ luminescence quenching, the energy position of the Ce 3+ 5d 1 excited state with respect to the host conduction band, and the host composition. - Graphical abstract: Ce 3+ decay times versus temperature for perovskites with nd 0 B-site cations.

Large ferroelectric polarization of TiN/Hf0.5Zr0.5O2/TiN capacitors due to stress-induced crystallization at low thermal budget

Science.gov (United States)

Kim, Si Joon; Narayan, Dushyant; Lee, Jae-Gil; Mohan, Jaidah; Lee, Joy S.; Lee, Jaebeom; Kim, Harrison S.; Byun, Young-Chul; Lucero, Antonio T.; Young, Chadwin D.; Summerfelt, Scott R.; San, Tamer; Colombo, Luigi; Kim, Jiyoung

2017-12-01

We report on atomic layer deposited Hf0.5Zr0.5O2 (HZO)-based capacitors which exhibit excellent ferroelectric (FE) characteristics featuring a large switching polarization (45 μC/cm2) and a low FE saturation voltage (˜1.5 V) as extracted from pulse write/read measurements. The large FE polarization in HZO is achieved by the formation of a non-centrosymmetric orthorhombic phase, which is enabled by the TiN top electrode (TE) having a thickness of at least 90 nm. The TiN films are deposited at room temperature and annealed at 400 °C in an inert environment for at least 1 min in a rapid thermal annealing system. The room-temperature deposited TiN TE acts as a tensile stressor on the HZO film during the annealing process. The stress-inducing TiN TE is shown to inhibit the formation of the monoclinic phase during HZO crystallization, forming an orthorhombic phase that generates a large FE polarization, even at low process temperatures.

Pure and Y-substituted BaZrO3 ceramics. A possible support material for fabrication of YBa2Cu3O7-x high-Tc superconductors

International Nuclear Information System (INIS)

Wang Xiandong.

1993-01-01

This thesis concerns the preparation and characterization of cuprate based high-T c superconductors (Y-123 and Bi-2223) and especially development and testing of BaZrO 3 based materials. The formation of YBa 2 Cu 3 O y (Y-123) by a CO 2 -free route involving reaction sintering of stoichiometric mixtures of chemically prepared fine powders of Y 2 BaCuO 5 , BaCuO 2 and CuO have been studied by thermal and XRD analysis. The synthesis and sintering of BaZrO 3 powders prepared by the hydroxide-alkoxide-methanol sol-gel route have been studied. The phase relations in the system BaO-Y 2 O 3 -ZrO 2 have been studied to determine the solid solubility limits for the perovskite phase Ba X Y Y Zr Z O N (X+X+Z=3) at 1500 deg. C. In the binary system Y 2 O 3 -BaZrO 3 the solubility limit was found to be ≅19 mol% Y 2 O 3 , i.e. Ba 0.81 Y 0. 4 2 Zr 0.81 O 3 . along the joint BaYO 2.5 -Ba the boundary was determined to be at BaY 0.21 Zr 0 . 79 O 2.895 . evidence for a new solid solution series between Ba 3 Y 4 O 9 and ZrO 2 are given, and a partial 1500 deg. C phase diagram for the ternary system BaO-Y 2 O 3 -ZrO 2 is presented. The growth of BaZrO 3 single crystals have been attempted both by a laser zone floating technique and flux methods. The compatibility between YBa 2 Cu 3 O 7 -X and BaZrO 3 , Ba X Y Y Zr Z O 3-δ as well as BaHfO 3 have been studied at 950 deg. and 1050 deg. C. The results show the four most promising candidates as support materials for fabrication of YBa 2 Cu 3 O y to be BaHfO 3 , BaY 0.05 Zr 0.95 O 2.975 , , BaZrO 3 and BaY 0.1 Zr 0.9 O 2.95 . (EG)

Capacitor Property and Leakage Current Mechanism of ZrO2 Thin Dielectric Films Prepared by Anodic Oxidation

Science.gov (United States)

Kamijyo, Masahiro; Onozuka, Tomotake; Shinkai, Satoko; Sasaki, Katsutaka; Yamane, Misao; Abe, Yoshio

2003-07-01

Polycrystalline ZrO2 thin film capacitors were prepared by anodizing sputter-deposited Zr films. Electrical measurements are performed for the parallel-plate anodized capacitors with an Al-ZrO2-Zr (metal-insulator-metal) structure, and a high capacitance density (0.6 μF/cm2) and a low dielectric loss of nearly 1% are obtained for a very thin-oxide capacitor anodized at 10 V. In addition, the leakage current density of this capacitor is about 1.8 × 10-8 A/cm2 at an applied voltage of 5 V. However, the leakage current is somewhat larger than that of a low-loss HfO2 capacitor. The leakage current density (J) of ZrO2 capacitors as a function of applied electric field (E) was investigated for several capacitors with different oxide thicknesses, by plotting \\ln(J) vs E1/2 curves. As a result, it is revealed that the conduction mechanism is due to the Poole-Frenkel effect, irrespective of the oxide thickness.

Improved method for Hf separation from silicate rocks for isotopic analysis using Ln-spec resin column

International Nuclear Information System (INIS)

Shinjo, Ryuichi; Ginoza, Yuko; Meshesha, Daniel

2010-01-01

An improved chemical separation method for Hf isotope ratio measurement using both the thermal ionization mass spectrometer (TIMS) and the multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) is presented in this paper. In the first column (2.5-ml Eichrom Ln-spec resin), Hf cut was collected with 2M HCl-0.2M HF after washing the major elements, HREE, Ti, Nb, and Zr. For further Hf purification, the second column (1-ml Ln-spec resin) chemistry was conducted in a manner similar to that of the first column. The first column is designed for treatment with a 0.5-g silicate rock sample for TIMS analysis. Thus, because the Hf amount required for MC-ICP-MS analysis is much lesser than that required for TIMS analysis, the column chemistry for MC-ICP-MS analysis can be scaled down, depending on the amount of digested sample. Although there is a need to improve the TIMS technique, the TIMS Hf data obtained for geological reference rocks and Ethiopian flood basalts after the application of the proposed separation methods are consistent, within analytical error, with the previously reported data obtained using the MC-ICP-MS. The advantages of the proposed method include a reduction in the amount of reagents used (hence, a consequent reduction in the blank contribution), reduction in the time required, and a simplified preparation requiring a fewer number of acids. (author)

Effect of alloying on elastic properties of ZrN based transition metal nitride alloys

KAUST Repository

Kanoun, Mohammed; Goumri-Said, Souraya

2014-01-01

We report the effect of composition and metal sublattice substitutional element on the structural, elastic and electronic properties of ternary transition metal nitrides Zr1-xMxN with M=Al, Ti, Hf, V, Nb, W and Mo. The analysis of the elastic constants, bulk modulus, shear modulus, Young's modulus, and Poisson's ratio provides insights regarding the mechanical behavior of Zr1-xMxN. We predict that ternary alloys are more ductile compared to their parent binary compounds. The revealed trend in the mechanical behavior might help for experimentalists on the ability of tuning the mechanical properties during the alloying process by varying the concentration of the transition metal. © 2014 Elsevier B.V.

Effect of alloying on elastic properties of ZrN based transition metal nitride alloys

KAUST Repository

Kanoun, Mohammed

2014-09-01

We report the effect of composition and metal sublattice substitutional element on the structural, elastic and electronic properties of ternary transition metal nitrides Zr1-xMxN with M=Al, Ti, Hf, V, Nb, W and Mo. The analysis of the elastic constants, bulk modulus, shear modulus, Young\\'s modulus, and Poisson\\'s ratio provides insights regarding the mechanical behavior of Zr1-xMxN. We predict that ternary alloys are more ductile compared to their parent binary compounds. The revealed trend in the mechanical behavior might help for experimentalists on the ability of tuning the mechanical properties during the alloying process by varying the concentration of the transition metal. © 2014 Elsevier B.V.

The Importance of Rare-Earth Additions in Zr-Based AB2 Metal Hydride Alloys

Directory of Open Access Journals (Sweden)

Kwo-Hsiung Young

2016-07-01

Full Text Available Effects of substitutions of rare earth (RE elements (Y, La, Ce, and Nd to the Zr-based AB2 multi-phase metal hydride (MH alloys on the structure, gaseous phase hydrogen storage (H-storage, and electrochemical properties were studied and compared. Solubilities of the RE atoms in the main Laves phases (C14 and C15 are very low, and therefore the main contributions of the RE additives are through the formation of the RENi phase and change in TiNi phase abundance. Both the RENi and TiNi phases are found to facilitate the bulk diffusion of hydrogen but impede the surface reaction. The former is very effective in improving the activation behaviors. −40 °C performances of the Ce-doped alloys are slightly better than the Nd-doped alloys but not as good as those of the La-doped alloys, which gained the improvement through a different mechanism. While the improvement in ultra-low-temperature performance of the Ce-containing alloys can be associated with a larger amount of metallic Ni-clusters embedded in the surface oxide, the improvement in the La-containing alloys originates from the clean alloy/oxide interface as shown in an earlier transmission electron microscopy study. Overall, the substitution of 1 at% Ce to partially replace Zr gives the best electrochemical performances (capacity, rate, and activation and is recommended for all the AB2 MH alloys for electrochemical applications.

Thermal cycling behavior of YSZ and La2(Zr0.7Ce0.3)2O7 as double-ceramic-layer systems EB-PVD TBCs

International Nuclear Information System (INIS)

Xu Zhenhua; He Limin; Mu Rende; Lu Feng; He Shimei; Cao Xueqiang

2012-01-01

Highlights: ► DCL coating has a longer lifetime than that of single layer coating of LZ7C3 or YSZ. ► The unique growth modes of columns within DCL coating. ► The presence of cerium in both Ce 3+ and Ce 4+ oxidation states within the coating surface. ► The spallation of DCL coating induced by transverse cracks may be the first emergence of delamination followed by spalling layer by layer. ► The outward diffusion of Cr element (bond coat) into LZ7C3 layer. - Abstract: Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La 2 (Zr 0.7 Ce 0.3 ) 2 O 7 (LZ7C3) and yttria stabilized zirconia (YSZ) were deposited by electron beam-physical vapor deposition (EB-PVD). The thermal cycling test at 1573 K in burner-rig with a coal gas flame indicates the thermal cycling life of DCL coating is not only much longer than that of LZ7C3 coating, but also approximately 27% longer than that of YSZ coating. The superior sintering-resistance of LZ7C3 coating and the unique growth modes of columns within DCL coating are all very helpful to the prolongation of thermal cycling life of DCL coating. The failure of DCL coating is mainly a result of the reduction–oxidation of cerium oxide, the re-crystallization of some LZ7C3 fine grains, the cracks initiation, propagation and extension, the abnormal oxidation of bond coat, the degradation of t′-phase in YSZ coating and the outward diffusion of Cr alloying element into LZ7C3 coating. Since no single material that has been studied so far satisfies all the requirements for high temperature applications, DCL coating is an important development direction of TBCs.

Synthesis of ceramic BaCe_0_._7Zr_0_,_1Y_0_._2O_3_-_δ electrolyte containing ZnO through the method hidrogel

International Nuclear Information System (INIS)

Vieira, J.H.A.; Fagury Neto, E.; Rabelo, A.A.

2014-01-01

The solid oxide fuel cells are promising sources of sustainable energy, once they produce electricity from an electrochemical reaction only with steam water as the product of this reaction. In this paper the synthesis of ceramic electrolyte BaCe_0_._7Zr_0_._1Y_0_._2O_3_-_δ using the hydrogel method which involves using an organic gelatin inexpensive and nontoxic modifying the conventional route of polymeric precursor was performed. It was used different amounts of the sintering additive ZnO to decrease the sintering temperature, typically around 1600 °C, towards a minimum relative density of 95%. The polymeric resin was pyrolyzed at 300 °C, subjected to calcination at 600 °C and sintering at temperatures of 1350, 1400 and 1450 °C for 2 hours. Characterizations were carried out by determination of relative density and apparent porosity and using the techniques of differential thermal analysis and simultaneous thermogravimetric, X-ray diffraction and scanning electron microscopy.(author)

Hf layer thickness dependence of resistive switching characteristics of Ti/Hf/HfO2/Au resistive random access memory device

Science.gov (United States)

Nakajima, Ryo; Azuma, Atsushi; Yoshida, Hayato; Shimizu, Tomohiro; Ito, Takeshi; Shingubara, Shoso

2018-06-01

Resistive random access memory (ReRAM) devices with a HfO2 dielectric layer have been studied extensively owing to the good reproducibility of their SET/RESET switching properties. Furthermore, it was reported that a thin Hf layer next to a HfO2 layer stabilized switching properties because of the oxygen scavenging effect. In this work, we studied the Hf thickness dependence of the resistance switching characteristics of a Ti/Hf/HfO2/Au ReRAM device. It is found that the optimum Hf thickness is approximately 10 nm to obtain good reproducibility of SET/RESET voltages with a small RESET current. However, when the Hf thickness was very small (∼2 nm), the device failed after the first RESET process owing to the very large RESET current. In the case of a very thick Hf layer (∼20 nm), RESET did not occur owing to the formation of a leaky dielectric layer. We observed the occurrence of multiple resistance states in the RESET process of the device with a Hf thickness of 10 nm by increasing the RESET voltage stepwise.

Characterization of catalysts Rh and Ni/CexZr1-xO2 for hydrogen production by ethanol steam reforming

International Nuclear Information System (INIS)

Birot, A.

2005-01-01

This work concerned a study on catalytic behaviour of metallic catalysts (Rh or Ni) supported on earth rare oxides Ce x Zr 1-x O 2 in ethanol steam reforming in order to produce hydrogen. Catalyst 1%Rh/Ce0,50Zr0,50O 2 showed a good activity with a good hydrogen yield. We turned a study onto understanding inter-conversion reaction between H 2 , CO and CO 2 which lead to CH 4 formation. We also studied intrinsic properties of catalysts. We confirmed basic character of catalysts and a good hydrogenation activity. A good activity in CO hydrogenation allowed to evidence a necessity to use a catalyst which is less active in hydrogenation reaction and with a basic character in order to improve hydrogen yield. (author)

Chromatographic purification of neutron capture molybdenum-99 from cross-contaminant radionuclides

International Nuclear Information System (INIS)

Mostafa, M.A.M.

2011-01-01

Technetium-99m is called the work horse, for many reasons, in nuclear medicine diagnostic purposes. It is produced as the β - decay of 99 Mo radionuclide. Molybdenum-99 gel type generators are considered as a suitable alternative of the conventional chromatographic alumina columns loaded with fission molybdenum-99. 99 Mo neutron-capture is cross-contaminated with radionuclides originated from activation of chemical impurities in the Mo target such 60 C0, 65 Zn, 95 Zr, 175 Hf, 181 Hf, 86 Rb, 134 Cs, 141 Ce, 152 Eu, 140 La, 51 Cr, 124 Sb, 46 Sc, 54 Mn, 59 Fe and / or fast neutrons interactions with the stable isotopes of molybdenum such as 92m Nb, 95 Nb and 95 Zr. To prevent contamination of the eluted 99m Tc, successive purification methods were made. After complete dissolution of the irradiated target wrapped with thin Al foil in 5 M NaOH solution, hydrogen peroxide was added to start precipitation of Fe(OH) 3 . The formed Fe (III) minerals allow complete elimination of some radio contaminants from the molybdate solute such as 152 Eu, 140 La, 141 Ce, 45 Mn and 92m Nb in addition to partial elimination of 46 Sc, 60 Co and 59 Fe radionuclides. The remaining supernatant was acidified by concentrated nitric acid to ph 9.5 for precipitation of Al(OH) 3 with complete elimination of radio contaminants such as 95 Zr 175 Hf, 181 Hf, 65 Zn, 124 Sb, 51 Cr, 46 Sc, 60 Co and 59 Fe. 134 Cs and 86 Rb radionuclides were not affected by precipitation of Fe(OH) 3 or Al(OH) 3 . Chromatographic column of potassium nickel hexacyanoferrate (II) (KNHCF) has high affinity towards elimination of 134 Cs and 86 Rb radionuclides. Highly pure molybdate- 99 Mo solution was processed for preparation of zirconium molybdate gel generator with 99m Tc eluate of high radionuclidic, radiochemical and chemical purity suitable for use in medical purposes.

Properties of phases in HfO2-TiO2 system

International Nuclear Information System (INIS)

Red'ko, V.P.; Terekhovskij, P.B.; Majster, I.M.; Shevchenko, A.V.; Lopato, L.M.; Dvernyakova, A.A.

1990-01-01

A study was made on axial and linear coefficients of thermal expansion (CTE) of HfO 2 -TiO 2 system samples in concentration range of 25-50 mol% TiO 2 . Samples, containing 35 and 37 mol% TiO 2 , are characterized by the lowest values of linear CTE. Dispersion of the basic substances doesn't affect CTE value. Correlation with axial and linear CTE of samples in ZrO 2 -TiO 2 system was conducted. Presence of anisotropy of change of lattice parameters was supported for samples, containing 37.5 and 40 mol% TiO 2 . Polymorphous transformations for hafnium titanate were not revealed

Comparison of HfCl4, HfI4, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO2 films deposited by ALD: A DFT study

International Nuclear Information System (INIS)

Cortez-Valadez, M.; Fierro, C.; Farias-Mancilla, J.R.; Vargas-Ortiz, A.; Flores-Acosta, M.; Ramírez-Bon, R.; Enriquez-Carrejo, J.L.

2016-01-01

Highlights: • Hafnium oxide growth on Si(100) by atomic layer deposition was simulated. • The interface structure was considered as silicate and silicide. • The interface was studied employing DFT. • TDMA-Hf precursor show better interface stability. - Abstract: The final structure of HfO 2 films grown by atomic layer deposition (ALD) after reaction with OH − ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl 4 (hafnium tetrachloride), HfI 4 (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO–H was studied employing the B3LYP (Becke 3-parameter, Lee–Yang–Parr) hybrid functional and the PBE (Perdew–Burke–Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

Synthesis and characterization of pure and (Ce, Zr, Ag) doped mesoporous CuO-Fe{sub 2}O{sub 3} as highly efficient and stable nanocatalysts for CO oxidation at low temperature

Energy Technology Data Exchange (ETDEWEB)

Said, Abd El-Aziz A., E-mail: aasaid55@yahoo.com; Abd El-Wahab, Mohamed M.M.; Goda, Mohamed N.

2016-12-30

Highlights: • Highly active and stable Fe-Cu mixed oxides were prepared by co-precipitation method. • Addition of CuO to Fe{sub 2}O{sub 3} increases the chemisorbed oxygen, the conductivity and S{sub BET}. • Activation energy of CO oxidation significantly decreased via doping with foreign ions. - Abstract: A series of single and mixed oxide nanocatalysts of mesoporous CuO-Fe{sub 2}O{sub 3} with different CuO contents (1–50 wt.%) were prepared by a co-precipitation method and further promoted by trace amounts of CeO{sub 2}, ZrO{sub 2} and Ag{sub 2}O (0.1–0.5 wt.%) dopants. The original and calcined catalysts were characterized by TG, DTA, XRD, TEM, VSM, N{sub 2} sorption analysis, surface chemisorbed oxygen and DC electrical conductivity measurements. The catalytic performance of these nanocatalysts toward CO oxidation was studied using a conventional fixed bed flow type reactor. The results revealed that the addition of 1–20 wt.% CuO to Fe{sub 2}O{sub 3} monotonically increases the specific surface area, the amount of surface chemisorbed oxygen, electrical conductivity and catalytic activity of the nanocatalysts. In addition, the catalytic activity indicated that Fe-Cu mixed oxide nanocatalyst promoted with the three dopants (CeO{sub 2}, ZrO{sub 2} and Ag{sub 2}O) exhibited the highest catalytic activity with a total conversion of CO into CO{sub 2} at 100 °C. Moreover, the activation energy of CO oxidation decreased from 38.4 to 23.1 kJmol{sup −1} upon treating the catalyst containing 20 wt.% CuO with the three dopants. Finally the effects of various operational parameters were also studied.

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

Science.gov (United States)

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

2018-03-01

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

Comparison of HfCl4, HfI4, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO2 films deposited by ALD: A DFT study

Science.gov (United States)

Cortez-Valadez, M.; Fierro, C.; Farias-Mancilla, J. R.; Vargas-Ortiz, A.; Flores-Acosta, M.; Ramírez-Bon, R.; Enriquez-Carrejo, J. L.; Soubervielle-Montalvo, C.; Mani-Gonzalez, P. G.

2016-06-01

The final structure of HfO2 films grown by atomic layer deposition (ALD) after reaction with OH- ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl4 (hafnium tetrachloride), HfI4 (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO-H was studied employing the B3LYP (Becke 3-parameter, Lee-Yang-Parr) hybrid functional and the PBE (Perdew-Burke-Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

Geometrically frustrated magnetic structures of the heavy-fermion compound CePdAl studied by powder neutron diffraction

Energy Technology Data Exchange (ETDEWEB)

Doenni, A.; Fischer, P.; Zolliker, M. [Laboratory for Neutron Scattering, ETH Zuerich and Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Ehlers, G.; Maletta, H. [Hahn Meitner Institute Berlin, Glienicker Strasse 100, D-14092 Berlin (Germany); Kitazawa, H. [National Research Institute for Metals, Tsukuba, Ibaraki 305 (Japan)

1996-12-09

The heavy-fermion compound CePdAl with ZrNiAl-type crystal structure (hexagonal space group P6-bar2m) was investigated by powder neutron diffraction. The triangular coordination symmetry of magnetic Ce atoms on site 3f gives rise to geometrical frustration. CePdAl orders below T{sub N} = 2.7 K with an incommensurate antiferromagnetic propagation vector k=[1/2, 0, {tau}], {tau} approx. 0.35, and a longitudinal sine-wave (LSW) modulated spin arrangement. Magnetically ordered moments at Ce(1) and Ce(3) coexist with frustrated disordered moments at Ce(2). The experimentally determined magnetic structure is in agreement with group theoretical symmetry analysis considerations, calculated by the program MODY, which confirm that for Ce(2) an ordered magnetic moment parallel to the magnetically easy c-axis is forbidden by symmetry. Further low-temperature experiments give evidence for a second magnetic phase transition in CePdAl between 0.6 and 1.3 K. Magnetic structures of CePdAl are compared with those of the isostructural compound TbNiAl, where a non-zero ordered magnetic moment for the geometrically frustrated Tb(2) atoms is allowed by symmetry. (author)

A Study of Different Doped Metal Cations on the Physicochemical Properties and Catalytic Activities of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) Composite Oxides for Nitric Oxide Reduction by Carbon Monoxide.

Science.gov (United States)

Deng, Changshun; Li, Min; Qian, Junning; Hu, Qun; Huang, Meina; Lin, Qingjin; Ruan, Yongshun; Dong, Lihui; Li, Bin; Fan, Minguang

2016-08-05

This work is mainly focused on investigating the effects of different doped metal cations on the formation of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) composite oxides and their physicochemical and catalytic properties for NO reduction by CO as a model reaction. The obtained samples were characterized by using N2 physisorption, X-ray diffraction, laser Raman spectroscopy, UV/Vis diffuse reflectance spectroscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction by hydrogen and by oxygen (H2 -TPR and O2 -TPD), in situ diffuse reflectance infrared Fourier transform spectroscopy, and the NO+CO model reaction. The results imply that the introduction of M(x+) into the lattice of CeO2 increases the specific surface area and pore volume, especially for variable valence metal cations, and enhances the catalytic performance to a great extent. In this regard, increases in the oxygen vacancies, reduction properties, and chemisorbed O2 (-) (and/or O(-) ) species of these Ce20 M1 Ox composite oxides (M refers to variable valence metals) play significant roles in this reaction. Among the samples, Ce20 Cr1 Ox exhibited the best catalytic performance, mainly because it has the best reducibility and more chemisorbed oxygen, and significant reasons for these attributes may be closely related to favorable synergistic interactions of the vacancies and near-surface Ce(3+) and Cr(3+) . Finally, a possible reaction mechanism was tentatively proposed to understand the reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2018-03-01

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

Surface exchange kinetics and chemical diffusivities of BaZr{sub 0.2}Ce{sub 0.65}Y{sub 0.15}O{sub 3−δ} by electrical conductivity relaxation

Energy Technology Data Exchange (ETDEWEB)

Lim, Dae-Kwang; Jeon, Sang-Yun; Singh, Bhupendra [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of); Park, Jun-Young [Department of Advanced Materials Engineering, Sejong University, Seoul 143-747 (Korea, Republic of); Song, Sun-Ju, E-mail: song@chonnam.ac.kr [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of)

2014-10-15

Highlights: • Electrical conductivity relaxation in BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} was monitored. • Monotonic relaxation behavior was observed during oxidation/reduction. • Nonmonotonic twofold relaxation behavior was observed during hydration/dehydration. • Surface exchange coefficients and diffusivities of O and H were calculated. - Abstract: Perovskite-type oxide BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} (BCZY2015) was synthesized by a solid state reaction method. BCZY2015 samples were characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The time dependent variation in electrical conductivity of BCZY2015 was monitored during the oxidation/reduction in oxygen partial pressure (pO{sub 2}) range of −2.28 ⩽ log (pO{sub 2}/atm) ⩽ −0.68 at a fixed water vapor pressure (pH{sub 2}O), and during the hydration/dehydration in −3.15 ⩽ log (pH{sub 2}O/atm) ⩽ −2.35 range in air. The electrical conductivity showed a monotonic relaxation behavior by the ambipolar diffusion of V{sub o}{sup ··} and OH{sub o}{sup ·} during the oxidation/reduction and the relaxation process was governed by the diffusivity of oxygen (D-tilde{sub vO}). On the other hand, during the hydration/dehydration process, a non-monotonic twofold relaxation behavior was observed due to the decoupled diffusion of H and O components with the mediation of holes, and the conductivity relaxation process was governed by the diffusivities of both H (D-tilde{sub iH}) and O (D-tlde{sub vH}). The values of surface exchange coefficients and diffusivities of oxygen and hydrogen were calculated from Fick’s second law by the nonlinear least squares fitting of the conductivity data, as proposed by Yoo et al. (2008)

Zr/ZrC modified layer formed on AISI 440B stainless steel by plasma Zr-alloying

Energy Technology Data Exchange (ETDEWEB)

Shen, H.H.; Liu, L.; Liu, X.Z.; Guo, Q.; Meng, T.X.; Wang, Z.X.; Yang, H.J.; Liu, X.P., E-mail: liuxiaoping@tyut.edu.cn

2016-12-01

Highlights: • A Zr/ZrC modified layer was formed on AISI 440B stainless steel using plasma surface Zr-alloying. • The thickness of the modified layer increases with alloying temperature and time. • Formation mechanism of the modified layer is dependent on the mutual diffusion of Zr and substrate elements. • The modified surface shows an improved wear resistance. - Abstract: The surface Zr/ZrC gradient alloying layer was prepared by double glow plasma surface alloying technique to increase the surface hardness and wear resistance of AISI 440B stainless steel. The microstructure of the Zr/ZrC alloying layer formed at different alloying temperatures and times as well as its formation mechanism were discussed by using scanning electron microscopy, glow discharge optical emission spectrum, X-ray diffraction and X-ray photoelectron spectroscopy. The adhesive strength, hardness and tribological property of the Zr/ZrC alloying layer were also evaluated in the paper. The alloying surface consists of the Zr-top layer and ZrC-subsurface layer which adheres strongly to the AISI 440B steel substrate. The thickness of the Zr/ZrC alloying layer increases gradually from 16 μm to 23 μm with alloying temperature elevated from 900 °C to 1000 °C. With alloying time from 0.5 h to 4 h, the alloyed depth increases from 3 μm to 30 μm, and the ZrC-rich alloyed thickness vs time is basically parabola at temperature of 1000 °C. Both the hardness and wear resistance of the Zr/ZrC alloying layer obviously increase compared with untreated AISI 440B steel.

Structural and morphological properties of HfxZr 1-xO2 thin films prepared by Pechini route

KAUST Repository

García-Cerda, L. A.

2010-03-01

In this study, HfxZr1-xO2 (0 < x < 1) thin films were deposited on silicon wafers using a dip-coating technique and by using a precursor solution prepared by the Pechini route. The effects of annealing temperature on the structure and morphological properties of the proposed films were investigated. HfxZr1-xO2 thin films with 1, 3 and 5 layers were annealed in air for 2 h at 600 and 800 °C and the structural and morphological properties studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD results show that the films have monoclinic and tetragonal structure depending of the Hf and Zr concentration. SEM photographs show that all films consist of nanocrystalline grains with sizes in the range of 6 - 13 nm. The total film thickness is about 90 nm. © (2010) Trans Tech Publications.

Stable, easily sintered BaCe{sub 0.5}Zr{sub 0.3}Y{sub 0.16}Zn{sub 0.04}O{sub 3-{delta}} electrolyte-based proton-conducting solid oxide fuel cells by gel-casting and suspension spray

Energy Technology Data Exchange (ETDEWEB)

Lin Bin; Dong Yingchao; Wang Songlin; Fang Daru; Ding Hanping; Zhang Xiaozhen; Liu Xingqin [Department of Materials Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China); Meng Guangyao [Department of Materials Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)], E-mail: bin@mail.ustc.edu.cn

2009-06-10

Protonic ceramic membrane fuel cells (PCMFCs) based on oxide proton conductors exhibit more advantages than traditional solid oxide fuel cells (SOFCs) based on oxygen-ion conducting electrolytes, such as low activation energy and high energy efficiency. In order to develop a simple and cost-effective route to fabricate PCMFCs with SrCo{sub 0.9}Sb{sub 0.1}O{sub 3-{delta}} (SCS) cubic perovskite cathode, a dense BaCe{sub 0.5}Zr{sub 0.3}Y{sub 0.16}Zn{sub 0.04}O{sub 3-{delta}} (BCZYZn) electrolyte was fabricated in situ metal oxide on a porous anode support by gel-casting and suspension spray, which is cost-effective, easy to realize, and suitable for mass-production. The key part of this process is to directly spray well-mixed suspension of BaCO{sub 3}, CeO{sub 2}, ZrO{sub 2}, Y{sub 2}O{sub 3} and ZnO instead of pre-synthesized BCZYZn ceramic powder on the anode substrate. With SCS cubic perovskite cathode synthesized by gel-casting on the bi-layer, single cells were assembled and tested with H{sub 2} as fuel and the static air as oxidant. An open-circuit potential of 0.987 V, a maximum power density of 364 mW cm{sup -2}, and a low polarization resistance of the electrodes of 0.07 {omega} cm{sup 2} was achieved at 700 deg. C.

Effect of heat treatment on the optical properties of perovskite BaZr0.5Ce0.3Y0.2O3-δ ceramic prepared by spark plasma sintering

Science.gov (United States)

Xing, Bohang; Cheng, Zhi; Wang, Cao; Zhao, Zhe

2017-09-01

The effect of heat treatment on the in-line transmittance of BaZr0.5Ce0.3Y0.2O3-δ (BZCY532) ceramics prepared by spark plasma sintering method was investigated. The loss of Ba in transparent BZCY532 ceramics is the key reason for the loss of transmittance during the annealing process. This problem can be effectively alleviated by using a powder bed of BZCY532. Heat treatment atmospheres, wet air and dry air, were also found to be critical for obtaining high quality transparent ceramics. A highly transparent BZCY532 ceramic with the in-line transmittance (Tin) of 71.4% at 2000 nm can be obtained by using SPS method followed by an annealing in powder bed at 1500 °C in wet air.

Zr/ZrC modified layer formed on AISI 440B stainless steel by plasma Zr-alloying

Science.gov (United States)

Shen, H. H.; Liu, L.; Liu, X. Z.; Guo, Q.; Meng, T. X.; Wang, Z. X.; Yang, H. J.; Liu, X. P.

2016-12-01

The surface Zr/ZrC gradient alloying layer was prepared by double glow plasma surface alloying technique to increase the surface hardness and wear resistance of AISI 440B stainless steel. The microstructure of the Zr/ZrC alloying layer formed at different alloying temperatures and times as well as its formation mechanism were discussed by using scanning electron microscopy, glow discharge optical emission spectrum, X-ray diffraction and X-ray photoelectron spectroscopy. The adhesive strength, hardness and tribological property of the Zr/ZrC alloying layer were also evaluated in the paper. The alloying surface consists of the Zr-top layer and ZrC-subsurface layer which adheres strongly to the AISI 440B steel substrate. The thickness of the Zr/ZrC alloying layer increases gradually from 16 μm to 23 μm with alloying temperature elevated from 900 °C to 1000 °C. With alloying time from 0.5 h to 4 h, the alloyed depth increases from 3 μm to 30 μm, and the ZrC-rich alloyed thickness vs time is basically parabola at temperature of 1000 °C. Both the hardness and wear resistance of the Zr/ZrC alloying layer obviously increase compared with untreated AISI 440B steel.

Greatly enhanced flux pinning properties of fluorine-free metal-organic decomposition YBCO films by co-addition of halogens (Cl, Br) and metals (Zr, Sn, Hf)

Science.gov (United States)

Motoki, Takanori; Ikeda, Shuhei; Nakamura, Shin-ichi; Honda, Genki; Nagaishi, Tatsuoki; Doi, Toshiya; Shimoyama, Jun-ichi

2018-04-01

Additive-free YBCO films, as well as those with halogen (X) added, metal (M) added and (X, M) co-added, have been prepared by the fluorine-free metal-organic decomposition method on SrTiO3(100) single crystalline substrates, where X = Cl, Br and M = Zr, Sn, Hf. It was revealed that the addition of both Cl and Br to the starting solution resulted in the generation of oxyhalide, Ba2Cu3O4 X 2, in the YBCO films, and that the oxyhalide was found to promote the bi-axial orientation of the YBCO crystals. By adding a decent amount of Cl or Br, highly textured YBCO films with high J c were reproducibly obtained, even when an impurity metal, M, was co-added, while the addition of M without X did not greatly improve J c owing to the poor bi-axial orientation of the YBCO crystals. Our results suggest that the addition of Br more effectively enhances J c than the addition of Cl. The pinning force density at 40 K in 4.8 T reached ˜55 GN m-3 with the co-addition of (Br, M). This value is much larger than that of the pure YBCO film, reaching ˜17 GN m-3.

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

Science.gov (United States)

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

2018-03-01

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

Tuning the acidity of niobia: Characterization and catalytic activity of Nb2O5–MeO2 (Me = Ti, Zr, Ce) mesoporous mixed oxides

International Nuclear Information System (INIS)

Stošić, Dušan; Bennici, Simona; Pavlović, Vladimir; Rakić, Vesna; Auroux, Aline

2014-01-01

Mesoporous Nb 2 O 5 –MeO 2 (Me = Ti, Zr, Ce) mixed oxides were successfully prepared using evaporation-induced self-assembly (EISA) method. The structural and textural properties of these materials have been fully characterized using appropriate techniques (low-temperature adsorption–desorption of nitrogen, thermogravimetric analysis, X-ray diffraction analysis (XRD) transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman spectroscopy). Acid–base properties were estimated by adsorption microcalorimetry of NH 3 and SO 2 molecules in order to determine the population, strength and strength distribution of acidic or basic sites. Formation of mesoporous structure was confirmed by the results of XRD, TEM and BET techniques. Results of adsorption microcalorimetry technique showed that the type of transition metal oxide added to niobia has a decisive role for acidic-basic character of investigated mixed oxides. Among the investigated mixed oxide formulations only Nb 2 O 5 –CeO 2 was amphoteric, while the other samples showed prominent acidic character. All the investigated materials are catalytically active in fructose dehydration; conversion of fructose and selectivity to 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) are proved to be dependant on the number of acidic sites on the surface of catalysts. Furthermore, presence of the basic sites on the surface of the catalyst decreases the activity in the fructose dehydration reaction, as in the case of Nb 2 O 5 –CeO 2 sample. - Highlights: • Mesoporous Nb 2 O 5 –MeO 2 mixed oxides were successfully prepared by EISA method. • Acidic–basic properties depend on the nature of the oxide that was mixed with niobia. • Catalytic activity was tested in fructose dehydration in aqueous phase. • Selectivity and conversion in reaction are correlated to the number of acid sites

HF i dag

DEFF Research Database (Denmark)

Lindstrøm, Maria Duclos; Simonsen, Birgitte

2008-01-01

Notatet er lavet på baggrund af uddannelsesbiografiske dybdeinterviews med kursister på toårigt HF. Indenfor rammerne af en pilotundersøgelse identificerer notatet fire gennemgående profiler: De pragmatiske, de fagligt usikre, second chance-kursisterne, og de HF-kursister, som har HF som first...

Determining the Sensitivity of the Hf-Nd Proxy to Glacial Weathering

Science.gov (United States)

Namsinh, A.; Scher, H.; Piotrowski, A. M.

2017-12-01

The history of polar ice sheets through the Cenozoic is incompletely known. Estimates of the onset of northern hemisphere glaciation range from the Pliocene to mid-Eocene and precursor Antarctic glaciations are believed to have commenced in the middle Eocene. Uncertainty surrounding the history of ice sheets has resulted in debates about the sensitivity of ice sheets to changes in atmospheric CO2 through the Cenozoic. Geochemical proxies for continental weathering — particularly those that are sensitive to mechanical breakdown of the upper continental crust by ice sheets — could improve the fidelity of paleoclimate reconstructions of ice sheet history. Coupled hafnium (Hf) and neodymium (Nd) isotopes in seawater and authigenic sediment phases show a strong correlation with mechanical weathering rates, however the proxy has not been systematically tested on Pleistocene time scales. We measured the Hf and Nd isotope ratios of authigenic and detrital phases of sediment cores from 1150 m to 4045 m depth on the Rockall Plateau in the NE Atlantic Ocean. Our study is limited to the LGM, deglaciation and Holocene intervals. The authigenic fraction was extracted from bulk sediments by leaching with dilute hydroxylamine hydrochloride and EDTA to prevent readsorption of Hf. A stronger leach solution was then used to isolate the terrigenous detrital fraction. The fidelity of the seawater signal obtained by leaching is assessed by comparison of leachate eNd values to previously published eNd values from uncleaned forams from the same depth intervals. Initial tests with Holocene and deglacial samples verify that leachate eNd values are statistically indistinguishable from uncleaned forams. Shale-normalized REE patterns for leachates reveal negative Ce anomalies and a MREE enrichment typical of Fe-Mn oxydydroxide phases. Coupled Hf-Nd isotopes from authigenic leachates from our initial tests fall along the Seawater Array when plotted on a Hf-Nd isotope diagram, confirming

Complementary methods of study for Zr1-xCexO2 compounds for applications in medical prosthesis

Science.gov (United States)

Savin, Adriana; Craus, Mihail-Liviu; Turchenko, Vitalii; Bruma, Alina; Dubos, Pierre-Antoine; Malo, Sylvie; Konstantinova, Tatiana E.; Burkhovetsky, Valerii V.

2017-08-01

Zirconia (ZrO2)-based ceramics are preferred due to their advanced mechanical properties such as high-fracture toughness and bulk modulus, corrosion resistance, high dielectric constant, chemical inertness, low chemical conductivity and biocompatibility. The medical prosthesis components made from ZrO2 oxides present a very good biocompatibility as well as especially mechanical properties. In order to ensure implant safety of these prostheses, wide ranges of examinations based on nondestructive testing are imperative for these medical implants. In this study, we aim to emphasize the improvement of Zr-based ceramics properties as a function of addition of Ce ions in the structure of the original ceramics. The substitution of the Zr with Ce in the Zr1-xCexO2 compounds, where x = 0.0-0.17, leads to a change of the phase composition, a gradual transition from the monoclinic to tetragonal structure, at room temperature. The structural investigations proposed in this paper are based on X-ray and neutron diffraction in order to establish a first indication of the variation of the phase composition and the structural parameters, as well as micro-hardness measurements and nondestructive evaluations in order to establish a correlation between the structural parameters and mechanical properties of the samples. These ranges of tests are imperative in order to ensure the safety and reliability of these composite materials, which are widely used as hip-implants or dental implants/coatings. In combination of Resonant Ultrasound Spectroscopy, which makes use of the resonance frequencies corresponding to the normal vibrational modes of a solid in order to evaluate the elastic constants of the materials, we emphasize a unique approach on evaluating the physical properties of these ceramics, which could help in advancing the understanding of properties and applications in medical fields.

Gamma decay of pygmy states in 90,94Zr from inelastic scattering of light ions

Science.gov (United States)

Crespi, F. C. L.; Bracco, A.; Tamii, A.; Blasi, N.; Camera, F.; Wieland, O.; Aoi, N.; Balabanski, D.; Bassauer, S.; Brown, A. S.; Carpenter, M. P.; Carroll, J. J.; Ciemala, M.; Czeszumska, A.; Davies, P. J.; Donaldson, L.; Fang, Y.; Fujita, H.; Gey, G.; Hoang, T. H.; Ichige, N.; Ideguchi, E.; Inoue, A.; Isaak, J.; Iwamoto, C.; Jenkins, D. G.; Jin, O. H.; Klaus, T.; Kobayashi, N.; Koike, T.; Krzysiek, M.; Raju, M. Kumar; Liu, M.; Maj, A.; Montanari, D.; Morris, L.; Noji, S.; Pickstone, S. G.; Savran, D.; Spieker, M.; Steinhilber, G.; Sullivan, C.; Wasilewska, B.; Werner, V.; Yamamoto, T.; Yamamoto, Y.; Zhou, X.; Zhu, S.

2018-05-01

We performed experiments to study the low-energy part of the E1 response (Pygmy Dipole Resonance) in 90,94Zr nuclei, by measuring the (p,p’γ) and (α,α’γ) inelastic scattering reactions at energies Ebeam,p = 80 MeV and Ebeam,α = 130 MeV respectively. The inelastically scattered particles were measured by employing the high-resolution spectrometer Grand Raiden. The gamma-rays emitted following the de-excitation of the Zr target nuclei were detected using both the clover type HPGe detectors of the CAGRA array and the large volume LaBr3:Ce scintillation detectors from the HECTOR+ array. Some preliminary results are presented here.

A combined experimental and computational study of water-gas shift reaction over rod-shaped Ce_0.75 M_0.25O₂ (M=Ti, Zr, and Mn) supported Cu catalysts

Energy Technology Data Exchange (ETDEWEB)

Ren, Zhibo; Peng, Fei; Chen, Biaohua; Mei, Donghai; Li, Jianwei

2017-11-02

Water-gas shift (WGS) reaction over a series of ceria-based mixed oxides supported Cu catalysts was investigated using a combined experimental and theoretical method. The mixed rod-shaped Ce_0.75M_0.25O₂ (M = Ti⁴⁺, Zr⁴⁺, Mn⁴⁺) solid solutions, which majorly expose the (110) and (100) facets, are synthesized by hydrothermal method and used to prepare supported Cu catalysts. We found that the Cu/Ce0.75Ti_0.25O₂ (Cu-CT) exhibits the highest CO conversion in the temperature range of 150-250 °C among all supported Cu catalysts. This is mainly attributed to (i) good dispersion of Cu; (ii) largest amount of moderate copper oxide; and (iii) strongest Cu-support interaction of Cu-CT. And compared to other mixed metals, periodic density functional theory calculations performed, this work further suggest that the introduction of Ti into CeO₂ not only promotes oxygen vacancy formation and CO adsorption, but also facilitates the carboxyl (COOH) formation at the interface of the Cu cluster and the support, which leads to the enhanced catalytic activity of the Cu-CT toward WGS reaction.

The Effect of Cerium Ions on the Structure, Porosity and Electrochemical Properties of Si/Zr-Based Hybrid Sol-Gel Coatings Deposited on Aluminum

Directory of Open Access Journals (Sweden)

Peter Rodič

2018-04-01

Full Text Available This study was focused on the synthesis and characterization of Si/Zr-based hybrid sol-gel coatings with and without the addition of cerium(III ions. The coatings were deposited on aluminum aiming to act as an effective and ecologically harmless alternative to toxic chromate coatings. The chemical composition, structure, thermal properties and porosity of the non-doped and Ce-doped coatings containing various Zr contents were examined by Raman spectroscopy and photothermal beam deflection spectroscopy. The corrosion properties of the coated aluminum substrates were studied using AC and DC electrochemical methods in 0.1 M NaCl electrolyte solution. Barrier and protecting properties of the coatings were monitored upon long-term immersion in chloride solution using electrochemical impedance spectroscopy. The effect of cerium ions was two-fold: on the formation of a more condensed Si−O−Zr network structure and on the formation of Ce-based deposits, which diminish the rate of cathodic reaction at the coating/metal interface. These effects acted synergistically and resulted in the creation of the coatings with effective barrier and active corrosion protection.

Comparison of HfCl{sub 4}, HfI{sub 4}, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO{sub 2} films deposited by ALD: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Cortez-Valadez, M. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Fierro, C.; Farias-Mancilla, J.R. [Instituto de Ingeniería y Tecnología, Departamento de Física y Matemáticas, Universidad Autónoma de Ciudad Juárez, Av. del Charro 450, Cd. Juárez C.P. 32310, Chihuahua (Mexico); Vargas-Ortiz, A. [Universidad Autónoma de Sinaloa, Facultad de Ingeniería Mochis, Ciudad Universitaria, C.P. 81223 Los Mochis, Sinaloa (Mexico); Flores-Acosta, M. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Ramírez-Bon, R. [Centro de Investigación y Estudios Avanzados del IPN, Unidad Querétaro, Apdo. Postal 1-798, 76001 Querétaro, Qro. (Mexico); Enriquez-Carrejo, J.L. [Instituto de Ingeniería y Tecnología, Departamento de Física y Matemáticas, Universidad Autónoma de Ciudad Juárez, Av. del Charro 450, Cd. Juárez C.P. 32310, Chihuahua (Mexico); and others

2016-06-15

Highlights: • Hafnium oxide growth on Si(100) by atomic layer deposition was simulated. • The interface structure was considered as silicate and silicide. • The interface was studied employing DFT. • TDMA-Hf precursor show better interface stability. - Abstract: The final structure of HfO{sub 2} films grown by atomic layer deposition (ALD) after reaction with OH{sup −} ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl{sub 4} (hafnium tetrachloride), HfI{sub 4} (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO–H was studied employing the B3LYP (Becke 3-parameter, Lee–Yang–Parr) hybrid functional and the PBE (Perdew–Burke–Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

Wet etching characteristics of a HfSiON high-k dielectric in HF-based solutions

International Nuclear Information System (INIS)

Li Yongliang; Xu Qiuxia

2010-01-01

The wet etching properties of a HfSiON high-k dielectric in HF-based solutions are investigated. HF-based solutions are the most promising wet chemistries for the removal of HfSiON, and etch selectivity of HF-based solutions can be improved by the addition of an acid and/or an alcohol to the HF solution. Due to densification during annealing, the etch rate of HfSiON annealed at 900 0 C for 30 s is significantly reduced compared with as-deposited HfSiON in HF-based solutions. After the HfSiON film has been completely removed by HF-based solutions, it is not possible to etch the interfacial layer and the etched surface does not have a hydrophobic nature, since N diffuses to the interface layer or Si substrate formation of Si-N bonds that dissolves very slowly in HF-based solutions. Existing Si-N bonds at the interface between the new high-k dielectric deposit and the Si substrate may degrade the carrier mobility due to Coulomb scattering. In addition, we show that N 2 plasma treatment before wet etching is not very effective in increasing the wet etch rate for a thin HfSiON film in our case. (semiconductor technology)

Microhardness evaluation alloys Hf-Si-B; Avaliacao de microdureza de ligas Hf-Si-B

Energy Technology Data Exchange (ETDEWEB)

Gigolotti, Joao Carlos Janio; Costa, Eliane Fernandes Brasil [Centro Universitario de Volta Redonda (UNIFOA), Volta Redonda, RJ (Brazil); Nunes, Carlos Angelo; Rocha, Elisa Gombio; Coelho, Gilberto Carvalho, E-mail: carlosjanio@uol.com.br, E-mail: eliane-costabrasi@hotmail.com, E-mail: cnunes@demar.eel.usp.br, E-mail: elisarocha@alunos.eel.usp.br, E-mail: coelho@demar.eel.usp.br [Universidade de Sao Paulo (USP), Lorena, SP (Brazil)

2014-08-15

The technological advance has generated increasing demand for materials that can be used under high temperature, what includes intermetallic MR-Si-B (MR = refractory metal) alloys with multiphase structures, that can also be applied in oxide environments. Thus, this work had for objective the micro hardness study of the Hf-Si-B system alloys, heat treated at 1600 deg C, in the Hf rich region. Hf-Si-B alloys had been produced with blades of Hf (min. 99.8%), Si (min. 99.998%) and B (min. 99.5%), in the voltaic arc furnace and heat treated at 1600 deg C under argon atmosphere. The relationship of the phases had been previously identified by X-ray diffraction and contrast in backscattered electron imaging mode. The alloys had their hardness analyzed by method Vickers (micro hardness) with load of 0.05 kgf and 0.2 kgf and application time of 20 s. The results, obtained from the arithmetic mean of measurements for each alloy on the heterogeneous region, showed a mean hardness of 11.08 GPA, with small coefficient of variation of 3.8%. The borides HfB2 (19.34 GPa) e HfB - 11.76 GPa, showed the hardness higher than the silicides Hf2Si (8.57 GPa), Hf5Si3 (9.63 GPa), Hf3Si2 (11.66 GPa), Hf5Si4 (10.00 GPa), HfSi (10.02 GPa) e HfSi2 (8.61 GPa). (author)

In situ DRIFTS investigation of NH3-SCR reaction over CeO2/zirconium phosphate catalyst

Science.gov (United States)

Zhang, Qiulin; Fan, Jie; Ning, Ping; Song, Zhongxian; Liu, Xin; Wang, Lanying; Wang, Jing; Wang, Huimin; Long, Kaixian

2018-03-01

A series of ceria modified zirconium phosphate catalysts were synthesized for selective catalytic reduction of NO with ammonia (NH3-SCR). Over 98% NOx conversion and 98% N2 selectivity were obtained by the CeO2/ZrP catalyst with 20 wt.% CeO2 loading at 250-425 °C. The interaction between CeO2 and zirconium phosphate enhanced the redox abilities and surface acidities of the catalysts, resulting in the improvement of NH3-SCR activity. The in situ DRIFTS results indicated that the NH3-SCR reaction over the catalysts followed both Eley-Rideal and Langmuir-Hinshelwood mechanisms. The amide (sbnd NH2) groups and the NH4+ bonded to Brønsted acid sites were the important intermediates of Eley-Rideal mechanism.

Ab initio study of mechanical and thermo-acoustic properties of tough ceramics: applications to HfO2 in its cubic and orthorhombic phase

International Nuclear Information System (INIS)

Ponce, C A; Casali, R A; Caravaca, M A

2008-01-01

By means of the ab initio all-electron new full-potential linear-muffin-tin orbitals method, calculations were made for elastic constants C 11 , C 12 and C 44 for Si, ZrO 2 and HfO 2 in their cubic phase, and constants C 11 , C 22 , C 33 , C 12 , C 13 , C 23 , C 44 , C 55 and C 66 for HfO 2 in its orthorhombic phase. Using the Voigt and Reuss theory, estimations were made for polycrystals of their bulk, shear and Young moduli, and Poisson coefficients. The speed of elastic wave propagations and Debye temperatures were estimated for polycrystals built from Si and the above mentioned compounds. The semicore 4f 14 electrons should be included in the valence set of Hf atom in this all-electron approach if accurate results for elastic properties under pressures are looked for

The 91Zr(d,t)90Zr reaction

International Nuclear Information System (INIS)

Gomes, L.C.

1975-01-01

Sixteen levels populated in the 91 Zr(d,t) 90 Zr pick-up reaction were studied with 16 MeV deuterons. Distorted waves Born approximation calculations were compared to the data, and yielded spectroscopic factors and l values. Particle-hole states in 90 Zr were observed. Some significant errors were found in Zr(d,t) reactions Q values recently compiled [pt

Order-disorder phase transition in ZrV2Dsub(3.6)

International Nuclear Information System (INIS)

Didisheim, J.-J.; Yvon, K.; Tissot, P.

1981-01-01

The deuterated C15-type Laves phase ZrV 2 Dsub(3.6) undergoes a structural phase transition near room temperature (T of the order of 325 K). In the cubic high-temperature phase the deuterium atoms are disordered over two types of tetrahedral interstices, the centres of which are 1.3 A apart. In the tetragonal low-temperature phase the D atoms are ordered and occupy only the energetically more favourable interstices. The tetragonal structure is isotypic with the low-temperature phase of HfV 2 D 4 . The shortest D-D distance is 2.1 A. (author)

Roles of texture of Zr alloys in ZrO{sub 2} film formation and δ-hydride orientation near ZrO{sub 2}/Zr interface

Energy Technology Data Exchange (ETDEWEB)

Qin, W.; Szpunar, J.A., E-mail: weq565@mail.usask.ca, E-mail: jerzy.szpunar@usask.ca [Univ. of Saskatchewan, Dept. of Mechanical Engineering, Saskatoon, SK (Canada); Kozinski, J., E-mail: janusz.kozinski@lassonde.yorku.ca [York Univ., Faculty of Science and Engineering, Toronto, ON (Canada)

2014-07-01

Oxidation and hydrogen embrittlement are related to formation of cracks and failure of Zr alloys used in nuclear reactor applications. An in-depth understanding of the formation of ZrO{sub 2} film and the hydride precipitation and orientation is important for improving the corrosion resistance of zirconium alloys. In this work a theoretical model is developed to analyze the microstructure of ZrO{sub 2} film formed on Zr alloys and the effect of stress that results from ZrO{sub 2} formation on hydride reorientation in the region near oxide/metal interface. Our work shows that the macroscopic stress produced due to Pilling-Bedworth ratio for ZrO{sub 2}/Zr could lead to the hydride re-orientation in the region near ZrO{sub 2}/Zr interface. Whether or not this effect can occur is dependent on the texture of the zirconium alloys. Control of texture of zirconium alloys can affect the microstructure of ZrO{sub 2} film and can be responsible for change of hydride orientation. (author)

Antibacterial activity and cell compatibility of TiZrN, TiZrCN, and TiZr-amorphous carbon coatings

Energy Technology Data Exchange (ETDEWEB)

Huang, Heng-Li [School of Dentistry, China Medical University, Taichung 404, Taiwan (China); Department of Bioinformatics and Medical Engineering, Asia University, Taichung 41354, Taiwan (China); Chang, Yin-Yu, E-mail: yinyu@nfu.edu.tw [Department of Mechanical and Computer-aided Engineering, National Formosa University, Yunlin 632, Taiwan (China); Liu, Jia-Xu [Department of Mechanical and Computer-aided Engineering, National Formosa University, Yunlin 632, Taiwan (China); Tsai, Ming-Tzu [Department of Biomedical Engineering, Hungkuang University, Taichung 433, Taiwan (China); Lai, Chih-Ho [Department of Microbiology and Immunology, Graduate Institute of Biomedical Sciences, Chang Gung University, Taoyuan, Taiwan (China)

2015-12-01

A cathodic-arc evaporation system with plasma-enhanced duct equipment was used to deposit TiZrN, TiZrCN, and TiZr/a-C coatings. Reactive gases (N{sub 2} and C{sub 2}H{sub 2}) activated by the Ti and Zr plasma in the evaporation process was used to deposit the TiZrCN and TiZr/a-C coatings with different C and nitrogen contents. The crystalline structures and bonding states of coatings were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy. The microbial activity of the coatings was evaluated against Staphylococcus aureus (Gram-positive bacteria) and Actinobacillus actinomycetemcomitans (Gram-negative bacteria) by in vitro antibacterial analysis using a fluorescence staining method employing SYTO9 and a bacterial-viability test on an agar plate. The cell compatibility and morphology related to CCD-966SK cell-line human skin fibroblast cells on the coated samples were also determined using the 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide assay, reverse-transcriptase-polymerase chain reaction, and scanning electron microscopy. The results suggest that the TiZrCN coatings not only possess better antibacterial performance than TiZrN and TiZr/a-C coatings but also maintain good compatibility with human skin fibroblast cells. - Highlights: • TiZrN, TiZrCN, and TiZr/a-C coatings were deposited using cathodic arc evaporation. • The TiZrCN showed a composite structure containing TiN, ZrN, and a-C. • The TiZrCN-coated Ti showed the least hydrophobicity among the samples. • The TiZrCN-coated Ti showed good human skin fibroblast cell viability. • The TiZrCN-coated Ti exhibited good antibacterial performance.

Phase equilibria in the Zr-Si-B ternary system (Zr-Si-ZrB{sub 2} region) at 1 173 K

Energy Technology Data Exchange (ETDEWEB)

Han, Feng; Luo, Hao [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Lab. of Processing for Non-ferrous Metal and Featured Materials; Zhan, Yongzhong [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Lab. of Processing for Non-ferrous Metal and Featured Materials; Guangxi Univ., Nanning (China). Center of Ecological Collaborative Innovation for Aluminum Industry

2017-10-15

The isothermal section of the Zr-Si-B ternary system (Zr-Si-ZrB{sub 2} region) at 1 173 K has been experimentally determined. All equilibrated alloys were characterized via X-ray powder diffraction and scanning electron microscopy equipped with energy-dispersive X-ray analysis. A ternary phase Zr{sub 5}(Si{sub 0.86}B{sub 0.14}){sub 3} was found at 1 173 K. The experimental results show that the isothermal section consists of 11 single-phase regions, 26 two-phase regions and 13 three-phase regions. The existence of eight compounds, i.e. ZrSi{sub 2}, ZrSi, Zr{sub 5}Si{sub 4}, Zr{sub 3}Si{sub 2}, Zr{sub 2}Si, ZrB, ZrB{sub 2} and Zr{sub 5}(Si{sub 0.86}B{sub 0.14}){sub 3} in this system has been confirmed in the Zr-Si-ZrB{sub 2} region at 1 173 K.

Thin-layer chromatography of 49 metal ions on stannic antimonate in aqueous and mixed solvent systems containing dimethylsulfoxide: quantitative separation of uranium from numerous metal ions

International Nuclear Information System (INIS)

Qureshi, M.; Varshney, K.G.; Rajput, R.P.S.

1976-01-01

Thin-layer chromatography of 40 metal ions in 31 aqueous and mixed solvent systems has been performed on stannic antimonate ion-exchange material. Dimethylsulfoxide has been utilized to resolve such binary mixtures as La 3+ and Ce 3+ from Pr 3+ , Nd 3+ , and Sm 3+ ; VO 2+ from Ti 4+ , Nb 5+ , and Ta 5+ ; Ga 3+ from In 3+ , Tl + , and Y 3+ ; Fe 3+ from VO 2+ ; and Mg 2+ from Al 3+ . Quantitative separation of 200 to 800 μg U from its binary mixtures and from the synthetic mixtures containing Mg 2+ , Bi 3+ , Fe 3+ , Th 4+ , Ce 4+ , Cr 3+ , Zr 4+ , Hf 4+ , Ti 4+ Mn 2+ , Cu 2+ , Ce 3+ , In 3+ , Y 3+ , Ca 2+ , Co 2+ , Tl + , Nb 5+ , and Ag + has been obtained

High performance fuel electrodes fabricated by electroless plating of copper on BaZr0.8Ce0.1Y0.1O3-δ proton-conducting ceramic

Science.gov (United States)

Patki, Neil S.; Way, J. Douglas; Ricote, Sandrine

2017-10-01

The stability of copper at high temperatures in reducing and hydrocarbon-containing atmospheres makes it a good candidate for fabricating fuel electrodes on proton-conducting ceramics, such as BaZr0.9-xCexY0.1O3-δ (BZCY). In this work, the electrochemical performance of Cu-based electrodes fabricated by electroless plating (ELP) on BaZr0.8Ce0.1Y0.1O3-δ is studied with impedance spectroscopy. Three activation catalysts (Pd, Ru, and Cu) are investigated and ELP is compared to a commercial Cu paste (ESL 2312-G) for electrode fabrication. The area specific resistances (ASR) for Pd, Ru, and Cu activations at 700 °C in moist 5% H2 in Ar are 2.1, 3.2, and 13.4 Ω cm2, respectively. That is a 1-2 orders of magnitude improvement over the commercial Cu paste (192 Ω cm2). Furthermore, the ASR has contributions from electrode processes and charge transfer at the electrode/electrolyte interface. Additionally, the morphology of the as-fabricated electrode is unaffected by the activation catalyst. However, heat treatment at 750 °C in H2 for 24 h leads to sintering and large reorganization of the electrode fabricated with Cu activation (micron sized pores seen in the tested sample), while Pd and Ru activations are immune to such reorganization. Thus, Pd and Ru are identified as candidates for future work with improvements to charge transfer required for the former, and better electrode processes required for the latter.

Experimental study of the lifetime and phase transition in neutron-rich Zr 98 ,100 ,102

Science.gov (United States)

Ansari, S.; Régis, J.-M.; Jolie, J.; Saed-Samii, N.; Warr, N.; Korten, W.; Zielińska, M.; Salsac, M.-D.; Blanc, A.; Jentschel, M.; Köster, U.; Mutti, P.; Soldner, T.; Simpson, G. S.; Drouet, F.; Vancraeyenest, A.; de France, G.; Clément, E.; Stezowski, O.; Ur, C. A.; Urban, W.; Regan, P. H.; Podolyák, Zs.; Larijani, C.; Townsley, C.; Carroll, R.; Wilson, E.; Mach, H.; Fraile, L. M.; Paziy, V.; Olaizola, B.; Vedia, V.; Bruce, A. M.; Roberts, O. J.; Smith, J. F.; Scheck, M.; Kröll, T.; Hartig, A.-L.; Ignatov, A.; Ilieva, S.; Lalkovski, S.; Mǎrginean, N.; Otsuka, T.; Shimizu, N.; Togashi, T.; Tsunoda, Y.

2017-11-01

Rapid shape changes are observed for neutron-rich nuclei with A around 100. In particular, a sudden onset of ground-state deformation is observed in the Zr and Sr isotopic chains at N = 60: Low-lying states in N ≤58 nuclei are nearly spherical, while those with N ≥60 have a rotational character. Nuclear lifetimes as short as a few picoseconds can be measured using fast-timing techniques with LaBr3(Ce) scintillators, yielding a key ingredient in the systematic study of the shape evolution in this region. We used neutron-induced fission of 241Pu and 235U to study lifetimes of excited states in fission fragments in the A ˜100 region with the EXILL-FATIMA array located at the PF1B cold neutron beam line at the Institut Laue-Langevin. In particular, we applied the generalized centroid difference method to deduce lifetimes of low-lying states for the nuclei 98Zr (N = 58), 100Zr, and 102Zr (N ≥60 ). The results are discussed in the context of the presumed phase transition in the Zr chain by comparing the experimental transition strengths with the theoretical calculations using the interacting boson model and the Monte Carlo shell model.

Contribution of slab melting to magmatism at the active rifts zone in the middle of the Izu-Bonin arc

Science.gov (United States)

Hirai, Y.; Okamura, S.; Sakamoto, I.; Shinjo, R.; Wada, K.; Yoshida, T.

2016-12-01

The active rifts zone lies just behind the Quaternary volcanic front in the middle of the Izu-Bonin arc. Volcanism at the active rifts zone has been active since ca. 2 Ma, and late Quaternary basaltic lavas (< 0.1 Ma) and hydrothermal activity occur along the central axis of the rifts (Taylor, 1992; Ishizuka et al., 2003). In this paper we present new Sr, Nd, and Hf isotope and trace element data for the basalts erupted in the active rifts zone, including the Aogashima, Myojin and Sumisu rifts. Two geochemical groups can be identified within the active rift basalts: High-Zr basalts (HZB) and Low-Zr basalts (LZB). In the case of the Sumisu rift, the HZB exhibits higher in K2O, Na2O, Y, Zr and Ni, and also has higher Ce/Yb and Zr/Y, lower Ba/Th than the LZB. Depletion of Zr-Hf in the N-MORB spidergram characterizes the LZB from the Aogashima, Myojin and Sumisu rifts. The 176Hf/177Hf ratios are slightly lower in the HZB than in the LZB, decoupling of 176Hf/177Hf ratios and 143Nd/144Nd ratios. Estimated primary magma compositions suggest that primary magma segregation for the HZB occurred at depths less than 70 km ( 2 GPa), whereas the LZB more than 70 km (2 3 GPa). ODP Leg126 site 788, 790, and 791 reached the basaltic basement of the Sumisu rift (Gill et al., 1992). The geochemical data and stratigraphic relations of the basement indicate that the HZB is younger than the LZB. Geochemical modelling demonstrates that slab-derived melt mixed with mantle wedge produces the observed isotopic and trace elemental characteristics. The LZB volcanism at the early stage of the back-arc rifting is best explained by a partial melting of subducted slab saturated with trace quantities of zircon under low-temperature conditions in the mantle wedge. On the other hand, the HZB requires a partial melt of subducted slab accompanied by full dissolution of zircon under high-temperature conditions in the mantle wedge, which could have been caused by hot asthenospheric injection during the

Strong broad green UV-excited photoluminescence in rare earth (RE = Ce, Eu, Dy, Er, Yb) doped barium zirconate

Energy Technology Data Exchange (ETDEWEB)

Borja-Urby, R. [Grupo de Espectroscopia de Materiales Avanzados y Nanoestructurados (EMANA), Centro de Investigaciones en Optica A. C., Leon, Gto. 37150 (Mexico); Diaz-Torres, L.A., E-mail: ditlacio@cio.mx [Grupo de Espectroscopia de Materiales Avanzados y Nanoestructurados (EMANA), Centro de Investigaciones en Optica A. C., Leon, Gto. 37150 (Mexico); Salas, P. [Centro de Fisica Aplicada y Tecnologia Avanzada, Universidad Nacional Autonoma de Mexico, A.P. 1-1010, Queretaro, Qro. 76000 (Mexico); Angeles-Chavez, C. [Instituto Mexicano del Petroleo, Ciudad de Mexico, D. F. 07730 (Mexico); Meza, O. [Grupo de Espectroscopia de Materiales Avanzados y Nanoestructurados (EMANA), Centro de Investigaciones en Optica A. C., Leon, Gto. 37150 (Mexico)

2011-10-25

Highlights: > Trivalent rare earth (RE) substitution on Zr{sup 4+} sites in BaZrO{sub 3} lead to band gap narrowing. > RE substitution lead to enhanced blue-green intrinsic emission of nanocrystalline BaZrO{sub 3} > Blue-green hue of BaZrO3:RE depends on RE dopant and excitation UV wavelength > BaZrO3: Dy{sup 3+} PL chromatic coordinates correspond to pure white color coordinates of CIE 1931 model - Abstract: The wet synthesis hydrothermal method at 100 deg. C was used to elaborate barium zirconate (BaZrO{sub 3}) unpurified with 0.5 mol% of different rare earth ions (RE = Yb, Er, Dy, Eu, Ce). Morphological, structural and UV-photoluminescence properties depend on the substituted rare earth ionic radii. While the crystalline structure of RE doped BaZrO{sub 3} remains as a cubic perovskite for all substituted RE ions, its band gap changes between 4.65 and 4.93 eV. Under 267 nm excitation the intrinsic green photoluminescence of the as synthesized BaZrO{sub 3}: RE samples is considerably improved by the substitution on RE ions. For 1000 deg. C annealed samples, under 267 nm, the photoluminescence is dominated by the intrinsic BZO emission. It is interesting to notice that Dy{sup 3+}, Er{sup 3+} and Yb{sup 3+} doped samples present whitish emissions that might be useful for white light generation under 267 nm excitation. CIE color coordinates are reported for all samples.

HF/DF chemical labs

International Nuclear Information System (INIS)

Meinzer, R.A.

1987-01-01

This paper provides the essential details to understand and design HF/DF and related types of chemical lasers. The basic operation of the HF/DF chemical laser is described. The details of the excitation chemistry are presented and the pertinent laser physics is described. A description of the various laser components is given and the analytical models for the HF/DF chemical laser are discussed. A brief description of the chain reaction HF/DF chemical laser is offered

Epithermal neutron activation analysis investigation of Clarion-Clipperton abyssal plane clay and polymetallic micronodules.

Science.gov (United States)

Duliu, O G; Cristache, C I; Culicovc, O A; Frontasyeva, M V; Szobotca, S A; Toma, M

2009-05-01

The content of seven major (Na, Al, Cl, Mn, K, Ca, Ti, Fe) and 30 trace (Sc, V, Cr, Ni, Co, Zn, Cu, As, Sr, Rb, Zr, Mo, Sn, In, Sb, Ba, Cs, La, Ce, Nd, Eu, Sm, Tb, Dy, Yb, Hf, Ta, W, Th, U) elements determined by INAA in 13 samples of abyssal clay and two samples of micronodules collected from the North pacific Ocean Clarion-Clipperton abyssal plane is presented and discussed with respect to some rocks models.

Epithermal neutron activation analysis investigation of Clarion-Clipperton abyssal plane clay and polymetallic micronodules

International Nuclear Information System (INIS)

Duliu, O.G.; Cristache, C.I.; Culicovc, O.A.; Frontasyeva, M.V.; Szobotca, S.A.; Toma, M.

2009-01-01

The content of seven major (Na, Al, Cl, Mn, K, Ca, Ti, Fe) and 30 trace (Sc, V, Cr, Ni, Co, Zn, Cu, As, Sr, Rb, Zr, Mo, Sn, In, Sb, Ba, Cs, La, Ce, Nd, Eu, Sm, Tb, Dy, Yb, Hf, Ta, W, Th, U) elements determined by INAA in 13 samples of abyssal clay and two samples of micronodules collected from the North pacific Ocean Clarion-Clipperton abyssal plane is presented and discussed with respect to some rocks models.

Epithermal neutron activation analysis investigation of Clarion-Clipperton abyssal plane clay and polymetallic micronodules

Energy Technology Data Exchange (ETDEWEB)

Duliu, O.G. [University of Bucharest, Department of Atomic and Nuclear Physics, P.O. Box MG-11, 077125 Magurele, Ilfov (Romania)], E-mail: duliu@b.astral.ro; Cristache, C.I. [National Institute of Research and Development for Physics and Nuclear Engineering ' Horia-Hulubei' , P.O. Box MG-6, 077125 Magurele, Ilfov (Romania)], E-mail: ocarmen@ifin.nipne.ro; Culicovc, O.A. [Joint Institute of Nuclear Research, 6, Joliot Curie str., 141980 Dubna (Russian Federation)], E-mail: otilia_culicov@yahoo.com; Frontasyeva, M.V. [Joint Institute of Nuclear Research, 6, Joliot Curie str., 141980 Dubna (Russian Federation)], E-mail: marina@nf.jinr.ru; Szobotca, S.A. [National Institute of Geoecology and Marine Geology, 34 Dimitrie Onciul str., 024504 Bucharest (Romania)], E-mail: szobi@geoecomar.ro; Toma, M. [National Institute of Research and Development for Physics and Nuclear Engineering ' Horia-Hulubei' , P.O. Box MG-6, 077125 Magurele, Ilfov (Romania)

2009-05-15

The content of seven major (Na, Al, Cl, Mn, K, Ca, Ti, Fe) and 30 trace (Sc, V, Cr, Ni, Co, Zn, Cu, As, Sr, Rb, Zr, Mo, Sn, In, Sb, Ba, Cs, La, Ce, Nd, Eu, Sm, Tb, Dy, Yb, Hf, Ta, W, Th, U) elements determined by INAA in 13 samples of abyssal clay and two samples of micronodules collected from the North pacific Ocean Clarion-Clipperton abyssal plane is presented and discussed with respect to some rocks models.

Applications of High Throughput (Combinatorial) Methodologies to Electronic, Magnetic, Optical, and Energy-Related Materials

Science.gov (United States)

2013-06-17

ray beams in transmission geome- try.48 Using 100 nm thick films in the Ce2O3–Al2O3–HfO2 system, they were able to obtain texture , epitaxial relation...is the identification of lead-free, high piezoelectric coefficient replacements for the commonly used compound Pb(Zr,Ti)O3 ( PZT ). Ferroelectric...Fig. 24 shows the variation in the electric-field induced transition in a bulk ceramic composition spread, where a subtle substitution effect of a

HF laser

International Nuclear Information System (INIS)

Suzuki, Kazuya; Iwasaki, Matae

1977-01-01

A review is made of the research and development of HF chemical laser and its related work. Many gaseous compounds are used as laser media successfully; reaction kinetics and technological problems are described. The hybrid chemical laser of HF-CO 2 system and the topics related to the isotope separation are also included. (auth.)

Evaluation of U-Zr hydride fuel for a thorium fuel cycle in an RTR concept

Energy Technology Data Exchange (ETDEWEB)

Lee, Kyung Taek; Cho, Nam Zin [Korea Advanced Institute of Science and Technology, Taejon (Korea, Republic of)

1999-12-31

In this paper, we performed a design study of a thorium fueled reactor according to the design concept of the Radkowsky Thorium Reactor (RTR) and evaluated its overall performance. To enhance its performance and alleviate its problems, we introduced a new metallic uranium fuel, uranium-zirconium hydride (U-ZrH{sub 1.6}), as a seed fuel. For comparison, typical ABB/CE-type PWR based on SYSTEM 80+and standard RTR-type thorium reactor were also studied. From the results of performance analysis, we could ascertain advantages of RTR-type thorium fueled reactor in proliferation resistance, fuel cycle economics, and back-end fuel cycle. Also, we found that enhancement of proliferation resistance and safer operating conditions may be achieved by using the U-ZrH{sub 1.6} fuel in the seed region without additional penalties in comparison with the standard RTR`s U-Zr fuel. 6 refs., 2 figs., 6 tabs. (Author)

Evaluation of U-Zr hydride fuel for a thorium fuel cycle in an RTR concept

Energy Technology Data Exchange (ETDEWEB)

Lee, Kyung Taek; Cho, Nam Zin [Korea Advanced Institute of Science and Technology, Taejon (Korea, Republic of)

1998-12-31

In this paper, we performed a design study of a thorium fueled reactor according to the design concept of the Radkowsky Thorium Reactor (RTR) and evaluated its overall performance. To enhance its performance and alleviate its problems, we introduced a new metallic uranium fuel, uranium-zirconium hydride (U-ZrH{sub 1.6}), as a seed fuel. For comparison, typical ABB/CE-type PWR based on SYSTEM 80+and standard RTR-type thorium reactor were also studied. From the results of performance analysis, we could ascertain advantages of RTR-type thorium fueled reactor in proliferation resistance, fuel cycle economics, and back-end fuel cycle. Also, we found that enhancement of proliferation resistance and safer operating conditions may be achieved by using the U-ZrH{sub 1.6} fuel in the seed region without additional penalties in comparison with the standard RTR`s U-Zr fuel. 6 refs., 2 figs., 6 tabs. (Author)

Analysis of monazite, zircon, and apatite from the southeastern Piedmont. National uranium resource evaluation program

International Nuclear Information System (INIS)

Karfunkel, B.S.; Fay, W.M.; Price, V. Jr.

1981-12-01

Two hundred sixty-three monazite, 191 zircon, and 16 apatite grains from 52 stream-sediment locations in the Southeastern Piedmont were analyzed by electron microprobe for one of the following suites of elements: Ca, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Dy, Y, Th, U, P, and F, or Ca, La, Ce, Fe, Er, Hf, Y, Th, U, P, Zr, Mg, Al, and Si. Monazite samples that had high uranium or thorium content and zircon samples that had high hafnium or iron content from a total of six locations were reanalyzed to confirm the initial results. This report contains a description of sample collection and preparation procedures, analytical methods, tables of analyses, and a statistical summary of analyses

Enhanced performance of flexible dye-sensitized solar cells using flexible Ag@ZrO2/C nanofiber film as low-cost counter electrode

Science.gov (United States)

Yin, Xin; Xie, Xueyao; Song, Lixin; Zhai, Jifeng; Du, Pingfan; Xiong, Jie

2018-05-01

Highly flexible ZrO2/C nanofibers (NFs) coated with Ag nanoparticles (NPs) have been fabricated by a combination of electrospinning, carbonization and hydrothermal treatment. The obtained Ag@ZrO2/C NFs serve as low-cost counter electrodes (CEs) for flexible dye-sensitized solar cells (FDSSCs). A considerable power conversion efficiency of 4.77% is achieved, which is 27.9% higher than the η of ZrO2/C NFs CEs (3.73%) and reaches about 90% of that of Pt CE (5.26%). It can be ascribed to the fact that the introduction of Ag NPs provides a large number of accessible reaction sites for electrolyte ions to rapidly participate in the I3-/I- reaction. Moreover, the Ag NPs can produce synergistic effect with ZrO2/C NFs to further enhance transport capacity and electro-catalytic activity of the Ag@ZrO2/C film. Therefore, the considerable performance together with characteristics of simple preparation, low cost and flexibility suggests the Ag@ZrO2/C film can be promising candidate for the future generation of FDSSC.

Oxidation kinetics of some zirconium alloys in flowing carbon dioxide at high temperatures

International Nuclear Information System (INIS)

Kohli, R.

1980-01-01

The oxidation kinetics of three zirconium alloys (Zr-2.2 wt% Hf, Zr-2.5 wt% Nb, and Zr-3 wt% Nb-1 wt% Sn) have been measured in flowing carbon dioxide in the temperature range from 873 to 1173 K to 120 ks (2000 min). At all oxidation temperatures, Zr-2.5 Nb and Zr-3 Nb-1 Sn showed a transition to rapid linear kinetics after initial parabolic oxidation. The Zr-2.2 Hf showed this transition at temperatures in the range from 973 to 1173 K; at 873 K, no transition was observed within the oxidation times reported. The Zr-2.2 Hf showed the smallest weight gains, followed in order by Zr-2.5 Nb and Zr-3 Nb-1 Sn. Increased oxidation rates and shorter times-to-rate-transition of Zr-2.2 Nb and Zr-1 Sn as compared with Zr-2.2 Hf can be attributed to the presence of niobium, tin, and hafnium in the alloys. This is considered in terms of the Nomura-Akutsu model, according to which hafnium should delay the rate transition, while niobium and tin lead to shorter times-to-rate-transition. The scale on Zr-2.2 Hf was identified as monoclinic zirconia, while the tetragonal phase, 6ZrO 2 .Nb 2 O 5 , was contained in the monoclinic zirconia scales on both other alloys

Leaching behavior of gamma-emitting fission products and Np from neutron-irradiated UO_2-ZrO_2 solid solutions in non-filtered surface seawater

International Nuclear Information System (INIS)

Sasaki, Takayuki; Takeno, Yuu; Kobayashi, Taishi; Kirishima, Akira; Sato, Nobuaki

2016-01-01

The gamma ray radionuclides Cs-137, Ba-140, I-131, Ce-141, Ru-103, Zr-95, and Np-239 were produced by neutron irradiation of UO_2-ZrO_2 solid solutions that were synthesized as simulated fuel debris under reducing and oxidizing conditions. The leaching ratio of radionuclides was investigated under atmospheric conditions at 25°C for non-filtered natural surface seawater, as well as deionized water after filtration with a membrane of 0.45-μm pore size or that of nominal molecular weight limit of 3 kDa. The uranium molar concentration was affected by the oxidation state in the solid solution samples. The congruent dissolution of Cs, I, and Ba with the hexavalent uranium of U_3O_8 was facilitated in the seawater samples, whereas a lower leaching ratio of nuclides was observed in the deionized water samples. Neptunium-239, originally produced from uranium-238 in U_3O_8, showed behavior that was similar to that of Cs, I, and Ba. However, the dissolution of Np (as a parent nuclide of Pu-239) in the debris of UO_2 and UO_2-ZrO_2 was suppressed in the same manner as Zr(IV) and Ce(IV). The concentration exhibited no filtration dependence after 15 d, which shows that most of the leached nuclides can exist in their ionic form in seawater. (author)

States in 94Zr from 94Zr(d,d')94Zr* at 15.5 Mev

International Nuclear Information System (INIS)

Frota-Pessoa, E.; Joffily, S.

1986-01-01

94 energy levels up to approx. 4.3 Mev excitation energy are studied in the 94 Zr(d,d') 94 Zr* reaction. Deuterons had a bombarding energy of 15.5 MeV. The emergent deuterons were analysed by a magnetic spectrograph and the detector was nuclear emulsion. The resolution in energy was about 11 KeV. The distorted-wave analysis was used to determine the l transferred, the β 2 l and J Π values for some 94 Zr excited states. These results are compared with previous ones. 32 levels of excitation energy in 94 Zr were found which did not appear in previous 94 Zr(d,d') reactions. 20 levels do not correspond to the ones. (Author) [pt

SEMICONDUCTOR TECHNOLOGY: Wet etching characteristics of a HfSiON high-k dielectric in HF-based solutions

Science.gov (United States)

Yongliang, Li; Qiuxia, Xu

2010-03-01

The wet etching properties of a HfSiON high-k dielectric in HF-based solutions are investigated. HF-based solutions are the most promising wet chemistries for the removal of HfSiON, and etch selectivity of HF-based solutions can be improved by the addition of an acid and/or an alcohol to the HF solution. Due to densification during annealing, the etch rate of HfSiON annealed at 900 °C for 30 s is significantly reduced compared with as-deposited HfSiON in HF-based solutions. After the HfSiON film has been completely removed by HF-based solutions, it is not possible to etch the interfacial layer and the etched surface does not have a hydrophobic nature, since N diffuses to the interface layer or Si substrate formation of Si-N bonds that dissolves very slowly in HF-based solutions. Existing Si-N bonds at the interface between the new high-k dielectric deposit and the Si substrate may degrade the carrier mobility due to Coulomb scattering. In addition, we show that N2 plasma treatment before wet etching is not very effective in increasing the wet etch rate for a thin HfSiON film in our case.

Ab initio study of mechanical and thermo-acoustic properties of tough ceramics: applications to HfO{sub 2} in its cubic and orthorhombic phase

Energy Technology Data Exchange (ETDEWEB)

Ponce, C A [Departamento de Fisica, Facultad de Ciencias Exactas, y Naturales y Agrimensura, UNNE, Campus Universitario, Avenida Libertad 5600, CP 3400, Corrientes (Argentina); Casali, R A [Departamento de Fisica, Facultad de Ciencias Exactas, y Naturales y Agrimensura, UNNE, Campus Universitario, Avenida Libertad 5600, CP 3400, Corrientes (Argentina); Caravaca, M A [Departamento de Fisico, Quimica, Facultad de Ingenieria, UNNE, Avenida Las Heras 727, CP 3500, Resistencia (Argentina)

2008-01-30

By means of the ab initio all-electron new full-potential linear-muffin-tin orbitals method, calculations were made for elastic constants C{sub 11}, C{sub 12} and C{sub 44} for Si, ZrO{sub 2} and HfO{sub 2} in their cubic phase, and constants C{sub 11}, C{sub 22}, C{sub 33}, C{sub 12}, C{sub 13}, C{sub 23}, C{sub 44}, C{sub 55} and C{sub 66} for HfO{sub 2} in its orthorhombic phase. Using the Voigt and Reuss theory, estimations were made for polycrystals of their bulk, shear and Young moduli, and Poisson coefficients. The speed of elastic wave propagations and Debye temperatures were estimated for polycrystals built from Si and the above mentioned compounds. The semicore 4f{sup 14} electrons should be included in the valence set of Hf atom in this all-electron approach if accurate results for elastic properties under pressures are looked for.

Effect of chemistry modifications and heat treatments on the mechanical properties of DS Mar-M200 superalloy

International Nuclear Information System (INIS)

Yunrong, Z.; Yuping, W.; Jizhou, X.; Caron, P.; Khan, T.

1988-01-01

This paper discusses how Hf and Zr can promote the formation of eutectic (γ + γ), MC 2 , and Ni 5 M phases. In the alloy with equal atomic percent Zr and Hf, the solubility of Zr in eutectic γ is lower than that of Hf, and Zr content in Ni 5 M is much higher than Hf. This distribution of Zr is beneficial to the formation of Ni 5 M and lowers the strengthening efficiency of Zr. A pretreatment of 1130 degrees C/3hr efficiently eliminates Ni 5 M and, as a consequence, increases the incipient melting temperature of the alloy. The precipitation treatment of 1100 degrees C/4hr leads to cuboidal γ precipitation of about 0.5 μm size and causes the Hf-containing alloy to have a much higher creep strength than the Hf-free alloy in the temperature range of 760 to 1050 degrees C. The Hf-containing alloy showed greater LCF (low cycle fatigue) life in comparison to the Hf-free alloy. A similar tendency was found when Zr was either partially or totally substituted for Hf. A higher rate of solidification facilitates enhanced LCF life due to a finer structure and more perfect orientation. Surface slip analysis showed that intersection of two sets of slip in adjacent grains occurred in the Hf-free and HF-containing alloys, but cracking at the columnar grain boundary easily took place in the Hf-free alloy. The number of surface cracks of LCF specimens and their length per unit area are much higher in the Mar-M200 alloy. Mc cracking preferentially occurs at long rod-shaped carbides perpendicular to the stress axis, and then propagates through the interdendritic region. The Hf-containing alloy cracks along the crystallographic planes by separation of slip bands

Subduction Contributions in the Trans-Mexican Volcanic Belt: Implications from Lava Chemistry and Hf-Nd-Pb Isotopes

Science.gov (United States)

Cai, Y.; Goldstein, S. L.; Langmuir, C. H.; Gómez-Tuena, A.; Lagatta, A.; Straub, S. M.; Martín Del Pozzo, A.

2007-05-01

Despite thick continental crust, near primitive lavas erupt throughout the Trans-Mexican Volcanic Belt (TMVB). In order to distinguish and better constrain subduction contributions and effects of crustal contamination, we analyzed samples representing subducting sediments from DSDP Site 487, and Quaternary lavas from stratovolcanoes and cinder cones, including alkaline "high-Nb" lavas from the Sierra Chichinautzin Volcanic Field (SCVF) showing negligible subduction signature in its trace element chemistry and representing melts of the mantle wedge. Our primary observations and implications are: (1) The high-Nb SCVF `intraplate' lavas define a linear trend along the "Nd-Hf mantle-crust array", defining the composition of the mantle wedge. (2) Popocatepetl and Nevado de Toluca stratovolcanoes show the highest Nd and Hf isotope ratios, higher than the `intraplate' lavas, indicating their sources are more "depleted mantle-like" than the regional mantle wedge. (3) The Popo and Toluca chemical and isotopic trends sharply contrast with Pico de Orizaba, which shows classic indications of crustal contamination (e.g. high 207Pb/204Pb, low Nd-Hf isotope ratios), consistent with contamination by local Precambrian crust. (4) Higher Nd-Hf isotopes in Popo and Toluca lavas also correlate with lower Pb isotope ratios, and lower Lu/Hf and Zr/Hf. Together, these data indicate contributions from subducted Pacific oceanic crust and hydrothermal sediment. (5) Popo and Toluca are also enriched in Th/LREE compared with `intraplate' lavas, reflecting subducted sediment contributions. (6) Nd-Hf isotope ratios of hydrothermal sediment from DSDP Site 487 lie on the "seawater array", with high Hf isotope ratios compared to the "mantle-crust array". Popo and Toluca Nd-Hf isotopes display a shallower slope than the "intraplate lava Nd-Hf array", reflecting contributions from hydrothermal sediment. Popocatepetl and Toluca lavas therefore avoid substantial crustal contamination of mantle wedge

HF-laser program

International Nuclear Information System (INIS)

Anon.

1978-01-01

Sandia's HF-laser program for FY 77 and FY 78 was revised in June 1977 in order to meet several new program milestones. Research progress is reported on: objective of HF oscillator-amplifier studies using H 2 -F 2 gas mixtures; characteristics of large-volume oscillator using H 2 -F 2 mixtures; characteristics of large-volume amplifier using H 2 -F 2 mixtures; experimental results of the oscillator-amplifier study; objective of high-quality discharge-initiated SF 6 -HI oscillator-preamplifier system; pin-discharge-initiated oscillator and first beam expander; fast-discharge-initiated preamplifiers; reflecting beam expanders for oscillator-preamplifier system; beam quality of discharge-initiated oscillator-preamplifier system; short pulse option for discharge initiated SF 6 -HI system; H 2 -F 2 electron-beam-initiated oscillator-preamplifier system; chamber for HF-laser focusing experiments; computer study of parasitic oscillations in HF amplifiers and oscillators; kinetics upgrade of HF-laser code; repetitivey ignited flowing H 2 -F 2 -O 2 mixtures; spontaneous detonations in multiatmosphere H 2 -F 2 -O 2 mixtures; high-pressure H 2 -F 2 laser studies; and time sequenced energy extraction on the high xenon laser

High-aspect-ratio HfC nanobelts accompanied by HfC nanowires: Synthesis, characterization and field emission properties

Energy Technology Data Exchange (ETDEWEB)

Tian, Song, E-mail: tiansong22@126.com [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072 (China); School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074 (China); Zhang, Yulei; Ren, Jincui; Qiang, Xinfa; Zhang, Shouyang [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072 (China); Li, Hejun, E-mail: lihejun@nwpu.edu.cn [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072 (China)

2017-04-30

Highlights: • HfC naobelts accompanied by HfC nanowires were synthesized by a catalytic CVD method. • HfC nanobelts as a novel structure of HfC ceramic are reported for the first time. • HfC nanobelts have 100–200 μm in lengths and reach up to 10 μm in widths. • The synthesized product is promising field nanoemitters. - Abstract: As a key refractory carbide, hafnium carbide (HfC) is commonly used as structural materials while the field emission (FE) application of HfC in the field of vacuum microelectronics is almost the only one for functional material purposes. Based on its outstanding physical and chemical characteristics, HfC is identified as a potential candidate with satisfactory mechanical properties and long-term and/or high-temperature FE stability for future applications in high-performance field emitters. However, the development of HfC in various FE applications is hindered because it is not facile to fabricate large-scale low-dimensional HfC field nanoemitters. Herein, High-aspect-ratio HfC nanobelts accompanied by HfC nanowires were synthesized on a large scale by a traditional and simple catalytic chemical vapor deposition (CVD) method. Classical vapor–liquid–solid (VLS) theory was employed to explain the growth of the HfC nanowires and nanobelts along axial direction. The thin HfO{sub 2} shell and thin C layer surrounding the nanostructures might give rise to the diameter fluctuation of HfC nanowires and the width increase of HfC nanobelts in lateral direction. Field emission results show that the high-aspect-ratio HfC nanobelts accompanied by the nanowires are promising field nanoemitters, which exhibit excellent field emission properties with a fairly low turn-on field of ∼1.5 V μm{sup −1} and a low current fluctuation less than ∼10%. This suggests that HfC ceramics with high-aspect-ratio nanostructures are ideal cathode material for various field emission applications.

Composition dependences of crystal structure and electrical properties of epitaxial Pb(Zr,Ti)O3 films grown on Si and SrTiO3 substrates

Science.gov (United States)

Okamoto, Shoji; Okamoto, Satoshi; Yokoyama, Shintaro; Akiyama, Kensuke; Funakubo, Hiroshi

2016-10-01

{100}-oriented Pb(Zr x ,Ti1- x )O3 (PZT) thin films of approximately 2 µm thickness and Zr/(Zr + Ti) ratios of 0.39-0.65 were epitaxially grown on (100)cSrRuO3//(100)SrTiO3 (STO) and (100)cSrRuO3//(100)cLaNiO3//(100)CeO2//(100)YSZ//(100)Si (Si) substrates having different thermal expansion coefficients by pulsed metal-organic chemical vapor deposition (MOCVD). The effects of Zr/(Zr + Ti) ratio and type of substrate on the crystal structure and dielectric, ferroelectric and piezoelectric properties of the films were systematically investigated. The X-ray diffraction measurement showed that both films changed from having a tetragonal symmetry to rhombohedral symmetry through the coexisting region with increasing Zr/(Zr + Ti) ratio. This region showed the Zr/(Zr + Ti) ratios of 0.45-0.59 for the films on the STO substrates that were wider than the films on the Si substrates. Saturation polarization values were minimum at approximately Zr/(Zr + Ti) = 0.50 for the films on the STO substrates, and no obvious Zr/(Zr + Ti) ratio dependence was detected in the films on the Si substrates. On the other hand, the maximum field-induced strain values measured by scanning force microscopy at approximately Zr/(Zr + Ti) = 0.50 at 100 kV/cm were about 0.5 and 0.1% in the films on the Si and STO, respectively.

Determination of the rate of HF hydration and the effects of HF on moisture condensation

International Nuclear Information System (INIS)

McCulla, W.H.

1982-01-01

There were four basic questions addressed in this report that relate to the HF interaction in the environment. As to whether HF hydrates in the vapor phase and what the rate of that hydration is, there seems ample evidence that HF hydrates readily in the vapor phase and the rate of that hydration is very fast, i.e., dHF/dt greater than or equal to 25 torr sec -1 . Concerning under what conditions condensation of the hydrate will occur and whether a third body is required for condensation, it was found that HF does effect the dew point or condensation of water and data was presented indicating the extent of that effect. It was also determined that condensation will occur without a third body present. Thus, in attempting to model an HF release for the Safety Analysis Report the hydration of HF and the subsequent heat released may be treated as occurring instantaneously; but the ultimate disposition of the HF will be strongly dependent upon the environmental conditions at the time of the release

Determination of the rate of HF hydration and the effects of HF on moisture condensation

Energy Technology Data Exchange (ETDEWEB)

McCulla, W H

1982-04-30

There were four basic questions addressed in this report that relate to the HF interaction in the environment. As to whether HF hydrates in the vapor phase and what the rate of that hydration is, there seems ample evidence that HF hydrates readily in the vapor phase and the rate of that hydration is very fast, i.e., dHF/dt greater than or equal to 25 torr sec/sup -1/. Concerning under what conditions condensation of the hydrate will occur and whether a third body is required for condensation, it was found that HF does effect the dew point or condensation of water and data was presented indicating the extent of that effect. It was also determined that condensation will occur without a third body present. Thus, in attempting to model an HF release for the Safety Analysis Report the hydration of HF and the subsequent heat released may be treated as occurring instantaneously; but the ultimate disposition of the HF will be strongly dependent upon the environmental conditions at the time of the release.

Preparation and characterization of segmented p-type Ti_0.3Zr_0.35Hf_0.35CoSb_0.8Sn_0.2/Ca₃Co₄O₉

DEFF Research Database (Denmark)

Le, Thanh Hung; Han, Li; Stamate, Eugen

with HH using an electrically conductive adhesive and brazing joining technique. The thermoelectric properties of the component materials as well as the interfacial resistance at high temperatures were characterized as a function of temperature up to 1100 K, and the results are discussed in details.......Misfit-layered cobaltite Ca3Co4O9+δ is considered as good p-type thermoelectric material in high temperature region (950 - 1100 K), while half-Heusler (HH) Ti0.3Zr0.35Hf0.35CoSb0.8Sn0.2 is high performance p-type material at temperatures below 950 K. In this work, oxide Ca3Co4O9+δ is segmented...

High-K rotational bands in {sup 174}Hf and {sup 175}Hf

Energy Technology Data Exchange (ETDEWEB)

Gjoerup, N L; Sletten, G [The Niels Bohr Institute, Roskilbe (Denmark); Walker, P M [Surrey Univ., Guildford (United Kingdom). Dept. of Physics; Bentley, M A [Daresbury Lab. (United Kingdom); Cullen, D M; Sharpey-Schafer, J F; Fallon, P; Smith, G [Liverpool Univ. (United Kingdom). Oliver Lodge Lab.

1992-08-01

High sensitivity experiments with {sup 48}Ca, {sup 18}O and {sup 9}Be induced reactions using the ESSA-30, TESSA-3 and NORDBALL arrays have provided extensive new information on the high spin level structures of {sup 174}Hf and {sup 175}Hf. During the series of experiments, several new bands have been found and most known bands have been extended considerably. Spin and excitation energy ranges for {sup 174}Hf are now {approx} 35 {Dirac_h} and {approx} 13 MeV, respectively, and for {sup 175}Hf ranges are {approx} 30 {Dirac_h} and {approx} 7 MeV. respectively. Several new high-K structures have been found in {sup 174}Hf and the structure of these and the already known high-K bands in both nuclei together with the new Tilted Axis Cranking approach might explain the small K-hindrances observed for K-isomers in this region. (author). 8 refs., 2 figs.

Comparison of results analysis of chemical composition of alloys inside the U-Zr-Nb by XRF and AAS techniques

International Nuclear Information System (INIS)

Masrukan; Tri Yulianto; Anwar Muchsin

2011-01-01

U-Zr-Nb alloy chemical composition analysis using X Ray Fluorescence (XRF) and Atomic Absorption Spectroscopy (AAS) techniques have been conducted, where U-Zr- Nb alloy was chosen as candidates for new high-density fuel for future research reactors . Composition analysis is necessary because the composition of elements in the fuel will determine the characteristics of fuel during the fabrication process and in the reactor. The use of two kinds of analysis techniques were designed to obtain accurate analysis results. The experiment was conducted to determine the major element composition and impurities in the alloy U-Zr-Nb. First U-Zr-Nb varying alloy composition Nb were respectively 1%, 4%, 7% (U10% Zr1% Nb, U10% Zr4% Nb and U10% 7% Nb) as results of the melting process of measuring the diameter of 120 mm crushed on the surface bottom. Once on the bottom surface is smooth, then analyzed using XRF techniques. To analyze the elements using AAS techniques, alloy U-Zr-Nb cut into 10 mm x 5 mm then dissolved using HF and nitric acid. Solution that occurred were analyzed using AAS technique. From the analysis using the XRF technique is obtained the alloy U-10% Zr-1% Nb, U-10% Zr-4% Nb and Zr-10% U-7% Nb) had a content of each element as follows: U (87.8858%), Zr (2.6097%) and Nb (0.2206%), U (87.8556%), Zr (2.6302%), and Nb (0.6573%); U (84.6334%), Zr (2.5773%), and Nb (1.0940) weight. Results of analysis using AAS techniques on samples obtained third consecutive Zr content of 9.25%, 8.90% and 9.80% while the content of Nb was not detected. Meanwhile, the results of elemental analysis of impurities in all three samples showed that almost all the elements are still qualify as fuel except Zn element. Element Zn at the three samples of each alloys U-10% Zr-1% Nb, U-10% Zr-4% Nb and U-10% Zr-7%Nb is 1.3266%, 3.2756% and 1.0927% weight. It could be concluded that the results of analysis of elemental content and impurities in the alloy U-Nb-Zr using both XRF and AAS visible

Semiquantitative spectrographic analysis of nuclear interest minerals and of various products

International Nuclear Information System (INIS)

Alvarez Gonzalez, F.; Roca Adell, M.; Fernandez Cellini, R.

1958-01-01

Because the great number of samples of various kinds receiving in the Chemical Division, minerals in the most part, for its complete analysis, a rapid spectrographic method has been developed. It permits the determination of the following elements with a semiquantitative character. Al, As, Ag, Au, B, Be, Bi, Ca, Cd, Ce, Co, Cr, Cu, Fe, Ga, Ge, Hf, Hn, In, K, La, Li, Mg, Mn, Mo, Na, Nb, P, Pb, Pt, Sb, Si, Sn, Sr, Ta, Ti, V, W, Y, Zn and Zr. (Author) 14 refs

Semiquantitative spectrographic analysis of nuclear interest minerals and of various products; Analisis espectrografico semicuantitativo de minerales de interes nuclear y productos diversos

Energy Technology Data Exchange (ETDEWEB)

Alvarez Gonzalez, F; Roca Adell, M; Fernandez Cellini, R

1958-07-01

Because the great number of samples of various kinds receiving in the Chemical Division, minerals in the most part, for its complete analysis, a rapid spectrographic method has been developed. It permits the determination of the following elements with a semiquantitative character. Al, As, Ag, Au, B, Be, Bi, Ca, Cd, Ce, Co, Cr, Cu, Fe, Ga, Ge, Hf, Hn, In, K, La, Li, Mg, Mn, Mo, Na, Nb, P, Pb, Pt, Sb, Si, Sn, Sr, Ta, Ti, V, W, Y, Zn and Zr. (Author) 14 refs.

Effect of pH and fluoride on behavior of dental ZrO2 ceramics in artificial saliva

International Nuclear Information System (INIS)

Mukaeda, L.E.; Robin, A.; Santos, C.; Taguchi, S.P.; Borges Junior, L.A.

2009-01-01

A considerable increase in the ceramic products demand occurred due to the evolution of dental restoration techniques and these materials must resist to the complex mouth environment. The pH of saliva can decrease significantly due to the ingestion of acidic foods and beverages and mainly due to reactions occurring during bacteria metabolism that lead to the formation of organic acids. Fluorides are also present in the mouth since fluorides are usually added in drinking water, mouth washes, tooth pastes and gels for the prevention of plaque and caries formation. The combination of low pH and presence of fluorides can lead to the formation of HF and HF 2 - which are detrimental to metallic and probably to ceramic devices. In this work, commercial blocks of ZrO 2 ceramics (ProtMat Materiais Avancados® and Ivoclar®) were immersed in Fusayama artificial saliva of different pHs and fluoride concentrations. The properties of the as-produced ceramics (crystalline phases (XRD), microstructure (SEM), roughness (3D surface topography AFM) and mechanical resistance - Vickers hardness (Hv) and fracture toughness (KIC) were evaluated. Some of these properties were also determined after the immersion tests as well as the mass variation of the samples in order to evaluate the resistance of these ZrO 2 ceramics to degradation under these conditions. (author)

Development of all chemical solution derived Ce0.9La0.1O2−y/Gd2Zr2O7 buffer layer stack for coated conductors: influence of the post-annealing process on surface crystallinity

International Nuclear Information System (INIS)

Zhao, Y; Li, X-F; He, D; Andersen, N H; Grivel, J-C; Khoryushin, A; Hansen, J B

2012-01-01

Preparation and characterization of a biaxially textured Gd 2 Zr 2 O 7 and Ce 0.9 La 0.1 O 2−y (CLO, cap)/Gd 2 Zr 2 O 7 (GZO, barrier) buffer layer stack by the metal–organic deposition route are reported. YBa 2 Cu 3 O 7−d (YBCO) superconductor films were deposited by the pulsed-laser deposition (PLD) technique to assess the efficiency of such a novel buffer layer stack. Biaxial texture quality and morphology of the buffer layers and the YBCO superconductor films were fully characterized. The surface crystallinity of the buffer layers is studied by the electron backscatter diffraction technique. It is revealed that post-annealing GZO films in 2% H 2 in Ar is an effective way to improve the surface crystallinity. As a result, a highly textured CLO film can grow directly on the GZO film at a lower crystallization temperature. The critical current density of a YBCO PLD film is higher than 1 MA cm −2 (77 K, in self-field), demonstrating that the novel CLO/GZO stack is very promising for further development of low cost buffer layer architectures for coated conductors.

High resolution TDPAC measurements on 181Ta in Hf2Fe, Hf2Co and Hf2Rh at high temperature

International Nuclear Information System (INIS)

Cekic, B.; Koicki, S.; Ivanovic, N.; Manasijevic, M.; Koteski, V.; Marjanovic, D.

1998-01-01

The time differential perturbed angular correlation measurements (TDPAC-method ) on 181 Ta ion probe in Hf 2 Co, Hf 2 Fe and Hf 2 Rh intermetallic compounds have been performed at 1170 K, using a fast - slow time spectrometer consisting of two BaF 2 detectors. The results of the measurements show the presence of two independent electric quadrupole interactions, compatible with the crystalline structure of these polycrystalline compounds. (authors)

Appendix to Health and Safety Laboratory environmental quarterly, March 1, 1976--June 1, 1976. [Tabulated data on content of lead in surface air and /sup 7/Be, /sup 95/Zr, /sup 137/Cs, /sup 144/Ce, and /sup 90/Sr in surface air, milk, drinking water, and foods sampled in USA

Energy Technology Data Exchange (ETDEWEB)

Hardy, E.P. Jr.

1976-07-01

Tabulated data are presented on: the monthly deposition of /sup 89/Sr and /sup 90/Sr at some 100 world land sites; the content of lead and /sup 7/Be, /sup 95/Zr, /sup 137/Cs, and /sup 144/Ce in samples of surface air from various world sites; and the content of /sup 90/Sr in samples of milk, drinking water, and animal and human diets collected at various locations throughout the USA. (CH)

High-temperature x-ray diffraction study of HfTiO4-HfO2 solid solutions

International Nuclear Information System (INIS)

Carpenter, D.A.

1975-01-01

High-temperature x-ray diffraction techniques were used to determine the axial thermal expansion curves of HfTiO 4 -HfO 2 solid solutions as a function of composition. Data show increasing anisotropy with increasing HfO 2 content. An orthorhombic-to-monoclinic phase transformation was detected near room temperature for compositions near the high HfO 2 end of the orthorhombic phase field and for compositions within the two-phase region (HfTiO 4 solid solution plus HfO 2 solid solution). An orthorhombic-to-cubic phase transformation is indicated by data from oxygen-deficient materials at greater than 1873 0 K. (U.S.)

Reduction behaviors of Zr for LiCl-KCl-ZrCl4 and LiCl-KCl-ZrCl4-CdCl2

International Nuclear Information System (INIS)

Kim, Si Hyung; Yoon, Jongho; Kim, Gha Young; Kim, Tack Jin; Shim, Joon Bo; Kim, Kwang Rag; Jung, Jae Hoo; Ahn, Do Hee; Paek, Seungwoo

2013-01-01

The reduction potentials of most of the zirconium ions on the solid cathode are smaller (about 0.4V) than that of uranium, and thus zirconium can be recovered prior to uranium during the reduction stage. In the case of a liquid cadmium cathode, which is one of the major cathodes, the reduction potential can be changed because zirconium reacts with the liquid cadmium. Up to now, it has not been well known what the reduction potential of Zr was on the liquid Cd cathode. According to the Cd-Zr phase diagram, there are four intermetallic compounds between cadmium and zirconium. It is easier to use the solid cathode than the liquid cadmium cathode in LiCl-KCl-ZrCl 4 containing CdCl 2 to identify the formation of the Cd-Zr phase. In this study, the reduction behaviors of zirconium were compared in the LiCl-KCl-ZrCl 4 and LiCl-KCl-ZrCl 4 -CdCl 2 solutions when using a solid cathode. The reduction behavior of Zr at a solid W cathode and a Cd-coated W cathode was compared in a LiCl-KCl-ZrCl 4 solution at 500 .deg. C. It was observed from the results using a solid W cathode that Zr 4+ ions were gradually oxidized to Zr 2+ , Zr, and ZrCl during the reduction sweep, but the final oxidation peak of Zr 2+ to Zr 4+ seemed to be unclear during the oxidation sweep. In the case of the Cd-coated W electrode, only a Cd 2 Zr phase was formed at 500 .deg. C, which seemed to be related to the melting point of Cd-Zr intermetallics. Through additional studies at different temperatures, the formation behavior will be studied

Cu-Zr-Ag bulk metallic glasses based on Cu8Zr5 icosahedron

International Nuclear Information System (INIS)

Xia Junhai; Qiang Jianbing; Wang Yingmin; Wang Qing; Dong Chuang

2007-01-01

Based on the cluster line criterion, the Ag addition into the Cu 8 Zr 5 cluster composition is investigated for the search of ternary Cu-Zr-Ag bulk metallic glasses with high glass forming abilities. Two initial binary compositions Cu 0.618 Zr 0.382 and Cu 0.64 Zr 0.36 are selected. The former one corresponds to a deep eutectic point; it is also the composition of the Cu 8 Zr 5 icosahedron, which is derived from the Cu 8 Zr 3 structure. The latter one, which can be regarded as the Cu 8 Zr 5 cluster plus a glue atom Cu, is the best glass-forming composition in the Cu-Zr binary system. Two composition lines (Cu 0.618 Zr 0.382 ) 1-x Ag x and (Cu 0.64 Zr 0.36 ) 1-x Ag x are thus constructed in the Cu-Zr-Ag system by linking these two compositions with the third constitute Ag. A series of Cu-Zr-Ag bulk metallic glasses are found with 2-8 at.% Ag contents in both composition lines. The optimum composition (Cu 0.618 Zr 0.382 ) 0.92 Ag 0.08 within the searched region with the highest T g /T l = 0.633, is located along the cluster line (Cu 0.618 Zr 0.382 ) 1-x Ag x , where the deep eutectic Cu 0.618 Zr 0.382 exactly corresponds to the dense packing cluster Cu 8 Zr 5 . The alloying mechanism is discussed in the light of atomic size and electron concentration factors

Self-diffusion of Er and Hf inpure and HfO2-doped polycrystalline Er2O3

International Nuclear Information System (INIS)

Scheidecker, R.W.

1979-01-01

Using a tracer technique, self-diffusion of Er and Hf was measured over the approximate temperature interval of 1600 to 1970 0 C in pure and HfO 2 -doped polycryatalline Er 2 O 3 . Up to about 10 m/o HfO 2 dopant level, the Er self-diffusion coefficients followed a relationship based on cation vacancies. Above 10 m/o HfO 2 , deviation from this relationship occurred, apparently due to clustering of cation vacancies and oxygen interstitials around the dopant hafnia ion. The activation energy for the self-diffusion of Er in pure Er 2 O 3 was 82.2 Kcal/mole and increased with the HfO 2 dopant level present. Self-diffusion of Hf was measured in pure Er 2 O 3 having two impurity levels, and a separation of the grain boundary. The volume diffusion of Hf showed both extrinsic and intrinsic behavior with the transition temperature increasing with the impurity level present in Er 2 O 3 . The activation energy for Hf volume diffusion in the intrinsic region was high, i.e. 235 -+ 9.5 Kcal/mole. The grain boundary diffusion was apparently extrinsic over the entire temperature interval Very low Hf self diffusion rates were found in both pure and HfO 2 doped Er 2 O 3 compositions. Despite a clustering effect, the HfO 2 dopant increased the Hf volume diffusion coefficients

Corrosion of high Ni-Cr alloys and Type 304L stainless steel in HNO3-HF

International Nuclear Information System (INIS)

Ondrejcin, R.S.; McLaughlin, B.D.

1980-04-01

Nineteen alloys were evaluated as possible materials of construction for steam heating coils, the dissolver vessel, and the off-gas system of proposed facilities to process thorium and uranium fuels. Commercially available alloys were found that are satisfactory for all applications. With thorium fuel, which requires HNO 3 -HF for dissolution, the best alloy for service at 130 0 C when complexing agents for fluoride are used is Inconel 690; with no complexing agents at 130 0 C, Inconel 671 is best. At 95 0 C, six other alloys tested would be adequate: Haynes 25, Ferralium, Inconel 625, Type 304L stainless steel, Incoloy 825, and Haynes 20 (in order of decreasing preference); based on composition, six untested alloys would also be adequate. The ions most effective in reducing fluoride corrosion were the complexing agents Zr 4+ and Th 4+ ; Al 3+ was less effective. With uranium fuel, modestly priced Type 304L stainless steel is adequate. Corrosion will be most severe in HNO 3 -HF used occasionally for flushing and in solutions of HNO 3 and corrosion products (ferric and dichromate ions). HF corrosion can be minimized by complexing the fluoride ion and by passivation of the steel with strong nitric acid. Corrosion caused by corrosion products can be minimized by operating at lower temperatures

In situ synthesis and formation mechanism of ZrC and ZrB2 by combustion synthesis from the Co-Zr-B4C system

Directory of Open Access Journals (Sweden)

Mengxian Zhang

2015-09-01

Full Text Available ZrC-ZrB2-based composites were prepared by combustion synthesis (CS reaction from 10 wt.% to 50 wt.% Co-Zr-B4C powder mixtures. With increasing Co contents, the particle sizes of near-spherical ZrC and platelet-like ZrB2 decreased from 1 μm to 0.5 μm and from 5 μm to 2 μm, respectively. In addition, the formation mechanism of ZrC and ZrB2 was explored by the phase transition and microstructure evolution on the combustion wave quenched sample in combination with differential scanning calorimeter analysis. The results showed that the production of ZrC was ascribed to the solid-solid reaction between Zr and C and the precipitation from the Co-Zr-B-C melt, while ZrB2 was prepared from the saturated liquid. The low B concentration in the Co-Zr-B-C liquid and high cooling rate during the CS process led to the presence of Co2B and ZrCo3B2 in the composites. The addition of Co in the Co-Zr-B4C system not only prevented ZrC and ZrB2 particulates from growing, but also promoted the occurrence of ZrC-ZrB2-forming reaction.

Zr-rich corner of the Zr-Sn-O diagram

International Nuclear Information System (INIS)

Roberti, L.A.; Arias, D.E.

1993-01-01

The understanding of the effect of light elements (in particular oxygen, nitrogen and hydrogen) on the behaviour of alloys for nuclear use is necessary because of its technological importance. The Zr-Sn-O system is perhaps the most representative of all possible ternary systems which can be used to simulate a simplified Zircaloy-type alloy in which the effect of O can be studied. However, in the specialized literature experimental data on phase equilibria and thermophysical properties of this system are not easily found. In the present work, the equilibrium compositions of the α and β phases of the Zr-Sn-O system at temperatures between 1150 and 1323 K are calculated, using the scarce available information. First results of the calculations show satisfactory coincidences with experimental data. Future work will be oriented towards the proposal of isothermal cross-sections calculated by a modelling of phases with wider Sn and O composition ranges, and involving equilibria with the phases Zr 4 Sn, Zr 5 Sn 3 , ZrO 2 , ZrSnO 4 . (Author)

Hf-Nd Isotopes in West Philippine Basin Basalts: Results from International Ocean Discovery Program (IODP) Site U1438 and Implications for the Early History of the Izu-Bonin-Mariana (IBM) Subduction System

Science.gov (United States)

Yogodzinski, G. M.; Hocking, B.; Bizimis, M.; Hickey-Vargas, R.; Ishizuka, O.; Bogus, K.; Arculus, R. J.

2015-12-01

Drilling at IODP Site U1438, located immediately west of Kyushu-Palau Ridge (KPR), the site of IBM subduction initiation, penetrated 1460 m of volcaniclastic sedimentary rock and 150 m of underlying basement. Biostratigraphic controls indicate a probable age for the oldest sedimentary rocks at around 55 Ma (51-64 Ma - Arculus et al., Nat Geosci in-press). This is close to the 48-52 Ma time period of IBM subduction initiation, based on studies in the forearc. There, the first products of volcanism are tholeiitic basalts termed FAB (forearc basalt), which are more depleted than average MORB and show subtle indicators of subduction geochemical enrichment (Reagan et al., 2010 - Geochem Geophy Geosy). Shipboard data indicate that Site U1438 basement basalts share many characteristics with FABs, including primitive major elements (high MgO/FeO*) and strongly depleted incompatible element patterns (Ti, Zr, Ti/V and Zr/Y below those of average MORB). Initial results thus indicate that FAB geochemistry may have been produced not only in the forearc, but also in backarc locations (west of the KPR) at the time of subduction initiation. Hf-Nd isotopes for Site 1438 basement basalts show a significant range of compositions from ɛNd of 7.0 to 9.5 and ɛHf of 14.5 to 19.8 (present-day values). The data define a well-correlated and steep array in Hf-Nd isotope space. Relatively radiogenic Hf compared to Nd indicates an Indian Ocean-type MORB source, but the dominant signature, with ɛHf >16.5, is more radiogenic than most Indian MORB. The pattern through time is from more-to-less radiogenic and more variable Hf-Nd isotopes within the basement section. This pattern culminates in basaltic andesite sills, which intrude the lower parts of the sedimentary section. The sills have the least radiogenic compositions measured so far (ɛNd ~6.6, ɛHf ~13.8), and are similar to those of boninites of the IBM forearc and modern IBM arc and reararc rocks. The pattern within the basement

Possibility of a two-dimensional spin liquid in CePdAl induced by partial geometric frustration?

Energy Technology Data Exchange (ETDEWEB)

Fritsch, V. [Universitaet Augsburg, Institut fuer Physik, Experimentalphysik VI (Germany); Karlsruher Institut fuer Technologie (Germany); Grube, K.; Kittler, W.; Taubenheim, C.; Loehneysen, H. von [Karlsruher Institut fuer Technologie (Germany); Huesges, Z.; Lucas, S.; Stockert, O. [Max-Planck-Institut fuer chemische Physik fester Stoffe, Dresden (Germany); Green, E. [Hochfeldzentrum Dresden-Rossendorf (Germany)

2015-07-01

CePdAl crystallizes in the hexagonal ZrNiAl structure, where the magnetic ions form a distorted kagome lattice. At T{sub N} = 2.7 K the onset of antiferromagnetic (AF) order is observed. Neutron scattering experiments revealed a partial frustration in the distorted kagome planes of this structure: two-thirds of the Ce moments form ferromagnetic chains, which are antiferromagnetically coupled, the remaining third do not participate in any long-range order. Along the c-axis the magnetic moments exhibit an amplitude modulation. Accordingly, the kagome planes are stacked on top of each other, resulting in corrugated AF planes parallel to the c-axis formed by the ordered magnetic moments, which are separated by the frustrated moments. It is an intriguing and yet unresolved question if this third of frustrated moments forms a spin liquid state in CePdAl. Based on measurements of specific heat, thermal expansion, magnetization and electrical resistivity we want to discuss this possibility.

Effect of pH and fluoride on behavior of dental ZrO{sub 2} ceramics in artificial saliva

Energy Technology Data Exchange (ETDEWEB)

Mukaeda, L.E.; Robin, A.; Santos, C.; Taguchi, S.P.; Borges Junior, L.A., E-mail: luizamukaeda@gmail.com, E-mail: alain@demar.eel.usp.br, E-mail: claudinei@demar.eel.usp.br, E-mail: simone@demar.eel.usp.br, E-mail: borges.jr@itelefonica.com.br [Universidade de Sao Paulo (EEL/DEMAR/USP), Lorena, SP (Brazil). Escola de Engenharia; Machado, J.P.B., E-mail: joaopaulo@las.inpe.br [Instituto Nacional de Pesquisas Espaciais (INPE), Sao Jose dos Campos, SP (Brazil)

2009-07-01

A considerable increase in the ceramic products demand occurred due to the evolution of dental restoration techniques and these materials must resist to the complex mouth environment. The pH of saliva can decrease significantly due to the ingestion of acidic foods and beverages and mainly due to reactions occurring during bacteria metabolism that lead to the formation of organic acids. Fluorides are also present in the mouth since fluorides are usually added in drinking water, mouth washes, tooth pastes and gels for the prevention of plaque and caries formation. The combination of low pH and presence of fluorides can lead to the formation of HF and HF{sub 2}{sup -} which are detrimental to metallic and probably to ceramic devices. In this work, commercial blocks of ZrO{sub 2} ceramics (ProtMat Materiais Avancados® and Ivoclar®) were immersed in Fusayama artificial saliva of different pHs and fluoride concentrations. The properties of the as-produced ceramics (crystalline phases (XRD), microstructure (SEM), roughness (3D surface topography AFM) and mechanical resistance - Vickers hardness (Hv) and fracture toughness (KIC) were evaluated. Some of these properties were also determined after the immersion tests as well as the mass variation of the samples in order to evaluate the resistance of these ZrO{sub 2} ceramics to degradation under these conditions. (author)

Separation of zirconium from hafnium by ion exchange

Energy Technology Data Exchange (ETDEWEB)

Felipe, Elaine C.B.; Palhares, Hugo G.; Ladeira, Ana Claudia Q., E-mail: elainecfelipe@yahoo.com.br, E-mail: hugopalhares@gmail.com, E-mail: ana.ladeira@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

2013-07-01

Zirconium and hafnium are two of the most important metals for the nuclear industry. Hafnium occurs in all zirconium ores usually in the range 2 - 3%. However, for the most nuclear industry applications, it is necessary to use a zirconium of extremely pure level. The current work consists in the separation of zirconium and hafnium by the ion exchange method in order to obtain a zirconium concentrate of high purity. The zirconium and hafnium liquors were produced from the leaching of the Zr(OH){sub 4} and Hf(OH){sub 4} with nitric acid for 24 hours. From these two liquors it was prepared one solution containing 7.5 x 10{sup -2} mol L{sup -1} of Zr and 5.8 x 10{sup -3} mol L{sup -1} of Hf with acidity of 1 M. Ion exchange experiments were carried out in batch with the resins Dowex 50WX4, Dowex 50WX8 100, Dowex 50WX8 50, Amberlite IR-120 and Marathon C at constant temperature 28 deg C. Other variables such as, acidity and agitation were kept constant. The data were adjusted to Langmuir equation in order to calculate the maximum loading capacity (q{sub max}) of the resins, the distribution coefficient (K{sub d}) for Zr and Hf and the separation factor (α{sub Hf}{sup Zr} ). The results of maximum loading capacity (q{sub max}) for Zr and Hf, in mmol g{sup -}1, showed that the most suitable resins for columns experiments are: Dowex 50WX4 50 (q{sub max} Z{sub r} = 2.21, Hf = 0.18), Dowex 50WX8 50 (q{sub max} Zr = 1.89, Hf = 0.13) and Amberlite (q{sub max} Zr = 1.64, Hf = 0.12). However, separations factors, α{sub Hf}{sup Zr}, showed that the resins are not selective. (author)

Zirconium tetrafluoride complexing with imidotetraphenyldiphosphinic acid in DMSO. Crystal structure of {ZrF2[Ph2P(O)NP(O)Ph2]2}. Trans effect of fluorine ion

International Nuclear Information System (INIS)

Il'in, E.G.; Kovalev, V.V.; Aleksandrov, G.G.; Shmidpeter, A.; Buslaev, Yu.A.

2000-01-01

The structure of complexes formed during interaction between ZrF 4 and imidotetraphenyldiphosphinic acid (HL) in mixed DMSO-CH 2 Cl 2 solvent (DMSO=dimethylsulfoxide) at temperatures of 218-273 K was studied by the method of 19 F and 31 P NMR. For complex [ZrF 2 L 2 ]·2HF cis configuration was ascertained, which is confirmed by the study of its monocrystals by the method of X-ray diffraction analysis. The revealed non-equivalence of chemical bonds of chelate cycle oxygen atoms in the complex suggests manifestation of trans-effect by fluorine ion [ru

Various magnetic behaviors of the hydrides deriving from the tetragonal CeFeSi-type compounds

International Nuclear Information System (INIS)

Chevalier, B.; Tence, S.; Gaudin, E.; Matar, S.F.; Bobet, J.-L.

2009-01-01

The hydrides RETXH (RE = rare earth, T = transition metal and X = Si, Ge) crystallizing in the tetragonal ZrSiCuAs-type are obtained by hydrogen absorption of the intermetallics adopting the tetragonal CeFeSi-type. The H-insertion induces interesting magnetic transitions governed by two effects: the increase of the unit cell volume linked to the H-absorption and the occurrence of the RE-H chemical bonding. Some typical examples are reported in this present brief review.

Orientation control and domain structure analysis of {100}-oriented epitaxial ferroelectric orthorhombic HfO{sub 2}-based thin films

Energy Technology Data Exchange (ETDEWEB)

Katayama, Kiliha [Department of Innovative and Engineered Materials, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Shimizu, Takao [Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan); Sakata, Osami [Synchrotron X-ray Station at SPring-8, National Institute for Materials Science (NIMS), 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); Shiraishi, Takahisa; Nakamura, Shogo; Kiguchi, Takanori; Akama, Akihiro; Konno, Toyohiko J. [Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Uchida, Hiroshi [Department of Materials and Life Sciences, Sophia University, Chiyoda, Tokyo 102-8554 (Japan); Funakubo, Hiroshi, E-mail: funakubo.h.aa@m.titech.ac.jp [Department of Innovative and Engineered Materials, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)

2016-04-07

Orientation control of {100}-oriented epitaxial orthorhombic 0.07YO{sub 1.5}-0.93HfO{sub 2} films grown by pulsed laser deposition was investigated. To achieve in-plane lattice matching, indium tin oxide (ITO) and yttria-stabilized zirconia (YSZ) were selected as underlying layers. We obtained (100)- and (001)/(010)-oriented films on ITO and YSZ, respectively. Ferroelastic domain formation was confirmed for both films by X-ray diffraction using the superlattice diffraction that appeared only for the orthorhombic symmetry. The formation of ferroelastic domains is believed to be induced by the tetragonal–orthorhombic phase transition upon cooling the films after deposition. The present results demonstrate that the orientation of HfO{sub 2}-based ferroelectric films can be controlled in the same manner as that of ferroelectric films composed of conventional perovskite-type material such as Pb(Zr, Ti)O{sub 3} and BiFeO{sub 3}.

Elemental analysis of soil and hair sample by instrumental neutron activation analysis

International Nuclear Information System (INIS)

Chung, Yong Sam; Quraishi, Shamshad Begum; Moon, Jong Hwa; Kim, Sun Ha; Baek, Sung Yeoil; Kang, Sang Hoon; Lim, Jong Myoung; Cho, Hyun Je; Kim, Young Jin

2004-03-01

Myanmar soil sample was analyzed by using the instrumental neutron activation analysis. The elemental concentrations in the sample, altogether 34 elements, Al As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Ga, Gd, Hf, Ir, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Yb, Zn and Zr were determined. The concentration of 17 elements (Al, Au, Br, Ca, Cl, Cr, Cu, Co, Fe, Hg, K, Na, Mn, Mg, Sb, Se, Zn) in human hair samples were determined by INAA For quality control of analytical method, certified reference material was used

Elemental analysis of soil and hair sample by instrumental neutron activation analysis

Energy Technology Data Exchange (ETDEWEB)

Chung, Yong Sam; Quraishi, Shamshad Begum; Moon, Jong Hwa; Kim, Sun Ha; Baek, Sung Yeoil; Kang, Sang Hoon; Lim, Jong Myoung; Cho, Hyun Je; Kim, Young Jin

2004-03-01

Myanmar soil sample was analyzed by using the instrumental neutron activation analysis. The elemental concentrations in the sample, altogether 34 elements, Al As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Ga, Gd, Hf, Ir, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Yb, Zn and Zr were determined. The concentration of 17 elements (Al, Au, Br, Ca, Cl, Cr, Cu, Co, Fe, Hg, K, Na, Mn, Mg, Sb, Se, Zn) in human hair samples were determined by INAA For quality control of analytical method, certified reference material was used.

Enthalpy of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys

International Nuclear Information System (INIS)

Witusiewicz, V.T.; Sommer, F.

2000-01-01

Since the Al-Cu-Ni-Zr system is a basis for the production of bulk amorphous materials by rapid solidification techniques from the liquid state, it is of great scientific interest to determine the partial and the integral thermodynamic functions of liquid and undercooled liquid alloys. Such data, as was pointed out previously, are important in order to understand their extremely good glass-forming ability in multicomponent metallic systems as well as for processing improvements. In order to measure the thermodynamic properties of the Al-Cu-Ni-Zr quaternary, it is necessary to have reliable thermochemical data for its constituent canaries and ternaries first. In a series of articles, the authors have reported in detail the thermodynamic properties of liquid Al-Cu, Al-Ni, Cu-Ni, Cu-Zr, Al-Zr, Al-Cu-Ni, and Al-Cu-Zr alloys. This article deals with the direct calorimetric measurements of the partial and the integral enthalpies of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys and the heat capacity of liquid Ni 26 Zr 74 . In a subsequent article, the authors will present similar data for the liquid ternary Al-Ni-Zr and for the liquid quaternary Al-Cu-Ni-Zr alloys

Recovery Ce from Ce - TBP Used Oxalic Acid

International Nuclear Information System (INIS)

Purwani, MV; Subagiono, R.; Suyanti

2007-01-01

Recovery or stripping Ce from Ce - TBP product of monazite sand used oxalic acid. Ce - TBP as organic phase and oxalic acid as aqueous phase and as strong precipitant compound to precipitate metal element. The stripping product as Ce - oxalic precipitate. The influence parameter were percentage of oxalic acid, volume ratio of Ce-TBP with oxalic acid, time and rate of stripping. At stripping of 25 ml Ce - TBP used oxalic acid, the optimum condition were achieve at using 5% oxalic acid, volume ratio of Ce - TBP : 5% oxalic acid = 1 : 1, time of stripping 7.5 minute and rate of stripping 150 rpm. At the optimum condition was obtained the recovery efficiency was 100%. (author)