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

PubMed Central

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

2009-01-01

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

Palladium-doped-ZrO2-multiwalled carbon nanotubes nanocomposite: an advanced photocatalyst for water treatment

NASA Astrophysics Data System (ADS)

Anku, William Wilson; Oppong, Samuel Osei-Bonsu; Shukla, Sudheesh Kumar; Agorku, Eric Selorm; Govender, Poomani Penny

2016-06-01

The photocatalytic degradation of organic pollutants from water using palladium-doped-zirconium oxide-multiwalled carbon nanotubes (Pd-ZrO2-MWCNTs) nanocomposites is presented. A series of Pd doped-ZrO2-MWCNTs nanocomposites with varying percentage compositions of Pd were prepared by the homogenous co-precipitation method. The photocatalytic applicability of the materials was investigated by the degradation of acid blue 40 dye in water under simulated solar light. The optical, morphological and structural properties of the nanocomposites were evaluated using X-ray powder diffraction, Fourier transformer infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, BET surface area analysis and (UV-Vis) spectroscopy. The Pd-ZrO2-MWCNTs nanocomposites showed enhanced photocatalytic activity toward the degradation of the acid blue 40 dye under visible light compared with bare ZrO2 and ZrO2-MWCNTs alone. The remarkable photocatalytic activity of Pd-ZrO2-MWCNTs nanocomposites in the visible light makes it an ideal photocatalyst for the removal of organic pollutants in water. The 0.5 % Pd-ZrO2-MWCNT was the most efficient photocatalyst with 98 % degradation after 3 h with corresponding K a and band gap values of 16.8 × 10-3 m-1 and 2.79 eV, respectively.

Isotopic composition of a sample enriched in 93Zr

DOE PAGES

Fujii, Toshiyuki; Hori, Jun-ichi; Du, Miting; ...

2015-10-22

A project to determine the neutron-capture cross section of long lived fission products and minor actinides has been started by using a beam-line at Japan Proton Accelerator Research Complex (J-PARC). We prepared one of the target nuclides is Zr-93, which in Oak Ridge National Laboratory. Qualitative and quantitative analyses on the sample were performed at Kyoto University. The isotopic composition of (m) Zr (m 90, 91, 92, 93, 94, and 96) was precisely determined by multi-collector thermal ionization mass spectrometry with < 0.1 % of 2 sigma uncertainty. We determined that the atomic abundance of Zr-93 in the sample tomore » be 18.86 ± A 0.05 %.« less

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

PubMed

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

2016-08-03

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

Technological developments for strontium-90 determination using AMS

NASA Astrophysics Data System (ADS)

Satou, Yukihiko; Sueki, Keisuke; Sasa, Kimikazu; Matsunaka, Tetsuya; Takahashi, Tsutomu; Shibayama, Nao; Izumi, Daiki; Kinoshita, Norikazu; Matsuzaki, Hiroyuki

2015-10-01

Accelerator mass spectrometry (AMS) is one of method used for 90Sr determination. It would enable rapid 90Sr measurements from environmental samples such as water, soil, and milk. However, routine analysis of 90Sr using AMS has not yet been achieved because of difficulties associated with isobaric separation and production of intense negative ion beams characterized by currents from hundreds of nanoamperes to several microamperes. We have developed a rapid procedure for preparing samples with optimum compositions for use with AMS, which enables production of intense Sr beam currents from an ion source. Samples of SrF2 were prepared from a standard Sr solution and agricultural soil. The time required to prepare a SrF2 sample from a soil sample was 10 h. Negative 88SrF3- ions were successfully extracted at 500 nA from mixed samples of SrF2 and PbF2. In the present work, negative ions of 90Zr, included as an impurity, were accelerated with a tandem accelerator operated at a terminal voltage of 5 MV. Ions characterized by a charge state of 6+ were channeled into a gas counter. An atomic ratio of 90Zr/88Sr of 3 × 10-8 was estimated for the soil sample. No signal was detected from the assay of PbF2, which was pressed in an aluminum cathode, for a mass number of 90. PbF2 revealed good performance in the production of negative SrF3- molecular ion beams and detection of 90Sr with a gas counter.

a Novel Catalyst for Reductive Dechlorination of Chlorobenzene in Subcritical Water:. Bifunctional Fe/ZrO2

NASA Astrophysics Data System (ADS)

Wei, Guang-Tao; Wei, Chao-Hai; He, Feng-Mei; Wu, Chao-Fei

Bifunctional Fe/ZrO2 was prepared by mechanical mixing method, and its bifunctional effect on reductive dechlorination of chlorobenzene in subcritical water was studied. Dechlorination efficiency increased with increasing iron content in catalyst and catalyst amount. Dechlorination efficiency slowed when the iron content in catalyst reached 30%; bifunctional catalyst of Fe/ZrO2 was more efficient in dechlorination of chlorobenzene than Fe alone. Catalyst of Fe (30%)/ZrO2 was characterized by means of X-ray diffraction (XRD), H2 temperature programmed desorption (H2-TPD), and N2 adsorption. The possible mechanism of dechlorination in subcritical water by this bifunctional catalyst was proposed. H+ produced in the water dissociation formed the highly reactive spillover hydrogen on the surface of catalyst, and then reacted with chlorobenzene adsorbed on the catalyst surface by ZrO2 to form benzene and chloride ions.

Highly effective removal of heavy metals by polymer-based zirconium phosphate: a case study of lead ion.

PubMed

Pan, B C; Zhang, Q R; Zhang, W M; Pan, B J; Du, W; Lv, L; Zhang, Q J; Xu, Z W; Zhang, Q X

2007-06-01

Zirconium phosphate (ZrP) has recently been demonstrated as an excellent sorbent for heavy metals due to its high selectivity, high thermal stability, and absolute insolubility in water. However, it cannot be readily adopted in fixed beds or any other flowthrough system due to the excessive pressure drop and poor mechanical strength resulting from its fine submicrometer particle sizes. In the present study a hybrid sorbent, i.e., polymer-supported ZrP, was prepared by dispersing ZrP within a strongly acidic cation exchanger D-001 and used for enhanced lead removal from contaminated waters. D-001 was selected as a host material for sorbent preparation mainly because of the Donnan membrane effect resulting from the nondiffusible negatively charged sulfonic acid group on the exchanger surface, which would enhance permeation of the targeted metal ions. The hybrid sorbent (hereafter denoted ZrP-001) was characterized using a nitrogen adsorption technique, scanning electron microscope (SEM), and X-ray diffraction (XRD). Lead sorption onto ZrP-001 was found to be pH dependent due to the ion-exchange mechanism, and its sorption kinetics onto ZrP-001 followed the pseudo-first-order model. Compared to D-001, ZrP-001 exhibited more favorable lead sorption particularly in terms of high selectivity, as indicated by its substantially larger distribution coefficients when other competing cations Na(+), Ca(2+), and Mg(2+) coexisted at a high level in solution. Fixed-bed column runs showed that lead sorption on ZrP-001 resulted in a conspicuous decrease of this toxic metal from 40 mg/L to below 0.05 mg/L. By comparison with D-001 and ZrP-CP (ZrP dispersion within a neutrally charged polymer CP), enhanced removal efficiency of ZrP-001 resulted from the Donnan membrane effect of the host material D-001. Moreover, its feasible regeneration by diluted acid solution and negligible ZrP loss during operation also helps ZrP-001 to be a potential candidate for lead removal from water. Thus, all the results suggested that ZrP-001 offers excellent potential for lead removal from contaminated water.

Pickering emulsions stabilized by a metal-organic framework (MOF) and graphene oxide (GO) for producing MOF/GO composites.

PubMed

Zhang, Fanyu; Liu, Lifei; Tan, Xiuniang; Sang, Xinxin; Zhang, Jianling; Liu, Chengcheng; Zhang, Bingxing; Han, Buxing; Yang, Guanying

2017-10-18

Herein we demonstrate the formation of a novel kind of Pickering emulsion that is stabilized by a Zr-based metal-organic framework (Zr-MOF) and graphene oxide (GO). It was found that the Zr-BDC-NO 2 and GO solids assembling at the oil/water interface can effectively stabilize the oil droplets that are dispersed in the water phase. Such a Pickering emulsion offers a facile route for fabricating Zr-MOF/GO composite materials. After removing water and oil by freeze drying from Pickering emulsions, the Zr-MOF/GO composites were obtained and their morphologies, structures and interaction properties were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectrometry, respectively. The influences of the concentration of GO and Zr-MOF on the emulsion microstructures and the properties of the MOF/GO composites were studied. Based on experimental results, the mechanisms for the emulsion formation by Zr-MOF and GO and the as-synthesized superstructures of the Zr-MOF/GO composite were proposed. It is expected that this facile and tunable route can be applied to the synthesis of different kinds of MOF-based or GO-based composite materials.

Phase transition, crystal water and low thermal expansion behavior of Al{sub 2−2x}(ZrMg){sub x}W{sub 3}O{sub 12}·n(H{sub 2}O)

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

Li, Fang; Liu, Xiansheng; Song, Wenbo

2014-10-15

Al{sub 2−2x}(ZrMg){sub x}W{sub 3}O{sub 12} for 0≤x≤1.0 are synthesized to reduce the phase transition temperature of Al{sub 2}W{sub 3}O{sub 12}. It is found that the incorporation of (ZrMg){sup 6+} into the lattice of Al{sub 2}W{sub 3}O{sub 12} not only reduces its orthorhombic-to-monoclinic phase transition temperature but also elevates its softening temperature, broadening its applicable temperature range considerably. Al{sub 2−2x}(ZrMg){sub x}W{sub 3}O{sub 12} with x<0.5 exhibit low coefficients of thermal expansion (CTEs) and non-hygroscopicity, while those for x≥0.7 are obviously hygroscopic and the CETs decrease with increasing the content of (ZrMg){sup 6+} so that Al{sub 0.2}(ZrMg){sub 0.9}W{sub 3}O{sub 12} and ZrMgW{submore » 3}O{sub 12} exhibit negative thermal expansion. Temperature-dependent Raman spectroscopic study shows the hardening of W–O bonds above 373 K which is attributed to the release of crystal water. The effect of crystal water on the thermal expansion property is discussed based on the hydrogen bond between H in crystal water and electronegative O in Al(ZrMg)–O–W linkages. - Graphical abstract: (a and b) Temperature dependent Raman spectra of Al{sub 2−x}(ZrMg){sub x}W{sub 3}O{sub 12} (x=0.1, 0.2), (c and d) Building block of a unit cell of Al{sub 2−x}(ZrMg){sub x}W{sub 3}O{sub 12}·n(H{sub 2}O) and schematic showing the effect of crystal water on Al(Zr, Mg)–O–W linkages. - Highlights: • (ZrMg){sup 6+} reduces orthorhombic-to-monoclinic phase transition of Al{sub 2}W{sub 3}O{sub 12}. • The incorporation of (ZrMg){sup 6+} elevates the softening temperature of Al{sub 2}W{sub 3}O{sub 12}. • Al{sub 2−2x}(ZrMg){sub x}W{sub 3}O{sub 12} (x<0.5) exhibit low CTEs and non-hygroscopicity. • Al{sub 0.2}(ZrMg){sub 0.9}W{sub 3}O{sub 12}·0.8H{sub 2}O and ZrMgW{sub 3}O{sub 12}·2H{sub 2}O present NTE. • Hydrogen bond between H in H{sub 2}O and O in Al(ZrMg)–O–W affects thermal expansion.« less

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Accelerated development of Zr-containing new generation ferritic steels for advanced nuclear reactors

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

Tan, Lizhen; Yang, Ying; Sridharan, K.

2015-12-01

The mission of the Nuclear Energy Enabling Technologies (NEET) program is to develop crosscutting technologies for nuclear energy applications. Advanced structural materials with superior performance at elevated temperatures are always desired for nuclear reactors, which can improve reactor economics, safety margins, and design flexibility. They benefit not only new reactors, including advanced light water reactors (LWRs) and fast reactors such as the sodium-cooled fast reactor (SFR) that is primarily designed for management of high-level wastes, but also life extension of the existing fleet when component exchange is needed. Developing and utilizing the modern materials science tools (experimental, theoretical, and computationalmore » tools) is an important path to more efficient alloy development and process optimization. The ultimate goal of this project is, with the aid of computational modeling tools, to accelerate the development of Zr-bearing ferritic alloys that can be fabricated using conventional steelmaking methods. The new alloys are expected to have superior high-temperature creep performance and excellent radiation resistance as compared to Grade 91. The designed alloys were fabricated using arc-melting and drop-casting, followed by hot rolling and conventional heat treatments. Comprehensive experimental studies have been conducted on the developed alloys to evaluate their hardness, tensile properties, creep resistance, Charpy impact toughness, and aging resistance, as well as resistance to proton and heavy ion (Fe 2+) irradiation.« less

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

NASA Astrophysics Data System (ADS)

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

2004-01-01

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

Adsorption of phosphate in water using one-step synthesized zirconium-loaded reduced graphene oxide

NASA Astrophysics Data System (ADS)

Luo, Xin; Wang, Xiurong; Bao, Shaopan; Liu, Xiawei; Zhang, Weicheng; Fang, Tao

2016-12-01

In this account, a one-step green hydrothermal method for zirconium-loaded reduced graphene oxide (RGO-Zr) adsorbent was developed in pure water. It is based on the formation of initially strong-coupling RGO-Zr nanocomposites followed by in situ reduction of GO to RGO during the hydrothermal treatment. The phosphate adsorption performance of the as-prepared nanocomposites was investigated in aqueous environment under various conditions. The characterization results of RGO-Zr nanocomposites showed that ZrO2 was successfully integrated onto the RGO sheets in amorphous. The data from equilibrium phosphate adsorption on RGO-Zr revealed that the adsorption kinetics followed a pseudo-second-order kinetic model, where the adsorption isotherm fitted the Langmuir isotherm model with a maximum adsorption capacity of 27.71 mg P/g at pH 5 and 298 K. The improved phosphate adsorption on RGO-Zr was caused by the dispersion of ZrO2 on the RGO surface. Furthermore, the phosphate adsorption was found insensitive to the increase in pH while it was sensitive to the increase in temperature. The coexisting anions of SO42-, F-, Cl-, NO3- and CO32- affected the phosphate adsorption in a different way. Results suggest that the present RGO-Zr adsorbent has the potential for controlling phosphorus pollution in water.

Fourier Transform IR Spectroscopic Study of Nano-ZrO2 + Nano-SiO2 + Nano-H2O Systems Upon the Action of Gamma Radiation

NASA Astrophysics Data System (ADS)

Agayev, T. N.; Gadzhieva, N. N.; Melikova, S. Z.

2018-05-01

The radiation decomposition of water in a nano-ZrO2 + nano-SiO2 + H2O system at 300 K by the action of gamma radiation has been studied by Fourier transform IR spectroscopy. Water adsorption in the zirconium and silicon nanooxides is attributed to molecular and dissociative mechanisms. Active intermediates in this radiation-induced heterogeneous decomposition of water were detected including zirconium and silicon hydrides and hydroxyl groups. Variation in the ratio of ZrO2 and SiO2 nanopowders was shown to lead to change in their radiation catalytic activity compared to initial ZrO2.

Effects of Zr/Ce molar ratio and water content on thermal stability and structure of ZrO{sub 2}–CeO{sub 2} mixed oxides prepared via sol–gel process

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

Huang, Wenzhi; Yang, Jili; Wang, Chunjie

2012-09-15

Highlights: ► Tetragonal t″ phase was stabilized in Zr{sub 0.5}Ce{sub 0.5}O{sub 2} solid solution at temperature as high as 1000 °C. ► Specific surface area of powders decreased with the increase of water addition and the Ce content. ► The single stable phase was controlled by adjusting the volume ratio of water and ethanol. ► Tetragonal (t″) phase dissociated into cubic and tetragonal (t′) phases at 1200 °C. -- Abstract: ZrO{sub 2}–CeO{sub 2} mixed oxides were synthesized via sol–gel process. Thermal stability, structure and morphology of samples were investigated by powder X-ray diffraction, FT-Raman spectroscopy, X-ray photoelectron spectroscopy and scanningmore » electron microscopy. In this approach, the solvent composition and Zr/Ce molar ratio have great influences on the structure and morphology of final products. With decreasing water content in the mixed solvent, specific surface area of powders increased and the single tetragonal phase was obtained. Only when the volume ratio of water and ethanol and the Zr/Ce molar ratio were 1:1, tetragonal t″-Zr{sub 0.5}Ce{sub 0.5}O{sub 2} could be stabilized in powders at temperature as high as 1000 °C. Meanwhile, tetragonal (t′) and (t″) phases coexisted in Zr{sub 0.5}Ce{sub 0.5}O{sub 2} solid solution without peak splitting after calcination at 1100 °C, further transforming into cubic and tetragonal (t′) phases at 1200 °C. The effective activation energy for Zr{sub 0.5}Ce{sub 0.5}O{sub 2} nanocrystallite growth during annealing is about 5.24 ± 0.15 kJ/mol.« less

Fluoride glass starting materials - Characterization and effects of thermal treatment

NASA Technical Reports Server (NTRS)

Chen, William; Dunn, Bruce; Shlichta, Paul; Neilson, George F.; Weinberg, Michael C.

1987-01-01

The production of heavy metal fluoride (HMF) glasses, and the effects of thermal treatments on the HMF glasses are investigated. ZrF4, BaF2, AlF3, LaF3, and NaF were utilized in the synthesis of zirconium-barium-lanthanum-aluminum-sodium fluoride glass. The purity of these starting materials, in particular ZrF4, is evaluated using XRD analysis. The data reveal that low temperature heating of ZrF4-H2O is effective in removing the water of hydration, but causes the production of ZrF4 and oxyfluorides; however, dehydration followed by sublimation results in the production of monoclinic ZrFe without water or oxyfluoride contaminants.

Microstructural characterization and mechanical properties of Excel alloy pressure tube material

NASA Astrophysics Data System (ADS)

Sattari, Mohammad

Microstructural characterization and mechanical properties of Excel (Zr-3.5%Sn-0.8%Mo-0.8%Nb), a dual phase alphaZr -hcp and betaZr-bcc pressure tube material, is discussed in the current study which is presented in manuscript format. Chapter 3 discusses phase transformation temperatures using different techniques such as quantitative metallography, differential scanning calorimetry (DSC), and electrical resistivity. It was found that the alphaZr → alphaZr+beta Zr and alphaZr+betaZr → betaZr transformation temperatures are in the range of 600-690°C and 960-970°C respectively. Also it was observed that upon quenching from temperatures below ˜860°C the martensitic transformation of betaZr to alpha'--hcp is halted and instead the microstructure transforms into retained Zr with o hexagonal precipitates inside betaZr grains. Chapter 4 deals with aging response of Excel alloy. Precipitation hardening was observed in samples water-quenched from high in the alphaZr+beta Zr or betaZr regions followed by aging. The optimum aging conditions were found to be 450°C for 1 hour. Transmission electron microscopy (TEM) showed dispersion of fine precipitates (˜10nm) inside the martensitic phase. Energy dispersive X-ray spectroscopy (EDS) showed the chemical composition of precipitates to be Zr-30wt%Mo-25wt%Nb-2wt%Fe. Electron crystallography using whole pattern symmetry of the convergent beam electron diffraction (CBED) patterns together with selected area diffraction (SAD) polycrystalline ring patterns, suggests the -6m2 point group for the precipitates belonging to hexagonal crystal structure, with a= 2.936 A and c=4.481 A, i.e. c/a =1.526. Crystallographic texture and high temperature tensile properties as well as creep-rupture properties of different microstructures are discussed in Chapter 5. Texture analysis showed that solution treatment high in the alpha Zr+betaZr or betaZr regions followed by water quenching or air cooling results in a more random texture compared to typical pressure tube texture. Variant selection was observed upon water quenching while partial memory effect and some transformation texture with variant selection was observed in the air-cooled sample. The results of creep-rupture tests suggest that fully martensitic and aged microstructure has better creep properties at high stress levels (>700 MPa) while the microstructure from air cooling from high in the alphaZr+betaZr region is less sensitive to stress and shows better creep properties compared to the as-received annealed microstructure at lower stresses (<560 MPa).

Explosive and pyrotechnic aging demonstration

NASA Technical Reports Server (NTRS)

Rouch, L. L., Jr.; Maycock, J. N.

1976-01-01

The survivability was experimentally verified of fine selected explosive and pyrotechnic propellant materials when subjected to sterilization, and prolonged exposure to space environments. This verification included thermal characterization, sterilization heat cycling, sublimation measurements, isothermal decomposition measurements, and accelerated aging at a preselected elevated temperature. Temperatures chosen for sublimation and isothermal decomposition measurements were those in which the decomposition processess occurring would be the same as those taking place in real-time aging. The elevated temperature selected (84 C) for accelerated aging was based upon the parameters calculated from the kinetic data obtained in the isothermal measurement tests and was such that one month of accelerated aging in the laboratory approximated one year of real-time aging at 66 C. Results indicate that HNS-IIA, pure PbN6, KDNBF, and Zr/KC10 are capable of withstanding sterilization. The accelerated aging tests indicated that unsterilized HNS-IIA and Zr/KC104 can withstand the 10 year, elevated temperature exposure, pure PbN6 and KDNBF exhibit small weight losses (less than 2 percent) and B/KC104 exhibits significant changes in its thermal characteristics. Accelerated aging tests after sterilization indicated that only HNS-IIA exhibited high stability.

Physical properties of ZrC/Al2O3 imbedded heat storage woven fabrics

NASA Astrophysics Data System (ADS)

Kim, S. J.; Song, M. K.; Seo, K. O.; Kim, H. A.

2017-10-01

This study investigated different physical properties of ZrC/Al2O3 imbedded heat storage woven fabrics. ZrC and Al2O3 imbedded heat storage PET filaments were spun on the pilot spinning equipment, respectively. Various physical properties of ceramic imbedded fabrics made of ZrC and Al2O3 imbedded filaments were measured and compared with those of the regular PET woven fabric. The surface temperatures of the ZrC and Al2O3 imbedded fabrics were higher than that of the regular fabric. Water absorption rate of ceramic imbedded fabrics was better than that of the regular fabric and drying property was inferior to that of regular fabric. Breathability by water vapour resistance(Ref) of ZrC imbedded fabric was superior to that of regular fabric. Heat keepability rates of the ceramic imbedded fabrics were higher than that of the regular fabrics, which revealed a good heat storage property of the ZrC/Al2O3 imbedded fabrics.

Solution treatment-delayed zirconium-strengthening behavior in Ti-7.5Mo-xZr alloy system

NASA Astrophysics Data System (ADS)

Chern Lin, Jiin-Huey; Fu, Yen-Han; Chen, Yen-Chun; Peng, Yu-Po; Ju, Chien-Ping

2018-01-01

The present study was devoted to investigate and compare the Zr-strengthening behavior in as-cast (AC) and solution-treated (ST) Ti-7.5Mo-xZr alloys. The experimental results indicated that AC Ti-7.5Mo and AC Ti-7.5Mo-1Zr alloys substantially had an orthorhombic {α }\\prime\\prime phase with a fine, acicular morphology. The content of equi-axed β phase continued to increase with increased Zr content at the expense of {α }\\prime\\prime phase. The threshold Zr content for the formation of β phase in the ST Ti-7.5Mo-xZr alloys was apparently higher than that in the AC Ti-7.5Mo-xZr alloys. The β granular structure was revealed in ST Ti-7.5Mo-5Zr alloy, which increased with increased Zr content. Unlike AC Ti-7.5Mo-9Zr alloy, within each grain of ST Ti-7.5Mo-9Zr alloy were still observed a significant portion of {α }\\prime\\prime morphology. AC Ti-7.5Mo alloy had the lowest YS, lowest tensile modulus and highest elongation among all AC Ti-7.5Mo-xZr alloys. When Zr content increased, both YS and modulus significantly increased while the elongation significantly decreased. Compared to AC Ti-7.5Mo alloy, AC Ti-7.5Mo-9Zr alloy had almost double YS, indicating the effectiveness of Zr-induced strengthening in the AC Ti-7.5Mo-xZr alloys. Compared to AC Ti-7.5Mo, ST Ti-7.5Mo alloys had lower YS, UTS and tensile modulus with almost the same elongation. All the XRD, metallography and tensile test results consistently indicated that the presence of Zr could accelerate the formation of β phase and effectively strengthen the AC Ti-7.5Mo-xZr alloys. A phenomenon of delayed β formation and delayed strengthening was noted in the ST Ti-7.5Mo-xZr alloys, compared to the AC Ti-7.5Mo-xZr alloys.

Development of Ultra-high Purity (UHP) Fe-Based Alloys with High Creep and Oxidation Resistance for A-USC Technology

NASA Astrophysics Data System (ADS)

Hamdani, Fethi; Das, Nishith K.; Shoji, Tetsuo

2018-06-01

The design of ultra-high purity (UHP) Fe-based model alloys for advanced ultra-supercritical (A-USC) technology is attempted in this work. Creep testing has been performed in air at 700 °C and a stress level of 150 MPa. Analysis of the fracture surface and cross section of the crept specimen was performed. To evaluate the oxidation resistance in A-USC conditions, oxidation testing was performed in supercritical water (SCW) at 700 °C and 25 MPa. Weight gain (WG) measurements and meticulous characterization of the oxide scale were carried out. Based on thermodynamics and density functional theory calculations, some reactive elements in the Fe-Cr-Ni system were designated to promote precipitation strengthening and to improve the hydrogen-accelerated oxidation resistance. The addition of a 2 wt pct Mo into Fe-22Cr-22Ni-0.6Nb wt pct-based matrix did not significantly improve the creep resistance. The addition of 0.26 wt pct Zr coupled with cold working was effective for improving creep properties. The Mo-modified model alloy showed almost the same WG value as SUS310, while the Zr-modified alloy showed a higher WG value. Meanwhile, a Cr-enriched continuous oxide layer was formed at the oxidation front of the Zr-modified alloy and SUS310S after exposure to SCW conditions.

Development of Ultra-high Purity (UHP) Fe-Based Alloys with High Creep and Oxidation Resistance for A-USC Technology

NASA Astrophysics Data System (ADS)

Hamdani, Fethi; Das, Nishith K.; Shoji, Tetsuo

2018-03-01

The design of ultra-high purity (UHP) Fe-based model alloys for advanced ultra-supercritical (A-USC) technology is attempted in this work. Creep testing has been performed in air at 700 °C and a stress level of 150 MPa. Analysis of the fracture surface and cross section of the crept specimen was performed. To evaluate the oxidation resistance in A-USC conditions, oxidation testing was performed in supercritical water (SCW) at 700 °C and 25 MPa. Weight gain (WG) measurements and meticulous characterization of the oxide scale were carried out. Based on thermodynamics and density functional theory calculations, some reactive elements in the Fe-Cr-Ni system were designated to promote precipitation strengthening and to improve the hydrogen-accelerated oxidation resistance. The addition of a 2 wt pct Mo into Fe-22Cr-22Ni-0.6Nb wt pct-based matrix did not significantly improve the creep resistance. The addition of 0.26 wt pct Zr coupled with cold working was effective for improving creep properties. The Mo-modified model alloy showed almost the same WG value as SUS310, while the Zr-modified alloy showed a higher WG value. Meanwhile, a Cr-enriched continuous oxide layer was formed at the oxidation front of the Zr-modified alloy and SUS310S after exposure to SCW conditions.

Microemulsion and Sol-Gel Synthesized ZrO₂-MgO Catalysts for the Liquid-Phase Dehydration of Xylose to Furfural.

PubMed

Parejas, Almudena; Montes, Vicente; Hidalgo-Carrillo, Jesús; Sánchez-López, Elena; Marinas, Alberto; Urbano, Francisco J

2017-12-18

Two series of catalysts were prepared by sol-gel and microemulsion synthetic procedure (SG and ME, respectively). Each series includes both pure Mg and Zr solids as well as Mg-Zr mixed solids with 25%, 50% and 75% nominal Zr content. The whole set of catalysts was characterized from thermal, structural and surface chemical points of view and subsequently applied to the liquid-phase xylose dehydration to furfural. Reactions were carried out in either a high-pressure autoclave or in an atmospheric pressure multi-reactor under a biphasic (organic/water) reaction mixture. Butan-2-ol and toluene were essayed as organic solvents. Catalysts prepared by microemulsion retained part of the surfactant used in the synthetic procedure, mainly associated with the Zr part of the solid. The MgZr-SG solid presented the highest surface acidity while the Mg3Zr-SG one exhibited the highest surface basicity among mixed systems. Xylose dehydration in the high-pressure system and with toluene/water solvent mixture led to the highest furfural yield. Moreover, the yield of furfural increases with the Zr content of the catalyst. Therefore, the catalysts constituted of pure ZrO₂ (especially Zr-SG) are the most suitable to carry out the process under study although MgZr mixed solids could be also suitable for overall processes with additional reaction steps.

Accumulation of zirconium phosphate by a Serratia sp.: a benign system for the removal of radionuclides from aqueous flows.

PubMed

Mennan, Claire; Paterson-Beedle, Marion; Macaskie, Lynne E

2010-10-01

Metal phosphate deposited enzymatically on Serratia sp. has been used successfully for the removal of radionuclides from aqueous flows. Previous studies using biogenic hydrogen uranyl phosphate (HUP) on Serratia sp. biofilm showed removal of 100% of (90)Sr, (137)Cs, and (60)Co via their intercalation into biogenic HUP crystals. Zirconium phosphates (ZrP) offer a potential non-toxic and non-radioactive alternative to HUP for water decontamination. A method was developed for biomanufacturing ZrP. Biogenic ZrP removed ca. 100% of Sr(2+) and Co(2+) (0.5 mM) from solutions to a molar ratio at saturation of ca. 1:0.6 for both Zr:Sr and Zr:Co. The potential for drinking water decontamination via bio-ZrP is discussed with respect to bio-HUP and also other commercially available materials.

Influences of multiple firings and aging on surface roughness, strength and hardness of veneering ceramics for zirconia frameworks.

PubMed

Tang, Xuehua; Luo, Huinan; Bai, Yang; Tang, Hui; Nakamura, Takashi; Yatani, Hirofumi

2015-09-01

To evaluate the effects of multiple firings and aging on surface roughness, strength, and hardness of veneering ceramics for zirconia frameworks. Five different veneering ceramics for zirconia frameworks were used: Vintage ZR (ZR), Cerabien ZR (CZR), VitaVM9 (VM9), Cercon ceram KISS (KISS), and IPS e.max ceram (e.max). Specimens were fired 2 or 10 times in order to accelerate aging. Surface roughness was evaluated using laser profilometry. Flexural strength and Vickers hardness were also measured. Surface topography was observed using scanning electron microscopy. After accelerated aging, the surface roughness of all specimens fired 10 times was significantly lower than that of the same specimens fired 2 times (P=0.000). Except for VM9, the flexural strength of all specimens fired 10 times was greater than that of the same specimens fired 2 times, and the differences were significant for ZR and CZR (P<0.01). The flexural strength of VM9 fired 10 times was significantly lower than that of VM9 fired 2 times (P=0.034). The Vickers hardness of ZR and VM9 fired 10 times was significantly higher than that of the same specimens fired 2 times (P<0.05), but that of KISS fired 10 times was significantly lower than that of KISS fired 2 times (P=0.000). Multiple firings had a positive effect on the surface roughness of all aged veneering ceramics used for zirconia restorations and on the strength and hardness of many aged veneering ceramics used for zirconia restorations. Copyright © 2015 Elsevier Ltd. All rights reserved.

Heterophase-structured nanocrystals as superior supports for Ru-based catalysts in selective hydrogenation of benzene

PubMed Central

Peng, Zhikun; Liu, Xu; Li, Shuaihui; Li, Zhongjun; Li, Baojun; Liu, Zhongyi; Liu, Shouchang

2017-01-01

ZrO2 heterophase structure nanocrystals (HSNCs) were synthesized with tunable ratios of monoclinic ZrO2 (m-ZrO2) to tetragonal ZrO2 (t-ZrO2). The phase mole ratio of m-ZrO2 versus t-ZrO2 in ZrO2 HSNCs was tuned from 40% to 100%. The concentration of the surface hydroxyl groups on m-ZrO2 is higher than that on t-ZrO2. ZrO2 HSNCs have different surface hydroxyl groups on two crystalline phases. This creates more intimate synergistic effects than their single-phase counterparts. The ZrO2 HSNCs were used as effective supports to fabricate heterophase-structured Ru/ZrO2 catalysts for benzene-selective hydrogenation. The excellent catalytic performance including high activity and selectivity is attributed to the heterogeneous strong/weak hydrophilic interface and water layer formed at the m-ZrO2/t-ZrO2 catalyst junction. PMID:28057914

Zirconia coated stir bar sorptive extraction combined with large volume sample stacking capillary electrophoresis-indirect ultraviolet detection for the determination of chemical warfare agent degradation products in water samples.

PubMed

Li, Pingjing; Hu, Bin; Li, Xiaoyong

2012-07-20

In this study, a sensitive, selective and reliable analytical method by combining zirconia (ZrO₂) coated stir bar sorptive extraction (SBSE) with large volume sample stacking capillary electrophoresis-indirect ultraviolet (LVSS-CE/indirect UV) was developed for the direct analysis of chemical warfare agent degradation products of alkyl alkylphosphonic acids (AAPAs) (including ethyl methylphosphonic acid (EMPA) and pinacolyl methylphosphonate (PMPA)) and methylphosphonic acid (MPA) in environmental waters. ZrO₂ coated stir bar was prepared by adhering nanometer-sized ZrO₂ particles onto the surface of stir bar with commercial PDMS sol as adhesion agent. Due to the high affinity of ZrO₂ to the electronegative phosphonate group, ZrO₂ coated stir bars could selectively extract the strongly polar AAPAs and MPA. After systematically optimizing the extraction conditions of ZrO₂-SBSE, the analytical performance of ZrO₂-SBSE-CE/indirect UV and ZrO₂-SBSE-LVSS-CE/indirect UV was assessed. The limits of detection (LODs, at a signal-to-noise ratio of 3) obtained by ZrO₂-SBSE-CE/indirect UV were 13.4-15.9 μg/L for PMPA, EMPA and MPA. The relative standard deviations (RSDs, n=7, c=200 μg/L) of the corrected peak area for the target analytes were in the range of 6.4-8.8%. Enhancement factors (EFs) in terms of LODs were found to be from 112- to 145-fold. By combining ZrO₂ coating SBSE with LVSS as a dual preconcentration strategy, the EFs were magnified up to 1583-fold, and the LODs of ZrO₂-SBSE-LVSS-CE/indirect UV were 1.4, 1.2 and 3.1 μg/L for PMPA, EMPA, and MPA, respectively. The RSDs (n=7, c=20 μg/L) were found to be in the range of 9.0-11.8%. The developed ZrO₂-SBSE-LVSS-CE/indirect UV method has been successfully applied to the analysis of PMPA, EMPA, and MPA in different environmental water samples, and the recoveries for the spiked water samples were found to be in the range of 93.8-105.3%. Copyright © 2012 Elsevier B.V. All rights reserved.

In situ high temperature oxidation analysis of Zircaloy-4 using acoustic emission coupled with thermogravimetry

NASA Astrophysics Data System (ADS)

Omar, Al Haj; Véronique, Peres; Eric, Serris; François, Grosjean; Jean, Kittel; François, Ropital; Michel, Cournil

2015-06-01

Zircaloy-4 oxidation behavior at high temperature (900 °C), which can be reached in case of severe accidental situations in nuclear pressurised water reactor, was studied using acoustic emission analysis coupled with thermogravimetry. Two different atmospheres were used to study the oxidation of Zircaloy-4: (a) helium and pure oxygen, (b) helium and oxygen combined with slight addition of air. The experiments with 20% of oxygen confirm the dependence on oxygen anions diffusion in the oxide scale. Under a mixture of oxygen and air in helium, an acceleration of the corrosion was observed due to the detrimental effect of nitrogen. The kinetic rate increased significantly after a kinetic transition (breakaway). This acceleration was accompanied by an acoustic emission activity. Most of the acoustic emission bursts were recorded after the kinetic transition (post-transition) or during the cooling of the sample. The characteristic features of the acoustic emission signals appear to be correlated with the different populations of cracks and their occurrence in the ZrO2 layer or in the α-Zr(O) layer. Acoustic events were recorded during the isothermal dwell time at high temperature under air. They were associated with large cracks in the zirconia porous layer. Acoustic events were also recorded during cooling after oxidation tests both under air or oxygen. For the latter, cracks were observed in the oxygen enriched zirconium metal phase and not in the dense zirconia layer after 5 h of oxidation.

The preparation and activity of Cu-Fe-Zr-Ce based catalysts for water gas shift

NASA Astrophysics Data System (ADS)

Wu, H. D.; Liu, T. S.; Liu, H. Z.

2018-01-01

CeO2-ZrO2 composite oxide was synthesized with precipitation method as support and CuaFeb(ZrCe4)8Ox catalysts were prepared by impregnation; X-ray diffraction, H2 temperature program reduction, and scanning electron microscope techniques were jointly used to characterize the crystal phases and reduction properties of catalysts. Then the activity of catalysts in water gas shift was studied, thus investigated how catalyst composition impacted the water gas shift. Conclusions drew from the results can be briefly stated. CuaFeb(ZrCe4)8Ox was provided with stable cubic crystalline framework and Cu and Fe, as the active components, was highly dispersed on the surface of supports in the form of CuO and Fe2O3 respectively. The strong interactions between copper and iron component enhanced the reducing capacity of CuO and Fe2O3. CuaFeb(ZrCe4)8Ox catalysts exhibited high catalytic activity and selectivity while the main active components were Cu and Fe3O4. The CO conversion rate reached 96% when Cu7Fe3(ZrCe4)8Ox catalysts was used in water gas shift at 623K and the only products were H2 and CO2. The activity was still desirable even the catalysts was applied at 723K.

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

PubMed

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.

Selective sorption of lead, cadmium and zinc ions by a polymeric cation exchanger containing nano-Zr(HPO3S)2.

PubMed

Zhang, Qingrui; Pan, Bingcai; Pan, Bingjun; Zhang, Weiming; Jia, Kun; Zhang, Quanxing

2008-06-01

A novel polymeric hybrid sorbent, namely ZrPS-001, was fabricated for enhanced sorption of heavy metal ions by impregnating Zr(HPO3S)2 (i.e., ZrPS) nanoparticles within a porous polymeric cation exchanger D-001. The immobilized negatively charged groups bound to the polymeric matrix D-001 would result in preconcentration and permeation enhancement of target metal ions prior to sequestration, and ZrPS nanoparticles are expected to sequester heavy metals selectively through an ion-exchange process. Highly effective sequestration of lead, cadmium, and zinc ions from aqueous solution can be achieved by ZrPS-001 even in the presence of competing calcium ion at concentration several orders of magnitude greater than the target species. The exhausted ZrPS-001 beads are amenable to regeneration with 6 M HCI solution for repeated use without any significant capacity loss. Fixed-bed column treatment of simulated waters containing heavy metals at high or trace levels was also performed. The content of heavy metals in treated effluent approached or met the WHO drinking water standard.

Nanocrystalline diamond protects Zr cladding surface against oxygen and hydrogen uptake: Nuclear fuel durability enhancement.

PubMed

Škarohlíd, Jan; Ashcheulov, Petr; Škoda, Radek; Taylor, Andrew; Čtvrtlík, Radim; Tomáštík, Jan; Fendrych, František; Kopeček, Jaromír; Cháb, Vladimír; Cichoň, Stanislav; Sajdl, Petr; Macák, Jan; Xu, Peng; Partezana, Jonna M; Lorinčík, Jan; Prehradná, Jana; Steinbrück, Martin; Kratochvílová, Irena

2017-07-25

In this work, we demonstrate and describe an effective method of protecting zirconium fuel cladding against oxygen and hydrogen uptake at both accident and working temperatures in water-cooled nuclear reactor environments. Zr alloy samples were coated with nanocrystalline diamond (NCD) layers of different thicknesses, grown in a microwave plasma chemical vapor deposition apparatus. In addition to showing that such an NCD layer prevents the Zr alloy from directly interacting with water, we show that carbon released from the NCD film enters the underlying Zr material and changes its properties, such that uptake of oxygen and hydrogen is significantly decreased. After 100-170 days of exposure to hot water at 360 °C, the oxidation of the NCD-coated Zr plates was typically decreased by 40%. Protective NCD layers may prolong the lifetime of nuclear cladding and consequently enhance nuclear fuel burnup. NCD may also serve as a passive element for nuclear safety. NCD-coated ZIRLO claddings have been selected as a candidate for Accident Tolerant Fuel in commercially operated reactors in 2020.

Adsorption of Arsenic on Multiwall Carbon Nanotube–Zirconia Nanohybrid for Potential Drinking Water Purification

PubMed Central

AddoNtim, Susana; Mitra, Somenath

2012-01-01

The adsorptive removal of arsenic from water using a multiwall carbon nanotube-zirconia nanohybrid (MWCNT-ZrO2) is presented. The MWCNT-ZrO2 with 4.85% zirconia was effective in meeting the drinking water standard levels of 10 μg L−1. The absorption capacity of the composite were 2000 μg g−1 and 5000 μg g−1 for As (III) and As (V) respectively, which were significantly higher than those reported previously for iron oxide coated MWCNTs. The adsorption of As (V) on MWCNT-ZrO2 was faster than that of As (III), and a pseudo-second order rate equation effectively described the uptake kinetics. The adsorption isotherms for As (III) and As (V) fitted both the Langmuir and Freundlich models. A major advantage of the MWCNT-ZrO2 was that the adsorption capacity was not a function of pH. PMID:22424815

Effects of Welding Parameters on Mechanical Properties in Electron Beam Welded CuCrZr Alloy Plates

NASA Astrophysics Data System (ADS)

Jaypuria, Sanjib; Doshi, Nirav; Pratihar, Dilip Kumar

2018-03-01

CuCrZr alloys are attractive structural materials for plasma-facing components (PFC) and heat sink element in the International Thermonuclear Experimental Reactor (ITER) fusion reactors. This material has gained so much attention because of its high thermal conductivity and fracture toughness, high resistance to radiation damage and stability at elevated temperatures. The objective of this work is to study the effects of electron beam welding parameters on the mechanical strength of the butt welded CuCrZr joint. Taguchi method is used as the design of experiments to optimize the input parameters, such as accelerating voltage, beam current, welding speed, oscillation amplitude and frequency. The joint strength and ductility are the desired responses, which are measured through ultimate tensile strength and percent elongation, respectively. Accelerating voltage and welding speed are found to have significant influence on the strength. A combination of low amplitude and high-frequency oscillation is suggested for the higher joint strength and ductility. There is a close agreement between Taguchi predicted results and experimental ones. Fractographic analysis of joint and weld zone analysis are carried out to study the failure behaviour and microstructural variation in the weld zone, respectively.

Experimental investigation of 150-KG-scale corium melt jet quenching in water

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

Magallon, D.; Hohmann, H.

This paper compares and discusses the results of two large scale FARO quenching tests known as L-11 and L-14, which involved, respectively, 151 kg of W% 76.7 UO{sub 2} + 19.2 ZrO{sub 2} + 4.1 Zr and 125 kg of W% 80 UO{sub 2} + 20 ZrO{sub 2} melts poured into 600-kg, 2-m-depth water at saturation at 5.0 MPa. The results are further compared with those of two previous tests performed using a pure oxidic melt, respectively 18 and 44 kg of W% 80 UO{sub 2} + 20 ZrO{sub 2} melt quenched in 1-m-depth water at saturation at 5.0 MPa.more » In all the tests, significant breakup and quenching took place during the melt fall through the water. No steam explosion occurred. In the tests performed with a pure oxide UO{sub 2}-ZrO{sub 2} melt, part of the corium (from 1/6 to 1/3) did not breakup and reached the bottom plate still molten whatever the water depth was. Test L-11 data suggest that full oxidation and complete breakup of the melt occurred during the melt fall through the water. A proportion of 64% of the total energy content of the melt was released to the water during this phase ({approximately}1.5 s), against 44% for L-14. The maximum temperature increase of the bottom plate was 330 K (L-14). The mean particle size of the debris ranged between 2.5 and 4.8mm.« less

Corrosion behavior in high-temperature pressurized water of Zircaloy-4 joints brazed with Zr-Cu-based amorphous filler alloys

NASA Astrophysics Data System (ADS)

Lee, Jung Gu; Lee, Gyoung-Ja; Park, Jin-Ju; Lee, Min-Ku

2017-05-01

The compositional effects of ternary Zr-Cu-X (X: Al, Fe) amorphous filler alloys on galvanic corrosion susceptibility in high-temperature pressurized water were investigated for Zircaloy-4 brazed joints. Through an Al-induced microgalvanic reaction that deteriorated the overall nobility of the joint, application of the Zr-Cu-Al filler alloy caused galvanic coupling to develop readily between the Al-bearing joint and the Al-free base metal, finally leading to massive localized corrosion of the joint. Contrastingly, joints prepared with a Zr-Cu-Fe filler alloy showed excellent corrosion resistance comparable to that of the Zircaloy-4 base metal, since the Cu and Fe elements forming fine intermetallic particles with Zr did not influence the electrochemical stability of the resultant joints. The present results demonstrate that Fe is a more suitable alloying element than Al for brazing filler alloys subjected to high-temperature corrosive environments.

Effects of incorporation of HA/ZrO(2) into glass ionomer cement (GIC).

PubMed

Gu, Y W; Yap, A U J; Cheang, P; Khor, K A

2005-03-01

Glass ionomer cements (GICs) are a class of bioactive cements that bond directly to bone. In this paper, a new bioactive hydroxyapatite (HA)/zirconia (ZrO(2))-filled GIC composite was developed to improve the biocompatibility and bioactivity of the GICs with the surrounding bone and connective tissues. Nano-sized HA/30 wt% ZrO(2) powders were heat treated at 700 degrees Celsius and 800 degrees Celsius for 3 h to elucidate the influence of the crystallinity of composite powders on the performance of HA/ZrO(2)-GICs. The effects of different volume percentages of HA/ZrO(2) powders (4, 12, 28 and 40 vol%) substituted within GICs were investigated based on their microhardness, compressive strength and diametral tensile strength. The HA/ZrO(2)-GICs composite was soaked in distilled water for 1 day and 1 week before subjecting the samples to mechanical testing. Results showed that the glass and HA/ZrO(2) particles were distributed uniformly in the GIC matrix. The substitution of highly crystalline HA/ZrO(2) improved the mechanical properties of the HA/ZrO(2)-GICs due to the slow resorption rate for highly crystalline powders in distilled water. The mechanical properties of HA/ZrO(2)-GICs increased with increasing soak time due to the continuous formation of aluminium salt bridges, which improved the final strength of the cements. The compositions 4 and 12 vol% HA/ZrO(2)-GICs exhibited superior mechanical properties than the original GICs. The mechanical properties of HA/ZrO(2)-GICs were found to be much better than those of HA-GICs because ZrO(2) has the attributes of high strength, high modulus, and is significantly harder than glass and HA particles. Furthermore, ZrO(2) does not dissolve with increasing soaking time.

Noninvasive Imaging of PSMA in prostate tumors with (89)Zr-Labeled huJ591 engineered antibody fragments: the faster alternatives.

PubMed

Viola-Villegas, Nerissa Therese; Sevak, Kuntal K; Carlin, Sean D; Doran, Michael G; Evans, Henry W; Bartlett, Derek W; Wu, Anna M; Lewis, Jason S

2014-11-03

Engineered antibody fragments offer faster delivery with retained tumor specificity and rapid clearance from nontumor tissues. Here, we demonstrate that positron emission tomography (PET) based detection of prostate specific membrane antigen (PSMA) in prostatic tumor models using engineered bivalent antibodies built on single chain fragments (scFv) derived from the intact antibody, huJ591, offers similar tumor delineating properties but with the advantage of rapid targeting and imaging. (89)Zr-radiolabeled huJ591 scFv (dimeric scFv-CH3; (89)Zr-Mb) and cysteine diabodies (dimeric scFv; (89)Zr-Cys-Db) demonstrated internalization and similar Kds (∼2 nM) compared to (89)Zr-huJ591 in PSMA(+) cells. Tissue distribution assays established the specificities of both (89)Zr-Mb and (89)Zr-Cys-Db for PSMA(+) xenografts (6.2 ± 2.5% ID/g and 10.2 ± 3.4% ID/g at 12 h p.i. respectively), while minimal accumulation in PSMA(-) tumors was observed. From the PET images, (89)Zr-Mb and (89)Zr-Cys-Db exhibited faster blood clearance than the parent huJ591 while tumor-to-muscle ratios for all probes show comparable values across all time points. Ex vivo autoradiography and histology assessed the distribution of the probes within the tumor. Imaging PSMA-expressing prostate tumors with smaller antibody fragments offers rapid tumor accumulation and accelerated clearance; hence, shortened wait periods between tracer administration and high-contrast tumor imaging and lower dose-related toxicity are potentially realized.

Development of a multi-sensor based urban discharge forecasting system using remotely sensed data: A case study of extreme rainfall in South Korea

NASA Astrophysics Data System (ADS)

Yoon, Sunkwon; Jang, Sangmin; Park, Kyungwon

2017-04-01

Extreme weather due to changing climate is a main source of water-related disasters such as flooding and inundation and its damage will be accelerated somewhere in world wide. To prevent the water-related disasters and mitigate their damage in urban areas in future, we developed a multi-sensor based real-time discharge forecasting system using remotely sensed data such as radar and satellite. We used Communication, Ocean and Meteorological Satellite (COMS) and Korea Meteorological Agency (KMA) weather radar for quantitative precipitation estimation. The Automatic Weather System (AWS) and McGill Algorithm for Precipitation Nowcasting by Lagrangian Extrapolation (MAPLE) were used for verification of rainfall accuracy. The optimal Z-R relation was applied the Tropical Z-R relationship (Z=32R1.65), it has been confirmed that the accuracy is improved in the extreme rainfall events. In addition, the performance of blended multi-sensor combining rainfall was improved in 60mm/h rainfall and more strong heavy rainfall events. Moreover, we adjusted to forecast the urban discharge using Storm Water Management Model (SWMM). Several statistical methods have been used for assessment of model simulation between observed and simulated discharge. In terms of the correlation coefficient and r-squared discharge between observed and forecasted were highly correlated. Based on this study, we captured a possibility of real-time urban discharge forecasting system using remotely sensed data and its utilization for real-time flood warning. Acknowledgement This research was supported by a grant (13AWMP-B066744-01) from Advanced Water Management Research Program (AWMP) funded by Ministry of Land, Infrastructure and Transport (MOLIT) of Korean government.

Degradation of Zr-based bulk metallic glasses used in load-bearing implants: A tribocorrosion appraisal.

PubMed

Zhao, Guo-Hua; Aune, Ragnhild E; Mao, Huahai; Espallargas, Nuria

2016-07-01

Owing to the amorphous structure, Bulk Metallic Glasses (BMGs) have been demonstrating attractive properties for potential biomedical applications. In the present work, the degradation mechanisms of Zr-based BMGs with nominal compositions Zr55Cu30Ni5Al10 and Zr65Cu18Ni7Al10 as potential load-bearing implant material were investigated in a tribocorrosion environment. The composition-dependent micro-mechanical and tribological properties of the two BMGs were evaluated prior to the tribocorrosion tests. The sample Zr65-BMG with a higher Zr content exhibited increased plasticity but relatively reduced wear resistance during the ball-on-disc tests. Both BMGs experienced abrasive wear after the dry wear test under the load of 2N. The cross-sectional subsurface structure of the wear track was examined by Focused Ion Beam (FIB). The electrochemical properties of the BMGs in simulated body fluid were evaluated by means of potentiodynamic polarization and X-ray Photoelectron Spectroscopy (XPS). The spontaneous passivation of Zr-based BMGs in Phosphate Buffer Saline solution was mainly attributed to the highly concentrated zirconium cation (Zr(4+)) in the passive film. The tribocorrosion performance of the BMGs was investigated using a reciprocating tribometer equipped with an electrochemical cell. The more passive nature of the Zr65-BMG had consequently a negative influence on its tribocorrosion resistance, which induced the wear-accelerated corrosion and eventually speeded-up the degradation process. It has been revealed the galvanic coupling was established between the depassivated wear track and the surrounding passive area, which is the main degradation mechanism for the passive Zr65-BMG subjected to the tribocorrosion environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface Cracking and Interface Reaction Associated Delamination Failure of Thermal and Environmental Barrier Coatings

NASA Technical Reports Server (NTRS)

Zhu, Dong-Ming; Choi, Sung R.; Eldridge, Jeffrey I.; Lee, Kang N.; Miller, Robert A.

2003-01-01

In this paper, surface cracking and interface reactions of a BSAS coating and a multi-layer ZrO2-8wt%Y2O3 and mullite/BSAS/Si thermal and environmental barrier coating system on SiC/SiC ceramic matrix composites were characterized after long-term combined laser thermal gradient and furnace cyclic tests in a water vapor containing environment. The surface cracking was analyzed based on the coating thermal gradient sintering behavior and thermal expansion mismatch stress characteristics under the thermal cyclic conditions. The interface reactions, which were largely enhanced by the coating surface cracking in the water vapor environment, were investigated in detail, and the reaction phases were identified for the coating system after the long-term exposure. The accelerated coating delamination failure was attributed to the increased delamination driving force under the thermal gradient cyclic loading and the reduced interface adhesion due to the detrimental interface reactions.

Microwave-hydrothermal method for the synthesis of composite materials for removal of arsenic from water.

PubMed

Andjelkovic, Ivan; Jovic, Bojan; Jovic, Milica; Markovic, Marijana; Stankovic, Dalibor; Manojlovic, Dragan; Roglic, Goran

2016-01-01

Composite material Zr-doped TiO2, suitable for the removal of arsenic from water, was synthetized with fast and simple microwave-hydrothermal method. Obtained material, Zr-TiO2, had uniform size and composition with zirconium ions incorporated into crystal structure of titanium dioxide. Synthetized composite material had large specific surface area and well-developed micropore and mesopore structure that was responsible for fast adsorption of As(III) and As(V) from water. The influence of pH on the adsorption capacity of arsenic was studied. The kinetics and isotherm experiments were also performed. The treatment of natural water sample containing high concentration of arsenic with composite material Zr-TiO2 was efficient. The concentration of arsenic was reduced to the value recommended by WHO.

A simple thick target for production of 89Zr using an 11MeV cyclotron

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

Link, Jeanne M.; Krohn, Kenneth A.; O'Hara, Matthew J.

2017-04-01

The growing interest but limited availability of 89Zr for PET led us to test targets for the 89(p,n) reaction. The goal was an easily constructed target for an 11 MeV Siements cyclotron. Yttrium foils were tested at different thicknesses, angles and currents. A 90 degree foil tolerated 41 microAmp without damage and produced ~800 MBq/hr, >20 mCi, an amount adequate for radiochemistry research and human doses in a widely available accelerator. This method should translate to higher energy cyclotrons.

Adsorption of arsenic on multiwall carbon nanotube-zirconia nanohybrid for potential drinking water purification.

PubMed

Ntim, Susana Addo; Mitra, Somenath

2012-06-01

The adsorptive removal of arsenic from water using a multiwall carbon nanotube-zirconia nanohybrid (MWCNT-ZrO(2)) is presented. The MWCNT-ZrO(2) with 4.85% zirconia was effective in meeting the drinking water standard levels of 10 μg L(-1). The absorption capacity of the composite were 2000 μg g(-1) and 5000 μg g(-1) for As(III) and As(V) respectively, which were significantly higher than those reported previously for iron oxide coated MWCNTs. The adsorption of As(V) on MWCNT-ZrO(2) was faster than that of As(III), and a pseudo-second order rate equation effectively described the uptake kinetics. The adsorption isotherms for As(III) and As(V) fitted both the Langmuir and Freundlich models. A major advantage of the MWCNT-ZrO(2) was that the adsorption capacity was not a function of pH. Copyright © 2012 Elsevier Inc. All rights reserved.

Descriptions of crack growth behaviors in glass-ZrO2 bilayers under thermal residual stresses.

PubMed

Belli, Renan; Wendler, Michael; Zorzin, José I; Petschelt, Anselm; Tanaka, Carina B; Meira, Josete; Lohbauer, Ulrich

2016-09-01

This study was intended to separate residual stresses arising from the mismatch in coefficients of thermal expansion between glass and zirconia (ZrO2) from those stresses arising solely from the cooling process. Slow crack growth experimentes were undertaken to demonstrate how cracks grow in different residual stress fields. Aluminosilicate glass discs were sintered onto ZrO2 to form glass-ZrO2 bilayers. Glass discs were allowed to bond to the ZrO2 substrate during sintering or prevented from bonding by means of coating the ZrO2 with a thin boron nitrade coating. Residual stress gradients on "bonded" and "unbonded" bilayers were assessed using birefringence measurements. Unbonded glass discs were further tested under biaxial flexure in dynamic fatigue conditions in order to evaluate the effect of residual stress on the slow crack growth behavior. When fast-ccoling was induced, residual tensile stresses on the glass increased significantly on the side toward the ZrO2 substrate. By allowing the bond between glass and ZrO2, those tensile stresses observed in unbonded specimens are overwhelmed by the contraction mismatch stresses between the ZrO2 substrate and the glassy overlayer. Specimens containing residual tensile stresses on the bending surface showed a time-dependent strength increase in relation to stress-free annealed samples in the dynamic biaxial bending test, with this effect being dependent on the magnitude of the residual tensile stress. The phenomenon observed is explained here on the basis of the water toughening effect, in which water diffuses into the glass promoting local swelling. An additional residual tensile stress at the crack tip adds an applied-stress-independent (Kres) term to the total tip stress intensity factor (Ktip), increasing the stress-enhanced diffusion and the shielding of the crack tip through swelling of the crack faces. Residual stresses in the glass influence the crack growth behavior of veneered-ZrO2 bilayered dental prostheses. The role of water in crack growth might be of higher complexity when residual stresses are present in the glass layer. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

New results in low-energy fusion of 40Ca+Zr,9290

NASA Astrophysics Data System (ADS)

Stefanini, A. M.; Montagnoli, G.; Esbensen, H.; Čolović, P.; Corradi, L.; Fioretto, E.; Galtarossa, F.; Goasduff, A.; Grebosz, J.; Haas, F.; Mazzocco, M.; Soić, N.; Strano, E.; Szilner, S.

2017-07-01

Background: Near- and sub-barrier fusion of various Ca + Zr isotopic combinations have been widely investigated. A recent analysis of 40Ca+96Zr data has highlighted the importance of couplings to multiphonon excitations and to both neutron and proton transfer channels. Analogous studies of 40Ca+90Zr tend to exclude any role of transfer couplings. However, the lowest measured cross section for this system is rather high (840 μ b ). A rather complete data set is available for 40Ca+94Zr , while no measurement of 40Ca+92Zr fusion has been performed in the past. Purpose: Our aim is to measure the full excitation function of 40Ca+92Zr near the barrier and to extend downward the existing data on 40Ca+90Zr , in order to estimate the transfer couplings that should be used in coupled-channels calculations of the fusion of these two systems and of 40Ca+94Zr . Methods: 40Ca beams from the XTU Tandem accelerator of INFN-Laboratori Nazionali di Legnaro were used, bombarding thin metallic 90Zr (50 μ g /cm2 ) and 92ZrO2 targets (same thickness) enriched to 99.36 % and 98.06 % in masses 90 and 92, respectively. An electrostatic beam deflector allowed the detection of fusion evaporation residues (ER) at very forward angles, and angular distributions of ER were measured. Results: The excitation function of 40Ca+92Zr has been measured down to the level of ≃60 μ b . Coupled-channels (CC) calculations using a standard Woods-Saxon (WS) potential and following the line of a previous analysis of 40Ca+96Zr fusion data give a good account of the new data, as well as of the existing data for 40Ca+94Zr . The previous excitation function of 40Ca+90Zr has been extended down to 40 μ b . Conclusions: Transfer couplings play an important role in explaining the fusion data for 40Ca+92Zr and 40Ca+94Zr . The strength of the pair-transfer coupling is deduced by applying a simple recipe based on the value obtained for 40Ca+96Zr . The logarithmic slopes and the S factors for fusion are reproduced fairly well for all three systems by the CC calculations, and there are no indications of a fusion hindrance at the lowest energies. In contrast, the new data for 40Ca+90Zr indicate the onset of a fusion hindrance at the lowest energies.

Dissolution process for ZrO.sub.2 -UO.sub.2 -CaO fuels

DOEpatents

Paige, Bernice E.

1976-06-22

The present invention provides an improved dissolution process for ZrO.sub.2 -UO.sub.2 -CaO-type pressurized water reactor fuels. The zirconium cladding is dissolved with hydrofluoric acid, immersing the ZrO.sub.2 -UO.sub.2 -CaO fuel wafers in the resulting zirconium-dissolver-product in the dissolver vessel, and nitric acid is added to the dissolver vessel to facilitate dissolution of the uranium from the ZrO.sub.2 -UO.sub.2 -CaO fuel wafers.

Plasma spraying of zirconia-reinforced hydroxyapatite composite coatings on titanium: part I: phase, microstructure and bonding strength.

PubMed

Chang, E; Chang, W J; Wang, B C; Yang, C Y

1997-04-01

Plasma-sprayed hydroxyapatite (HA) coatings applied to metal substrates can induce a direct chemical bond with bone and hence achieve biological fixation of the implant. However, the poor bonding strength between HA and substrate has been of concern to orthopaedists. In this study, two submicrometre ZrO2 powders stabilized with both 3 and 8 mol% Y2O3 (TZ3Y and TZ8Y, respectively) were incorporated in a plasma-sprayed HA coating on Ti-6Al-4V substrate to investigate the change in phase, microstructure and bonding strength. The results show that ZrO2 composite coatings contain more unmelted particles and greater porosity. During plasma spraying, ZrO2 reacts with the CaO in HA to form CaZrO3 and accelerates HA decomposition to alpha-TCP and Ca4P2O9. Nevertheless, bonding strength increases with increase of ZrO2 content in the range 0 to 10 wt% studied. The higher Y2O3-containing TZ8Y apparently exerts a greater strengthening effect than the lower Y2O3-containing TZ3Y.

Effects of chemical composition and test conditions on the dynamic tensile response of Zr-based metallic glasses

NASA Astrophysics Data System (ADS)

Wang, F.; Laws, K.; Martinez, D.; Trujillo, C. P.; Brown, A. D.; Cerreta, E. K.; Hazell, P. J.; Ferry, M.; Quadir, M. Z.; Jiang, J.; Escobedo, J. P.

2017-01-01

The effects of impact velocity and temperature on the dynamic mechanical behavior of two bulk metallic (BMG) alloys with slightly different elemental compositions (Zr55Cu30Ni5Al30 and Zr46Cu38Ag8Al38) have been investigated. Bullet-shaped samples were accelerated by a gas gun to speeds in the 400˜600m/s range and tested at both room temperature and 250°C. The samples impacted steel extrusion dies which subjected the bullets to high strains at relatively high strain-rates. The extruded fragments were subsequently soft recovered by using low density foams and examined by means of optical/scanning electron microscopy and differential scanning calorimetry. It was found that shear banding was the dictating mechanism responsible for the fracture of all BMGs. At room temperature, the Zr55Cu30Ni5Al30 alloy exhibited a higher resistance to fragmentation than the Zr46Cu38Ag8Al38 alloy. At 250°C, significant melting was observed in the recovered fragments of both alloys, which indicates that the BMG glassy structure undergoes a melting process and deformation likely occurs homogeneously.

Preparation of graphene-ZrO2 nanocomposites by heat treatment and photocatalytic degradation of organic dyes.

PubMed

Cho, Bum Hwi; Ko, Weon Bae

2013-11-01

ZrO2 nanoparticles were synthesized by combining a solution containing zinconyl chloride in distilled water with a NH4OH solution under microwave irradiation. Graphene and ZrO2 nanocomposites were synthesized in an electric furnace at 700 degrees C for 2 hours. The heated graphene-ZrO2 nanocomposites were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. In addition, UV-vis spectrophotometry was used to evaluate the heated graphene-ZrO2 nanocomposites as a catalyst in the photocatalytic degradation of organic dyes. The photocatalytic effect of the heated graphene-ZrO2 nanocomposites was compared with that of unheated graphene nanoparticles, heated graphene nanoparticles, and unheated graphene-ZrO2 nanocomposites in organic dyes (methylene blue, methyl orange, and rhodamine B) under ultraviolet light at 254 nm.

Effect of HIP temperature on microstructure and low cycle fatigue strength of CuCrZr alloy

NASA Astrophysics Data System (ADS)

Nishi, Hiroshi; Enoeda, Mikio

2011-10-01

In order to investigate the effect of the HIP cycle temperatures on the metallurgic degradation and the mechanical properties of CuCrZr alloy, assessments of the microstructure, tensile test, Charpy impact test and low cycle fatigue test are performed for various heat treated CuCrZr alloys, which were solution-annealed followed by water-quenched and aged state of CuCrZr with simulated HIP cycle at temperatures of 980 and 1045 °C. Grain growth occurred on 1045 °C HIP CuCrZr, though slightly on 980 °C HIP CuCrZr. Metallurgic degradation such as voids was not found by optical and SEM observations. There were coarse precipitates in all the CuCrZr and the precipitates did not easily dissolve at 980 °C. The low cycle fatigue strength of 1045 °C HIP CuCrZr was lower than that of other CuCrZr because of the metallurgic degradation caused by the heat cycle, while that of other CuCrZr was corresponding to the best fit curve of ITER MPH.

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters by use of solid-phase extraction, and its applications to brackish lake waters.

PubMed

Okumura, M; Tong, L; Fujinaga, K; Seike, Y

2001-05-01

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters has been developed for field analysis. This method is based on solid-phase extraction on a zirconium-loaded Sep-Pack Accell CM cartridge (Zr-SP) and is applicable to studies in which sampling is performed by use of a graduated syringe to prevent contamination and to ensure easy operation at sampling sites. The Zr-SP cartridge was prepared by passing 0.1 mol L(-1) zirconium solution through a Sep-Pak Accell CM cartridge, packed with cation exchange sorbent based on a silica matrix. The adsorption of phosphate and its desorption depend only on the pH of the solution. A water sample containing phosphate was adjusted to pH 2 and passed through the Zr-SP cartridge to collect it. The retained phosphate was quantitatively eluted with 0.5 mol L(-1) sodium hydroxide solution. The phosphate retained in the Zr-SP cartridge was stable for at least one month. The established preconcentration method was successfully applied to brackish lake waters to investigate seasonal changes in the distribution and behavior of phosphate in a brackish lake.

Single-Crystalline UiO-67-Type Porous Network Stable to Boiling Water, Solvent Loss, and Oxidation.

PubMed

Wong, Yan-Lung; Yee, Ka-Kit; Hou, Yun-Long; Li, Jiaqian; Wang, Zuankai; Zeller, Matthias; Hunter, Allen D; Xu, Zhengtao

2018-06-04

With methylthio groups flanking the carboxyl groups, the 3,3',5,5'-tetrakis(methylthio)biphenyl dicarboxylate (TMBPD) linker forms a zirconium(IV) carboxylate porous framework featuring the topology of the UiO-67 prototype, i.e., with a face-centered-cubic array of the Zr 6 O 4 (OH) 4 clusters. Thioether functionalization proves valuable because the ZrTMBPD crystal is found to be exceptionally stable not only upon long-term exposure to air but also in boiling water and a broad range of pH conditions. The hydrophobicity of the metal-organic framework can also be tuned by simple H 2 O 2 oxidation, as illustrated in the water contact-angle measurement of the pristine and H 2 O 2 -treated ZrTMBPD solid.

A simple thick target for production of 89Zr using an 11 MeV cyclotron

PubMed Central

Link, Jeanne M.; Krohn, Kenneth A.; O’Hara, Matthew J.

2017-01-01

The growing interest but limited availability of 89Zr for PET led us to test targets for the 89Y(p,n) reaction. The goal was an easily constructed target for an 11 MeV Siemens cyclotron. Yttrium foils were tested at different thicknesses, angles and currents. A 90° foil tolerated 41 μA without damage and produced ~800 MBq/h, > 20 mCi, an amount adequate for radiochemistry research and human doses in a widely available accelerator. This method should translate to higher energy cyclotrons. PMID:28187357

Summary of SLAC's SEY Measurement On Flat Accelerator Wall Materials

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

Le Pimpec, F.; /PSI, Villigen /SLAC

The electron cloud effect (ECE) causes beam instabilities in accelerator structures with intense positively charged bunched beams. Reduction of the secondary electron yield (SEY) of the beam pipe inner wall is effective in controlling cloud formation. We summarize SEY results obtained from flat TiN, TiZrV and Al surfaces carried out in a laboratory environment. SEY was measured after thermal conditioning, as well as after low energy, less than 300 eV, particle exposure.

Zirconium: biomedical and nephrological applications.

PubMed

Lee, David B N; Roberts, Martin; Bluchel, Christian G; Odell, Ross A

2010-01-01

Recent years have witnessed a rapid increase in the use of zirconium (Zr)-containing compounds in artificial internal organs. Examples include dental implants and other restorative practices, total knee and hip replacement, and middle-ear ossicular chain reconstruction. In nephrological practice, Zr-containing sorbents have been used in hemofiltration, hemodialysis, peritoneal dialysis, and in the design and construction of wearable artificial kidneys. Zr compounds continue to be widely and extensively used in deodorant and antiperspirant preparations. In the public health arena, Zr compounds have been studied or used in controlling phosphorus pollution and in the reclamation of poison and bacteria-contaminated water. Experimental and clinical studies support the general consensus that Zr compounds are biocompatible and exhibit low toxicity. Reports on possible Zr-associated adverse reactions are rare and, in general, have not rigorously established a cause-and-effect relationship. Although publications on the use of Zr compounds have continued to increase in recent years, reports on Zr toxicity have virtually disappeared from the medical literature. Nevertheless, familiarity with, and continued vigilant monitoring of, the use of these compounds are warranted. This article provides an updated review on the biomedical use of Zr compounds.

Critical size of crystalline ZrO(2) nanoparticles synthesized in near- and supercritical water and supercritical isopropyl alcohol.

PubMed

Becker, Jacob; Hald, Peter; Bremholm, Martin; Pedersen, Jan S; Chevallier, Jacques; Iversen, Steen B; Iversen, Bo B

2008-05-01

Nanocrystalline ZrO(2) samples with narrow size distributions and mean particle sizes below 10 nm have been synthesized in a continuous flow reactor in near and supercritical water as well as supercritical isopropyl alcohol using a wide range of temperatures, pressures, concentrations and precursors. The samples were comprehensively characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS), and the influence of the synthesis parameters on the particle size, particle size distribution, shape, aggregation and crystallinity was studied. On the basis of the choice of synthesis parameters either monoclinic or tetragonal zirconia phases can be obtained. The results suggest a critical particle size of 5-6 nm for nanocrystalline monoclinic ZrO(2) under the present conditions, which is smaller than estimates reported in the literature. Thus, very small monoclinic ZrO(2) particles can be obtained using a continuous flow reactor. This is an important result with respect to improvement of the catalytic properties of nanocrystalline ZrO(2).

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Lattice Thermal Conductivity from Atomistic Simulations: ZrB2 and HfB2

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Structural and Kinetic Hydrogen Sorption Properties of Zr0.8Ti0.2Co Alloy Prepared by Ball Milling

PubMed Central

He, Hui; Tang, Tao; Huang, Zhiyong; Sang, Ge; Zhang, Guanghui; Ba, Jingwen; Liu, Meng

2018-01-01

The effects of ball milling on the hydrogen sorption kinetics and microstructure of Zr0.8Ti0.2Co have been systematically studied. Kinetic measurements show that the hydrogenation rate and amount of Zr0.8Ti0.2Co decrease with increasing the ball milling time. However, the dehydrogenation rate accelerates as the ball milling time increases. Meanwhile, the disproportionation of Zr0.8Ti0.2Co speeds up after ball milling and the disproportionation kinetics is clearly inclined to be linear with time at 500°C. It is found from X-ray powder diffraction (XRD) results that the lattice parameter of Zr0.8Ti0.2Co gradually decreases from 3.164 Å to 3.153 Å when the ball milling time extends from 0 h to 8 h, which is mainly responsible for the hydrogen absorption/desorption behaviors. In addition, scanning electron microscope (SEM) images demonstrate that the morphology of Zr0.8Ti0.2Co has obviously changed after ball milling, which is closely related to the hydrogen absorption kinetics. Besides, high-resolution transmission electron microscopy (HRTEM) images show that a large number of disordered microstructures including amorphous regions and defects exist after ball milling, which also play an important role in hydrogen sorption performances. This work will provide some insights into the principles of how to further improve the hydrogen sorption kinetics and disproportionation property of Zr0.8Ti0.2Co. PMID:29721128

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

A bench-scale study on the removal and recovery of phosphate by hydrous zirconia-coated magnetite nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Zhe; Fang, Wenkan; Xing, Mingchao; Wu, Deyi

2017-02-01

Owing to the easy magnetic separation from water for reuse, magnetic nanoparticles have drawn great interest as adsorbents. Herein hydrous zirconia-coated magnetite nanoparticles (Fe3O4@ZrO2) were created by a facile method and a bench-scale study was undertaken to evaluate its effectiveness and mechanism to remove phosphate at low concentrations. Results indicated that phosphate removal by Fe3O4@ZrO2 was fast (95% of phosphate removal within 10 min) and nearly complete removal could be achieved at the adsorbent dosage >0.6 g/L. In tap water or wastewater where competitive anions coexist, regulation of pH was found to be quite effective to augment the performance of phosphate removal. In pH-lowered adsorption systems, phosphate removal followed a good pattern similarly to pure water, i.e., a continuous high efficiency removal followed by a rapid saturation. Adsorption-desorption-regeneration studies showed that Fe3O4@ZrO2 could be repeatedly used for phosphate removal and adsorbed phosphate could be stripped for recovery. The fractionation of adsorbed phosphorus suggested that NaOH-P fraction was dominant. We also found that the adsorption reaction of phosphate with Fe3O4@ZrO2 shifted the isoelectric point of Fe3O4@ZrO2 from 9.0 to 3.0. FTIR measurements further showed the direct coordination of phosphate onto zirconium by replacement of hydroxyl groups. The formation of the monodentate (ZrO)PO2(OH) complex was proposed.

High Temperature Corrosion and Heat Transfer Studies of Zirconium-Silicide Coatings for Light Water Reactor Cladding Applications

NASA Astrophysics Data System (ADS)

Yeom, Hwasung

Experimental results investigating the feasibility of zirconium-silicide coating for accident tolerance of LWR fuel cladding coating was presented. The oxidation resistance of ZrSi2 appeared to be superior to bare Zircaloy-4 in high temperature air. It was shown that micro- and nanostructures consisting of alternating SiO2 and ZrO2 evolved during transient oxidation of ZrSi2, which was explained by spinodal phase decomposition of Zr-Si-O oxide. Coating optimization regarding oxidation resistance was performed mainly using magnetron sputter deposition method. ZrSi 2 coatings ( 3.9 microm) showed improvement of almost two orders of magnitude when compared to bare Zircaloy-4 after air-oxidation at 700 °C for 20-hours. Pre-oxidation of ZrSi2 coating at 700 °C for 5 h significantly mitigated oxygen diffusion in air-oxidation tests at 1000 °C for 1-hour and 1200 °C for 10-minutes. The ZrSi2 coating with the pre-oxidation was found to be the best condition to prevent oxide formation in Zircaloy-4 substrate in the steam condition even if the top surface of the coating was degraded by formation of zirconium-rich oxide layer. Only the ZrSiO4 phase, formed by exposing the ZrSi2 coating at 1400 °C in air, allowed for immobilization of silicon species in the oxide scale in the aqueous environments. A quench test facility was designed and built to study transient boiling heat transfer of modified Zircaloy-4 surfaces (e.g., roughened surfaces, oxidized surfaces, ZrSi2 coated surfaces) at various system conditions (e.g., elevated pressures and water subcooling). The minimum film boiling temperature increased with increasing system pressure and water subcooling, consistent with past literature. Quenching behavior was affected by the types of surface modification regardless of the environmental conditions. Quenching heat transfer was improved by the ZrSi 2 coating, a degree of surface oxidation (deltaox = 3 to 50 microm), and surface roughening (Ra 20 microm). A plausible hypothesis based on transient heat conduction models for liquid-solid contact in quenching process was proposed to explain the enhanced quenching performance. The theoretical model incorporated localized temperature behavior on superheated surface and elucidated bubble dynamics qualitatively, and predicts minimum film boiling temperature of oxidized Zirc-4 surfaces, which were in good agreement with experimental data.

Exceptional arsenic (III,V) removal performance of highly porous, nanostructured ZrO2 spheres for fixed bed reactors and the full-scale system modeling.

PubMed

Cui, Hang; Su, Yu; Li, Qi; Gao, Shian; Shang, Jian Ku

2013-10-15

Highly porous, nanostructured zirconium oxide spheres were fabricated from ZrO2 nanoparticles with the assistance of agar powder to form spheres with size at millimeter level followed with a heat treatment at 450 °C to remove agar network, which provided a simple, low-cost, and safe process for the synthesis of ZrO2 spheres. These ZrO2 spheres had a dual-pore structure, in which interconnected macropores were beneficial for liquid transport and the mesopores could largely increase their surface area (about 98 m(2)/g) for effective contact with arsenic species in water. These ZrO2 spheres demonstrated an even better arsenic removal performance on both As(III) and As(V) than ZrO2 nanoparticles, and could be readily applied to commonly used fixed-bed adsorption reactors in the industry. A short bed adsorbent test was conducted to validate the calculated external mass transport coefficient and the pore diffusion coefficient. The performance of full-scale fixed bed systems with these ZrO2 spheres as the adsorber was estimated by the validated pore surface diffusion modeling. With the empty bed contact time (EBCT) at 10 min and the initial arsenic concentration at 30 ppb, the number of bed volumes that could be treated by these dry ZrO2 spheres reached ~255,000 BVs and ~271,000 BVs for As(III) and As(V), respectively, until the maximum contaminant level of 10 ppb was reached. These ZrO2 spheres are non-toxic, highly stable, and resistant to acid and alkali, have a high arsenic adsorption capacity, and could be easily adapted for various arsenic removal apparatus. Thus, these ZrO2 spheres may have a promising potential for their application in water treatment practice. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hot Deformation and Dynamic Recrystallization Behavior of the Cu-Cr-Zr-Y Alloy

NASA Astrophysics Data System (ADS)

Zhang, Yi; Huili, Sun; Volinsky, Alex A.; Tian, Baohong; Chai, Zhe; Liu, Ping; Liu, Yong

2016-03-01

To study the workability and to optimize the hot deformation processing parameters of the Cu-Cr-Zr-Y alloy, the strain hardening effect and dynamic softening behavior of the Cu-Cr-Zr-Y alloy were investigated. The flow stress increases with the strain rate and stress decreases with deformation temperature. The critical conditions, including the critical strain and stress for the occurrence of dynamic recrystallization, were determined based on the alloy strain hardening rate. The critical stress related to the onset of dynamic recrystallization decreases with temperature. The evolution of DRX microstructure strongly depends on the deformation temperature and the strain rate. Dynamic recrystallization appears at high temperatures and low strain rates. The addition of Y can refine the grain and effectively accelerate dynamic recrystallization. Dislocation generation and multiplication are the main hot deformation mechanisms for the alloy. The deformation temperature increase and the strain rate decrease can promote dynamic recrystallization of the alloy.

Quantification of effective plant rooting depth: advancing global hydrological modelling

NASA Astrophysics Data System (ADS)

Yang, Y.; Donohue, R. J.; McVicar, T.

2017-12-01

Plant rooting depth (Zr) is a key parameter in hydrological and biogeochemical models, yet the global spatial distribution of Zr is largely unknown due to the difficulties in its direct measurement. Moreover, Zr observations are usually only representative of a single plant or several plants, which can differ greatly from the effective Zr over a modelling unit (e.g., catchment or grid-box). Here, we provide a global parameterization of an analytical Zr model that balances the marginal carbon cost and benefit of deeper roots, and produce a climatological (i.e., 1982-2010 average) global Zr map. To test the Zr estimates, we apply the estimated Zr in a highly transparent hydrological model (i.e., the Budyko-Choudhury-Porporato (BCP) model) to estimate mean annual actual evapotranspiration (E) across the globe. We then compare the estimated E with both water balance-based E observations at 32 major catchments and satellite grid-box retrievals across the globe. Our results show that the BCP model, when implemented with Zr estimated herein, optimally reproduced the spatial pattern of E at both scales and provides improved model outputs when compared to BCP model results from two already existing global Zr datasets. These results suggest that our Zr estimates can be effectively used in state-of-the-art hydrological models, and potentially biogeochemical models, where the determination of Zr currently largely relies on biome type-based look-up tables.

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

PubMed

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.

A Generic Metallographic Preparation Method for Magnesium Alloys

DTIC Science & Technology

2013-05-01

treated castings or wrought alloys. Stains solid solution, leaves compound white. 9: 100-ml water 0.2–2-g oxalic acid For pure Mg and most alloys. Swab...water 2-g oxalic acid Pure Mg Mg-Mn Mg-Al, Mg-Al-Zn (Al+Znɝ%) Mg-Al, Mg-Al-Zn (Al+Zn>5%) Mg-Zn-Zr Mg-Th-Zr Swab...using a 100-ml ethanol, 10-ml distilled water, 10-ml acetic acid , and 5-g picric acid etchant. Immersed and using gentle agitation 5–20 s. Though not

Behavior of an improved Zr fuel cladding with oxidation resistant coating under loss-of-coolant accident conditions

NASA Astrophysics Data System (ADS)

Park, Dong Jun; Kim, Hyun Gil; Jung, Yang Il; Park, Jung Hwan; Yang, Jae Ho; Koo, Yang Hyun

2016-12-01

This study investigates protective coatings for improving the high temperature oxidation resistance of Zr fuel claddings for light water nuclear reactors. FeCrAl alloy and Cr layers were deposited onto Zr plates and tubes using cold spraying. For the FeCrAl/Zr system, a Mo layer was introduced between the FeCrAl coating and the Zr matrix to prevent inter-diffusion at high temperatures. Both the FeCrAl and Cr coatings improved the oxidation resistance compared to that of the uncoated Zr alloy when exposed to a steam environment at 1200 °C. The ballooning behavior and mechanical properties of the coated cladding samples were studied under simulated loss-of-coolant accident conditions. The coated samples showed higher burst temperatures, lower circumferential strain, and smaller rupture openings compared to the uncoated Zr. Although 4-point bend tests of the coated samples showed a small increase in the maximum load, ring compression tests of a sectioned sample showed increased ductility.

Synergistic effect of PANI-ZrO2 composite as antibacterial, anti-corrosion, and phosphate adsorbent material: synthesis, characterization and applications.

PubMed

Masim, Frances Camille P; Tsai, Cheng-Hsien; Lin, Yi-Feng; Fu, Ming-Lai; Liu, Minghua; Kang, Fei; Wang, Ya-Fen

2017-11-03

The increasing number of bacteria-related problems and presence of trace amounts of phosphate in treated wastewater effluents have become a growing concern in environmental research. The use of antibacterial agents and phosphate adsorbents for the treatment of wastewater effluents is of great importance. In this study, the potential applications of a synthesized polyaniline (PANI)-zirconium dioxide (ZrO 2 ) composite as an antibacterial, phosphate adsorbent and anti-corrosion material were systematically investigated. The results of an antibacterial test reveal an effective area of inhibition of 14 and 18 mm for the Escherichia coli and Staphylococcus aureus bacterial strains, respectively. The antibacterial efficiency of the PANI-ZrO 2 composite is twice that of commercial ZrO 2 . In particular, the introduction of PANI increased the specific surface area and roughness of the composite material, which was beneficial to increase the contact area with bacterial and phosphate. The experimental results demonstrated that phosphate adsorption studies using 200 mg P/L phosphate solution showed a significant phosphate removal efficiency of 64.4%, and the maximum adsorption capacity of phosphate on the solid surface of PANI-ZrO 2 is 32.4 mg P/g. Furthermore, PANI-ZrO 2 coated on iron substrate was tested for anti-corrosion studies by a natural salt spray test (7.5% NaCl), which resulted in the formation of no rust. To the best of our knowledge, no works have been reported on the synergistic effects of the PANI-ZrO 2 composite as an antibacterial, anti-corrosion, and phosphate adsorbent material. PANI-ZrO 2 composite is expected to be a promising comprehensive treatment method for water filters in the aquaculture industry and for use in water purification applications.

Changes in the state of iron atoms in Zr alloys during corrosion tests in an autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.; Kargin, N. I.; Petrov, V. I.

2014-04-01

Mössbauerinvestigations were carried out on oxide films formed on specimens of zirconium alloys Zr-1.0 %wtFe-1.2 %wtSn-0.5 %wtCr subjected to corrosion in steam-water environment at a temperature of 360 °C and at a pressure of 16.8 MPa with lithium and boron additions, and on Zr-1.4 %wtFe-0.7 %wtCr corroded in steam-water environment at 350 °C and 16.8 MPa as well as in steam-water environment at 500 °C and 10 MPa. In the metal part of the samples, under the oxide film, the iron atoms are in form of intermetallic precipitates of Zr(Fe, Cr)2. The corrosion process decomposes the intermetallic precipitates and particles are formed of metallic iron with inclusions of chromium atoms -Fe(Cr), α-Fe2O3 and Fe3O4 compounds. Part of the iron ions are in divalent and part in trivalent paramagnetic states. It is proposed that some part of the iron containing oxide precipitates in the oxide film may be in the form of nanoparticles which pass from the superparamagnetic to the ferromagnetic state with decreasing temperature.

Mesoporous ZrO2 fibers with enhanced surface area and the application as recyclable absorbent

NASA Astrophysics Data System (ADS)

Yu, Zhichao; Liu, Benxue; Zhou, Haifeng; Feng, Cong; Wang, Xinqiang; Yuan, Kangkang; Gan, Xinzhu; Zhu, Luyi; Zhang, Guanghui; Xu, Dong

2017-03-01

Highly crystalline mesoporous zirconia fibers with high surface area have been prepared by the use of electrospinning combined with precursors method. The obtained precursor fibers were treated in water steam and directly in air at different temperature respectively. Compared with the direct calcination in air, the water steam cannot only promote the crystallization of ZrO2 but also effectively remove off the organics and prevent the pore structure collapse. Moreover, through adding hydrochloric acid to modify the solution pH value, the obtained t-ZrO2 fibers treated in water steam at 300 °C have high surface area and large pore volume of 232.70 m2 g-1 and 0.36 cm3 g-1. The formation mechanism of the mesostucture was studied and the schematic was represented. Compared with the previous reports of mesoporous ZrO2 fibers, the as-synthesized materials exhibited the high crystallinity, large surface area and the long-range order mesostructure.The adsorption of Congo red indicates that the samples have a high adsorption capacity of 103.46 mg g-1 and long-periodic repeated availability.

High temperature investigation of the solid/liquid transition in the PuO2-UO2-ZrO2 system

NASA Astrophysics Data System (ADS)

Quaini, A.; Guéneau, C.; Gossé, S.; Sundman, B.; Manara, D.; Smith, A. L.; Bottomley, D.; Lajarge, P.; Ernstberger, M.; Hodaj, F.

2015-12-01

The solid/liquid transitions in the quaternary U-Pu-Zr-O system are of great interest for the analysis of core meltdown accidents in Pressurised Water Reactors (PWR) fuelled with uranium-dioxide and MOX. During a severe accident the Zr-based cladding can become completely oxidised due to the interaction with the oxide fuel and the water coolant. In this framework, the present analysis is focused on the pseudo-ternary system UO2-PuO2-ZrO2. The melting/solidification behaviour of five pseudo-ternary and one pseudo-binary ((PuO2)0.50(ZrO2)0.50) compositions have been investigated experimentally by a laser heating method under pre-set atmospheres. The effects of an oxidising or reducing atmosphere on the observed melting/freezing temperatures, as well as the amount of UO2 in the sample, have been clearly identified for the different compositions. The oxygen-to-metal ratio is a key parameter affecting the melting/freezing temperature because of incongruent vaporisation effects. In parallel, a detailed thermodynamic model for the UO2-PuO2-ZrO2 system has been developed using the CALPHAD method, and thermodynamic calculations have been performed to interpret the present laser heating results, as well as the high temperature behaviour of the cubic (Pu,U,Zr)O2±x-c mixed oxide phase. A good agreement was obtained between the calculated and experimental data points. This work enables an improved understanding of the major factors relevant to severe accident in nuclear reactors.

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

PubMed

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

2018-04-18

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

Superconductivity in zirconium-rhodium alloys

NASA Technical Reports Server (NTRS)

Zegler, S. T.

1969-01-01

Metallographic studies and transition temperature measurements were made with isothermally annealed and water-quenched zirconium-rhodium alloys. The results clarify both the solid-state phase relations at the Zr-rich end of the Zr-Rh alloy system and the influence upon the superconducting transition temperature of structure and composition.

Capture of Hydrogen Using ZrNi

NASA Technical Reports Server (NTRS)

Patton, Lisa; Wales, Joshua; Lynch, David; Parrish, Clyde

2005-01-01

Water, as ice, is thought to reside in craters at the lunar poles along with CH4 and H2 . A proposed robotic mission for 2012 will utilize metal/metal hydrides for H2 recovery. Specifications are 99% capture of H2 initially at 5 bar and 100C (or greater), and degassing completely at 300C. Of 47-systems examined using the van't Hoff equation, 4 systems, Mg/MgH2, Mg2Ni/Mg2NiH4, ZrNi/ZrNiH2.8, and Pd/PdH0.77, were considered likely candidates for further examination. It is essential, when selecting a system, to also examine questions regarding activation, kinetics, cyclic stability, and gas impurity effects. After considering those issues, ZrN1 was selected as the most promising candidate, as it is easily activated and rapidly forms ZrNiH 2.8 . In addition, it resists oxide poisoning by CO2, and H2O, while some oxidation by O2 is recommended for improved activation . The presence of hydrogen in the as received Zr-Ni alloy from Alfa Aesar posed additional technical problems. X-ray diffraction of the Zr-Ni powder (-325 mesh), with a Zr:Ni wt% ratio of 70:30, was found to consist of ZrH2, ZrNiH2.8, and ZrNi. ZrH2 in the alloy presented the risk that after degassing that both Zr and ZrNi would be present, and thus lead to erroneous results regarding the reactivity of ZrNi with H2 . Fortunately, ZrH2 is a highly stable hydride that does not degas H2 to any significant extent at temperatures below 300C. Based on equilibrium calculations for the decomposition of ZrH2, only 1 millionth of the hydride decomposed at 300C under a N2 atmosphere flowing at 25 ccm for 64 hours, the longest time for pretreatment employed in the investigation. It was possible, from the X-ray results and knowledge of the Zr:Ni ratio, to compute the composition of a pretreated specimen as being 76 wt% ZrNi and the balance ZrH2.

Fabrication of Thin Electrolytes for Second-Generation Solid Oxide Fuel Cells

DTIC Science & Technology

1999-05-05

stabilized zirconia but are equally applicable to components, have been developed. Halogen com- other oxide electrolytes. pounds such as ZrCl4 and YC13...substrates. They used ZrCl4 and an oxygen source reactant. EVD is a two-step YC13 vapor mixtures as the metal compound sources process. The first step...thin zirconia layers on ited film. In this step oxygen ions formed on the porous alumina substrates. ZrCl4 and YC13 vapor water vapor side of the

Microstructural Improvement of Hydroxyapatite-ZrO2 Composite Ceramics via Thermal Precipitation Techniques.

NASA Astrophysics Data System (ADS)

Sangmala, A.; Limsuwan, P.; Kaewwiset, W.; Naemchanthara, K.

2017-09-01

Hydroxyapatite-ZrO2 composite ceramic were synthesized using a thermal precipitation techniques. The chemical precursors were prepared from di-ammonium hydrogen orthophosphate, calcium oxide (CaO) derived from chicken eggshell, zirconium dioxide (ZrO2) and distilled water. The mixture were heated at the various temperatures from 100 to 700 °C in the furnace with an incremental temperature of 100 °C. The ZrO2 contents in the composite ceramic were varied from 0 to 15 percent weight of CaO. The prepared composites were then annealed at 300, 600 and 700 °C for 4 h in air. The crystal structure, function group and morphology of all samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM) and universal testing machine (UTM), respectively. The results indicated that the undoped-ZrO2 samples hydroxyapatite phase with a hexagonal structure. However, the hydroxyapatite was transformed to the tri-calcium phosphate after thermal treatment at 700 °C. For the doped-ZrO2 samples, the hydroxyapatite and ZrO2 phases were found. Moreover, the result showed that the compressive strength of hydroxyapatite-ZrO2 composite ceramic increased with increasing the ZrO2 content.

Protein Adsorption to Titanium and Zirconia Using a Quartz Crystal Microbalance Method

PubMed Central

Kusakawa, You

2017-01-01

Protein adsorption onto titanium (Ti) or zirconia (ZrO2) was evaluated using a 27 MHz quartz crystal microbalance (QCM). As proteins, fibronectin (Fn), a cell adhesive protein, and albumin (Alb), a cell adhesion-inhibiting protein, were evaluated. The Ti and ZrO2 sensors for QCM were characterized by atomic force microscopy and electron probe microanalysis observation, measurement of contact angle against water, and surface roughness. The amounts of Fn and Alb adsorbed onto the Ti and ZrO2 sensors and apparent reaction rate were obtained using QCM measurements. Ti sensor showed greater adsorption of Fn and Alb than the ZrO2 sensor. In addition, amount of Fn adsorbed onto the Ti or ZrO2 sensors was higher than that of Alb. The surface roughness and hydrophilicity of Ti or ZrO2 may influence the adsorption of Fn or Alb. With regard to the adsorption rate, Alb adsorbed more rapidly than Fn onto Ti. Comparing Ti and ZrO2, Alb adsorption rate to Ti was faster than that to ZrO2. Fn adsorption will be effective for cell activities, but Alb adsorption will not. QCM method could simulate in vivo Fn and Alb adsorption to Ti or ZrO2. PMID:28246591

Effect of Zirconium Addition on Microstructure and Mechanical Property of TiC/Ti6A14V Composites

NASA Astrophysics Data System (ADS)

Ma, Xuliang; Wang, Xiang; Li, Li; Gai, Pengtao; Zhu, Chengwu

TiC/Ti6A14V composites with different Zr additions were prepared successfully in a consumable vacuum arc furnace equipped with a water-cooled copper crucible and the effect of the Zr content on the microstructure and mechanical property of 15 vol.%TiC/Ti6A14V composites was investigated by XRD, SEM and hardness testing. The results show that when the level of Zr addition is less than 4 wt.%, the morphology of the primary TiC in the composites is dendrite, and the petal-shape, piece-shape or palpus-shape eutectic TiC separates out around the primary TiC. The average size of the primary TiC decreases and the amount of eutectic TiC increases gradually with increasing Zr content. The effects of Zr on morphology of the primary TiC weaken with further addition of Zr. And the hardness (HRC) of composites was obviously increased in the whole range of Zr addition. The refinement mechanism of Zr was attributed to the combined effects of increase in nucleation rate at the constitutionally supercooled zone ahead of the solidification front and reduction in growth rate.

Environmental Effects on Zirconium Hydroxide Nanoparticles and Chemical Warfare Agent Decomposition: Implications of Atmospheric Water and Carbon Dioxide.

PubMed

Balow, Robert B; Lundin, Jeffrey G; Daniels, Grant C; Gordon, Wesley O; McEntee, Monica; Peterson, Gregory W; Wynne, James H; Pehrsson, Pehr E

2017-11-15

Zirconium hydroxide (Zr(OH) 4 ) has excellent sorption properties and wide-ranging reactivity toward numerous types of chemical warfare agents (CWAs) and toxic industrial chemicals. Under pristine laboratory conditions, the effectiveness of Zr(OH) 4 has been attributed to a combination of diverse surface hydroxyl species and defects; however, atmospheric components (e.g., CO 2 , H 2 O, etc.) and trace contaminants can form adsorbates with potentially detrimental impact to the chemical reactivity of Zr(OH) 4 . Here, we report the hydrolysis of a CWA simulant, dimethyl methylphosphonate (DMMP) on Zr(OH) 4 determined by gas chromatography-mass spectrometry and in situ attenuated total reflectance Fourier transform infrared spectroscopy under ambient conditions. DMMP dosing on Zr(OH) 4 formed methyl methylphosphonate and methoxy degradation products on free bridging and terminal hydroxyl sites of Zr(OH) 4 under all evaluated environmental conditions. CO 2 dosing on Zr(OH) 4 formed adsorbed (bi)carbonates and interfacial carbonate complexes with relative stability dependent on CO 2 and H 2 O partial pressures. High concentrations of CO 2 reduced DMMP decomposition kinetics by occupying Zr(OH) 4 active sites with carbonaceous adsorbates. Elevated humidity promoted hydrolysis of adsorbed DMMP on Zr(OH) 4 to produce methanol and regenerated free hydroxyl species. Hydrolysis of DMMP by Zr(OH) 4 occurred under all conditions evaluated, demonstrating promise for chemical decontamination under diverse, real-world conditions.

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

DOE PAGES

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

2016-02-15

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

Development of phase analysis methods of impurity elements in alloys based on iron and nickel

NASA Astrophysics Data System (ADS)

Andreeva, N. A.; Anuchkin, S. N.; Volchenkova, V. A.; Kazenas, E. K.; Penkina, T. N.; Fomina, A. A.

2018-04-01

Using the method of AES with ICP, new methods have been developed for quantifying the content of various forms of existence of impurity elements: Al-Al2O3; Zr-ZrO2 in alloys based on iron (Fe-Sn) and nickel (Ni-Sn). Open systems were used to dissolve Al and Zr. To translate difficult-to-open aluminum oxides (corundum) and zirconium oxide (baddeleyite) into the solution, accelerated techniques were developed using the microwave system Mars 5. To confirm the completeness of the dissolution of oxides, a classical scheme of alloy fusion with alkali metal salts was used. Optimal analytical parameters for determining the elements: Al and Zr were chosen. The influence of matrix elements (iron and nickel) and methods of its elimination were studied. This made it possible to determine the elements in a wide concentration range from 1 • 10-3 to n% Al and from 1 • 10-4 to n% Zr without preliminary separation of the matrix with good metrological characteristics. The relative standard deviation (Sr) does not exceed 0,2. The separate determination of the contents of aluminum and aluminium oxide in the model melt of Fe-Sn-Al2O3 and zirconium and zirconium oxide in the Ni-Sn-ZrO2 model melt allowed us to estimate the number of nanoparticles participating in the heterophase interaction with tin and retired to the interface in the form of ensembles and the number of nanoparticles present in the melt and affecting the crystallization process and the structure of the metal.

[Radioactive nuclides in the marine environment--distribution and behaviour of 95Zr, 95Nb originated from fallout].

PubMed

Yamato, A; Miyagawa, N; Miyanaga, N

1984-07-01

To investigate behaviour of 95Zr, 95Nb in the marine environment, various samples have been collected and measured by means of Ge(Li) gamma-ray spectrometry and/or radiochemical analysis during a period from 1974 to 1982 at coastal area of Tokai-mura, Ibaraki prefecture. Concentration of the nuclides in seaweeds increased remarkably after atmospheric nuclear detonation by P.R. of China, and the activity ratio between the nuclides changed by time was not fit well by the transient decay equation. Concentration variation in sea water was smaller than that in sea weeds, and the minimum change in sea sediment. Increase of concentration in these environmental samples was observed in chronological order of sea water, sea weeds then sediment after detonations, suggesting that the uptake of the nuclides by these sea weeds from sea water is faster than that via root. Observed concentration factors on the nuclides by sea weeds were calculated from the observed concentrations in sea water and sea weeds. Maximum values on 95Zr and 95Nb were 2110, 2150, respectively for Ecklonia cava and Eisenia bicyclis.

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

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

Physically based DC lifetime model for lead zirconate titanate films

NASA Astrophysics Data System (ADS)

Garten, Lauren M.; Hagiwara, Manabu; Ko, Song Won; Trolier-McKinstry, Susan

2017-09-01

Accurate lifetime predictions for Pb(Zr0.52Ti0.48)O3 thin films are critical for a number of applications, but current reliability models are not consistent with the resistance degradation mechanisms in lead zirconate titanate. In this work, the reliability and lifetime of chemical solution deposited (CSD) and sputtered Pb(Zr0.52Ti0.48)O3 thin films are characterized using highly accelerated lifetime testing (HALT) and leakage current-voltage (I-V) measurements. Temperature dependent HALT results and impedance spectroscopy show activation energies of approximately 1.2 eV for the CSD films and 0.6 eV for the sputtered films. The voltage dependent HALT results are consistent with previous reports, but do not clearly indicate what causes device failure. To understand more about the underlying physical mechanisms leading to degradation, the I-V data are fit to known conduction mechanisms, with Schottky emission having the best-fit and realistic extracted material parameters. Using the Schottky emission equation as a base, a unique model is developed to predict the lifetime under highly accelerated testing conditions based on the physical mechanisms of degradation.

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

DOEpatents

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

2016-09-06

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

Microbial BOD sensors based on Zr (IV)-loaded collagen fiber.

PubMed

Zhao, Lei; He, Li; Chen, Shujuan; Zou, Likou; Zhou, Kang; Ao, Xiaolin; Liu, Shuliang; Hu, Xinjie; Han, Guoquan

2017-03-01

Biochemical oxygen demand (BOD) sensors based on Zr (IV)-loaded collagen fiber (ZrCF), a novel material with great porous structure, were developed. This novel material shows adsorbability by microorganisms. Saccharomyces cerevisiae and Escherichia coli were used for the construction of BOD sensors. Factors affecting BOD sensor performance were examined. The ZrCF-based BOD sensor showed different sensitivities and linear response ranges with different biofilm densities. The amount of microorganisms strongly affected the performance of the BOD sensor. Poor permeability of previously reported immobilization carriers were greatly circumvented by ZrCF. The service life of the ZrCF-based BOD sensor was more than 42 days. The immobilized microorganisms can be stored for more than 6 months under 4°C in PB solution. There was good correlation between the results of the sensor method and the standard 5-day BOD method in the determination of pure organic substrates and real water samples. Copyright © 2016 Elsevier Inc. All rights reserved.

Photoluminescence and cathodoluminescence of Tb-doped Al 2O 3-ZrO 2 nanostructures obtained by sol-gel method

NASA Astrophysics Data System (ADS)

Zawadzki, M.; Hreniak, D.; Wrzyszcz, J.; Miśta, W.; Grabowska, H.; Malta, O. L.; Stręk, W.

2003-07-01

Terbium-doped Al 2O 3-ZrO 2 mixed oxides of 10 wt% zirconia content were prepared by the alkoxide sol-gel method. The obtained samples were characterized by XRD, SEM, thermal analysis, textural and TPR studies. The effect of thermal treatment of Tb-doped Al 2O 3-ZrO 2 samples on photo- and cathodoluminescence spectra was investigated. It was found that the photoluminescence spectrum induced by UV excitation was characterized by a green luminescence pattern arising from the 5D 4 → 7F J ( J=6-0) transitions of the Tb 3+ ion. This photoluminescence became almost completely damped for the samples sintered at 1200 °C. However, these samples have demonstrated an intense cathodoluminescence under high electron accelerating potential (60 kV). Moreover, it was observed that apart of the green luminescence, the blue emission lines arising from 5D 3 → 7F J transitions of Tb 3+ were observed. The nature of such behavior is discussed.

Characterization and Evaluation of Ti-Zr-V Non-evaporable Getter Films Used in Vacuum Systems

NASA Astrophysics Data System (ADS)

Ferreira, M. J.; Seraphim, R. M.; Ramirez, A. J.; Tabacniks, M. H.; Nascente, P. A. P.

Among several methods used to obtain ultra-high vacuum (UHV) for particles accelerators chambers, it stands out the internal coating with metallic films capable of absorbing gases, called NEG (non-evaporable getter). Usually these materials are constituted by elements of great chemical reactivity and solubility (such as Ti, Zr, and V), at room temperature for oxygen and other gases typically found in UHV, such as H2, CO, and CO2. Gold and ternary Ti-Zr-V films were produced by magnetron sputtering, and their composition, structure, morphology, and aging characteristics were characterized by energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field emission gun sc anning electronmicroscopy (FEG-SEM), atomic force microscopy (AFM), high resolution transmission electron microscopy (HRTEM). The comparison between the produced films and commercial samples indicated that the desirable characteristics depend on the nanometric structure of the films and that this structure is sensitive to the heat treatments.

Zirconium(IV) functionalized magnetic nanocomposites for extraction of organophosphorus pesticides from environmental water samples.

PubMed

Jiang, Li; Huang, Tengjun; Feng, Shun; Wang, Jide

2016-07-22

The widespread use of organophosphate pesticides (OPPs) in agriculture leads to residue accumulation in the environment which is dangerous to human health and disrupts the ecological balance. In this work, one nanocomposite immobilized zirconium (Zr, IV) was prepared and used as the affinity probes to quickly and selectively extract organophosphorus pesticides (OPPs) from water samples. The Fe3O4-ethylenediamine tetraacetic acid (EDTA)@Zr(IV) nanocomposites (NPs) were prepared by simply mixing Zr(IV) ions with Fe3O4-EDTA NPs synthesized by one-pot chemical co-precipitation method. The immobilized Zr(IV) ions were further utilized to capture OPPs based on their high affinity for the phosphate moiety in OPPs. Coupled with GC-MS, four OPPs were used as models to demonstrate the feasibility of this approach. Under the optimum conditions, the limits of detection for target OPPs were in the range of 0.10-10.30ngmL(-1) with relative standard deviations (RSDs) of 0.61-4.40% (n=3), respectively. The linear ranges were over three orders of magnitudes (correlation coefficients, R(2)>0.9995). The Fe3O4-EDTA@Zr(IV) NPs were successfully applied to extract OPPs samples with recoveries of 86.95-112.60% and RSDs of 1.20-10.42% (n=3) from two spiked real water. By the proposed method, the matrix interference could be effectively eliminated. We hope our finding can provide a promising alternative for the fast extraction of OPPs from complex real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

DOE PAGES

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

2017-04-22

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

Zetameter for microelectrophoresis studies of the oxide/water interface at temperatures up to 200 °C

NASA Astrophysics Data System (ADS)

Zhou, X. Y.; Wei, X. J.; Fedkin, M. V.; Strass, K. H.; Lvov, S. N.

2003-04-01

The zeta potential (ZP) is an important and measurable parameter related to the electrical double layer structure at a solid-aqueous solution interface. A high temperature zetameter based on the microelectrophoresis technique was developed to determine the zeta potential and the isoelectric point (IEP) of the metal oxide/water interfaces at temperatures up to 200 °C and pressures up to 50 bar. Design of the microelectrophoresis cell, the main unit of the zetameter, utilized a flow-through concept and the cell internals were made from corrosion resistant materials in order to minimize materials degradation and solution contamination. Two sapphire windows were installed to the microelectrophoresis cell to enable observation of the particle movement under an imposed electrical field. A ZrO2 powder was used to test the zetameter. The ZP for the ZrO2/water system was measured over wide ranges of temperature and pH. The IEP of the ZrO2/water system was found equal to 6.05 at room temperature, 5.00 at 120 °C, and 4.67 at 200 °C. Thus, at room temperature, the IEP obtained was within the confidence interval of the averaged literature data. In addition, it was found that the IEP of ZrO2 was sensitive to temperature and the difference between the IEP and 0.5pKw remained constant (1.00±0.2) with temperatures up to 200 °C.

Synthesis of antimicrobial Nisin-phosphorylated soybean protein isolate/poly(L-lactic acid)/ZrO2 membranes.

PubMed

Jiang, Suwei; Wang, Hualin; Chu, Chenjiang; Ma, Xingkong; Sun, Min; Jiang, Shaotong

2015-01-01

Electrospinning technique was used to fabricate the model drug Nisin loaded phosphorylated soybean protein isolate/poly(l-lactic acid)/zirconium dioxide (Nisin-PSPI/PLLA/ZrO2) nanofibrous membranes. The average diameter of drug carrier PSPI/PLLA/ZrO2 nanofibers increased with the increase of content PSPI and some spindle-shape beads appeared when PSPI content reached 25 wt%. The loading dosage of Nisin caused no significant changes in the size and morphology of nanofibers when Nisin content was below 9 wt%. There existed hydrogen and Zr-O-C bonds among PSPI, PLLA and ZrO2 units, and the crystalline of PLLA matrix decreased owning to the introducing of PSPI and ZrO2 units. Moreover, the water absorption capability and degradation rate of PSPI/PLLA/ZrO2 nanofibrous membranes increased with increasing PSPI content. The antimicrobial activity and release experimental results showed that Nisin-PSPI/PLLA/ZrO2 nanofibrous membranes displayed well controlled release and better antimicrobial activity against Staphylococcus aureus (S. aureus), and the Nisin release from the medicated nanofibers could be described by Fickian diffusion model. The Nisin-PSPI/PLLA/ZrO2 nanofibrous membranes may have potential as a new nanofibrous membrane in drug delivery, food active packaging and wound dressing. Copyright © 2014 Elsevier B.V. All rights reserved.

Silica-gel Particles Loaded with an Ionic Liquid for Separation of Zr(IV) Prior to Its Determination by ICP-OES.

PubMed

Marwani, Hadi M; Alsafrani, Amjad E; Asiri, Abdullah M; Rahman, Mohammed M

2016-06-29

A new ionic liquid loaded silica gel amine (SG-APTMS-N,N-EPANTf₂) was developed, as an adsorptive material, for selective adsorption and determination of zirconium, Zr(IV), without the need for a chelating intermediate. Based on a selectivity study, the SG-APTMS-N,N-EPANTf₂ phase showed a perfect selectivity towards Zr(IV) at pH 4 as compared to other metallic ions, including gold [Au(III)], copper [Cu(II)], cobalt [Co(II)], chromium [Cr(III)], lead [Pb(II)], selenium [Se(IV)] and mercury [Hg(II)] ions. The influence of pH, Zr(IV) concentration, contact time and interfering ions on SG-APTMS-N,N-EPANTf₂ uptake for Zr(IV) was evaluated. The presence of incorporated donor atoms in newly synthesized SG-APTMS-N,N-EPANTf₂ phase played a significant role in enhancing its uptake capacity of Zr(IV) by 78.64% in contrast to silica gel (activated). The equilibrium and kinetic information of Zr(IV) adsorption onto SG-APTMS-N,N-EPANTf₂ were best expressed by Langmuir and pseudo second-order kinetic models, respectively. General co-existing cations did not interfere with the extraction and detection of Zr(IV). Finally, the analytical efficiency of the newly developed method was also confirmed by implementing it for the determination of Zr(IV) in several water samples.

Effect of the SiO2 Support on the Catalytic Performance of Ag/ZrO2/SiO2 Catalysts for the Single-Bed Production of Butadiene from Ethanol

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

Dagle, Vanessa; Flake, Matthew D.; Lemmon, Teresa

2018-05-18

A ternary Ag/ZrO2/SiO2 catalyst system was studied for the single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO2 loading, and choice of SiO2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO2/SiO2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325ºC, 1 atm, 0.23 hr-1). Several classes of silica (i.e., silica gels, fumed silicas, meoporous silicas) were evaluated as support, and SBA-16 was found to be the most promising. The nature of the SiO2 support wasmore » found to have a strong influence on both conversion and selectivity. Higher SiO2 catalyst surface areas lead to greater conversion due to increased Ag dispersion thus accelerating the initial ethanol dehydrogenation reaction. By independently varying Ag and ZrO2 loading, Ag was found to be the main component affecting ethanol conversion. Butadiene selectivity varied depending on the concentration of ZrO2 and acidic characteristics of the SiO2 support. A direct relationship between butadiene selectivity and concentration of Lewis acid sites was evidenced. Also, adding H2 to the feed had little effect on conversion while improving catalytic stability, however, selectivity to butadiene was decreased. Finally, catalyst regenerability was successfully demonstrated for several cycles.« less

Effect of the SiO 2 support on the catalytic performance of Ag/ZrO 2 /SiO 2 catalysts for the single-bed production of butadiene from ethanol

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

Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L.

A ternary Ag/ZrO2/SiO2 catalyst system was studied for the single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO2 loading, and choice of SiO2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO2/SiO2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325ºC, 1 atm, 0.23 hr-1). Several classes of silica (i.e., silica gels, fumed silicas, meoporous silicas) were evaluated as support, and SBA-16 was found to be the most promising. The nature of the SiO2 support wasmore » found to have a strong influence on both conversion and selectivity. Higher SiO2 catalyst surface areas lead to greater conversion due to increased Ag dispersion thus accelerating the initial ethanol dehydrogenation reaction. By independently varying Ag and ZrO2 loading, Ag was found to be the main component affecting ethanol conversion. Butadiene selectivity varied depending on the concentration of ZrO2 and acidic characteristics of the SiO2 support. A direct relationship between butadiene selectivity and concentration of Lewis acid sites was evidenced. Also, adding H2 to the feed had little effect on conversion while improving catalytic stability, however, selectivity to butadiene was decreased. Finally, catalyst regenerability was successfully demonstrated for several cycles.« less

In situ crystallized zirconium phenylphosphonate films with crystals vertically to the substrate and their hydrophobic, dielectric, and anticorrosion properties.

PubMed

Cui, Zhaohui; Zhang, Fazhi; Wang, Lei; Xu, Sailong; Guo, Xiaoxiao

2010-01-05

The in situ crystallization technique has been utilized to fabricate zirconium phenylphosphonate (ZrPP) films with their hexagonal crystallite perpendicular to the copper substrate. The micro/nano roughness surface structure, as well as the intrinsic hydrophobic characteristic of the surface functional groups, affords ZrPP films excellent hydrophobicity with water contact angle (CA) ranging from 134 degrees to 151 degrees , without any low-surface-energy modification. Particularly, in the corrosive solutions such as acidic or basic solutions over a wide pH from 2 to 12, no obvious fluctuation in CA was observed for all the ZrPP film. The k values of the hydrophobic ZrPP films are in the low-k range (k < 3.0), meeting the development of ultra-large-scale integration (ULSI) circuits. The hydrophobicity feature is proposed to bear ZrPP film a more stable low-k value in an ambient atmosphere. Besides, the polarization current of ZrPP films is reduced by 2 orders of magnitude, compared to that of the untreated copper substrate. Even deposited in a vacuum oven for 30 days at room temperature, ZrPP films also show excellent corrosion resistance, indicating a stable anticorrosion property.

Novel one-pot synthesis of dicarboxylic acids mediated alginate-zirconium biopolymeric complex for defluoridation of water.

PubMed

Prabhu, Subbaiah Muthu; Meenakshi, Sankaran

2015-04-20

The present investigation explains the fluoride removal from aqueous solution using alginate-zirconium complex prepared with respective dicarboxylic acids like oxalic acid (Ox), malonic acid (MA) and succinic acid (SA) as a medium. The complexes viz., alginate-oxalic acid-zirconium (Alg-Ox-Zr), alginate-malonic acid-zirconium (Alg-MA-Zr) and alginate-succinic acid-zirconium (Alg-SA-Zr) were synthesized and studied for fluoride removal. The synthesized complexes were characterized by FTIR, XRD, SEM with EDAX and mapping images. The effects of various operating parameters were optimized. The result showed that the maximum removal of fluoride 9653mgF(-)/kg was achieved by Alg-Ox-Zr complex at acidic pH in an ambient atmospheric condition. Equilibrium data of Alg-Ox-Zr complex was fitted well with Freundlich isotherm. The calculated values of thermodynamic parameters indicated that the fluoride adsorption is spontaneous and endothermic in nature. The mechanism of fluoride removal behind Alg-Ox-Zr complex has been proposed in detail. The suitability of the Alg-Ox-Zr complex has been tested with the field sample collected in a nearby fluoride endemic area. Copyright © 2014 Elsevier Ltd. All rights reserved.

Study of corrosion-related defects of zirconium alloys with slow positron beam

NASA Astrophysics Data System (ADS)

Zhu, Zhejie; Yao, Meiyi; Shi, Jianjian; Yao, Chunlong; Lu, Eryang; Cao, Xingzhong; Wang, Baoyi; Wu, Yichu

2018-09-01

The corrosion behavior of Zr-4 and N5 alloy specimens corroded in 0.01 mol/L LiOH aqueous solution at 360 °C/18.6 MPa and in super heated steam at 400 °C/10.3 MPa for 1, 3 and 14 days were investigated by slow positron beam based Doppler broadening spectroscopy. Results showed that there was an evident interfacial layer with pre-existed vacancies and voids in uncorroded Zr-4 specimens, while in uncorroded N5 specimen, the interfacial defect layer can not be identified or a thin interfacial layer was only contained. When the specimens were corroded in super heated steam at 400 °C/10.3 MPa for a few days, the existence of the interface layer in the Zr-4 specimen would delay the diffusion rate of the oxygen atoms and decelerated the oxidation rate of the corrosion process. However, at very early stage of the corrosion, as Zr-4 and N5 specimens were corrded in 0.01 mol/L LiOH aqueous solution at 360 °C/18.6 MPa, the effect of Li+ accelerated the diffusion rate of the oxygen atoms, while the effect of the interface defect layer became a minor effect.

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

PubMed

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

2017-05-01

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

Performance modeling of Deep Burn TRISO fuel using ZrC as a load-bearing layer and an oxygen getter

NASA Astrophysics Data System (ADS)

Wongsawaeng, Doonyapong

2010-01-01

The effects of design choices for the TRISO particle fuel were explored in order to determine their contribution to attaining high-burnup in Deep Burn modular helium reactor fuels containing transuranics from light water reactor spent fuel. The new design features were: (1) ZrC coating substituted for the SiC, allowing the fuel to survive higher accident temperatures; (2) pyrocarbon/SiC "alloy" substituted for the inner pyrocarbon coating to reduce layer failure and (3) pyrocarbon seal coat and thin ZrC oxygen getter coating on the kernel to eliminate CO. Fuel performance was evaluated using General Atomics Company's PISA code. The only acceptable design has a 200-μm kernel diameter coupled with at least 150-μm thick, 50% porosity buffer, a 15-μm ZrC getter over a 10-μm pyrocarbon seal coat on the kernel, an alloy inner pyrocarbon, and ZrC substituted for SiC. The code predicted that during a 1600 °C postulated accident at 70% FIMA, the ZrC failure probability is <10-4.

The Effect of Platinum-coatings on Hydrogen- and Water-absorption and Desorption Characteristics of Lithium Zirconate

NASA Astrophysics Data System (ADS)

Tsuchiya, B.; Bandow, S.; Nagata, S.; Saito, K.; Tokunaga, K.; Morita, K.

Hydrogen (H)- and water (H2O)-storage and desorption characteristics of 25 nm thick Pt films onLi2ZrO3composite materials, exposed to normal air at room temperature, have been investigated by means of elastic recoil detection (ERD), Rutherford backscattering spectrometry (RBS), weight gain measurement (WGM), and thermal desorption spectroscopy (TDS) techniques. It was found by the ERD and TDS that H and H2O were absorbed into the Pt-coated Li2ZrO3 in air at room temperature and desorbed from it in vacuum at much low temperatures of approximately 317 and 309 K, respectively. In addition, the WGM and TDS spectra revealed that the absorption and desorption characters ofsome gases such as CH4, CO, and CO2including H as well as H2Ointo the Li2ZrO3 bulk were improved by Pt deposition.

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

NASA Astrophysics Data System (ADS)

Esmaeilzadeh, Pouriya; Bahramian, Alireza; Fakhroueian, Zahra

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

The use of functionalized zirconocenes as precursors to silica-supported zirconocene olefin polymerization catalysts

NASA Astrophysics Data System (ADS)

Cheng, Xu

2001-07-01

Me3Si substituents adjacent to Cp2MCl2 (M = Ti, Zr, Hf) are converted to BrMe2Si groups using BBr 3. The high reactivity of the Si-Br bonds toward nucleophiles such as water suggested that these substituents could react with hydroxylated silica surfaces, immobilizing the metallocenes. This dissertation concerns the syntheses of electrophile-functionalized zirconocene dihalide complexes and their use as precursors to silica-supported metallocene olefin polymerization catalysts. First we extended the metallocene "functionalization" chemistry to obtain substituents bearing more than one electrophilic bond. (Me3Sn) 2C5H4 combined with CpZrCl3 in toluene to afford (eta5-Me3Sn-C5H4)CpZrCl 2 (A). Reactions of A with electrophiles (E-X = Cl2B-Cl, I-Cl, and I-I) afforded (eta5-XMe 2Sn-C5H4)CpZrCl2 (and E-Me) cleanly. The reaction of A with BBr3 afforded either (eta5-BrMe2Sn-C5H4)CpZrBr2 (25 °C, 10 min) or (eta5-Br2MeSn-C5H 4)CpZrBr2 (25 °C, 15 h). Ph2MeSi-C5H 4Li combined with ZrCl4•2THF to afford (eta 5-Ph2MeSi-C5H4)2ZrCl 2 (B). The reaction of B with BCl3 led to incomplete cleavage of the Ph-Si bonds, however treatment of B with BBr3 afforded (eta5-Br2MeSi-C 5H4)2ZrBr2 (C) efficiently. X-ray crystal structures of (eta5-ClMe2Sn-C 5H4)CpZrCl2•1/2toluene, (eta 5-Br2MeSn-C5H4)CpZrBr2•THF, B, and C were obtained. Metallocene C reacts with water to afford an oligosiloxane-supported zirconocene dibromide. Spectroscopic characterization suggested a stereoregular structure in which the metallocene units have meso symmetry. The oligomeric substance showed high activity for homogeneous ethylene polymerization. Supported metallocene olefin polymerization catalysts were prepared by combining a functionalized metallocene precursor (Cp2ZrBr 2 bearing either BrMe2Si or Br2MeSi groups) and partially dehydroxylated silica. The activities of the immobilized zirconocene catalysts decreased and the stabilities increased with increasing number of tethers. The immobilized catalyst prepared from (eta5-Br 2MeSi-C5H4)2ZrBr2, which is assumed to form two "double-tethers" to silica, was significantly more active than the catalyst prepared from [eta5-1,3-(BrMe 2Si)2C5H3]2ZrBr2, which is assumed to form four "single-tethers" to silica. Catalyst leaching was observed in all the immobilized zirconocene catalysts. Finally we report model studies on the stability of the Si-O-Si bonds toward methylaluminoxane (MAO). The reaction of (eta5-BrMe 2Si-C5H4)CpZrBr2 with tBuMe 2SiOH results in the formation of Si-O-Si bonds; addition of NEt 3 results in further reaction to afford Si-O-Zr bonds. The reaction of Me3Si-O-SiMe3 with MAO showed that Si-O-Si bonds can be cleaved under the conditions of our polymerization reactions.

Calculations of hydrogen diffusivity in Zr-based alloys: Influence of alloying elements and effect of stress

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

Yu, J.; Jiang, C.; Zhang, Y.

This report summarizes the progress on modeling hydrogen diffusivity in Zr-based alloys. The presence of hydrogen (H) can detrimentally affect the mechanical properties of many metals and alloys. To mitigate these detrimental effects requires fundamental understanding of the thermodynamics and kinetics governing H pickup and hydride formation. In this work, we focus on H diffusion in Zr-based alloys by studying the effects of alloying elements and stress, factors that have been shown to strongly affect H pickup and hydride formation in nuclear fuel claddings. A recently developed accelerated kinetic Monte Carlo method is used for the study. It is foundmore » that for the alloys considered here, H diffusivity depends weakly on composition, with negligible effect at high temperatures in the range of 600-1200 K. Therefore, the small variation in compositions of these alloys is likely not a major cause of the very different H pickup rates. In contrast, stress strongly affects H diffusivity. This effect needs to be considered for studying hydride formation and delayed hydride cracking.« less

Nuclear Structure of the Closed Subshell Nucleus 90Zr Studied with the (n,n'(gamma)) Reaction

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

Garrett, P E; Younes, Y; Becker, J A

States in {sup 90}Zr have been observed with the (n,n{prime}{gamma}) reaction using both spallation and monoenergetic accelerator-produced neutrons. A scheme comprised of 81 levels and 157 transitions was constructed concentrating on levels below 5.6 MeV in excitation energy. Spins have been determined by considering data from all experimental studies performed for {sup 90}Zr. Lifetimes have been deduced using the Doppler-shift attenuation method for many of the states and transition rates have been obtained. A spherical shell-model interpretation in terms of particle-hole excitations assuming a {sup 88}Sr closed core is given. In some cases, enhancements in B(M1) and B(E2) values aremore » observed that cannot be explained by assuming simple particle-hole excitations. Shell-model calculations using an extended f pg-shell model space reproduce the spectrum of excited states very well, and the gross features of the B(M1) and B(E2) transition rates. Transition rates for individual levels show discrepancies between calculations and experimental values.« less

Cascade Reductive Etherification of Bioderived Aldehydes over Zr-Based Catalysts.

PubMed

Shinde, Suhas; Rode, Chandrashekhar

2017-10-23

An efficient one-pot catalytic cascade sequence has been developed for the production of value-added ethers from bioderived aldehydes. Etherification of 5-(hydroxymethyl)furfural with different aliphatic alcohols over acidic Zr-montmorillonite (Zr-Mont) catalyst produced a mixture of 5-(alkoxymethyl)furfural and 2-(dialkoxymethyl)-5-(alkoxymethyl)furan. The latter was selectively converted back into 5-(alkoxymethyl)furfural by treating it with water over the same catalyst. The synthesis of 2,5-bis(alkoxymethyl)furan was achieved through a cascade sequence involving etherification, transfer hydrogenation, and re-etherification over a combination of acidic Zr-Mont and the charge-transfer hydrogenation catalyst [ZrO(OH) 2 ]. This catalyst combination was further explored for the cascade conversion of 2-furfuraldehyde into 2-(alkoxymethyl)furan. The scope of this strategy was then extended for the reductive etherification of lignin-derived arylaldehydes to obtain the respective benzyl ethers in >80 % yield. Additionally, the mixture of Zr-Mont and ZrO(OH) 2 does not undergo mutual destruction, which was proved by recycling experiments and XRD analysis. Both the catalysts were thoroughly characterized using BET, temperature-programmed desorption of NH 3 and CO 2 , pyridine-FTIR, XRD, inductively coupled plasma optical emission spectroscopy, and X-ray photoelectron spectroscopy techniques. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Fournelle, J.; Hanchar, J. M.

2013-12-01

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

Hierarchical Na-doped cubic ZrO2 synthesis by a simple hydrothermal route and its application in biodiesel production

NASA Astrophysics Data System (ADS)

Lara-García, Hugo A.; Romero-Ibarra, Issis C.; Pfeiffer, Heriberto

2014-10-01

Hierarchical growth of cubic ZrO2 phase was successfully synthesized via a simple hydrothermal process in the presence of different surfactants (cationic, non-ionic and anionic) and sodium hydroxide. The structural and microstructural characterizations of different ZrO2 powders were performed using various techniques, such as X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption, scanning electron microscopy and infrared. Results indicated that sodium addition stabilized the cubic ZrO2 phase by a Na-doping process, independently of the surfactant used. In contrast, microstructural characteristics varied as a function of the surfactant and sodium presence. In addition, water vapor (H2O) and carbon dioxide (CO2) sorption properties were evaluated on ZrO2 samples. Results evidenced that sample surface reactivity changed as a function of the sodium content. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction using the different synthesized samples, obtaining yields of 93%.

An in situ neutron diffraction study of plastic deformation in a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite

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

Wang, D. M.; Chen, Yan; Mu, Juan

Micro-mechanical behaviors of a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite in the plastic regime were investigated by continuous in situ neutron diffraction during compression. Three stages of the plastic deformation were observed according to the work-hardening rate. Here, the underlying natures of the work hardening, correlating with the lattice/microscopic strain evolution, are revealed for the three stages: (1) the initiation of shear bands, (2) the phase load transferring from the amorphous phase to the B2 phase and (3) the accelerated martensitic transformation and the work hardening of the polycrystalline phases promoted by the rapid propagation of the shearmore » bands.« less

An in situ neutron diffraction study of plastic deformation in a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite

DOE PAGES

Wang, D. M.; Chen, Yan; Mu, Juan; ...

2018-05-21

Micro-mechanical behaviors of a Cu 46.5Zr 46.5Al 7 bulk metallic glass composite in the plastic regime were investigated by continuous in situ neutron diffraction during compression. Three stages of the plastic deformation were observed according to the work-hardening rate. Here, the underlying natures of the work hardening, correlating with the lattice/microscopic strain evolution, are revealed for the three stages: (1) the initiation of shear bands, (2) the phase load transferring from the amorphous phase to the B2 phase and (3) the accelerated martensitic transformation and the work hardening of the polycrystalline phases promoted by the rapid propagation of the shearmore » bands.« less

AN ATTEMPT TO LOCATE INTERMETALLIC PARTICLES IN ZIRCONIUM ALLOYS USING A BITTER FIGURE TECHNIQUE

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

Cox, B.; Harder, B.R.

1961-10-01

The compound ZrFe/sub 2/ is known to be ferromagnetic, and an attempt to locate particles of magnetic material in zircaloy-2 and dilute Zr- Fe alloys by a Bitter figure technlque is described. An Fe/sub 3/O/sub 4/ sol in water-soluble plastic was used to prepare Bitter figures of the alloy surfaces in the form of replicas, which were then examined in an electron microscope. No magnetic particles were located in either zircaloy-2 or a Zr-O.3% Fe alloy. Subsequent work on specimens of ZrFe/sub 2/ showed that the failure to detect it in the dilute alloys arose because the size of themore » intermetallic particles in the latter was smaller than the size of the magnetic domains. (auth)« less

Interfacial Energy Transfer during Gamma Radiolysis of Water on the Surface of ZrO2 and Some Other Oxides

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

Petrik, Nikolay G.; Alexandrov, Alexandr B.; Vall, Andrey I.

Effect of oxide interface on 60Co gamma radiolysis of water molecules was studied. Based on the molecular hydrogen yield when compared with that from the radiolysis of pure gas-phase water, all tested oxides can be classified into three groups: (i) inhibitors - MnO2, Co3O4, CuO and Fe2O3; (ii) oxides with H2 yields, which are similar to or slightly greater than radiolysis of pure gas-phase water - MgO, CaO, SrO, BaO, ZnO, CdO, Cu2O, NiO, Cr2O3, Al2O3, CeO2, SiO2, TiO2, Nb2O5 and WO3; (iii) promoters - Ga2O3, Y2O3, La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Yb2O3, Er2O3, HfO2, and ZrO2. H2O radiolysis enhancementmore » for ZrO2 and other promoters is result of effective energy transfer at the oxide/water interface, presumably due to migration of excitons to the surface and their resonant coupling with the H2O adsorption complex. Plot''effective H2 yield vs. band-gap (Eg) energy'' shows a maximum near 5 eV.« less

Effects of alloying elements and heat treatments on mechanical properties of Korean reduced-activation ferritic-martensitic steel

NASA Astrophysics Data System (ADS)

Chun, Y. B.; Kang, S. H.; Noh, S.; Kim, T. K.; Lee, D. W.; Cho, S.; Jeong, Y. H.

2014-12-01

As part of an alloy development program for Korean reduced-activation ferritic-martensitic (RAFM) steel, a total of 37 program alloys were designed and their mechanical properties were evaluated with special attention being paid to the effects of alloying elements and heat treatments. A reduction of the normalizing temperature from 1050 °C to 980 °C was found to have a positive effect on the impact resistance, resulting in a decrease in ductile-brittle transition-temperature (DBTT) of the program alloys by an average of 30 °C. The yield strength and creep rupture time are affected strongly by the tempering time at 760 °C but at the expense of ductility. Regarding the effects of the alloying elements, the addition of trace amounts of Zr enhances both the creep and impact resistance: the lowest DBTT was observed for the alloys containing 0.005 wt.% Zr, whereas the addition of 0.01 wt.% Zr extends the creep rupture-time under an accelerated condition. The enhanced impact resistance owing to the normalizing at lower temperature is attributed to a more refined grain structure, which provides more barriers to the propagation of cleavage cracks. Solution softening by Zr addition is suggested as a possible mechanism for enhanced resistance to both impact and creep of the program alloys.

Improved production and processing of ⁸⁹Zr using a solution target.

PubMed

Pandey, Mukesh K; Bansal, Aditya; Engelbrecht, Hendrik P; Byrne, John F; Packard, Alan B; DeGrado, Timothy R

2016-01-01

The objectives of the present work were to improve the cyclotron production yield of (89)Zr using a solution target, develop a practical synthesis of the hydroxamate resin used to process the target, and develop a biocompatible medium for (89)Zr elution from the hydroxamate resin. A new solution target (BMLT-2) with enhanced heat dissipation capabilities was designed by using helium-cooled dual foils (0.2 mm Al and 25 μ Havar) and an enhanced water-cooled, elongated solution cavity in the target insert. Irradiations were performed with 14 MeV protons on a 2M solution of yttrium nitrate in 1.25 M nitric acid at 40-μA beam current for 2 h in a closed system. Zirconium-89 was separated from Y by use of a hydroxamate resin. A one-pot synthesis of hydroxamate resin was accomplished by activating the carboxylate groups on a carboxymethyl cation exchange resin using methyl chloroformate followed by reaction with hydroxylamine hydrochloride. After trapping of (89)Zr on hydroxamate resin and rinsing the resin with HCl and water to release Y, (89)Zr was eluted with 1.2 M K2HPO4/KH2PO4 buffer (pH3.5). ICP-MS was used to measure metal contaminants in the final (89)Zr solution. The BMLT-2 target produced 349±49 MBq (9.4±1.2 mCi) of (89)Zr at the end of irradiation with a specific activity of 1.18±0.79 GBq/μg. The hydroxamate resin prepared using the new synthesis method showed a trapping efficiency of 93% with a 75 mg resin bed and 96-97% with a 100-120 mg resin bed. The elution efficiency of (89)Zr with 1.2M K2HPO4/KH2PO4 solution was found to be 91.7±3.7%, compared to >95% for 1 M oxalic acid. Elution with phosphate buffer gave very small levels of metal contaminants: Al=0.40-0.86 μg (n=2), Fe=1.22±0.71 μg (n=3), Y=0.29 μg (n=1). The BMLT-2 target allowed doubling of the beam current for production of (89)Zr, resulting in a greater than 2-fold increase in production yield in comparison with a conventional liquid target. The new one-pot synthesis of hydroxamate resin provides a simpler synthesis method for the (89)Zr trapping resin. Finally, phosphate buffer elutes the (89)Zrfrom the hydroxamate resin in high efficiency while at the same time providing a more biocompatible medium for subsequent use of (89)Zr. Copyright © 2015 Elsevier Inc. All rights reserved.

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

PubMed

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

2018-05-09

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

Removal of model viruses, E. coli and Cryptosporidium oocysts from surface water by zirconium and chitosan coagulants.

PubMed

Christensen, Ekaterina; Nilsen, Vegard; Håkonsen, Tor; Heistad, Arve; Gantzer, Christophe; Robertson, Lucy J; Myrmel, Mette

2017-10-01

The present work evaluates the effect of contact filtration, preceded by coagulation with zirconium (Zr) and chitosan coagulants, on model microorganisms and waterborne pathogens. River water intended for potable water production was spiked with MS2 and Salmonella Typhimurium 28B bacteriophages, Escherichia coli, and Cryptosporidium parvum oocysts prior to coagulation. The hygienic performance demonstrated by Zr comprised 3.0-4.0 log 10 removal of viruses and 5.0-6.0 log 10 removal of E. coli and C. parvum oocysts. Treatment with chitosan resulted in a removal of 2.5-3.0 log 10 of viruses and parasites, and 4.5-5.0 log 10 of bacteria. A reference coagulant, polyaluminium chloride (PACl), gave a 2.5-3.0 log 10 removal of viruses and 4.5 log 10 of E. coli. These results indicate that both Zr and chitosan enable adequate removal of microorganisms from surface water. The present study also attempts to assess removal rates of the selected microorganisms with regard to their size and surface properties. The isoelectric point of the Salmonella Typhimurium 28B bacteriophage is reported for the first time. The retention of the selected microorganisms in the filter bed appeared to have some correlation with their size, but the effect of the charge remained unclear.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Beneficial effect of Cu on Ti-Nb-Ta-Zr sputtered uniform/adhesive gum films accelerating bacterial inactivation under indoor visible light.

PubMed

Alhussein, Akram; Achache, Sofiane; Deturche, Regis; Sanchette, Frederic; Pulgarin, Cesar; Kiwi, John; Rtimi, Sami

2017-04-01

This article presents the evidence for the significant effect of copper accelerating the bacterial inactivation on Ti-Nb-Ta-Zr (TNTZ) sputtered films on glass up to a Cu content of 8.3 at.%. These films were deposited by dc magnetron co-sputtering of an alloy target Ti-23Nb-0.7Ta-2Zr (at.%) and a Cu target. The fastest bacterial inactivation of E. coli on this later TNTZ-Cu surface proceeded within ∼75min. The films deposited by magnetron sputtering are chemically homogenous. The film roughness evaluated by atomic force spectroscopy (AFM) on the TNTZ-Cu 8.3 at.% Cu sample presented an RMS-value of 20.1nm being the highest RMS of any Cu-sputtered TNTZ sample. The implication of the RMS value found for this sample leading to the fastest interfacial bacterial inactivation kinetics is also discussed. Values for the Young's modulus and hardness are reported for the TNTZ films in the presence of various Cu-contents. Evaluation of the bacterial inactivation kinetics of E. coli under low intensity actinic hospital light and in the dark was carried out. The stable repetitive bacterial inactivation was consistent with the extremely low Cu-ion release from the samples of 0.4 ppb. Evidence is presented by the bacterial inactivation dependence on the applied light intensity for the intervention of Cu as semiconductor CuO during the bacterial inactivation at the TNTZ-Cu interface. The mechanism of CuO-intervention under light is suggested based on the pH/and potential changes registered during bacterial disinfection. Copyright © 2017 Elsevier B.V. All rights reserved.

The production of radionuclides for nuclear medicine from a compact, low-energy accelerator system.

PubMed

Webster, William D; Parks, Geoffrey T; Titov, Dmitry; Beasley, Paul

2014-05-01

The field of nuclear medicine is reliant on radionuclides for medical imaging procedures and radioimmunotherapy (RIT). The recent shut-downs of key radionuclide producers have highlighted the fragility of the current radionuclide supply network, however. To ensure that nuclear medicine can continue to grow, adding new diagnostic and therapy options to healthcare, novel and reliable production methods are required. Siemens are developing a low-energy, high-current - up to 10 MeV and 1 mA respectively - accelerator. The capability of this low-cost, compact system for radionuclide production, for use in nuclear medicine procedures, has been considered. The production of three medically important radionuclides - (89)Zr, (64)Cu, and (103)Pd - has been considered, via the (89)Y(p,n), (64)Ni(p,n) and (103)Rh(p,n) reactions, respectively. Theoretical cross-sections were generated using TALYS and compared to experimental data available from EXFOR. Stopping power values generated by SRIM have been used, with the TALYS-generated excitation functions, to calculate potential yields and isotopic purity in different irradiation regimes. The TALYS excitation functions were found to have a good agreement with the experimental data available from the EXFOR database. It was found that both (89)Zr and (64)Cu could be produced with high isotopic purity (over 99%), with activity yields suitable for medical diagnostics and therapy, at a proton energy of 10MeV. At 10MeV, the irradiation of (103)Rh produced appreciable quantities of (102)Pd, reducing the isotopic purity. A reduction in beam energy to 9.5MeV increased the radioisotopic purity to 99% with only a small reduction in activity yield. This work demonstrates that the low-energy, compact accelerator system under development by Siemens would be capable of providing sufficient quantities of (89)Zr, (64)Cu, and (103)Pd for use in medical diagnostics and therapy. It is suggested that the system could be used to produce many other isotopes currently useful to nuclear medicine. Copyright © 2014 Elsevier Inc. All rights reserved.

Structural, vibrational and morphological properties of layered double hydroxides containing Ni{sup 2+}, Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+} cations

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

Bezerra, Débora M.

2017-03-15

Layered double hydroxides are anionic clays with formula [M{sup II}{sub 1−x} M{sup III}{sub x}(OH){sub 2}]{sup q+}[A{sup n−}]{sub q/n}·mH{sub 2}O, finding possible uses as catalyst support, adsorbents and so on. In this paper, we address the phase formation of layered double hydroxides containing Ni{sup 2+}, Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+} cations, namely, NiZn-Al, NiZn-AlZr and NiZn-Zr compositions obtained by the coprecipitation method. Such systems were characterized by X-ray diffraction, confirming the phase formation for NiZn-Al and NiZn-AlZr samples. Infrared and Raman spectroscopies elucidated the anion and water molecules occurrence in the interlayer. Nitrogen physisorption (BET method) determined the presencemore » of pores and specific surface area. The isotherm shapes were Type IV, according to the IUPAC, and represent a mesoporous structure. A morphological study was performed by means of scanning and transmission electron microscopies, and particle size values of 120, 131 and 235 nm for NiZn-Al, NiZn-AlZr and NiZn-Zr, respectively, were determined. Thermogravimetric analysis of the decomposition of the systems revealed that their complete disintegration occurred at ~ 450 °C and resulted in mixed oxides.« less

Effect of the SiO 2 support on the catalytic performance of Ag/ZrO 2/SiO 2 catalysts for the single-bed production of butadiene from ethanol

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

Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L.

A ternary Ag/ZrO 2/SiO 2 catalyst system was studied for single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO 2 loading, and choice of SiO 2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO 2/SiO 2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325°C, 1 atm, and 0.23 h –1). Several classes of silica—silica gels, fumed silicas, mesoporous silicas)—were evaluated as catalyst supports, and SBA-16 was found to be the most promising choice. Themore » SiO 2 support was found to significantly influence both conversion and selectivity. A higher SiO 2 catalyst surface area facilitates increased Ag dispersion which leads to greater conversion due to the accelerated initial ethanol dehydrogenation reaction step. By independently varying Ag and ZrO 2 loading, Ag was found to be the main component that affects ethanol conversion. ZrO 2 loading and thus Lewis acid sites concentration was found to have little impact on the ethanol conversion. Butadiene selectivity depends on the concentration of Lewis acid site, which in turn differs depending on the choice of SiO 2 support material. We observed a direct relationship between butadiene selectivity and concentration of Lewis acid sites. Butadiene selectivity decreases as the concentration of Lewis acid sites increases, which corresponds to an increase in ethanol dehydration to ethylene and diethyl ether. Additionally, adding H 2 to the feed had little effect on conversion while improving catalytic stability; however, selectivity to butadiene decreased. Lastly, catalyst regenerability was successfully demonstrated for several cycles.« less

Effect of the SiO 2 support on the catalytic performance of Ag/ZrO 2/SiO 2 catalysts for the single-bed production of butadiene from ethanol

DOE PAGES

Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L.; ...

2018-05-19

A ternary Ag/ZrO 2/SiO 2 catalyst system was studied for single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO 2 loading, and choice of SiO 2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO 2/SiO 2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325°C, 1 atm, and 0.23 h –1). Several classes of silica—silica gels, fumed silicas, mesoporous silicas)—were evaluated as catalyst supports, and SBA-16 was found to be the most promising choice. Themore » SiO 2 support was found to significantly influence both conversion and selectivity. A higher SiO 2 catalyst surface area facilitates increased Ag dispersion which leads to greater conversion due to the accelerated initial ethanol dehydrogenation reaction step. By independently varying Ag and ZrO 2 loading, Ag was found to be the main component that affects ethanol conversion. ZrO 2 loading and thus Lewis acid sites concentration was found to have little impact on the ethanol conversion. Butadiene selectivity depends on the concentration of Lewis acid site, which in turn differs depending on the choice of SiO 2 support material. We observed a direct relationship between butadiene selectivity and concentration of Lewis acid sites. Butadiene selectivity decreases as the concentration of Lewis acid sites increases, which corresponds to an increase in ethanol dehydration to ethylene and diethyl ether. Additionally, adding H 2 to the feed had little effect on conversion while improving catalytic stability; however, selectivity to butadiene decreased. Lastly, catalyst regenerability was successfully demonstrated for several cycles.« less

Impedance spectroscopy of water soluble resin modified by zirconium sulphate

NASA Astrophysics Data System (ADS)

Joseph, Anandraj; Joshi, Girish M.

2018-04-01

We successfully modified water soluble resin polyvinyl alcohol (PVA) by loading zirconium sulphate (ZrSO4). We demonstrated the measurement of electrical properties by using impedance analyser across frequency range (10 Hz-1 MHz) and the temperature range of (30°C to 150°C). The impedance spectroscopy demonstrates decrease in bulk resistance as a function of temperature loading of zirconia 2.5 wt. %. Increase in AC (10-5 S/cm and DC conductivity (10- 2 S/m) observed due to ionic contribution of zirconia. However, the electrical properties of PVA/ZrSO4 composite useful to develop battery electrolyte applications.

In-reactor oxidation of zircaloy-4 under low water vapor pressures

NASA Astrophysics Data System (ADS)

Luscher, Walter G.; Senor, David J.; Clayton, Kevin K.; Longhurst, Glen R.

2015-01-01

Complementary in- and ex-reactor oxidation tests have been performed to evaluate the oxidation and hydrogen absorption performance of Zircaloy-4 (Zr-4) under relatively low partial pressures (300 and 1000 Pa) of water vapor at specified test temperatures (330 and 370 °C). Data from these tests will be used to support the fabrication of components intended for isotope-producing targets and provide information regarding the temperature and pressure dependence of oxidation and hydrogen absorption of Zr-4 over the specified range of test conditions. Comparisons between in- and ex-reactor test results were performed to evaluate the influence of irradiation.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Synthesis of UiO-66-OH zirconium metal-organic framework and its application for selective extraction and trace determination of thorium in water samples by spectrophotometry

NASA Astrophysics Data System (ADS)

Moghaddam, Zahra Safaei; Kaykhaii, Massoud; Khajeh, Mostafa; Oveisi, Ali Reza

2018-04-01

In this study, a zirconium-based metal-organic framework (Zr-MOF), named UiO-66-OH, was synthesized by the solvo-thermal method and characterized by Fourier transform-infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). This Zr-MOF was then employed as a sorbent for selective extraction and preconcentration of thorium ions after their complexation with 2-(2,4-dihydroxyphenyl)-3,5,7-trihydroxychromen-4-one (morin) from environmental water samples prior to its spectrophotometrical determination. The experimental parameters affecting extraction, such as pH of sample solution, amount of Zr-MOF, type and volume of eluting solvent, adsorption and desorption time, and concentration of complexing agent were evaluated and optimized. Under the optimized conditions, an enrichment factor of 250 was achieved. The limit of detection was calculated to be 0.35 μg·L- 1 with a linear range between 10 and 2000 μg·L- 1of thorium. The maximum sorption capacity of MOF toward thorium was found to be 47.5 mg·g- 1. The proposed procedure was successfully applied to the analysis of real water samples.

Density functional theory calculations of the water interactions with ZrO2 nanoparticles Y2O3 doped

NASA Astrophysics Data System (ADS)

Subhoni, Mekhrdod; Kholmurodov, Kholmirzo; Doroshkevich, Aleksandr; Asgerov, Elmar; Yamamoto, Tomoyuki; Lyubchyk, Andrei; Almasan, Valer; Madadzada, Afag

2018-03-01

Development of a new electricity generation techniques is one of the most relevant tasks, especially nowadays under conditions of extreme growth in energy consumption. The exothermic heterogeneous electrochemical energy conversion to the electric energy through interaction of the ZrO2 based nanopowder system with atmospheric moisture is one of the ways of electric energy obtaining. The questions of conversion into the electric form of the energy of water molecules adsorption in 3 mol% Y2O3 doped ZrO2 nanopowder systems were investigated using the density functional theory calculations. The density functional theory calculations has been realized as in the Kohn-Sham formulation, where the exchange-correlation potential is approximated by a functional of the electronic density. The electronic density, total energy and band structure calculations are carried out using the all-electron, full potential, linear augmented plane wave method of the electronic density and related approximations, i.e. the local density, the generalized gradient and their hybrid approximations.

Dielectric, thermal and mechanical properties of zirconium silicate reinforced high density polyethylene composites for antenna applications.

PubMed

Varghese, Jobin; Nair, Dinesh Raghavan; Mohanan, Pezholil; Sebastian, Mailadil Thomas

2015-06-14

A low cost and low dielectric loss zirconium silicate (ZrSiO4) reinforced HDPE (high-density polyethylene) composite has been developed for antenna applications. The 0-3 type composite is prepared by dispersing ZrSiO4 fillers for various volume fractions (0.1 to 0.5) in the HDPE matrix by the melt mixing process. The composite shows good microwave dielectric properties with a relative permittivity of 5.6 and a dielectric loss of 0.003 at 5 GHz at the maximum filler loading of 0.5 volume fraction. The composite exhibits low water absorption, excellent thermal and mechanical properties. It shows a water absorption of 0.03 wt%, a coefficient of thermal expansion of 70 ppm per °C and a room temperature thermal conductivity of 2.4 W mK(-1). The composite shows a tensile strength of 22 MPa and a microhardness of 13.9 kg mm(-2) for the filler loading of 0.5 volume fraction. The HDPE-ZrSiO4 composites show good dielectric, thermal and mechanical properties suitable for microwave soft substrate applications. A microstrip patch antenna is designed and fabricated using the HDPE-0.5 volume fraction ZrSiO4 substrate and the antenna parameters are investigated.

Hierarchical Na-doped cubic ZrO{sub 2} synthesis by a simple hydrothermal route and its application in biodiesel production

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

Lara-García, Hugo A.; Romero-Ibarra, Issis C.; Pfeiffer, Heriberto, E-mail: pfeiffer@iim.unam.mx

Hierarchical growth of cubic ZrO{sub 2} phase was successfully synthesized via a simple hydrothermal process in the presence of different surfactants (cationic, non-ionic and anionic) and sodium hydroxide. The structural and microstructural characterizations of different ZrO{sub 2} powders were performed using various techniques, such as X-ray diffraction, transmission electron microscopy, N{sub 2} adsorption–desorption, scanning electron microscopy and infrared. Results indicated that sodium addition stabilized the cubic ZrO{sub 2} phase by a Na-doping process, independently of the surfactant used. In contrast, microstructural characteristics varied as a function of the surfactant and sodium presence. In addition, water vapor (H{sub 2}O) and carbonmore » dioxide (CO{sub 2}) sorption properties were evaluated on ZrO{sub 2} samples. Results evidenced that sample surface reactivity changed as a function of the sodium content. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction using the different synthesized samples, obtaining yields of 93%. - Graphical abstract: Hierarchical growth of cubic Na-ZrO{sub 2} phase was synthesized by hydrothermal processes in the presence of surfactants and sodium. Sodium addition stabilized the cubic phase by a Na-doping process, while the microstructural characteristics varied with surfactants. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction. - Highlights: • Cubic-ZrO{sub 2} phase was synthesized via a simple hydrothermal process. • ZrO{sub 2} structure and microstructures changed as a function of the surfactant. • Cubic-ZrO{sub 2} phase was evaluated on the biodiesel transesterification reaction.« less

Effects of TiN coating on the corrosion of nanostructured Ti-30Ta-xZr alloys for dental implants

NASA Astrophysics Data System (ADS)

Kim, Won-Gi; Choe, Han-Cheol

2012-01-01

Electrochemical characteristics of a titanium nitride (TiN)-coated/nanotube-formed Ti-Ta-Zr alloy for biomaterials have been researched by using the magnetic sputter and electrochemical methods. Ti-30Ta-xZr (x = 3, 7 and 15 wt%) alloys were prepared by arc melting and heat treated for 24 h at 1000 °C in an argon atmosphere and then water quenching. The formation of oxide nanotubes was achieved by anodizing a Ti-30Ta-xZr alloy in H3PO4 electrolytes containing small amounts of fluoride ions at room temperature. Anodization was carried out using a scanning potentiostat, and all experiments were conducted at room temperature. The microstructure and morphology of nanotube arrays were characterized by optical microscopy (OM), field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The TiN coatings were obtained by the radio-frequency (RF) magnetron sputtering technique. The depositions were performed from pure Ti targets on Ti-30Ta-xZr alloys substrates. The corrosion properties of the specimens were examined using potentiodynamic test in a 0.9% NaCl solution by using potentiostat. The microstructures of Ti-30Ta-xZr alloys were changed from an equiaxed to a needle-like structure with increasing Zr content. The interspace between the nanotubes was approximately 20, 80 and 200 nm for Zr contents of 3, 7 and 15 wt%, respectively. The corrosion resistance of the TiN-coated on the anodized Ti-30Ta-xZr alloys was higher than that of the untreated Ti alloys, indicating a better protective effect.

Preparation of ZrO II/nano-TiO II composite powder by sol-gel method

NASA Astrophysics Data System (ADS)

Baharvandi, H. R.; Mohammadi, E.; Abdizadeh, H.; Hadian, A. M.; Ehsani, N.

2007-07-01

The effects of concentration of TTIP, amount of distilled water, and calcination temperature on morphology and particle size distribution of ZrO II/nano-TiO II catalysts were investigated. Mixed ZrO II/nano-TiO II powders were prepared by a modified sol-gel method by varying the mole fraction of TTIP from 0.002 to 0.01, H IIO/TTIP fraction from 2 to 8, and various stirring time (2, 4, and 10 h). The prepared ZrO II/nano-TiO II powders have been characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and TG/DTA. Each oxide was calcined at the temperature between 110 and 1000°C. The results showed that the calcinations temperature has a pronounced effect on the phase formation and particle size of the calcined zirconium titanate (ZT) powders.

In situ Raman spectroscopic investigation of zirconium-niobium alloy corrosion under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Maslar, J. E.; Hurst, W. S.; Bowers, W. J.; Hendricks, J. H.

2001-10-01

In situ Raman spectroscopy was employed to investigate corrosion of a zirconium-niobium alloy in air-saturated water at a pressure of 15.5 MPa and temperatures ranging from 22 to 407 °C in an optically accessible flow cell. Monoclinic ZrO 2 (m-ZrO 2) was identified under all conditions after the coupon was heated to 255 °C for 19 h. Cubic ZrO 2 (c-ZrO 2) was tentatively identified in situ during heating at temperatures between 306 and 407 °C, but was not observed under any other conditions. Species tentatively identified as α-CrOOH and a Cr VI and/or Cr III/Cr VI compound were observed in situ during heating at temperatures between 255 and 407 °C, but were not observed under any other conditions. The chromium compounds were identified as corrosion products released from the optical cell and/or flow system.

High Temperature Steam Corrosion of Cladding for Nuclear Applications: Experimental

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

McHugh, Kevin M; Garnier, John E; Sergey Rashkeev

2013-01-01

Stability of cladding materials under off-normal conditions is an important issue for the safe operation of light water nuclear reactors. Metals, ceramics, and metal/ceramic composites are being investigated as substitutes for traditional zirconium-based cladding. To support down-selection of these advanced materials and designs, a test apparatus was constructed to study the onset and evolution of cladding oxidation, and deformation behavior of cladding materials, under loss-of-coolant accident scenarios. Preliminary oxidation tests were conducted in dry oxygen and in saturated steam/air environments at 1000OC. Tube samples of Zr-702, Zr-702 reinforced with 1 ply of a ß-SiC CMC overbraid, and sintered a-SiC weremore » tested. Samples were induction heated by coupling to a molybdenum susceptor inside the tubes. The deformation behavior of He-pressurized tubes of Zr-702 and SiC CMC-reinforced Zr-702, heated to rupture, was also examined.« less

Cyclic Failure Mechanisms of Thermal and Environmental Barrier Coating Systems Under Thermal Gradient Test Conditions

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Lee, Kang N.; Miller, Robert A.

2002-01-01

Plasma-sprayed ZrO2-8wt%Y2O3 and mullite+BSAS/Si multilayer thermal and environmental barrier coating (TBC-EBC) systems on SiC/SiC ceramic matrix composite (CMC) substrates were thermally cyclic tested under high thermal gradients using a laser high-heat-flux rig in conjunction with furnace exposure in water-vapor environments. Coating sintering and interface damage were assessed by monitoring the real-time thermal conductivity changes during the laser heat-flux tests and by examining the microstructural changes after exposure. Sintering kinetics of the coating systems were also independently characterized using a dilatometer. It was found that the coating failure involved both the time-temperature dependent sintering and the cycle frequency dependent cyclic fatigue processes. The water vapor environments not only facilitated the initial coating conductivity increases due to enhanced sintering and interface reaction, but also promoted later conductivity reductions due to the accelerated coating cracking and delamination. The failure mechanisms of the coating systems are also discussed based on the cyclic test results and are correlated to the sintering and thermal stress behavior under the thermal gradient test conditions.

Popcorn balls-like ZnFe2O4-ZrO2 microsphere for photocatalytic degradation of 2,4-dinitrophenol

NASA Astrophysics Data System (ADS)

Chen, Xi; Liu, Yutang; Xia, Xinnian; Wang, Longlu

2017-06-01

In this paper, novel popcorn balls-like ZnFe2O4-ZrO2 composite microspheres were successfully fabricated by a simple hydrothermal method. The morphology, structure and optical property of the microspheres were characterized. The microspheres were used as the photocatalysts to degrade 2,4-dinitrophenol, and exhibited superior photocatalytic performance. Under simulated solar visible light irradiation, the degradation rate of ZnFe2O4-ZrO2 photocatalyst (mass ratio of ZnFe2O4/ZrO2 = 2:1) was almost 7.4 and 2.4 times higher than those of pure ZnFe2O4 and ZrO2. The enhancement could attribute to stronger light absorption, lower carrier recombination and multi-porous structure of the microspheres. Moreover, the popcorn balls-like photocatalysts can be easily separated, because of the magnetism of the samples. After five times runs, the photocatalyst still showed 90% of its photocatalytic degradation efficiency. This work demonstrated a good prospect for removing organic pollutants in water.

Synthesis of Transparent Aqueous ZrO2 Nanodispersion with a Controllable Crystalline Phase without Modification for a High-Refractive-Index Nanocomposite Film.

PubMed

Xia, Yi; Zhang, Cong; Wang, Jie-Xin; Wang, Dan; Zeng, Xiao-Fei; Chen, Jian-Feng

2018-05-30

The controllable synthesis of metal oxide nanoparticles is of fundamental and technological interest. In this article, highly transparent aqueous nanodispersion of ZrO 2 with controllable crystalline phase, high concentration, and long-term stability was facilely prepared without any modification via the reaction of inexpensive inorganic zirconium salt and sodium hydroxide in water under an acid surrounding, combined with hydrothermal treatment. The as-prepared transparent nanodispersion had an average particle size of 7 nm, a high stability of 18 months, and a high solid content of 35 wt %. ZrO 2 nanocrystals could be readily dispersed in many solvents with high polarity including ethanol, dimethyl sulfoxide, acetic acid, ethylene glycol, and N, N-dimethylformamide, forming stable transparent nanodispersions. Furthermore, highly transparent polyvinyl alcohol/ZrO 2 nanocomposite films with high refractive index were successfully prepared with a simple solution mixing route. The refractive index could be tuned from 1.528 to 1.754 (@ 589 nm) by changing the mass fraction (0-80 wt %) of ZrO 2 in transparent nanocomposite films.

A simple method for the sonochemical synthesis of PVA/ZrO2-vitamin B1 nanocomposites: Morphology, mechanical, thermal and wettability investigations.

PubMed

Mallakpour, Shadpour; Shafiee, Elaheh

2018-01-01

Poly(vinyl alcohol) (PVA) based nanocomposites (NCs) filled by various weight percent of modified ZrO 2 nanoparticles (NPs) with vitamin B 1 (VB 1 ) up to 7wt% were fabricated via ultrasonication method then was cast to thin films. The ultrasonication was applied for the preparation and modification process asan easy, safe and fast method. Ultrasonic was responsible for great homogeneities of NPs into PVA matrix, which could not be achieved by mechanical or magnetically stirring. The creation of polymer NCs and changes in the structural properties were examined by X-ray diffraction. FT-IR spectroscopy indicated the possible interactions of the ZrO 2 -VB 1 NPs with the PVA backbones and also, existence of absorption bands related to PVA and ZrO 2 NPs in the NC structures. The distribution of nano-fillers and uniform morphology of the NCs showed that the ZrO 2 -VB 1 NPs were homogeneously dispersed in the polymer matrix in the nanosized scale. UV-Vis analysis shown that the the optical absorption were improved by evolution of ZrO 2 -VB 1 NPs content. The tensile strength of PVA film was increased significantly with increasing the ZrO 2 -VB 1 NPs content. Thermal gravimetric analysis confirmed that NCs displayed higher thermal stability than the pristine PVA. Also, water contact angle analysis indicated that the hydrophilicity of NC films was enhanced with increasing the concentration of ZrO 2 NPs. Copyright © 2017 Elsevier B.V. All rights reserved.

ZIRCONIA RODS FOR COATING ARTICLES BY FLAME SPRAYING

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

None

1960-04-21

An improved ZrO/sub 2/ rod for flame spraying guns is described which consists of a sintered ZrO/sub 2/ rod of mostly cubic and tetragonal crystals and has a porosity of 8% to 40% by volume. These rods are prepared by mixing 100 parts of ZrO/sub 2/ 75 parts fused, stabilized, 216 mu size, containing 5% CaO, 15 parts fused, stabilized, 25 to 50 mu size, with 5% CaO, 10 parts fused, unstabilized lime-free with 17 parts water, 1 part dextrine, 2 parts corn starch, and extruding. They are then dried and fired in a kiln heated to cone 35 Orton.more » (T.R.H.)« less

The synthesis and application of pillared clays prepared from charge reduced montmorillonite

NASA Astrophysics Data System (ADS)

Engwall, Erik Edwin

The synthesis of pillared interlayered clays (PILCs) makes use of the cation exchange capacity (CEC) of clay minerals to prop their structures open with large hydroxy-metal cations. Homo-ionic Ca-Montmorillonite with a CEC of 83.9 meq/100 g has been partially exchanged with varied amounts of Li+ and heated to 200°C for 24 hours. These have been used to produce Zr and Al PILCs making use of ethanol/water synthesis solutions to overcome the hydrophobic nature of the clay. For the Zr-PILC system, the d(001) spacings determined by x-ray diffraction (XRD) were relatively constant at 19.0--20.1 A with respect to changing the unpillared CEC. The Zr-PILCs had type I isotherms for argon at 87 K and for benzene, p-xylene and 1,3,5-trimethylbenzene adsorption at 30°C. Several Al-PILC synthesis procedures were evaluated and all produced materials whose adsorption capacity decreased with decreasing unpillared CEC. This reduction in adsorption capacity with unpillared CEC could be partially overcome by the combined use of ethanol/water pillaring solutions with ethanol/water washing. Previously unreported d(001) values in the range of 26.8 to 29.8 A were observed in Al-PILCs and were often bimodal with the expected values of about 18 A. These larger d(001) values were most prevalent at lower CEC values, if pillaring conditions favored the formation of polymeric species other than the Keggin cation. A new micropore size distribution model was developed to better understand PILC pore structure. The new model was compared to the Horvath and Kawazoe (1983) model (HK) and the Cheng and Yang (1994) model (CY) using argon adsorption at 87 K on Zr and Al-PILCs. The interlayer spacings determined by XRD for the test PILCs were 9.5 and 8.5 A for Zr and Al-PILCs respectively. Pore sizes predicted by the new model were 7.5 and 7.3 A for Zr and Al-PILCs respectively. The new model consistently predicts values that are closer to the interlayer spacing than either the HK or CY models. The new model showed little change in pore size with changes in unpillared CEC for the Zr-PILC system. These results indicate that the limiting dimension in the PILC pore system is the inter-layer spacing and not the inter-pillar spacing. (Abstract shortened by UMI.)

The adhesion performance of epoxy coating on AA6063 treated in Ti/Zr/V based solution

NASA Astrophysics Data System (ADS)

Zhu, Wen; Li, Wenfang; Mu, Songlin; Yang, Yunyu; Zuo, Xi

2016-10-01

An environment-friendly titanium/zirconium/vanadium-based (Ti/Zr/V) conversion coating was prepared on aluminum alloy 6063 (AA6063). The epoxy powder coatings were applied on the AA6063 samples with/without Ti/Zr/V conversion coatings via electrostatic spraying. The morphology and composition of the conversion coating were studied by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The surface free energy components of AA6063 samples were measured by a static contact angle measuring device with Owens method. The adhesion properties of the epoxy coating on AA6063 treated with different conversion times were evaluated using a pull-off tester. The Ti/Zr/V conversion coating was mainly composed of metal oxide (TiO2, ZrO2, V2O5, Al2O3, etc.), metal fluoride (ZrF4, AlF3, etc.) and metal organic complex. The formation time of this conversion coating was reduced to 50 s. After such surface treatment, the samples' surface roughness was increased and the contact angle with water was decreased. Both the surface free energy and the work of adhesion were increased. The adhesion strength between the epoxy coating and AA6063 was enhanced significantly.

Zirconium-carbon hybrid sorbent for removal of fluoride from water: oxalic acid mediated Zr(IV) assembly and adsorption mechanism

PubMed Central

Halla, Velazquez-Jimenez Litza; Hurt Robert, H; Juan, Matos; Rene, Rangel-Mendez Jose

2014-01-01

When activated carbon (AC) is modified with zirconium(IV) by impregnation or precipitation, the fluoride adsorption capacity is typically improved. There is significant potential to improve these hybrid sorbent by controlling the impregnation conditions, which determine the assembly and dispersion of the Zr phases on carbon surfaces. Here, commercial activated carbon was modified with Zr(IV) together with oxalic acid (OA) used to maximize the zirconium dispersion and enhance fluoride adsorption. Adsorption experiments were carried out at pH 7 and 25 °C with a fluoride concentration of 40 mg L−1. The OA/Zr ratio was varied to determine the optimal conditions for subsequent fluoride adsorption. The data was analyzed using the Langmuir and Freundlich isotherm models. FTIR, XPS and the surface charge distribution were performed to elucidate the adsorption mechanism. Potentiometric titrations showed that the modified activated carbon (ZrOx-AC) possesses positive charge at pH lower than 7, and FTIR analysis demonstrated that zirconium ions interact mainly with carboxylic groups on the activated carbon surfaces. Moreover, XPS analysis demonstrated that Zr(IV) interacts with oxalate ions, and the fluoride adsorption mechanism is likely to involve –OH− exchange from zirconyl oxalate complexes. PMID:24359079

Synthesis of monodisperse spherical nanometer ZrO{sub 2} (Y{sub 2}O{sub 3}) powders via the coupling route of w/o emulsion with urea homogenous precipitation

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

Chang, Ying; Dong, Shijie, E-mail: dongsjsj@163.com; Wang, Huihu

2012-03-15

Graphical abstract: In this paper, the weight loss and reaction evolution of ZrO{sub 2} precursor powders are determined by TG-DTA, and 600 Degree-Sign C is the most reasonable calcination temperature of precursor according to the TG-DTA. At the same time, we study the effect of reaction conditions upon the particle sizes, such as concentration of zirconium nitrate solution, reaction temperature and urea content. TEM micrographs of zirconia powders indicated that ZrO{sub 2} nano-powders prepared via the coupling route of w/o emulsion with homogenous precipitation possess spherical shape and excellent dispersing. Highlights: Black-Right-Pointing-Pointer The monodisperse spherical nanometer ZrO{sub 2} (Y{sub 2}O{submore » 3}) powders have been prepared via the coupling route of w/o emulsion with urea homogenous precipitation. Black-Right-Pointing-Pointer The principle of the coupling route of emulsion with homogenous precipitation has been studied. Black-Right-Pointing-Pointer The concentration of zirconium nitrate, reaction temperature of water bath and the quantity of urea effect regularly on the average particle size of products. -- Abstract: Using xylol as the oil phase, span-80 as the surfactant, and an aqueous solution containing zirconium (3 mol% Y{sub 2}O{sub 3}) and urea as the water phase, tetragonal phase ZrO{sub 2} nano-powders have been prepared via the coupling route of w/o emulsion with urea homogenous precipitation. The effects of the zirconium concentration, the reaction temperature and the urea content on the average size of the products have been examined. The as-prepared ZrO{sub 2} powders and the precursor powders were characterized by TGA-DTA, XRD, TEM and BET. Experimental results indicate that ZrO{sub 2} powders prepared via the coupling route of w/o emulsion with urea homogenous precipitation possess some excellent characteristics, such as well-rounded spherical shape and excellent dispersing.« less

Electron-stimulated desorption from polished and vacuum fired 316LN stainless steel coated with Ti-Zr-Hf-V

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

Malyshev, Oleg B., E-mail: oleg.malyshev@stfc.ac.uk; Valizadeh, Reza; Hogan, Benjamin T.

2014-11-01

In this study, two identical 316LN stainless steel tubular samples, which had previously been polished and vacuum-fired and then used for the electron-stimulated desorption (ESD) experiments, were coated with Ti-Zr-Hf-V with different morphologies: columnar and dense. ESD measurement results after nonevaporable getter (NEG) activation to 150, 180, 250, and 350 °C indicated that the values for the ESD yields are significantly (2–20 times) lower than the data from our previous study with similar coatings on nonvacuum-fired samples. Based on these results, the lowest pressure and best long-term performance in particle accelerators will be achieved with a vacuum-fired vacuum chamber coated withmore » dense Ti-Zr-Hf-V coating activated at 180 °C. This is likely due to the following facts: after NEG activation, the hydrogen concentration inside the NEG was lower than in the bulk stainless steel substrate; the NEG coating created a barrier for gas diffusion from the sample bulk to vacuum; the dense NEG coating performed better as a barrier than the columnar NEG coating.« less

Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

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

Stengl, Vaclav, E-mail: stengl@uach.cz; Houskova, Vendula; Bakardjieva, Snejana

2010-11-15

Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr{sup 4+} dopant can increase both the surface area and the surface hydroxylation of the resultingmore » doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr{sup 4+} converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.« less

Direct Conversion of Cellulose into Ethyl Lactate in Supercritical Ethanol-Water Solutions.

PubMed

Yang, Lisha; Yang, Xiaokun; Tian, Elli; Lin, Hongfei

2016-01-08

Biomass-derived ethyl lactate is a green solvent with a growing market as the replacement for petroleum-derived toxic organic solvents. Here we report, for the first time, the production of ethyl lactate directly from cellulose with the mesoporous Zr-SBA-15 silicate catalyst in a supercritical mixture of ethanol and water. The relatively strong Lewis and weak Brønsted acid sites on the catalyst, as well as the surface hydrophobicity, were beneficial to the reaction and led to synergy during consecutive reactions, such as depolymerization, retro-aldol condensation, and esterification. Under the optimum reaction conditions, ∼33 % yield of ethyl lactate was produced from cellulose with the Zr-SBA-15 catalyst at 260 °C in supercritical 95:5 (w/w) ethanol/water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

Zirconia based Ho3+-Yb3+ codoped upconverting nanophosphors for green light emitting devices applications

NASA Astrophysics Data System (ADS)

Dutta, Joydip; Rai, Vineet Kumar

2018-04-01

Photoluminescence study of the Ho3+-Yb3+ codoped ZrO, AlZrO and YZrO nanophosphors, synthesized by chemical co-precipitation method, upon excitation at 450 and 980 nm radiations have been performed. An improvement of about ˜4.5 times in the downconversion emission intensity of green band corresponding to the 5F4, 5S2 → 5I8 transition for codoped YZrO nanophosphors compared to ZrO codoped nanophosphors has been observed. On varying the pump power density upon 980 nm excitation the colour tunability in the codoped YZrO nanophosphors has been observed. UC emission intensity of the green band arising from the Ho3+ ion in the codoped YZrO nanophosphors is enhanced about ˜22 times compared to that of the codoped ZrO nanophosphors. The absorption and UC emission study for the codoped YZrO nanophosphors dispersed in different biologically compatible solvents viz. water, methanol, ethanol and dimethyl sulfoxide (DMSO) has been performed. The green UC emission intensity of about ˜1.3 and ˜1.7 times for the efficient codoped YZrO nanophosphors dispersed in methanol compared to that dispersed in water and DMSO respectively has been observed. The absorption spectra of an efficient upconverting YZrO nanophosphors dispersed in methanol exhibit no change with the passage of time.

Failure mechanisms of thermal barrier coatings exposed to elevated temperatures

NASA Technical Reports Server (NTRS)

Miller, R. A.; Lowell, C. E.

1982-01-01

The failure of a ZrO2-8%Y2O3/Ni-14% Al-0.1% Zr coating system on Rene 41 in Mach 0.3 burner rig tests was characterized. High flame and metal temperatures were employed in order to accelerate coating failure. Failure by delamination was shown to precede surface cracking or spalling. This type of failure could be duplicated by cooling down the specimen after a single long duration isothermal high temperature cycle in a burner rig or a furnace, but only if the atmosphere was oxidizing. Stresses due to thermal expansion mismatch on cooling coupled with the effects of plastic deformation of the bond coat and oxidation of the irregular bond coat are the probable life limiting factors. Heat up stresses alone could not fail the coating in the burner rig tests. Spalling eventually occurs on heat up but only after the coating has already failed through delamination.

Study of structural and magnetic properties of melt spun Nd2Fe13.6Zr0.4B ingot and ribbon

NASA Astrophysics Data System (ADS)

Amin, Muhammad; Siddiqi, Saadat A.; Ashfaq, Ahmad; Saleem, Murtaza; Ramay, Shahid M.; Mahmood, Asif; Al-Zaghayer, Yousef S.

2015-12-01

Nd2Fe13.6Zr0.4B hard magnetic material were prepared using arc-melting technique on a water-cooled copper hearth kept under argon gas atmosphere. The prepared samples, Nd2Fe13.6Zr0.4B ingot and ribbon are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) for crystal structure determination and morphological studies, respectively. The magnetic properties of the samples have been explored using vibrating sample magnetometer (VSM). The lattice constants slightly increased due to the difference in the ionic radii of Fe and that of Zr. The bulk density decreased due to smaller molar weight and low density of Zr as compared to that of Fe. Ingot sample shows almost single crystalline phase with larger crystallite sizes whereas ribbon sample shows a mixture of amorphous and crystalline phases with smaller crystallite sizes. The crystallinity of the material was highly affected with high thermal treatments. Magnetic measurements show noticeable variation in magnetic behavior with the change in crystallite size. The sample prepared in ingot type shows soft while ribbon shows hard magnetic behavior.

Ultrasonic-assisted synthesis of ZrO2 nanoparticles and their application to improve the chemical stability of Nafion membrane in proton exchange membrane (PEM) fuel cells.

PubMed

Taghizadeh, Mohammad Taghi; Vatanparast, Morteza

2016-12-01

Zirconium dioxide (ZrO2) nanoparticles were fabricated successfully via ultrasonic-assisted method using ZrO(NO3)2·H2O, ethylenediamine and hydrazine as precursors in aqueous solution. Morphology, structure and composition of the obtained products were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR) and diffuse reflectance spectroscopy (DRS). Then, the synthesized nanoparticles were used to prepare Nafion/ZrO2 nanocomposite membranes. The properties of the membranes were studied by ion exchange capacity (IEC) proton conductivity (σ), thermal stability and water uptake measurements. The ex-situ Fenton's test was used to investigate the chemical stability of the membranes. From our results, compared with Nafion membrane, the nanocomposite membrane exhibited lower fluoride release and weight loss. Therefore, it can concluded that Nafion/ZrO2 nanocomposite exhibit more chemical stability than the pure Nafion membrane. ATR-FTIR spectra and SEM surface images of membranes also confirm these results. Copyright © 2016 Elsevier Inc. All rights reserved.

Comparison of the octadentate bifunctional chelator DFO*-pPhe-NCS and the clinically used hexadentate bifunctional chelator DFO-pPhe-NCS for 89Zr-immuno-PET.

PubMed

Vugts, Danielle J; Klaver, Chris; Sewing, Claudia; Poot, Alex J; Adamzek, Kevin; Huegli, Seraina; Mari, Cristina; Visser, Gerard W M; Valverde, Ibai E; Gasser, Gilles; Mindt, Thomas L; van Dongen, Guus A M S

2017-02-01

All clinical 89 Zr-immuno-PET studies are currently performed with the chelator desferrioxamine (DFO). This chelator provides hexadentate coordination to zirconium, leaving two coordination sites available for coordination with, e.g., water molecules, which are relatively labile ligands. The unsaturated coordination of DFO to zirconium has been suggested to result in impaired stability of the complex in vivo and consequently in unwanted bone uptake of 89 Zr. Aiming at clinical improvements, we report here on a bifunctional isothiocyanate variant of the octadentate chelator DFO* and the in vitro and in vivo comparison of its 89 Zr-DFO*-mAb complex with 89 Zr-DFO-mAb. The bifunctional chelator DFO*-pPhe-NCS was prepared from previously reported DFO* and p-phenylenediisothiocyanate. Subsequently, trastuzumab was conjugated with either DFO*-pPhe-NCS or commercial DFO-pPhe-NCS and radiolabeled with Zr-89 according to published procedures. In vitro stability experiments were carried out in saline, a histidine/sucrose buffer, and blood serum. The in vivo performance of the chelators was compared in N87 tumor-bearing mice by biodistribution studies and PET imaging. In 0.9 % NaCl 89 Zr-DFO*-trastuzumab was more stable than 89 Zr-DFO-trastuzumab; after 72 h incubation at 2-8 °C 95 % and 58 % intact tracer were left, respectively, while in a histidine-sucrose buffer no difference was observed, both products were ≥ 92 % intact. In vivo uptake at 144 h post injection (p.i.) in tumors, blood, and most normal organs was similar for both conjugates, except for skin, liver, spleen, ileum, and bone. Tumor uptake was 32.59 ± 11.95 and 29.06 ± 8.66 % ID/g for 89 Zr-DFO*-trastuzumab and 89 Zr-DFO-trastuzumab, respectively. The bone uptake was significantly lower for 89 Zr-DFO*-trastuzumab compared to 89 Zr-DFO-trastuzumab. At 144 h p.i. for 89 Zr-DFO*-trastuzumab and 89 Zr-DFO-trastuzumab, the uptake in sternum was 0.92 ± 0.16 and 3.33 ± 0.32 % ID/g, in femur 0.78 ± 0.11 and 3.85, ± 0.80 and in knee 1.38 ± 0.23 and 8.20 ± 2.94 % ID/g, respectively. The uptake in bone decreased from 24 h to 144 h p.i. about two fold for the DFO* conjugate, while it increased about two fold for the DFO conjugate. Zr-DFO*-trastuzumab showed superior in vitro stability and in vivo performance when compared to 89 Zr-DFO-trastuzumab. This makes the new octadentate DFO* chelator a candidate successor of DFO for future clinical 89 Zr-immuno-PET.

One-step production of biodiesel from rice bran oil catalyzed by chlorosulfonic acid modified zirconia via simultaneous esterification and transesterification.

PubMed

Zhang, Yue; Wong, Wing-Tak; Yung, Ka-Fu

2013-11-01

Due to the high content (25-50%) of free fatty acid (FFA), crude rice bran oil usually requires a two steps conversion or one step conversion with very harsh condition for simultaneous esterification and transesterification. In this study, chlorosulfonic acid modified zirconia (HClSO3-ZrO2) with strong acidity and durability is prepared and it shows excellent catalytic activity toward simultaneous esterification and transesterification. Under a relative low reaction temperature of 120 °C, HClSO3-ZrO2 catalyzes a complete conversion of simulated crude rice bran oil (refined oil with 40 wt% FFA) into biodiesel and the conversion yield keep at above 92% for at least three cycles. Further investigation on the tolerance towards FFA and water reveals that it maintains high activity even with the presence of 40 wt% FFA and 3 wt% water. It shows that HClSO3-ZrO2 is a robust and durable catalyst which shows high potential to be commercial catalyst for biodiesel production from low grade feedstock. Copyright © 2013 Elsevier Ltd. All rights reserved.

Testing the Chemical/Structural Stability of Proton Conducting Perovskite Ceramic Membranes by in Situ/ex Situ Autoclave Raman Microscopy.

PubMed

Slodczyk, Aneta; Zaafrani, Oumaya; Sharp, Matthew D; Kilner, John A; Dabrowski, Bogdan; Lacroix, Olivier; Colomban, Philippe

2013-10-25

Ceramics, which exhibit high proton conductivity at moderate temperatures, are studied as electrolyte membranes or electrode components of fuel cells, electrolysers or CO2 converters. In severe operating conditions (high gas pressure/high temperature), the chemical activity towards potentially reactive atmospheres (water, CO2, etc.) is enhanced. This can lead to mechanical, chemical, and structural instability of the membranes and premature efficiency loss. Since the lifetime duration of a device determines its economical interest, stability/aging tests are essential. Consequently, we have developed autoclaves equipped with a sapphire window, allowing in situ Raman study in the 25-620 °C temperature region under 1-50 bar of water vapor/gas pressure, both with and without the application of an electric field. Taking examples of four widely investigated perovskites (BaZr0.9Yb0.1O3-δ, SrZr0.9Yb0.1O3-δ, BaZr0.25In0.75O3-δ, BaCe0.5Zr0.3Y0.16Zn0.04O3-δ), we demonstrate the high potential of our unique set-up to discriminate between good/stable and instable electrolytes as well as the ability to detect and monitor in situ: (i) the sample surface reaction with surrounding atmospheres and the formation of crystalline or amorphous secondary phases (carbonates, hydroxides, hydrates, etc.); and (ii) the structural modifications as a function of operating conditions. The results of these studies allow us to compare quantitatively the chemical stability versus water (corrosion rate from ~150 µm/day to less than 0.25 µm/day under 200-500 °C/15-80 bar PH2O) and to go further in comprehension of the aging mechanism of the membrane.

Pharmacokinetics study of Zr-89-labeled melanin nanoparticle in iron-overload mice.

PubMed

Zhang, Pengjun; Yue, Yuanyuan; Pan, Donghui; Yang, Runlin; Xu, Yuping; Wang, Lizhen; Yan, Junjie; Li, Xiaotian; Yang, Min

2016-09-01

Melanin, a natural biological pigment present in many organisms, has been found to exhibit multiple functions. An important property of melanin is its ability to chelate metal ions strongly, which might be developed as an iron chelator for iron overload therapy. Herein, we prepared the ultrasmall water-soluble melanin nanoparticle (MP) and firstly evaluate the pharmacokinetics of MP in iron-overload mice to provide scientific basis for treating iron-overload. To study the circulation time and biodistribution, MP was labeled with (89)Zr, a long half-life (78.4h) positron-emitting metal which is suited for the labeling of nanoparticles and large bioactive molecule. MP was chelated with (89)Zr directly at pH5, resulting in non-decay-corrected yield of 89.6% and a radiochemical purity of more than 98%. The specific activity was at least190 MBq/μmol. The (89)Zr-MP was stable in human plasma and PBS for at least 48h. The half-life of (89)Zr-MP was about 15.70±1.74h in iron-overload mice. Biodistribution studies and MicroPET imaging showed that (89)Zr-MP mainly accumulated in liver and spleen, which are the target organ of iron-overload. The results indicate that the melanin nanoparticle is promising for further iron overload therapy. Copyright © 2016 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

Multifunctional phosphate-based inorganic-organic hybrid nanoparticles.

PubMed

Heck, Joachim G; Napp, Joanna; Simonato, Sara; Möllmer, Jens; Lange, Marcus; Reichardt, Holger M; Staudt, Reiner; Alves, Frauke; Feldmann, Claus

2015-06-17

Phosphate-based inorganic-organic hybrid nanoparticles (IOH-NPs) with the general composition [M](2+)[Rfunction(O)PO3](2-) (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3](2-) is a fluorescent dye anion ([RdyeOPO3](2-)), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO](2+)[PUP](2-), [ZrO](2+)[MFP](2-), [ZrO](2+)[RRP](2-), and [ZrO](2+)[DUT](2-) (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3](2-)), drug transport and release of anti-inflammatory ([ZrO](2+)[BMP](2-)) and antitumor agents ([ZrO](2+)[FdUMP](2-)) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5'-fluoro-2'-deoxyuridine 5'-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO](2+)[BMP](2-)0.996[DUT](2-)0.004. Merging of functional anions, in general, results in [ZrO](2+)([RdrugOPO3]1-x[RdyeOPO3]x)(2-) nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO](2+)[RaminePO3](2-) IOH-NPs, finally, show CO2 sorption (up to 180 mg g(-1)) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP](2-), 1-aminoethyl phosphonate [1AEP](2-), 2-aminoethyl phosphonate [2AEP](2-), aminopropyl phosphonate [APP](2-), and aminobutyl phosphonate [ABP](2-). All [M](2+)[Rfunction(O)PO3](2-) IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Conjoint corrosion and wear in titanium alloys.

PubMed

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

1999-04-01

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

Hydrothermal catalytic deoxygenation of palmitic acid over nickel catalyst

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

Miao, Chao; Marin-Flores, Oscar; Davidson, Stephen D.

2016-02-01

Fatty acid has recently received considerable interest as a possible precursor for producing renewable hydrocarbon. In this study, we investigated hydrothermal catalytic deoxygenation of palmitic acid to produce paraffin over a Ni/ZrO2 catalyst with no or low-pressure (100 psi) external supply of H2. The results show that the presence of water greatly improved conversion of palmitic acid and paraffin yield. Significant improvement was attributed to the formation of in-situ H2. Without an external H2 supply, a 64.2 C% conversion of palmitic acid was achieved in the presence of water, while only a 17.2 C% conversion was achieved without water. Themore » results also show that the presence of water suppressed the side reactions of palmitic acid, specifically ketonization and esterification. We concluded that, compared with decarboxylation and hydrodeoxygenation, decarbonylation was the major route for palmitic acid deoxygenation catalyzed by Ni/ZrO2. Varieties of shorter-chain paraffin (C8–C14) were formed through hydrogenolysis, which also produced a considerable amount of CH4. A viable reaction pathway for hydrothermal catalytic deoxygenation of palmitic acid in the presence of Ni/ZrO2 was suggested. The results show that hydrogenolysis and decarbonylation were the major reactions that occurred. This study demonstrates that this hydrothermal catalytic process is a promising approach for producing liquid paraffin (C8–C15) from fatty acids under no or low-pressure H2.« less

Energy Harvesting Characteristics from Water Flow by Piezoelectric Energy Harvester Device Using Cr/Nb Doped Pb(Zr,Ti)O3 Bimorph Cantilever

NASA Astrophysics Data System (ADS)

Kim, Kyoung-Bum; Kim, Chang Il; Jeong, Young Hun; Cho, Jeong-Ho; Paik, Jong-Hoo; Nahm, Sahn; Lim, Jong Bong; Seong, Tae-Hyeon

2013-10-01

A water flow energy harvester, which can convert water flow energy to electric energy, was fabricated for its application to rivers. This harvester can generate power from the bending and releasing motion of piezoelectric bimorph cantilevers. A Pb(Zr0.54Ti0.46)O3 + 0.2 wt % Cr2O3 + 1.0 wt % Nb2O5 (PZT-CN) thick film and a 250-µm-thick stainless steel were used as a bimorph cantilever. The electrical impedance matching was achieved across a resistive load of 1 kΩ. Four bimorph cantilevers can generate power from 5 to 105 rpm. The output powers were steadily increased by increasing the rpm. The maximum output power was 68 mW by 105 rpm. It was found that the water flow energy harvester can generate 58 mW by a flow velocity of (2 m/s) from the stream with the four bimorph cantilevers.

Benzimidazole-functionalized Zr-UiO-66 nanocrystals for luminescent sensing of Fe3+ in water

NASA Astrophysics Data System (ADS)

Dong, Yingying; Zhang, Hanzhuo; Lei, Fan; Liang, Mei; Qian, Xuefeng; Shen, Peilian; Xu, Hui; Chen, Zhihui; Gao, Junkuo; Yao, Juming

2017-01-01

Zr-based MOF structure UiO-66 exhibits unprecedented high thermal and chemical stability, making it to be one of the most used MOFs in various applications. Yet, the poor photoluminescent (PL) properties of UiO-66 limit its applications in luminescent sensing. Herein, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe3+ ions in water.

Benzimidazole-functionalized Zr-UiO-66 nanocrystals for luminescent sensing of Fe{sup 3+} in water

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

Dong, Yingying; Zhang, Hanzhuo; Lei, Fan

2017-01-15

Zr-based MOF structure UiO-66 exhibits unprecedented high thermal and chemical stability, making it to be one of the most used MOFs in various applications. Yet, the poor photoluminescent (PL) properties of UiO-66 limit its applications in luminescent sensing. Herein, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ionsmore » were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe{sup 3+} ions in water.« less

Investigation of proton induced reactions on niobium at low and medium energies

NASA Astrophysics Data System (ADS)

Ditrói, F.; Hermanne, A.; Corniani, E.; Takács, S.; Tárkányi, F.; Csikai, J.; Shubin, Yu. N.

2009-10-01

Niobium is a metal with important technological applications: use as alloying element to increase strength of super alloys, as thin layer for tribological applications, as superconductive material, in high temperature engineering systems, etc. In the frame of a systematic study of activation cross-sections of charged particle induced reactions on structural materials proton induced excitation functions on Nb targets were determined with the aim of applications in accelerator and reactor technology and for thin layer activation (TLA). The charged particle activation cross-sections on this element are also important for yield calculation of medical isotope production ( 88,89Zr, 86,87,88Y) and for dose estimation in PET targetry. As niobium is a monoisotopic element it is an ideal target material to test nuclear reaction theories. We present here the experimental excitation functions of 93Nb(p,x) 90,93mMo, 92m,91m,90Nb, 88,89Zr and 88Y in the energy range 0-37 MeV. The results were compared with the theoretical cross-sections calculated by means of the code ALICE-IPPE, EMPIRE-3, TALYS and with the literature data. The theory reproduces the shape of the measured results well and magnitude is also acceptable. Thick target yields calculated from our fitted cross-section give reliable estimations for production of medically relevant radioisotopes and for dose estimation in accelerator technology.

Development of bone-like zirconium oxide nanoceramic modified chitosan based porous nanocomposites for biomedical application.

PubMed

Bhowmick, Arundhati; Pramanik, Nilkamal; Jana, Piyali; Mitra, Tapas; Gnanamani, Arumugam; Das, Manas; Kundu, Patit Paban

2017-02-01

Here, zirconium oxide nanoparticles (ZrO 2 NPs) were incorporated for the first time in organic-inorganic hybrid composites containing chitosan, poly(ethylene glycol) and nano-hydroxypatite (CS-PEG-HA) to develop bone-like nanocomposites for bone tissue engineering application. These nanocomposites were characterized by FT-IR, XRD, TEM combined with SAED. SEM images and porosity measurements revealed highly porous structure having pore size of less than 1μm to 10μm. Enhanced water absorption capacity and mechanical strengths were obtained compared to previously reported CS-PEG-HA composite after addition of 0.1-0.3wt% of ZrO 2 NPs into these nanocomposites. The mechanical strengths and porosities were similar to that of human spongy bone. Strong antimicrobial effects against gram-negative and gram-positive bacterial strains were also observed. Along with getting low alkalinity pH (7.4) values, similar to the pH of human plasma, hemocompatibility and cytocompatibility with osteoblastic MG-63 cells were also established for these nanocomposites. Addition of 15wt% HA-ZrO 2 (having 0.3wt% ZrO 2 NPs) into CS-PEG (55:30wt%) composite resulted in greatest mechanical strength, porosity, antimicrobial property and cytocompatibility along with suitable water absorption capacity and compatibility with human pH and blood. Thus, this nanocomposite could serve as a potential candidate to be used for bone tissue engineering. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of N2 partial pressure on structural and microhardness properties of TiN/ZrN multilayers deposited by Ar/N2 vacuum arc discharge

NASA Astrophysics Data System (ADS)

Naddaf, M.; Abdallah, B.; Ahmad, M.; A-Kharroub, M.

2016-08-01

The influence of N2 partial pressure on structural, mechanical and wetting properties of multilayered TiN/ZrN thin films deposited on silicon substrates by vacuum arc discharge of (N2 + Ar) gas mixtures is investigated. X-ray diffraction (XRD) results show that the average texturing coefficient of (1 1 1) orientation and the grain size of both TiN and ZrN individual layers increase with increasing the N2 partial pressure. The Rutherford back scattering (RBS) measurements and analysis reveal that incorporation of the nitrogen in the film increases with increasing the N2 partial pressure and both TiN and ZrN individual layers have a nitrogen over-stoichiometry for N2 partial pressure ⩾50%. The change in the film micro-hardness is correlated to the changes in crystallographic texture, grain size, stoichiometry and the residual stress in the film as a function of the N2 partial pressure. In particular, stoichiometry of ZrN and TiN individual is found to play the vital role in determining the multilayer hardness. The multilayer film deposited at N2 partial pressure of 25% has the best stoichiometric ratio of both TiN and ZrN layers and the highest micro-hardness of about 32 GPa. In addition, water contact angle (WCA) measurements and analysis show a decrease in the work of adhesion on increasing the N2 partial pressure.

Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework

DOE PAGES

Wang, Hao; Wang, Qining; Teat, Simon J.; ...

2017-02-15

Porous metal-organic framework (MOF) materials with high thermal and water stability are desirable for various adsorption based applications. Early transition metal based MOFs such as those built on zirconium metal have been well recognized for their excellent stability toward heat and/or moisture. However, the difficulty growing large single crystals makes their structural characterization challenging. Herein we report a porous Zr-MOF, [Zr 6O 4(OH) 4(cca) 6] (Zr-cca), which is assembled from zirconium and 4-carboxycinnamic acid (H 2cca) under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the structure of Zr-cca is isoreticular to the prototype zirconium based MOF, UiO-66. Zr-ccamore » shows permanent porosity upon removal of solvent molecules initially residing inside the pores, with a BET surface area of 1178 m 2/g. As expected, it exhibits good thermal stability (stable up to 400 °C) and high resistance to acidity over a wide pH range. Evaluation of its gas adsorption performance on various hydrocarbons and fluorocarbons indicates that it preferentially adsorbs C 3 and C 4 hydrocarbons over C 2 analogues. At 30°C Zr-cca takes up more than 50 wt % of perfluorohexane and the adsorption-desorption process is fully recyclable. We have compared this material with UiO-66 and studied the underlying reasons for the difference in their adsorption performance toward perfluorohexane.« less

The RaDIATE High-Energy Proton Materials Irradiation Experiment at the Brookhaven Linac Isotope Producer Facility

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

Ammigan, Kavin; et al.

The RaDIATE collaboration (Radiation Damage In Accelerator Target Environments) was founded in 2012 to bring together the high-energy accelerator target and nuclear materials communities to address the challenging issue of radiation damage effects in beam-intercepting materials. Success of current and future high intensity accelerator target facilities requires a fundamental understanding of these effects including measurement of materials property data. Toward this goal, the RaDIATE collaboration organized and carried out a materials irradiation run at the Brookhaven Linac Isotope Producer facility (BLIP). The experiment utilized a 181 MeV proton beam to irradiate several capsules, each containing many candidate material samples formore » various accelerator components. Materials included various grades/alloys of beryllium, graphite, silicon, iridium, titanium, TZM, CuCrZr, and aluminum. Attainable peak damage from an 8-week irradiation run ranges from 0.03 DPA (Be) to 7 DPA (Ir). Helium production is expected to range from 5 appm/DPA (Ir) to 3,000 appm/DPA (Be). The motivation, experimental parameters, as well as the post-irradiation examination plans of this experiment are described.« less

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water.

PubMed

Brady, Michael P; Ievlev, Anton V; Fayek, Mostafa; Leonard, Donovan N; Frith, Matthew G; Meyer, Harry M; Ramirez-Cuesta, Anibal J; Daemen, Luke L; Cheng, Yongqiang; Guo, Wei; Poplawsky, Jonathan D; Ovchinnikova, Olga S; Thomson, Jeffrey; Anovitz, Lawrence M; Rother, Gernot; Shin, Dongwon; Song, Guang-Ling; Davis, Bruce

2017-11-01

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2 O/D isotopic tracer and H 2 O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at room temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2-3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2 . These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water

DOE PAGES

Brady, Michael P.; Ievlev, Anton V.; Fayek, Mostafa; ...

2017-10-10

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2O/D isotopic tracer and H 2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at roommore » temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.« less

Oxidation of Ultra-High Temperature Ceramics in Water Vapor

NASA Technical Reports Server (NTRS)

Nguyen, QuynhGiao N.; Opila, Elizabeth J.; Robinson, Raymond C.

2003-01-01

Ultra high temperature ceramics (UHTCs) including HfB2 + SiC (20% by volume), ZrB2 + SiC (20% by volume) and ZrB2 + SiC (14% by volume) + C (30% by volume) have historically been evaluated as reusable thermal protection systems for hypersonic vehicles. This study investigates UHTCs for use as potential combustion and aeropropulsion engine materials. These materials were oxidized in water vapor (90%) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 hours at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline comparison. Weight change measurements, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results will be compared with tests ran in static air at temperatures of 1327, 1627, and 1927 C. Oxidation comparisons will also be made to the study by Tripp. A small number of high pressure burner rig (HPBR) results at 1100 and 1300 C will also be discussed. Specific weight changes at all three temperatures along with the SIC results are shown. SiC weight change is negligible at such short duration times. HB2 + SiC (HS) performed the best out of all the tested UHTCS for all exposure temperatures. ZrB2 + Sic (ZS) results indicate a slightly lower oxidation rate than that of ZrBl + SiC + C (ZCS) at 1200 and 1400 C, but a clear distinction can not be made based on the limited number of tested samples. Scanning electron micrographs of the cross-sections of all the UHTCs were evaluated. A representative area for HS is presented at 1400 C for 26 hours which was the composition with the least amount of oxidation. A continuous SiO2 scale is present in the outer most edge of the surface. An image of ZCS is presented at 1400 C for 10 hours, which shows the most degradation of all the compositions studied. Here, the oxide surface is a mixture of ZrSiO4, ZrO2 and SO2.

Visual and surface plasmon resonance sensor for zirconium based on zirconium-induced aggregation of adenosine triphosphate-stabilized gold nanoparticles.

PubMed

Qi, Wenjing; Zhao, Jianming; Zhang, Wei; Liu, Zhongyuan; Xu, Min; Anjum, Saima; Majeed, Saadat; Xu, Guobao

2013-07-17

Owing to its high affinity with phosphate, Zr(IV) can induce the aggregation of adenosine 5'-triphosphate (ATP)-stabilized AuNPs, leading to the change of surface plasmon resonance (SPR) absorption spectra and color of ATP-stabilized AuNP solutions. Based on these phenomena, visual and SPR sensors for Zr(IV) have been developed for the first time. The A(660 nm)/A(518 nm) values of ATP-stabilized AuNPs in SPR absorption spectra increase linearly with the concentrations of Zr(IV) from 0.5 μM to 100 μM (r=0.9971) with a detection limit of 95 nM. A visual Zr(IV) detection is achieved with a detection limit of 30 μM. The sensor shows excellent selectivity against other metal ions, such as Cu(2+), Fe(3+), Cd(2+), and Pb(2+). The recoveries for the detection of 5 μM, 10 μM, 25 μM and 75 μM Zr(IV) in lake water samples are 96.0%, 97.0%, 95.6% and 102.4%, respectively. The recoveries of the proposed SPR method are comparable with those of ICP-OES method. Copyright © 2013 Elsevier B.V. All rights reserved.

Manufacturing and High Heat Flux Testing of Brazed Flat-Type W/CuCrZr Plasma Facing Components

NASA Astrophysics Data System (ADS)

Lian, Youyun; Liu, Xiang; Feng, Fan; Chen, Lei; Cheng, Zhengkui; Wang, Jin; Chen, Jiming

2016-02-01

Water-cooled flat-type W/CuCrZr plasma facing components with an interlayer of oxygen-free copper (OFC) have been developed by using vacuum brazing route. The OFC layer for the accommodation of thermal stresses was cast onto the surface of W at a temperature range of 1150 °C-1200 °C in a vacuum furnace. The W/OFC cast tiles were vacuum brazed to a CuCrZr heat sink at 940 °C using the silver-free filler material CuMnSiCr. The microstructure, bonding strength, and high heat flux properties of the brazed W/CuCrZr joint samples were investigated. The W/Cu joint exhibits an average tensile strength of 134 MPa, which is about the same strength as pure annealed copper. High heat flux tests were performed in the electron beam facility EMS-60. Experimental results indicated that the brazed W/CuCrZr mock-up experienced screening tests of up to 15 MW/m2 and cyclic tests of 9 MW/m2 for 1000 cycles without visible damage. supported by National Natural Science Foundation of China (No. 11205049) and the National Magnetic Confinement Fusion Science Program of China (No. 2011GB110004)

Fabrication of a Biomass-Based Hydrous Zirconium Oxide Nanocomposite for Preferable Phosphate Removal and Recovery.

PubMed

Qiu, Hui; Liang, Chen; Zhang, Xiaolin; Chen, Mindong; Zhao, Yunxia; Tao, Tao; Xu, Zhengwen; Liu, Gang

2015-09-23

Advanced removal of phosphate by low-cost adsorbents from municipal wastewater or industrial effluents is an effective and economic way to prevent the occurrence of eutrophication. Here, we proposed a novel method to immobilize hydrous zirconium oxide nanoparticle within quaternary-aminated wheat straw, and obtained an inexpensive, eco-friendly nanocomposite Ws-N-Zr. The biomass-based Ws-N-Zr exhibited higher preference toward phosphate than commercial anion exchanger IRA-900 when competing sulfate ions coexisted at relatively high levels. Such excellent performance of Ws-N-Zr resulted from its specific hybrid structure, the quaternary ammonium groups bonded on the host favor the preconcentration of phosphate ions inside the wheat straw based on Donnan effect, and the encapsulated HZO nanoparticle exhibits preferable sequestration of phosphate ions through specific interaction, as further demonstrated by FTIR and X-ray photoelectron spectroscopy. Cycle adsorption and regeneration experiments demonstrated that Ws-N-Zr could be employed for repeated use without significant capacity loss, when the binary NaOH-NaCl solution was employed as the regenerant. The influence of solution pH and contact time was also examined. The results suggested that Ws-N-Zr has a great potential in efficient removal of phosphate in contaminated waters.

Exploiting the biosynthetic machinery of Streptomyces pilosus to engineer a water-soluble zirconium(iv) chelator.

PubMed

Richardson-Sanchez, Tomas; Tieu, William; Gotsbacher, Michael P; Telfer, Thomas J; Codd, Rachel

2017-07-21

The water solubility of a natural product-inspired octadentate hydroxamic acid chelator designed to coordinate Zr(iv)-89 has been improved by using a combined microbiological-chemical approach to engineer four ether oxygen atoms into the main-chain region of a methylene-containing analogue. First, an analogue of the trimeric hydroxamic acid desferrioxamine B (DFOB) that contained three main-chain ether oxygen atoms (DFOB-O 3 ) was generated from cultures of the native DFOB-producer Streptomyces pilosus supplemented with oxybis(ethanamine) (OBEA), which competed against the native 1,5-diaminopentane (DP) substrate during DFOB assembly. This precursor-directed biosynthesis (PDB) approach generated a suite of DFOB analogues containing one (DFOB-O 1 ), two (DFOB-O 2 ) or three (DFOB-O 3 ) ether oxygen atoms, with the latter produced as the major species. Log P measurements showed DFOB-O 3 was about 45 times more water soluble than DFOB. Second, a peptide coupling chain-extension reaction between DFOB-O 3 and the synthetic ether-containing endo-hydroxamic acid monomer 4-((2-(2-aminoethoxy)ethyl)(hydroxy)amino)-4-oxobutanoic acid (PBH-O 1 ) gave the water soluble tetrameric hydroxamic acid DFOB-O 3 -PBH-O 1 as an isostere of sparingly water soluble DFOB-PBH. The complex between DFOB-O 3 -PBH-O 1 and nat Zr(iv), examined as a surrogate measure of the radiolabelling procedure, analysed by LC-MS as the protonated adduct ([M + H] + , m/z obs = 855.2; m/z calc = 855.3), with supporting HRMS data. The use of a microbiological system to generate a water-soluble analogue of a natural product for downstream semi-synthetic chemistry is an attractive pathway for developing new drugs and imaging agents. The improved water solubility of DFOB-O 3 -PBH-O 1 could facilitate the synthesis and purification of downstream products, as part of the ongoing development of ligands optimised for Zr(iv)-89 immunological PET imaging.

Detoxification of Chemical Warfare Agents Using a Zr6 -Based Metal-Organic Framework/Polymer Mixture.

PubMed

Moon, Su-Young; Proussaloglou, Emmanuel; Peterson, Gregory W; DeCoste, Jared B; Hall, Morgan G; Howarth, Ashlee J; Hupp, Joseph T; Farha, Omar K

2016-10-10

Owing to their high surface area, periodic distribution of metal sites, and water stability, zirconium-based metal-organic frameworks (Zr 6 -MOFs) have shown promising activity for the hydrolysis of nerve agents GD and VX, as well as the simulant, dimethyl 4-nitrophenylphosphate (DMNP), in buffered solutions. A hurdle to using MOFs for this application is the current need for a buffer solution. Here the destruction of the simulant DMNP, as well as the chemical warfare agents (GD and VX) through hydrolysis using a MOF catalyst mixed with a non-volatile, water-insoluble, heterogeneous buffer is reported. The hydrolysis of the simulant and nerve agents in the presence of the heterogeneous buffer was fast and effective. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase separation of metal-added corium and its effect on a steam explosion

NASA Astrophysics Data System (ADS)

Min, B. T.; Kim, J. H.; Hong, S. W.; Hong, S. H.; Park, I. K.; Song, J. H.; Kim, H. D.

2008-07-01

To simulate a relocation of molten core material and its interaction phenomenon with water during a severe accident in a nuclear reactor, a typical corium of UO 2/ZrO 2/Zr/Stainless steel mixed at a 62 wt%, 15 wt%, 12 wt% and 11 wt%, respectively, was melted and then cooled down to become a solidified ingot. It was shown that the molten corium was separated into two layers, of which the upper layer was oxide mixtures and the lower layer was metal alloys. The upper layer was UO 2 and ZrO 2 and the lower layer mostly consisted of metal mixtures such as uranium, zirconium and stainless steel. Iron content varied with the positions and about a half of it existed as an alloy such as Fe 2U. Uranium metal was produced by reduction of UO 2 by zirconium metal. The average densities of the upper oxide layer and the lower metal layer were 8.802 and 9.411 g/cm 3, respectively. In another test, metal-added molten corium was poured into water and it showed that a steam explosion could occur by applying an external trigger.

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

Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C,more » steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.« less

Programming MOFs for water sorption: amino-functionalized MIL-125 and UiO-66 for heat transformation and heat storage applications.

PubMed

Jeremias, Felix; Lozan, Vasile; Henninger, Stefan K; Janiak, Christoph

2013-12-07

Sorption-based heat transformation and storage appliances are very promising for utilizing solar heat and waste heat in cooling or heating applications. The economic and ecological efficiency of sorption-based heat transformation depends on the availability of suitable hydrophilic and hydrothermally stable sorption materials. We investigated the feasibility of using the metal-organic frameworks UiO-66(Zr), UiO-67(Zr), H2N-UiO-66(Zr) and H2N-MIL-125(Ti) as sorption materials in heat transformations by means of volumetric water adsorption measurements, determination of the heat of adsorption and a 40-cycle ad/desorption stress test. The amino-modified compounds H2N-UiO-66 and H2N-MIL-125 feature high heat of adsorption (89.5 and 56.0 kJ mol(-1), respectively) and a very promising H2O adsorption isotherm due to their enhanced hydrophilicity. For H2N-MIL-125 the very steep rise of the H2O adsorption isotherm in the 0.1 < p/p0 < 0.2 region is especially beneficial for the intended heat pump application.

Isomeric yield ratios of 87m,gY from different nuclear reactions

NASA Astrophysics Data System (ADS)

Naik, H.; Kim, G. N.; Kim, K.; Zaman, M.; Sahid, M.; Yang, S.-C.; Lee, M. W.; Kang, Y. R.; Shin, S. G.; Cho, M.-H.; Goswami, A.; Song, T. Y.

2014-07-01

The independent isomeric yield ratios of 87m,gY produced from the 93Nb( γ, α2n) and natZr( γ, p xn) reactions with the end-point bremsstrahlung energy of 45-70 MeV have been determined by an off-line γ-ray spectrometric technique using 100 MeV electron linac at the Pohang accelerator laboratory, Korea. The isomeric yield ratios of 87m,gY were also determined from the natZr(p, αxn) and the 89Y(p,p2n) reactions with E P = 15-45 MeV as well as those from the 89Y( α, α2n) reaction with E α = 32-43 MeV using the MC-50 cyclotron at the Korea Institute of Radiological and Medical Science, Korea. The isomeric yield ratios of 87m,gY from the present work in the 93Nb( γ, α2n), natZr( γ, p xn), natZr(p, αxn), 89Y(p,p2n), and 89Y( α, α2n) reactions were compared with those of the literature data in the 85Rb( α, 2n), the 86,87,88Sr(d, xn), 89Y(n,3n), and the 89Y( γ, 2n) reactions to examine the role of target, projectiles, and ejectiles through compound nucleus excitation energy and input angular momentum. The isomeric yield ratios of 87m,gY in the above eleven reactions were also calculated using the computer code TALYS 1.4 and compared with the experimental data. The different behaviors between photon- and neutron-induced reactions and charged-particle-induced reactions are discussed from the viewpoint of compound and non-compound (pre-equilibrium) process.

Superactivity of MOF-808 toward Peptide Bond Hydrolysis.

PubMed

Ly, Hong Giang T; Fu, Guangxia; Kondinski, Aleksandar; Bueken, Bart; De Vos, Dirk; Parac-Vogt, Tatjana N

2018-05-03

MOF-808, a Zr(IV)-based metal-organic framework, has been proven to be a very effective heterogeneous catalyst for the hydrolysis of the peptide bond in a wide range of peptides and in hen egg white lysozyme protein. The kinetic experiments with a series of Gly-X dipeptides with varying nature of amino acid side chain have shown that MOF-808 exhibits selectivity depending on the size and chemical nature of the X side chain. Dipeptides with smaller or hydrophilic residues were hydrolyzed faster than those with bulky and hydrophobic residues that lack electron rich functionalities which could engage in favorable intermolecular interactions with the btc linkers. Detailed kinetic studies performed by 1 H NMR spectroscopy revealed that the rate of glycylglycine (Gly-Gly) hydrolysis at pD 7.4 and 60 °C was 2.69 × 10 -4 s -1 ( t 1/2 = 0.72 h), which is more than 4 orders of magnitude faster compared to the uncatalyzed reaction. Importantly, MOF-808 can be recycled several times without significantly compromising the catalytic activity. A detailed quantum-chemical study combined with experimental data allowed to unravel the role of the {Zr 6 O 8 } core of MOF-808 in accelerating Gly-Gly hydrolysis. A mechanism for the hydrolysis of Gly-Gly by MOF-808 is proposed in which Gly-Gly binds to two Zr(IV) centers of the {Zr 6 O 8 } core via the oxygen atom of the amide group and the N-terminus. The activity of MOF-808 was also demonstrated toward the hydrolysis of hen egg white lysozyme, a protein consisting of 129 amino acids. Selective fragmentation of the protein was observed with 55% yield after 25 h under physiological pH.

Influence of Solvent on Liquid Phase Hydrodeoxygenation of Furfural-Acetone Condensation Adduct using Ni/Al2O3-ZrO2 Catalysts

NASA Astrophysics Data System (ADS)

Ulfa, S. M.; Mahfud, A.; Nabilah, S.; Rahman, M. F.

2017-02-01

Influence of water and acidic protic solvent on hydrodeoxygenation (HDO) of the furfural-acetone adduct (FAA) over Ni/Al2O3-ZrO2 (NiAZ) catalysts were investigated. The HDO of FAA was carried out in a batch reactor at 150°C for 8 hours. The NiAZ catalysts were home-made catalysts which were prepared by wet impregnation method with 10 and 20% nickel loading. The HDO reaction of FAA using 10NiAZ in water at 150°C gave alkane and oxygenated hydrocarbons at 31.41% with selectivity over tridecane (C13) in 6.67%. On the other hand, a reaction using acetic acid:water (1:19 v/v) in similar reaction condition gave only oxygenated compounds and hydrocracking product (C8-C10). The formation of tridecane (C13) was proposed by hydrogenation of C=O and C=C followed by decarboxylation without hydrocracking process. The presence of water facilitated decarboxylation mechanism by stabilized dehydrogenated derivatives of FAA.

Microstructural and Textural Differences Induced by Water and Furnace Cooling in Commercially Pure Zr Annealed in the α + β Region

NASA Astrophysics Data System (ADS)

Chai, Linjiang; Wang, Tingting; Ren, Yi; Song, Bo; Guo, Ning; Chen, Liangyu

2018-07-01

In this work, a commercially pure Zr sheet with a typical bimodal basal texture was annealed in an α + β region and then subjected to different coolings (in water and furnace). Microstructures and textures of both the as-received and the heat-treated specimens were investigated by electron channeling contrast imaging and electron backscatter diffraction techniques. Results show that a duplex microstructure consisting of untransformed bulk α grains and twinned martensitic plates is produced in the water-cooled specimen, which possesses a weakened texture compared to the initial one. For the specimen cooled in furnace, however, a uniform microstructure fully comprised of coarser equiaxed grains with a strengthened texture is obtained. Analyses reveal that the rapid cooling in water could suppress variant selection behaviors during β → α transformation and allow α plates with scattered orientations to be nucleated inside β phases, contributing to the weakened texture. In contrast, during slow cooling in furnace, β boundaries would act as preferred nucleation sites of α embryos, resulting in a strong variant selection that accounts for the intensified texture.

Microstructural and Textural Differences Induced by Water and Furnace Cooling in Commercially Pure Zr Annealed in the α + β Region

NASA Astrophysics Data System (ADS)

Chai, Linjiang; Wang, Tingting; Ren, Yi; Song, Bo; Guo, Ning; Chen, Liangyu

2018-03-01

In this work, a commercially pure Zr sheet with a typical bimodal basal texture was annealed in an α + β region and then subjected to different coolings (in water and furnace). Microstructures and textures of both the as-received and the heat-treated specimens were investigated by electron channeling contrast imaging and electron backscatter diffraction techniques. Results show that a duplex microstructure consisting of untransformed bulk α grains and twinned martensitic plates is produced in the water-cooled specimen, which possesses a weakened texture compared to the initial one. For the specimen cooled in furnace, however, a uniform microstructure fully comprised of coarser equiaxed grains with a strengthened texture is obtained. Analyses reveal that the rapid cooling in water could suppress variant selection behaviors during β → α transformation and allow α plates with scattered orientations to be nucleated inside β phases, contributing to the weakened texture. In contrast, during slow cooling in furnace, β boundaries would act as preferred nucleation sites of α embryos, resulting in a strong variant selection that accounts for the intensified texture.

The evaluation of enhanced nitrification by immobilized biofilm on a clinoptilolite carrier.

PubMed

Park, Se Jin; Lee, Hyung Sool; Yoon, Tae Il

2002-04-01

This study was conducted to evaluate the effect of clinoptilolite on nitrification in activated sludge (AS), and was focused on a relationship between ammonium exchange capacity of this mineral and improvement of nitrification. In batch experiments, the adsorption property of biofilm-attached clinoptilolite did not show substantial difference from that of natural clinoptilolite, indicating that bioregeneration became completely achieved without any regenerant in the AS. The AS with added clinoptilolite (ZR) was compared to the control AS (CR) when the ratio of chemical oxygen demand (COD) to total kjeldahl nitrogen (TKN) of influent, i.e. C/N ratio, was varied from 3.25 to 7.5 at a hydraulic retention time (HRT) of 3 h. Enhanced nitrification was comparatively observed for the ZR as C/N ratio gradually increased. The results indicated that the clinoptilolite provided a relatively low C/N ratio for nitrifiers, due to ammonium adsorption of this mineral, and consequently nitrification was accelerated.

Rapid Relaxation and Embrittlement of Zr-based Bulk Metallic Glasses by Electropulsing

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

Yiu, P; Chen, Y. C.; Chu, J. P.

2013-01-01

Mechanical relaxation and embrittlement of Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glasses were achieved rapidly by the direct current electropulsing treatment. The temperature profile was recorded by an infrared camera and it was found to be non-uniform in the treated specimen. Specifically, temperatures below the glass transition temperature, near and above the crystallization temperature could be ach- ieved, respectively, at different locations in the same treated specimen. Two sets of nanoindentation were conducted. While the first set investigated the mechanical properties of three individually elec- tropulsed specimens with different conditions, the second set indented a single treated specimen along its temperature gradient. Bothmore » sets of indentation revealed that by Joule heating to different tempera- tures, relaxation, embrittlement, and crystallization were significantly accelerated by electrical pulses. Results suggest that electropulsing provides an opportunity to simultaneously achieve plastic forming and mechanical property control of metallic glasses.« less

Sub-kT/q Subthreshold-Slope Using Negative Capacitance in Low-Temperature Polycrystalline-Silicon Thin-Film Transistor

PubMed Central

Park, Jae Hyo; Jang, Gil Su; Kim, Hyung Yoon; Seok, Ki Hwan; Chae, Hee Jae; Lee, Sol Kyu; Joo, Seung Ki

2016-01-01

Realizing a low-temperature polycrystalline-silicon (LTPS) thin-film transistor (TFT) with sub-kT/q subthreshold slope (SS) is significantly important to the development of next generation active-matrix organic-light emitting diode displays. This is the first time a sub-kT/q SS (31.44 mV/dec) incorporated with a LTPS-TFT with polycrystalline-Pb(Zr,Ti)O3 (PZT)/ZrTiO4 (ZTO) gate dielectrics has been demonstrated. The sub-kT/q SS was observed in the weak inversion region at −0.5 V showing ultra-low operating voltage with the highest mobility (250.5 cm2/Vsec) reported so far. In addition, the reliability of DC negative bias stress, hot carrier stress and self-heating stress in LTPS-TFT with negative capacitance was investigated for the first time. It was found that the self-heating stress showed accelerated SS degradation due to the PZT Curie temperature. PMID:27098115

Structure and Mechanical and Corrosion Properties of a Magnesium Mg-Y-Nd-Zr Alloy after High Pressure Torsion

NASA Astrophysics Data System (ADS)

Lukyanova, E. A.; Martynenko, N. S.; Serebryany, V. N.; Belyakov, A. N.; Rokhlin, L. L.; Dobatkin, S. V.; Estrin, Yu. Z.

2017-11-01

The structure and the properties of an Mg-Y-Nd-Zr alloy (WE43) are studied after high pressure torsion (HPT) in the temperature range 20-300°C. Structure refinement proceeds mainly by deformation twinning with the formation of a partial nanocrystalline structure with a grain size of 30-100 nm inside deformation twins. The WE43 alloy is shown to be aged during heating after HPT due to the decomposition of a magnesium solid solution. HPT at room temperature and subsequent aging causes maximum hardening. It is shown that HPT significantly accelerates the decomposition of a magnesium solid solution. HPT at all temperatures considerably increases the tensile strength and the yield strength upon tensile tests and significantly decreases plasticity. Subsequent aging additionally hardens the WE43 alloy. A potentiodynamic study shows that the corrosion resistance of this alloy after HPT increases. However, subsequent aging degrades the corrosion properties of the alloy.

Analyzing and Modelling the Corrosion Behavior of Ni/Al2O3, Ni/SiC, Ni/ZrO2 and Ni/Graphene Nanocomposite Coatings

PubMed Central

Saeed, Adil; Braun, Wolfgang; Bajwa, Rizwan; Rafique, Saqib

2017-01-01

A study has been presented on the effects of intrinsic mechanical parameters, such as surface stress, surface elastic modulus, surface porosity, permeability and grain size on the corrosion failure of nanocomposite coatings. A set of mechano-electrochemical equations was developed by combining the popular Butler–Volmer and Duhem expressions to analyze the direct influence of mechanical parameters on the electrochemical reactions in nanocomposite coatings. Nanocomposite coatings of Ni with Al2O3, SiC, ZrO2 and Graphene nanoparticles were studied as examples. The predictions showed that the corrosion rate of the nanocoatings increased with increasing grain size due to increase in surface stress, surface porosity and permeability of nanocoatings. A detailed experimental study was performed in which the nanocomposite coatings were subjected to an accelerated corrosion testing. The experimental results helped to develop and validate the equations by qualitative comparison between the experimental and predicted results showing good agreement between the two. PMID:29068395

Testing the Chemical/Structural Stability of Proton Conducting Perovskite Ceramic Membranes by in Situ/ex Situ Autoclave Raman Microscopy

PubMed Central

Slodczyk, Aneta; Zaafrani, Oumaya; Sharp, Matthew D.; Kilner, John A.; Dabrowski, Bogdan; Lacroix, Olivier; Colomban, Philippe

2013-01-01

Ceramics, which exhibit high proton conductivity at moderate temperatures, are studied as electrolyte membranes or electrode components of fuel cells, electrolysers or CO2 converters. In severe operating conditions (high gas pressure/high temperature), the chemical activity towards potentially reactive atmospheres (water, CO2, etc.) is enhanced. This can lead to mechanical, chemical, and structural instability of the membranes and premature efficiency loss. Since the lifetime duration of a device determines its economical interest, stability/aging tests are essential. Consequently, we have developed autoclaves equipped with a sapphire window, allowing in situ Raman study in the 25–620 °C temperature region under 1–50 bar of water vapor/gas pressure, both with and without the application of an electric field. Taking examples of four widely investigated perovskites (BaZr0.9Yb0.1O3−δ, SrZr0.9Yb0.1O3−δ, BaZr0.25In0.75O3−δ, BaCe0.5Zr0.3Y0.16Zn0.04O3−δ), we demonstrate the high potential of our unique set-up to discriminate between good/stable and instable electrolytes as well as the ability to detect and monitor in situ: (i) the sample surface reaction with surrounding atmospheres and the formation of crystalline or amorphous secondary phases (carbonates, hydroxides, hydrates, etc.); and (ii) the structural modifications as a function of operating conditions. The results of these studies allow us to compare quantitatively the chemical stability versus water (corrosion rate from ~150 µm/day to less than 0.25 µm/day under 200–500 °C/15–80 bar PH2O) and to go further in comprehension of the aging mechanism of the membrane. PMID:24957060

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties

NASA Astrophysics Data System (ADS)

Marcellini, Moreno; Fernandes, Francisco M.; Dedovets, Dmytro; Deville, Sylvain

2017-04-01

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties.

PubMed

Marcellini, Moreno; Fernandes, Francisco M; Dedovets, Dmytro; Deville, Sylvain

2017-04-14

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Determination of diphenylarsinic acid, phenylarsonic acid and inorganic arsenic in drinking water by graphite-furnace atomic-absorption spectrometry after simultaneous separation and preconcentration with solid-phase extraction disks.

PubMed

Hagiwara, Kenta; Inui, Tetsuo; Koike, Yuya; Nakamura, Toshihiro

2013-01-01

A simple method of graphite-furnace atomic-absorption spectrometry (GFAAS) after solid-phase extraction (SPE) was developed for the determination of diphenylarsinic acid (DPAA), phenylarsonic acid (PAA), and inorganic arsenic (iAs) in drinking water. This method involves the simultaneous collection of DPAA, PAA, and iAs using three stacked SPE disks, i.e., an Empore SDB-XD disk (the upper layer), an activated carbon disk (the middle layer), and a Cation-SR disk loaded with Zr and Ca (ZrCa-CED; the lower layer). A 200-mL aqueous sample was adjusted to pH 3 with nitric acid and passed through the SPE disks at a flow rate of 15 mL min(-1), to concentrate DPAA on the SDB-XD disk, PAA on the activated carbon disk, and iAs on the ZrCa-CED. The As compounds were eluted from the disks with 10 mL of ethanol containing 0.5 mol L(-1) ammonia solution for DPAA, 20 mL of 1 mol L(-1) ammonia solution for PAA, and 20 mL of 6 mol L(-1) hydrochloric acid for iAs. The eluates of DPAA, PAA, and iAs were diluted to 20, 25, and 25 mL, respectively, with deionized water, and then analyzed by GFAAS. The detection limits of As (three-times the standard deviation (n = 3) of the blank values) were 0.13 and 0.16 μg L(-1) at enrichment factors of 10 and 8, respectively, using a 200-mL water sample. Spike tests with 2 μg (10 μg L(-1)) of DPAA, PAA, and iAs in 200 mL of tap water and bottled drinking water showed good recoveries (96.1-103.8%).

Adsorption Analysis of Lactoferrin to Titanium, Stainless Steel, Zirconia, and Polymethyl Methacrylate Using the Quartz Crystal Microbalance Method

PubMed Central

Yoshida, Eiji; Hayakawa, Tohru

2016-01-01

It is postulated that biofilm formation in the oral cavity causes some oral diseases. Lactoferrin is an antibacterial protein in saliva and an important defense factor against biofilm development. We analyzed the adsorbed amount of lactoferrin and the dissociation constant (K d) of lactoferrin to the surface of different dental materials using an equilibrium analysis technique in a 27 MHz quartz crystal microbalance (QCM) measurement. Four different materials, titanium (Ti), stainless steel (SUS), zirconia (ZrO2) and polymethyl methacrylate (PMMA), were evaluated. These materials were coated onto QCM sensors and the surfaces characterized by atomic force microscopic observation, measurements of surface roughness, contact angles of water, and zeta potential. QCM measurements revealed that Ti and SUS showed a greater amount of lactoferrin adsorption than ZrO2 and PMMA. Surface roughness and zeta potential influenced the lactoferrin adsorption. On the contrary, the K d value analysis indicated that the adsorbed lactoferrin bound less tightly to the Ti and SUS surfaces than to the ZrO2 and PMMA surfaces. The hydrophobic interaction between lactoferrin and ZrO2 and PMMA is presumed to participate in better binding of lactoferrin to ZrO2 and PMMA surfaces. It was revealed that lactoferrin adsorption behavior was influenced by the characteristics of the material surface. PMID:26998486

High pressure hydriding of sponge-Zr in steam-hydrogen mixtures

NASA Astrophysics Data System (ADS)

Soo Kim, Yeon; Wang, Wei-E.; Olander, D. R.; Yagnik, S. K.

1997-07-01

Hydriding kinetics of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk has been studied by thermogravimetry in the temperature range 350-400°C in 7 MPa hydrogen-steam mixtures. Some specimens were prefilmed with a thin oxide layer prior to exposure to the reactant gas; all were coated with a thin layer of gold to avoid premature reaction at edges. Two types of hydriding were observed in prefilmed specimens, viz., a slow hydrogen absorption process that precedes an accelerated (massive) hydriding. At 7 MPa total pressure, the critical ratio of H 2/H 2O above which massive hydriding occurs at 400°C is ˜ 200. The critical H 2/H 20 ratio is shifted to ˜2.5 × 103 at 350°C. The slow hydriding process occurs only when conditions for hydriding and oxidation are approximately equally favorable. Based on maximum weight gain, the specimen is completely converted to δ-ZrH 2 by massive hydriding in ˜5 h at a hydriding rate of ˜10 -6 mol H/cm 2 s. Incubation times of 10-20 h prior to the onset of massive hydriding increases with prefilm oxide thickness in the range of 0-10 μm. By changing to a steam-enriched gas, massive hydriding that initially started in a steam-starved condition was arrested by re-formation of a protective oxide scale.

Enhanced Adsorption of p-Arsanilic Acid from Water by Amine-Modified UiO-67 as Examined Using Extended X-ray Absorption Fine Structure, X-ray Photoelectron Spectroscopy, and Density Functional Theory Calculations.

PubMed

Tian, Chen; Zhao, Jian; Ou, Xinwen; Wan, Jieting; Cai, Yuepeng; Lin, Zhang; Dang, Zhi; Xing, Baoshan

2018-03-20

p-Arsanilic acid ( p-ASA) is an emerging organoarsenic pollutant comprising both inorganic and organic moieties. For the efficient removal of p-ASA, adsorbents with high adsorption affinity are urgently needed. Herein, amine-modified UiO-67 (UiO-67-NH 2 ) metal-organic frameworks (MOFs) were synthesized, and their adsorption affinities toward p-ASA were 2 times higher than that of the pristine UiO-67. Extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculation results revealed adsorption through a combination of As-O-Zr coordination, hydrogen bonding, and π-π stacking, among which As-O-Zr coordination was the dominant force. Amine groups played a significant role in enhancing the adsorption affinity through strengthening the As-O-Zr coordination and π-π stacking, as well as forming new adsorption sites via hydrogen bonding. UiO-67-NH 2 s could remove p-ASA at low concentrations (<5 mg L -1 ) in simulated natural and wastewaters to an arsenic level lower than that of the drinking water standard of World Health Organization (WHO) and the surface water standard of China, respectively. This work provided an emerging and promising method to increase the adsorption affinity of MOFs toward pollutants containing both organic and inorganic moieties, via modifying functional groups based on the pollutant structure to achieve synergistic adsorption effect.

Producing Zirconium Diboride Components with Complex, Near-Net Shape Geometries by Aqueous Room-Temperature Injection Molding

NASA Technical Reports Server (NTRS)

Wiesner, Valerie L.; Youngblood, Jeffrey; Trice, Rodney

2014-01-01

Room-temperature injection molding is proposed as a novel, low-cost and more energy efficient manufacturing process capable of forming complex-shaped zirconium diboride (ZrB2) parts. This innovative processing method utilized aqueous suspensions with high powder loading and a minimal amount (5 vol.) of water-soluble polyvinylpyrrolidone (PVP), which was used as a viscosity modifier. Rheological characterization was performed to evaluate the room-temperature flow properties of ZrB2-PVP suspensions. ZrB2 specimens were fabricated with high green body strength and were machinable prior to binder removal despite their low polymer content. After binder burnout and pressureless sintering, the bulk density and microstructure of specimens were characterized using Archimedes technique and scanning electron microscopy. X-Ray Diffraction was used to determine the phase compositions present in sintered specimens. Ultimate strength of sintered specimens will be determined using ASTM C1323-10 compressive C-ring test.

Effect of He implantation on the microstructure of zircaloy-4 studied using in situ TEM

NASA Astrophysics Data System (ADS)

Tunes, M. A.; Harrison, R. W.; Greaves, G.; Hinks, J. A.; Donnelly, S. E.

2017-09-01

Zirconium alloys are of great importance to the nuclear industry as they have been widely used as cladding materials in light-water reactors since the 1960s. This work examines the behaviour of these alloys under He ion implantation for the purposes of developing understanding of the fundamental processes behind their response to irradiation. Characterization of zircaloy-4 samples using TEM with in situ 6 keV He irradiation up to a fluence of 2.7 ×1017ions ·cm-2 in the temperature range of 298 to 1148 K has been performed. Ordered arrays of He bubbles were observed at 473 and 1148 K at a fluence of 1.7 ×1017ions ·cm-2 in αZr, the hexagonal compact (HCP) and in βZr, the body centred cubic (BCC) phases, respectively. In addition, the dissolution behaviour of cubic Zr hydrides under He irradiation has been investigated.

Development of Fe3O4/ZrO2 Composite Powered by Nanographene Platelets (NGP) for Degradation of Water Pollutants via Photo- and Sonocatalysis

NASA Astrophysics Data System (ADS)

Kristianto, Yogi; Taufik, Ardiansyah; Saleh, Rosari

2017-03-01

In this study, a series of Fe3O4/ZrO2/nanographene platelets (NGP) composite, with various weight percent (wt%) of NGP (5%, 10% and 15%), were prepared successfully using ultrasonic-assisted followed by simple hydrothermal method. Their physicochemical properties were fairly characterized by X-ray diffraction, fourier transform infrared and thermal gravimetric analysis. Furthermore, their catalytic activities were investigated toward anionic congo red (CR) and cationic methylene blue (MB) as models of organic pollutant under ultraviolet (UV) and ultrasonic (US) irradiation, respectively. The experimental results showed that the incorporation of NGP in Fe3O4/ZrO2 composite improved its efficiency in degrading CR and MB and became maximum at 10wt% of NGP. In addition, the role of active radicals involved in catalytic activities were discussed.

Fully Depleted Ti-Nb-Ta-Zr-O Nanotubes: Interfacial Charge Dynamics and Solar Hydrogen Production.

PubMed

Chiu, Yi-Hsuan; Lai, Ting-Hsuan; Chen, Chun-Yi; Hsieh, Ping-Yen; Ozasa, Kazunari; Niinomi, Mitsuo; Okada, Kiyoshi; Chang, Tso-Fu Mark; Matsushita, Nobuhiro; Sone, Masato; Hsu, Yung-Jung

2018-05-01

Poor kinetics of hole transportation at the electrode/electrolyte interface is regarded as a primary cause for the mediocre performance of n-type TiO 2 photoelectrodes. By adopting nanotubes as the electrode backbone, light absorption and carrier collection can be spatially decoupled, allowing n-type TiO 2 , with its short hole diffusion length, to maximize the use of the available photoexcited charge carriers during operation in photoelectrochemical (PEC) water splitting. Here, we presented a delicate electrochemical anodization process for the preparation of quaternary Ti-Nb-Ta-Zr-O mixed-oxide (denoted as TNTZO) nanotube arrays and demonstrated their utility in PEC water splitting. The charge-transfer dynamics for the electrodes was investigated using time-resolved photoluminescence, electrochemical impedance spectroscopy, and the decay of open-circuit voltage analysis. Data reveal that the superior photoactivity of TNTZO over pristine TiO 2 originated from the introduction of Nd, Ta, and Zr elements, which enhanced the amount of accessible charge carriers, modified the electronic structure, and improved the hole injection kinetics for expediting water splitting. By modulating the water content of the electrolyte employed in the anodization process, the wall thickness of the grown TNTZO nanotubes can be reduced to a size smaller than that of the depletion layer thickness, realizing a fully depleted state for charge carriers to further advance the PEC performance. Hydrogen evolution tests demonstrate the practical efficacy of TNTZO for realizing solar hydrogen production. Furthermore, with the composition complexity and fully depleted band structure, the present TNTZO nanotube arrays may offer a feasible and universal platform for the loading of other semiconductors to construct a sophisticated heterostructure photoelectrode paradigm, in which the photoexcited charge carriers can be entirely utilized for efficient solar-to-fuel conversion.

Microstructure and mechanical properties of a newly developed low Young's modulus Ti-15Zr-5Cr-2Al biomedical alloy.

PubMed

Wang, Pan; Wu, Lihong; Feng, Yan; Bai, Jiaming; Zhang, Baicheng; Song, Jie; Guan, Shaokang

2017-03-01

The Ti-15Zr-5Cr-2Al alloy has been developed and various heat treatments have been investigated to develop new biomedical materials. It is found that the heat treatment conditions strongly affect the phase constitutions and mechanical properties. The as-cast specimen is comprised of β phase and a small fraction of α phase, which is attributed to the suppression of ω phase caused by adding Al. A high yield strength of 1148±36MPa and moderate Young's modulus of 96±3GPa are obtained in the as-cast specimen. Besides the β phase and α phase, ω phase is also detected in the air cooled and liquid nitrogen quenched specimens, which increases the Young's modulus and lowers the ductility. In contrast, only β phase is detected after ice water quenching. The ice water quenched specimen exhibits a good combination of mechanical properties with a high microhardness of 302±10HV, a large plastic strain of 23±2%, a low Young's modulus of 58±4GPa, a moderate yield strength of 625±32MPa and a high compressive strength of 1880±59MPa. Moreover, the elastic energies of the ice water quenched specimen (3.22MJ/m 3 ) and as-cast specimen (6.86MJ/m 3 ) are higher than that of c.p. Ti (1.25MJ/m 3 ). These results demonstrate that as-cast and ice water quenched Ti-15Zr-5Cr-2Al alloys with a superior combination of mechanical properties are potential materials for biomedical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

SiC Composite for Fuel Structure Applications

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

Yueh, Ken

Extensive evaluation was performed to determine the suitability of using SiC composite as a boiling water reactor (BWR) fuel channel material. A thin walled SiC composite box, 10 cm in dimension by approximately 1.5 mm wall thickness was fabricated using chemical vapor deposition (CVD) for testing. Mechanical test results and performance evaluations indicate the material could meet BWR channel mechanical design requirement. However, large mass loss of up to 21% was measured in in-pile corrosion test under BWR-like conditions in under 3 months of irradiation. A fresh sister sample irradiated in a follow-up cycle under PWR conditions showed no measureablemore » weight loss and thus supports the hypothesis that the oxidizing condition of the BWR-like coolant chemistry was responsible for the high corrosion rate. A thermodynamic evaluation showed SiC is not stable and the material may oxidize to form SiO 2 and CO 2. Silica has demonstrated stability in high temperature steam environment and form a protective oxide layer under severe accident conditions. However, it does not form a protective layer in water under normal BWR operational conditions due to its high solubility. Corrosion product stabilization by modifying the SiC CVD surface is an approach evaluated in this study to mitigate the high corrosion rate. Titanium and zirconium have been selected as stabilizing elements since both TiSiO 4 and ZrSiO 4 are insoluble in water. Corrosion test results in oxygenated water autoclave indicate TiSiO4 does not form a protective layer. However, zirconium doped test samples appear to form a stable continuous layer of ZrSiO 4 during the corrosion process. Additional process development is needed to produce a good ZrSiC coating to verify functionality of the mitigation concept.« less

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

NASA Astrophysics Data System (ADS)

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 and may not only cause or modify Ce anomalies and Th-U fractionation, but also mobilization of and fractionation between Zr, Hf, Th and redox-insensitive REY during weathering, pedogenesis, diagenesis and incongruent dissolution of particles in seawater and freshwater. Siderophores may significantly affect the use of HFSE as geochemical tools. Concave downward light REY patterns may be used as a biosignature for water-rock interaction in the presence of siderophores. Enhanced and preferential mobilization of U relative to Th in the presence of siderophores may produce Th-U signals comparable to those indicative of weathering under oxidized conditions, which might constrain the use of U concentrations and Th/U ratios as a paleoredox-proxy. The enhanced mobilization of Zr and especially Hf from igneous rocks in the presence of DFOB might have implications for the use of the latter as a tracer for the impact of continental weathering on seawater chemistry. Because siderophore complexes affect the particle-reactivity of Hf and Zr, they may prevent effective removal of terrigenous Hf and Zr during aggregation/coagulation of riverine particles in estuaries. Siderophore-promoted solubilization and stabilization might hence be an additional way to transport continental Hf and Zr to the oceans. Furthermore, siderophore-enhanced mobilization may also have implications for the remediation techniques employed to immobilize HFSE such as U, Th and REY, at nuclear waste and reprocessing sites and at REY ore processing plants, where soils are commonly contaminated with these (sometimes radioactive) heavy metals.

Lake Qinghai sediment geochemistry linked to hydroclimate variability since the last glacial

NASA Astrophysics Data System (ADS)

Jin, Zhangdong; An, Zhisheng; Yu, Jimin; Li, Fuchun; Zhang, Fei

2015-08-01

Geochemistry of basin sediments from semi-arid regions is valuable to understand past hydroclimatic changes. Here, we investigate the links of sedimentary geochemistry (Rb, Sr, Ca/Zr, TOC, and %CaCO3), carbonate mineralogy and ostracod shell δ18O of Lake Qinghai, a basin proximal to major dust production centers at mid-latitudes of the Northern Hemisphere, to changes in depositional conditions and hydroclimate during the past 32 ka. Surface lacustrine sediments are characterized by low-Rb, high-Sr, low-Rb/Sr, high-%CaCO3 and high-Ca/Zr values, in contrast to the chemical compositions of eolian loess (high-Rb, low-Sr, high-Rb/Sr, low-%CaCO3, and low-Ca/Zr). A direct comparison of soluble Ca and Sr in two short cores with instrumental water discharge data suggests that lacustrine precipitates in Lake Qinghai are dominated by authigenic aragonite formed under Ca2+-limited water conditions, and that the accumulation rate of aragonite dominantly depends on solute fluxes into the lake during the rainy seasons (late May to September). Our high-resolution down-core records show that sediments during the last glacial (∼32-19.8 ka) had high-Rb, low-Sr, low-%CaCO3, and low-Ca/Zr, indicating eolian dust (loess) accumulation in a desiccated basin under dry glacial conditions, further supported by grain size and pollen results. This type of sedimentation was maintained during the last deglacial (∼19.8-11.5 ka), but interrupted by episodic lacustrine precipitates with high-Sr, high-%CaCO3, high-Ca/Zr, and low-Rb. At ∼11.5 ka, sedimentary Rb/Sr, Ca/Zr, %CaCO3 and TOC show dramatic and permanent changes, implying an abrupt shift in the atmospheric circulation at the onset of the Holocene in the Lake Qinghai region. Lacustrine precipitates have persisted throughout the Holocene with a maximum during the early to mid-Holocene (∼10.5-8.0 ka). Since ∼8.0 ka, the gradual and significant decreases in aragonite and Sr accumulations in tandem with increasing dust deposit and more positive ostracod δ18O may be linked to a weakening of Asian summer monsoons during the mid-to-late Holocene. Overall, our records appear to show a high sensitivity of sediment development and geochemistry in Lake Qinghai to the regional hydroclimate changes since the last glacial.

Influence of growth temperature on properties of zirconium dioxide films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Kukli, Kaupo; Ritala, Mikko; Aarik, Jaan; Uustare, Teet; Leskela, Markku

2002-08-01

ZrO2 films were grown by atomic layer deposition from ZrCl4 and H2O or a mixture of H2O and H2O2 on Si(100) substrates in the temperature range of 180-600 degC. The films were evaluated in the as-deposited state, in order to follow the effect of deposition temperature on the film quality. The rate of crystal growth increased and the content of residual impurities decreased with increasing temperature. The zirconium-to-oxygen atomic ratio, determined by ion-beam analysis, corresponded to the stoichiometric dioxide regardless of the growth temperature. The effective permittivity of ZrO2 in Al/ZrO2/Si capacitor structures increased from 13-15 in the films grown at 180 degC to 19 in the films grown at 300-600 degC, measured at 100 kHz. The permittivity was relatively high in the crystallized films, compared to the amorphous ones, but rather insensitive to the crystal structure. The permittivity was higher in the films grown using water. The leakage current density tended to be lower and the breakdown field higher in the films grown using hydrogen peroxide.

Morphology evaluation of ZrO2 dip coating on mild steel and its corrosion performance in NaOH solution

NASA Astrophysics Data System (ADS)

Anwar, M. A.; Kurniawan, T.; Asmara, Y. P.; Harun, W. S. W.; Oumar, A. N.; Nandyanto, A. B. D.

2017-10-01

In this work, the morphology of ZrO2 thin film from dip coating process on mild steel has been investigated. Mild steel was dip-coated on solution made of zirconium butoxide as a precursor, ethanol as solvent, acetylacetone as chelating agent and water for hydrolysis. Number of dipping was adjusted at 3, 5 and 7 times. The dipped sample then annealed at 350°C for two hours by adjusting the heating rate at 1°C/min respectively. The optical microscope showed that micro-cracks were observed on the surface of the coating with its concentration reduced as dipping sequence increased. The XRD result showed that annealing process can produce polycrystalline tetragonal-ZrO2. Meanwhile, SEM image showed that the thicknesses of the ZrO2 coatings were in between 400-600 nm. The corrosion resistance of uncoated and coated substrates was studied by polarization test through potentio-dynamic polarization curve at 1mV/s immersed in with 3.5% NaCl. The coating efficiency was improved as the number of layer dip coated increased, which showed improvement in corrosion protection.

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

Brady, Michael P.; Ievlev, Anton V.; Fayek, Mostafa

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2O/D isotopic tracer and H 2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at roommore » temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.« less

Zr 2Ir 6B with an eightfold superstructure of the cubic perovskite-like boride ZrIr 3B 0.5: Synthesis, crystal structure and bonding analysis

NASA Astrophysics Data System (ADS)

Hermus, Martin; Fokwa, Boniface P. T.

2010-04-01

Single phase powder samples and single crystals of Zr 2Ir 6B were successfully synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. Superstructure reflections were observed both on powder and on single crystal diffraction data, leading to an eightfold superstructure of ZrIr 3B x phase. The new phase, which has a metallic luster, crystallizes in space group Fm3¯m (no. 225) with the lattice parameters a=7.9903(4) Å, V=510.14(4) Å 3. Its crystal structure was refined on the basis of powder as well as single crystal data. The single crystal refinement converged to R1=0.0239 and w R2=0.0624 for all 88 unique reflections and 6 parameters. Zr 2Ir 6B is isotypic to Ti 2Rh 6B and its structure can be described as a defect double perovskite, A2BB' O6, where the A site is occupied by zirconium, the B site by boron, the O site by iridium but the B' site is vacant, leading to the formation of empty and boron-filled octahedral Ir 6 clusters. According to the result of tight-binding electronic structure calculations, Ir-B and Ir-Zr interactions are mainly responsible for the structural stability of the phase. According to COHP bonding analysis, the strongest bonding occurs for the Ir-B contacts, and the Ir-Ir bonding within the empty clusters is two times stronger than that in the BIr 6 octahedra.

Assessment of reliability of CAD-CAM tooth-colored implant custom abutments.

PubMed

Guilherme, Nuno Marques; Chung, Kwok-Hung; Flinn, Brian D; Zheng, Cheng; Raigrodski, Ariel J

2016-08-01

Information is lacking about the fatigue resistance of computer-aided design and computer-aided manufacturing (CAD-CAM) tooth-colored implant custom abutment materials. The purpose of this in vitro study was to investigate the reliability of different types of CAD-CAM tooth-colored implant custom abutments. Zirconia (Lava Plus), lithium disilicate (IPS e.max CAD), and resin-based composite (Lava Ultimate) abutments were fabricated using CAD-CAM technology and bonded to machined titanium-6 aluminum-4 vanadium (Ti-6Al-4V) alloy inserts for conical connection implants (NobelReplace Conical Connection RP 4.3×10 mm; Nobel Biocare). Three groups (n=19) were assessed: group ZR, CAD-CAM zirconia/Ti-6Al-4V bonded abutments; group RC, CAD-CAM resin-based composite/Ti-6Al-4V bonded abutments; and group LD, CAD-CAM lithium disilicate/Ti-6Al-4V bonded abutments. Fifty-seven implant abutments were secured to implants and embedded in autopolymerizing acrylic resin according to ISO standard 14801. Static failure load (n=5) and fatigue failure load (n=14) were tested. Weibull cumulative damage analysis was used to calculate step-stress reliability at 150-N and 200-N loads with 2-sided 90% confidence limits. Representative fractured specimens were examined using stereomicroscopy and scanning electron microscopy to observe fracture patterns. Weibull plots revealed β values of 2.59 for group ZR, 0.30 for group RC, and 0.58 for group LD, indicating a wear-out or cumulative fatigue pattern for group ZR and load as the failure accelerating factor for groups RC and LD. Fractographic observation disclosed that failures initiated in the interproximal area where the lingual tensile stresses meet the compressive facial stresses for the early failure specimens. Plastic deformation of titanium inserts with fracture was observed for zirconia abutments in fatigue resistance testing. Significantly higher reliability was found in group ZR, and no significant differences in reliability were determined between groups RC and LD. Differences were found in the failure characteristics of group ZR between static and fatigue loading. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Possible origin and roles of nano-porosity in ZrO2 scales for hydrogen pick-up in Zr alloys

NASA Astrophysics Data System (ADS)

Lindgren, Mikaela; Geers, Christine; Panas, Itai

2017-08-01

A mechanistic understanding of Wagnerian build-up and subsequent non-Wagnerian break-down of barrier oxide upon oxidation of zirconium alloys by water is reiterated. Hydrogen assisted build-up of nano-porosity is addressed. Growth of sub-nanometer wide stalactitic pores owing to increasing aggregation of neutral oxygen vacancies offering a means to permeate hydrogen into the alloy is explored by density functional theory. The Wagnerian channel utilizes charge separation allowing charged oxygen vacancies and electrons to move separately from nominal anode to nominal cathode. This process becomes increasingly controlled by the charging of the barrier oxide resulting in sub-parabolic rate law for oxide growth. The break-down of the barrier oxide is understood to be preceded by avalanching hydrogen pick-up in the alloy. Pore mediated diffusion allows water to effectively short circuit the barrier oxide.

Excellent fluoride decontamination and antibacterial efficacy of Fe-Ca-Zr hybrid metal oxide nanomaterial.

PubMed

Dhillon, Ankita; Nair, Manjula; Bhargava, Suresh K; Kumar, Dinesh

2015-11-01

The aim of the present study is to develop an efficient nanomaterial for the removal of fluoride and disinfection of harmful bacteria in order to make water potable according to Environmental Protection Agency (EPA) guidelines. Hydrous hybrid Fe-Ca-Zr oxide nanoadsorbent presented a marked fluoride adsorption capacity of 250 mg/g at pH 7.0 (±0.1) much greater than other commercially accessible adsorbents for both synthetic and real water samples. The adsorption isotherms, Freundlich and Dubinin-Radushkevich (D-R) fitted reasonably well fine having high coefficient of regression values. The adsorption of fluoride was established well using pseudo-second-order kinetics. The fluoride loaded adsorbent was efficiently regenerated by using an alkali solution. Interestingly, the developed nanomaterial not only showed excellent fluoride removal capacity but also demonstrated good antibacterial activity against Escherichia coli with IC50 (25 μg/mL). Copyright © 2015 Elsevier Inc. All rights reserved.

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

PubMed

Tepe, Nathalie; Bau, Michael

2014-08-01

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

Characterization of CuCrZr and CuCrZr/SS joint strength for different blanket components manufacturing conditions

NASA Astrophysics Data System (ADS)

Gillia, Olivier; Briottet, Laurent; Chu, Isabelle; Lemoine, Patrick; Rigal, Emmanuel; Peacock, Alan

2009-04-01

This work describes studies on the strength of CuCrZr/SS joints for different manufacturing conditions foreseen for the fabrication of blanket components. In the meantime, as junction strength is expected to be strongly related to CuCrZr properties, investigation on the properties of the CuCrZr itself after the different manufacturing conditions is also presented. The initial manufacturing conditions retained were made of a HIP treatment combined with a fast cooling plus a subsequent ageing treatment. For security reasons, the HIP-quenching operation was not possible. A supplementary solutionning cycle with fast cooling has thus been inserted in the heat treatment process just after the HIP bonding treatment. The influence of solutionning temperature (1040 °C or 980 °C), the cooling rate after solutionning (70 °C/min to water quench), the ageing temperature (480 °C or 560 °C) and the HIP temperature (1040 °C or 980 °C) have been addressed. Test results show that the ageing temperature is very important for keeping high strength of material whereas elongation properties are not very sensible to the manufacturing conditions. 1040 °C HIP or solutionning temperature gives better strength properties, as well as a higher cooling rate after solutionning. Concerning samples with joints, it appears that CT test is more selective than other tests since tensile test does not give rupture at joint and KCU test eliminates a route without classifying other routes.

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

PubMed

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

2016-01-01

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

Fish debris record the hydrothermal activity in the Atlantis II deep sediments (Red Sea)

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

Oudin, E.; Cocherie, A.

1988-01-01

The REE and U, Th, Zr, Hf, Sc have been analyzed in samples from Atlantis II and Shaban/Jean Charcot Deeps in the Red Sea. The high Zr/Hf ratio in some sediments indicates the presence of fish debris or of finely crystallized apatite. The positive ..sigma..REE vs P/sub 2/O/sub 5/ and ..sigma..REE vs Zr/Hf correlations show that fish debris and finely crystallized apatite are the main REE sink in Atlantis II Deep sediments as in other marine environments. The hydrothermal sediments and the fish debris concentrates have similar REE patterns, characterized by a LREE enrichment and a large positive Eu anomaly.more » This REE pattern is also observed in E.P.R. hydrothermal solutions. Fish debris from marine environments acquire their REE content and signature mostly from sea water during early diagenesis. The hydrothermal REE signature of Atlantis II Deep fish debris indicate that they probably record the REE signature of their hydrothermal sedimentation and diagenetic environment. The different REE signatures of the Shaban/Jean Charcot and Atlantis II Deep hydrothermal sediments suggest a sea water-dominated brine in the Shaban/Jean Charcot Deep as opposed to the predominantly hydrothermal brine in Atlantis II Deep. Atlantis II Deep fish debris are also characterized by their high U but low Th contents. Their low Th contents probably reflect the low Th content of the various possible sources (sea water, brine, sediments). Their U contents are probably controlled by the redox conditions of sedimentation.« less

Upper Ocean Circulation in the Glacial Northeast Atlantic during Heinrich Stadials Ice-Sheet Retreat

NASA Astrophysics Data System (ADS)

Toucanne, S.; Soulet, G.; Bosq, M.; Marjolaine, S.; Zaragosi, S.; Bourillet, J. F.; Bayon, G.

2016-12-01

Intermediate ocean water variability is involved in climate changes over geological timescales. As a prominent example, changes in North Atlantic subsurface water properties (including warming) during Heinrich Stadials may have triggered the so-called Heinrich events through ice-shelf loss and attendant ice-stream acceleration. While the origin of Heinrich Stadials and subsequent iceberg calving remains controversial, paleoceanographic research efforts mainly focus on the deep Atlantic overturning, leaving the upper ocean largely unexplored. To further evaluate variability in upper ocean circulation and its possible relationship with ice-sheet instabilities, a depth-transect of eight cores (BOBGEO and GITAN-TANDEM cruises) from the Northeast Atlantic (down to 2 km water depth) have been used to investigate kinematic and chemical changes in the upper ocean during the last glacial period. Our results reveal that near-bottom flow speeds (reconstructed by using sortable silt mean grain-size and X-ray fluorescence core-scanner Zr/Rb ratio) and water-masses chemistry (carbon and neodymium isotopes performed on foraminifera) substantially changed in phase with the millennial-scale climate changes recognized in the ice-core records. Our results are compared with paleoceanographic reconstructions of the 'Western Boundary Undercurrent' in order to discuss regional hydrographic differences at both sides of the North Atlantic, as well as with the fluctuations of both the marine- (through ice-rafted debris) and terrestrial-terminating ice-streams (through meltwater discharges) of the circum-Atlantic ice-sheets. Particular attention will be given to the Heinrich Stadials and concomitant Channel River meltwater discharges into the Northeast Atlantic in response to the melting of the European Ice-Sheet. This comparison helps to disentangle the cryosphere-ocean interactions throughout the last ice age, and the sequence of events occurring in the course of the Heinrich Stadials.

Performance evaluation and post-irradiation examination of a novel LWR fuel composed of U0.17ZrH1.6 fuel pellets bonded to Zircaloy-2 cladding by lead bismuth eutectic

NASA Astrophysics Data System (ADS)

Balooch, Mehdi; Olander, Donald R.; Terrani, Kurt A.; Hosemann, Peter; Casella, Andrew M.; Senor, David J.; Buck, Edgar C.

2017-04-01

A novel light water reactor fuel has been designed and fabricated at the University of California, Berkeley; irradiated at the Massachusetts Institute of Technology Reactor; and examined within the Radiochemical Processing Laboratory at the Pacific Northwest National Laboratory. This fuel consists of U0.17ZrH1.6 fuel pellets core-drilled from TRIGA reactor fuel elements that are clad in Zircaloy-2 and bonded with lead-bismuth eutectic. The performance evaluation and post irradiation examination of this fuel are presented here.

Numerical modeling of heat transfer during hydrogen absorption in thin double-layered annular ZrCo beds

NASA Astrophysics Data System (ADS)

Cui, Yehui; Zeng, Xiangguo; Kou, Huaqin; Ding, Jun; Wang, Fang

2018-06-01

In this work a three-dimensional (3D) hydrogen absorption model was proposed to study the heat transfer behavior in thin double-layered annular ZrCo beds. Numerical simulations were performed to investigate the effects of conversion layer thickness, thermal conductivity, cooling medium and its flow velocity on the efficiency of heat transfer. Results reveal that decreasing the layer thickness and improving the thermal conductivity enhance the ability of heat transfer. Compared with nitrogen and helium, water appears to be a better medium for cooling. In order to achieve the best efficiency of heat transfer, the flow velocity needs to be maximized.

Study on the leaching behavior of actinides from nuclear fuel debris

NASA Astrophysics Data System (ADS)

Kirishima, Akira; Hirano, Masahiko; Akiyama, Daisuke; Sasaki, Takayuki; Sato, Nobuaki

2018-04-01

For the prediction of the leaching behavior of actinides contained in the nuclear fuel debris generated by the Fukushima Daiichi nuclear power plant accident in Japan, simulated fuel debris consisting of a UO2-ZrO2 solid solution doped with 137Cs, 237Np, 236Pu, and 241Am tracers was synthesized and investigated. The synthesis of the debris was carried out by heat treatment at 1200 °C at different oxygen partial pressures, and the samples were subsequently used for leaching tests with Milli-Q water and seawater. The results of the leaching tests indicate that the leaching of actinides depends on the redox conditions under which the debris was generated; for example, debris generated under oxidative conditions releases more actinide nuclides to water than that generated under reductive conditions. Furthermore, we found that, as Zr(IV) increasingly substituted U(IV) in the fluorite crystal structure of the debris, the actinide leaching from the debris decreased. In addition, we found that seawater leached more actinides from the debris than pure water, which seems to be caused by the complexation of actinides by carbonate ions in seawater.

Properties of experimental titanium cast investment mixing with water reducing agent solution.

PubMed

Zhang, Zutai; Ding, Ning; Tamaki, Yukimichi; Hotta, Yasuhiro; Han-Cheol, Cho; Miyazaki, Takashi

2012-01-01

This study aimed to develop a dental investment for titanium casting. ZrO(2) and Al(2)O(3) were selected as refractory materials to prepare three investments (Codes: A-C) according to the quantity of Zr. Al(2)O(3) cement was used as a binder at a ratio of 15%, they were mixed with special mixing liquid. B1 was used as a control mixed with water. Fundamental examinations were statistically evaluated. A casting test was performed with investment B. Fluidities, setting times, and green strengths showed no remarkable differences; however, they were significantly different from those of B1. Expansion values for A, B, C, and B1 at 850°C were 1.03%±0.08%, 1.96%±0.17%, 4.35%±0.23%, and 1.50%±0.28%, respectively. Castings were covered by only small amounts of mold materials. The hardness test showed no significant differences between castings from B and the ones from commercial investments. The experimental special mixing liquid effectively reduced the water/powder ratio and improved the strength and thermal expansion.

Synthesis and characterization of thick PZT films via sol-gel dip coating method

NASA Astrophysics Data System (ADS)

Shakeri, Amid; Abdizadeh, Hossein; Golobostanfard, Mohammad Reza

2014-09-01

Thick films of lead zirconate titanate (PZT) offer possibilities for micro-electro-mechanical systems such as high frequency ultrasonic transducers. In this paper, crack-free thick films of PZT have been prepared up to 45 μm thickness via modified sol-gel dip coating method. In this procedure, acetic acid-alcoholic based sol is used by applying diethanolamine (DEA) and deionized water as additives. The effects of DEA and water on the crystal structure and surface morphology of the films are investigated. The mechanisms of acetic acid and DEA complexations are introduced by using FTIR spectrometer which illustrates suitable substitution of complexing agents with alkoxide groups. DEA/(Ti + Zr) = 0.5 or water/(Ti + Zr) = 0.5 are determined as the optimum molar ratio of additives, which lead to the formation of almost pure perovskite phase with the tetragonal lattice parameters of ct = 4.16 Ǻ and at = 4.02 Ǻ and a distortion of 2%. Values of remanent polarization and dielectric constant of 7.8 μC cm-2 and 1630 were obtained for 45 μm thick films, respectively.

Investigation of mechanism and critical parameters for removal of arsenic from water using Zr-TiO2 composite.

PubMed

Anđelković, I; Amaizah, N R R; Marković, S B; Stanković, D; Marković, M; Kuzmanović, D; Roglić, G

2017-09-01

Using the microwave-hydrothermal method for the synthesis of composite, high surface density of hydroxyl groups, as an active adsorption sites for arsenic, was obtained. Adsorption mechanisms of As(III) and As(V) onto zirconium-doped titanium dioxide (Zr-TiO 2 ) were investigated and proposed using macroscopic and microscopic methods. Obtained results are suggesting inner-sphere and outer-sphere adsorption mechanisms for As(III) and As(V), respectively. This allowed us to identify parameters that are critical for the successful removal of arsenic from water, which is essential information for further optimization of the removal process. The composite was further applied for the removal of As(III) and As(V) from water in a dynamic flow through the reactor. Column study proved that the removal of both arsenic species below the value recommended by WHO can be achieved. Elution of As(III) and As(V) from the composite can be done by using small amounts of 0.01 M NaOH solution resulting in preconcentration of arsenic species and possible multiple usage of composite.

Accelerator mass spectrometry of strontium-90 for homeland security, environmental monitoring and human health

NASA Astrophysics Data System (ADS)

Tumey, Scott J.; Brown, Thomas A.; Hamilton, Terry E.; Hillegonds, Darren J.

2008-05-01

Strontium-90 is one of the most hazardous materials managed by agencies charged with protecting the public from radiation. Traditional radiometric methods have been limited by low sample throughput and slow turnaround times. Mass spectrometry offers the advantage of shorter analysis times and the ability to measure samples immediately after processing, however conventional mass spectrometric techniques are susceptible to molecular isobaric interferences that limit their overall sensitivity. In contrast, accelerator mass spectrometry is insensitive to molecular interferences and we have therefore begun developing a method for determination of 90Sr by accelerator mass spectrometry. Despite a pervasive interference from 90Zr, our initial development has yielded an instrumental background of ∼108 atoms (75 mBq) per sample. Further refinement of our system (e.g. redesign of our detector, use of alternative target materials) is expected to push the background below 106 atoms, close to the theoretical limit for AMS. Once we have refined our system and developed suitable sample preparation protocols, we will utilize our capability in applications to homeland security, environmental monitoring and human health.

Membrane electrode assembly fabricated with the combination of Pt/C and hollow shell structured-Pt-SiO2@ZrO2 sphere for self-humidifying proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Ko, Y. D.; Yang, H. N.; Züttel, Andreas; Kim, S. D.; Kim, W. J.

2017-11-01

The Pt-supported hollow structured Pt-HZrO2 with the shell thickness of 27 nm is successfully synthesized. The water retention ability of Pt-HZrO2 is significantly enhanced compared with that of SiO2@ZrO2 due to the hydrophilic hollow structured HZrO2with high BET surface area. Pt-C and Pt-HZrO2 are combined with different weight fractions to prepare the double catalyst electrode (DCE). The membrane electrode assembly with the DCE is fabricated and applied to both anode and cathode or anode side only. The water flooding and thus rapid voltage drop is affected by the presence/or absence of the DCE at the cathode side. The cell test and visual experiment suggests that the Pt-HZrO2 layer adsorb the water molecules generated by the oxygen reduction reaction (ORR), preventing the water flooding. The power generation under RH 0% strongly suggests the back-diffusion of water molecules generated by the ORR. The flow rate to the cathode significantly affects the water flooding and cell performance. Higher flow rate to the cathode is advantageous to expel the water generated by the ORR, thus preventing water flooding and enhancing the cell performance. Therefore, the weight fraction of Pt-C to Pt-HZrO2 and the flow rate to the cathode should be well balanced.

A reassessment study of multi-material-shell gas puff z-pinches as a pulsed neutron source on the sandia ZR

NASA Astrophysics Data System (ADS)

Chong, Y. K.; Velikovich, A. L.; Thornhil, J. W.; Giuliani, J. L.; Knapp, P.; Jennings, C.

2013-10-01

Over the last few years, numerous 1D and 2D MHD simulation studies of deuterium (D) based double-shell gas-puff Z-pinch implosions driven by the Sandia ZR accelerator have been carried out to assess the Z-pinch as a pulsed thermal fusion neutron source. In these studies, an ad-hoc time-dependent shunt impedance model was used within the external driving circuit model in order to account for the unresolved current loss in the MITL and the load. In this study, we incorporate an improved ZR circuit model recently formulated based on the recent Sandia argon gas-puff experiment circuit data into the multi-material version of the Mach +DDTCRE RMHD code. We reinvestigate the effects of multidimensional structure and nonuniform gradients as well as the outer- and inner-shell material interaction on the implosion physics and dynamics of both D-on-D and argon-on-D Z-pinch loads using the model. Then, we characterize the neutron production performance of the Z-pinch loads as a function of total mass, mass ratio and/or radius toward their optimization as a pulsed thernonuclear neutron source. Work supported by DOE/NNSA. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's NNSA under contract DE-AC04-94AL85000.

Accelerated discovery of metallic glasses through iteration of machine learning and high-throughput experiments

PubMed Central

Wolverton, Christopher; Hattrick-Simpers, Jason; Mehta, Apurva

2018-01-01

With more than a hundred elements in the periodic table, a large number of potential new materials exist to address the technological and societal challenges we face today; however, without some guidance, searching through this vast combinatorial space is frustratingly slow and expensive, especially for materials strongly influenced by processing. We train a machine learning (ML) model on previously reported observations, parameters from physiochemical theories, and make it synthesis method–dependent to guide high-throughput (HiTp) experiments to find a new system of metallic glasses in the Co-V-Zr ternary. Experimental observations are in good agreement with the predictions of the model, but there are quantitative discrepancies in the precise compositions predicted. We use these discrepancies to retrain the ML model. The refined model has significantly improved accuracy not only for the Co-V-Zr system but also across all other available validation data. We then use the refined model to guide the discovery of metallic glasses in two additional previously unreported ternaries. Although our approach of iterative use of ML and HiTp experiments has guided us to rapid discovery of three new glass-forming systems, it has also provided us with a quantitatively accurate, synthesis method–sensitive predictor for metallic glasses that improves performance with use and thus promises to greatly accelerate discovery of many new metallic glasses. We believe that this discovery paradigm is applicable to a wider range of materials and should prove equally powerful for other materials and properties that are synthesis path–dependent and that current physiochemical theories find challenging to predict. PMID:29662953

Accelerated discovery of metallic glasses through iteration of machine learning and high-throughput experiments

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

Ren, Fang; Ward, Logan; Williams, Travis

With more than a hundred elements in the periodic table, a large number of potential new materials exist to address the technological and societal challenges we face today; however, without some guidance, searching through this vast combinatorial space is frustratingly slow and expensive, especially for materials strongly influenced by processing. We train a machine learning (ML) model on previously reported observations, parameters from physiochemical theories, and make it synthesis method–dependent to guide high-throughput (HiTp) experiments to find a new system of metallic glasses in the Co-V-Zr ternary. Experimental observations are in good agreement with the predictions of the model, butmore » there are quantitative discrepancies in the precise compositions predicted. We use these discrepancies to retrain the ML model. The refined model has significantly improved accuracy not only for the Co-V-Zr system but also across all other available validation data. We then use the refined model to guide the discovery of metallic glasses in two additional previously unreported ternaries. Although our approach of iterative use of ML and HiTp experiments has guided us to rapid discovery of three new glass-forming systems, it has also provided us with a quantitatively accurate, synthesis method–sensitive predictor for metallic glasses that improves performance with use and thus promises to greatly accelerate discovery of many new metallic glasses. We believe that this discovery paradigm is applicable to a wider range of materials and should prove equally powerful for other materials and properties that are synthesis path–dependent and that current physiochemical theories find challenging to predict.« less

Study of proton induced reactions on niobium targets up to 70 MeV

NASA Astrophysics Data System (ADS)

Ditrói, F.; Takács, S.; Tárkányi, F.; Baba, M.; Corniani, E.; Shubin, Yu. N.

2008-12-01

Niobium is a metal with important technological applications: use as alloying element to increase strength of super alloys, as thin layer for tribological applications, as superconductive material, in high temperature engineering systems, etc. In the frame of a systematic study of activation cross-sections of charged particle induced reactions on structural materials proton induced excitation functions on Nb targets were determined with the aim of applications in accelerator and reactor technology and for thin layer activation (TLA). The charged particle activation cross-sections on this element are also important for yield calculation of medical isotope production ( 88,89Zr, 86,87,88Y) and for dose estimation in PET targetry. As Niobium is a monoisotopic element it is an ideal target material to test nuclear reaction theories. We present here the integral excitation functions of 93Nb(p,x) 90,93mMo, 92m,91m,90Nb, 86,88,89Zr, 86,87mg,88Y and 85Sr in the energy range 30-70 MeV, some measured for the first time at this energy range. The results were compared with the theoretical cross-sections calculated by means of the code ALICE-IPPE and with the literature data. The calculations have been carried out without any parameter adjustment. The theory reproduces the shape of the measured results well and magnitude is also acceptable. Thick target yields calculated from our fitted cross-section give reliable estimations for production of medically relevant radioisotopes and for dose estimation in accelerator technology.

Accelerated discovery of metallic glasses through iteration of machine learning and high-throughput experiments

DOE PAGES

Ren, Fang; Ward, Logan; Williams, Travis; ...

2018-04-01

With more than a hundred elements in the periodic table, a large number of potential new materials exist to address the technological and societal challenges we face today; however, without some guidance, searching through this vast combinatorial space is frustratingly slow and expensive, especially for materials strongly influenced by processing. We train a machine learning (ML) model on previously reported observations, parameters from physiochemical theories, and make it synthesis method–dependent to guide high-throughput (HiTp) experiments to find a new system of metallic glasses in the Co-V-Zr ternary. Experimental observations are in good agreement with the predictions of the model, butmore » there are quantitative discrepancies in the precise compositions predicted. We use these discrepancies to retrain the ML model. The refined model has significantly improved accuracy not only for the Co-V-Zr system but also across all other available validation data. We then use the refined model to guide the discovery of metallic glasses in two additional previously unreported ternaries. Although our approach of iterative use of ML and HiTp experiments has guided us to rapid discovery of three new glass-forming systems, it has also provided us with a quantitatively accurate, synthesis method–sensitive predictor for metallic glasses that improves performance with use and thus promises to greatly accelerate discovery of many new metallic glasses. We believe that this discovery paradigm is applicable to a wider range of materials and should prove equally powerful for other materials and properties that are synthesis path–dependent and that current physiochemical theories find challenging to predict.« less

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

PubMed

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

2011-09-01

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

Effect of Zirconia Nanoparticles in Epoxy-Silica Hybrid Adhesives to Join Aluminum Substrates.

PubMed

Figueroa-Lara, José de Jesús; Torres-Rodríguez, Miguel; Gutiérrez-Arzaluz, Mirella; Romero-Romo, Mario

2017-09-27

This research presents the interaction of the epoxy polymer diglicydil ether of bisphenol-A (DGEBA) with silica (SiO₂) nanoparticles plus zirconia (ZrO₂) nanoparticles obtained via the sol-gel method in the synthesis of an epoxy-silica-zirconia hybrid adhesive cured with polyamide. ZrO₂ nanoparticles were added to the epoxy-silica hybrid adhesive produced in situ to modify the apparent shear strength of two adhesively bonded aluminum specimens. The results showed that the addition of different amounts of ZrO₂ nanoparticles increased the shear strength of the adhesively bonded aluminum joint, previously treated by sandblasting, immersion in hot water and silanized with a solution of hydrolyzed 3-glycidoxipropyltrimethoxysilane (GPTMS). The morphology and microstructure of the nanoparticles and aluminum surfaces were examined by scanning electron microscopy (SEM), and elemental analysis was performed with the Energy-dispersive X-ray spectroscopy (EDS) detector; the chemical groups were investigated during the aluminum surface modification using Fourier transform infrared spectroscopy (FTIR).

Effect of Zirconia Nanoparticles in Epoxy-Silica Hybrid Adhesives to Join Aluminum Substrates

PubMed Central

Figueroa-Lara, José de Jesús; Torres-Rodríguez, Miguel

2017-01-01

This research presents the interaction of the epoxy polymer diglicydil ether of bisphenol-A (DGEBA) with silica (SiO2) nanoparticles plus zirconia (ZrO2) nanoparticles obtained via the sol-gel method in the synthesis of an epoxy-silica-zirconia hybrid adhesive cured with polyamide. ZrO2 nanoparticles were added to the epoxy-silica hybrid adhesive produced in situ to modify the apparent shear strength of two adhesively bonded aluminum specimens. The results showed that the addition of different amounts of ZrO2 nanoparticles increased the shear strength of the adhesively bonded aluminum joint, previously treated by sandblasting, immersion in hot water and silanized with a solution of hydrolyzed 3-glycidoxipropyltrimethoxysilane (GPTMS). The morphology and microstructure of the nanoparticles and aluminum surfaces were examined by scanning electron microscopy (SEM), and elemental analysis was performed with the Energy-dispersive X-ray spectroscopy (EDS) detector; the chemical groups were investigated during the aluminum surface modification using Fourier transform infrared spectroscopy (FTIR). PMID:28953243

Effect of KOH added to ethylene glycol electrolyte on the self-organization of anodic ZrO{sub 2} nanotubes

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

Rozana, Monna; Soaid, Nurul Izza; Lockman, Zainovia, E-mail: zainovia@usm.my

ZrO{sub 2} nanotube arrays were formed by anodizing zirconium sheet in ethylene glycol (EG) and EG added to it KOH (EG/KOH) electrolytes. The effect of KOH addition into EG electrolyte to the morphology of nanotubes and their crystallinity was investigated. It was observed that the tubes with diameter of ∼80 nm were formed in EG electrolyte with <0.1 vol % water, but the wall smoothness is rather poor. When KOH was added into EG, the wall smoothness of the nanotubes improve, but the diameter of tubes is smaller (∼40 nm). Despite smoother wall and small tube diameter, the degradation ofmore » methyl orange (MO) on the tubes made in EG/KOH is less compared to the tubes made in EG only. This could be due to the less tetragonal ZrO{sub 2} presence in the tubes made in EG/KOH.« less

A digital output piezoelectric accelerometer using a Pb(Zr, Ti)O3 thin film array electrically connected in series

NASA Astrophysics Data System (ADS)

Kobayashi, T.; Okada, H.; Masuda, T.; Maeda, R.; Itoh, T.

2010-10-01

A digital output piezoelectric accelerometer is proposed to realize an ultra-low power consumption wireless sensor node. The accelerometer has patterned piezoelectric thin films (piezoelectric plates) electrically connected in series accompanied by CMOS switches at the end of some of the piezoelectric plates. The connected piezoelectric plates amplify the output voltage without the use of amplifiers. The CMOS switches turn on when the output voltage of the piezoelectric plates is higher than the CMOS threshold voltage. The piezoelectric accelerometer converts the acceleration into a number of on-state CMOS switches, which can be called the digital output. The proposed digital output piezoelectric accelerometer, using Pb(Zr, Ti)O3 (PZT) thin films as the piezoelectric material, was fabricated through a microelectromechanical system (MEMS) microfabrication process. The output voltage was found to be amplified by the number of connected piezoelectric plates. The DC output voltage obtained by using an AC to DC conversion circuit is proportional to the number of connections. The results show the potential for realizing the proposed digital output piezoelectric accelerometer.

Learning a force field for the martensitic phase transformation in Zr

NASA Astrophysics Data System (ADS)

Zong, Hongxiang; Pilania, Ghanshyam; Ramprasad, Rampi; Lookman, Turab

Atomic simulations provide an effective means to understand the underlying physics of martensitic transformations under extreme conditions. However, this is still a challenge for certain phase transforming metals due to the lack of an accurate classical force field. Quantum molecular dynamics (QMD) simulations are accurate but expensive. During the course of QMD simulations, similar configurations are constantly visited and revisited. Machine Learning can effectively learn from past visits and, therefore, eliminate such redundancies. In this talk, we will discuss the development of a hybrid ML-QMD method in which on-demand, on-the-fly quantum mechanical (QM) calculations are performed to accelerate calculations of interatomic forces at much lower computational costs. Using Zirconium as a model system for which accurate atomisctic potentials are currently unvailable we will demonstrate the feasibility and effectiveness of our approach. Specifically, the computed structural phase transformation behavior within the ML-QMD approach will be compared with available experimental results. Furthermore, results on phonons, stacking fault energies, and activation barriers for the homogeneous martensitic transformation in Zr will be presented.

Mechanical characterization and modeling of brazed tungsten and Cu-Cr-Zr alloy using stress relief interlayers

NASA Astrophysics Data System (ADS)

Qu, Dandan; Zhou, Zhangjian; Yum, Youngjin; Aktaa, Jarir

2014-12-01

A rapidly solidified foil-type Ti-Zr based amorphous filler with a melting temperature of 850 °C was used to braze tungsten to Cu-Cr-Zr alloy for water cooled divertors and plasma facing components application. Brazed joints of dissimilar materials suffer from a mismatch in coefficients of thermal expansion. In order to release the residual stress caused by the mismatch, brazed joints of tungsten and Cu-Cr-Zr alloy using different interlayers were studied. The shear strength tests of brazed W/Cu joints show that the average strength of the joint with a W70Cu30 composite plate interlayer reached 119.8 MPa, and the average strength of the joint with oxygen free high conductivity copper (OFHC Cu)/Mo multi-interlayers reached 140.8 MPa, while the joint without interlayer was only 16.6 MPa. Finite element method (FEM) has been performed to investigate the stress distribution and effect of stress relief interlayers. FEM results show that the maximum von Mises stress occurs in the tungsten/filler interface and that the filler suffers the peak residual stresses and becomes the weakest zone. And the use of OFHC Cu/Mo multi-interlayers can reduce the residual stress significantly, which agrees with the mechanical experiment data.

Systematic investigation of the strontium zirconium phosphate ceramic form for nuclear waste immobilization

NASA Astrophysics Data System (ADS)

Pet'kov, Vladimir; Asabina, Elena; Loshkarev, Vladimir; Sukhanov, Maksim

2016-04-01

We have summarized our data and literature ones on the thermophysical properties and hydrolytic stability of Sr0.5Zr2(PO4)3 compound as a host NaZr2(PO4)3-type (NZP) structure for immobilization of 90Sr-containing radioactive waste. Absence of any polymorphic transformations on the temperature dependence of its heat capacity between 7 and 665 K is caused by the stability of crystalline Sr0.5Zr2(PO4)3. Calculated values of thermal conductivity coefficients at zero porosity in the range 298-673 K were 1.86-2.40 W·m-1 K-1. The compound may be classified as low thermal expanding material due to its average linear thermal expansion coefficient. Study of the hydrolytic stability in acid and alkaline media has shown that the relative mass fraction of Sr2+ ions, released into aggressive leaching media, didn't exceed 1% of the mass of sample. Soxhlet leaching studies have shown substantial resistance towards the release of Sr2+ ions into distilled water. Feeble sinterability constrains practical applications of NZP substances, that is why known in literature methods of Sr0.5Zr2(PO4)3 dense ceramics obtaining have been reviewed.

Severe Accident Test Station Activity Report

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

Pint, Bruce A.; Terrani, Kurt A.

2015-06-01

Enhancing safety margins in light water reactor (LWR) severe accidents is currently the focus of a number of international R&D programs. The current UO2/Zr-based alloy fuel system is particularly susceptible since the Zr-based cladding experiences rapid oxidation kinetics in steam at elevated temperatures. Therefore, alternative cladding materials that offer slower oxidation kinetics and a smaller enthalpy of oxidation can significantly reduce the rate of heat and hydrogen generation in the core during a coolant-limited severe accident. In the U.S. program, the high temperature steam oxidation performance of accident tolerant fuel (ATF) cladding solutions has been evaluated in the Severe Accidentmore » Test Station (SATS) at Oak Ridge National Laboratory (ORNL) since 2012. This report summarizes the capabilities of the SATS and provides an overview of the oxidation kinetics of several candidate cladding materials. A suggested baseline for evaluating ATF candidates is a two order of magnitude reduction in the steam oxidation resistance above 1000ºC compared to Zr-based alloys. The ATF candidates are categorized based on the protective external oxide or scale that forms during exposure to steam at high temperature: chromia, alumina, and silica. Comparisons are made to literature and SATS data for Zr-based alloys and other less-protective materials.« less

Defluoridation using biomimetically synthesized nano zirconium chitosan composite: kinetic and equilibrium studies.

PubMed

Prasad, Kumar Suranjit; Amin, Yesha; Selvaraj, Kaliaperumal

2014-07-15

The present study reports a novel approach for synthesis of Zr nanoparticles using aqueous extract of Aloe vera. Resulting nanoparticles were embedded into chitosan biopolymer and termed as CNZr composite. The composite was subjected to detailed adsorption studies for removal of fluoride from aqueous solution. The synthesized Zr nanoparticles showed UV-vis absorption peak at 420nm. TEM result showed the formation of polydispersed, nanoparticles ranging from 18nm to 42nm. SAED and XRD analysis suggested an fcc (face centered cubic) Zr crystallites. EDAX analysis suggested that Zr was an integral component of synthesized nanoparticles. FT-IR study indicated that functional group like NH, CO, CN and CC were involved in particle formation. The adsorption of fluoride on to CNZr composite worked well at pH 7.0, where ∼99% of fluoride was found to be adsorbed on adsorbent. Langmuir isotherm model best fitted the equilibrium data since it presented higher R(2) value than Freundlich model. In comparison to pseudo-first order kinetic model, the pseudo-second order model could explain adsorption kinetic behavior of F(-) onto CNZr composite satisfactorily with a good correlation coefficient. The present study revealed that CNZr composite may work as an effective tool for removal of fluoride from contaminated water. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of ZrO x /ZrC-ZrN/Zr thin-film structural evolution and their degradation using X-ray diffraction and Raman spectrometry

NASA Astrophysics Data System (ADS)

Usmani, B.; Vijay, V.; Chhibber, R.; Dixit, A.

2016-11-01

The thin-film structures of DC/FR magnetron-sputtered ZrO x /ZrC-ZrN/Zr tandem solar-selective coatings are investigated using X-ray diffraction and room-temperature Raman spectroscopic measurements. These studies suggest that the major contribution is coming from h-ZrN0.28, c-ZrC, h-Zr3C2 crystallographic phases in ZrN-ZrC absorber layer, in conjunction with mixed ZrO x crystallographic phases. The change in structure for thermally annealed samples has been examined and observed that cubic and hexagonal ZrO x phase converted partially into tetragonal and monoclinic ZrO x phases, whereas hexagonal and cubic ZrN phases, from absorber layer, have not been observed for these thermally treated samples in air. These studies suggest that thermal treatment may lead to the loss of ZrN phase in absorber, degrading the thermal response for the desired wavelength range in open ambient conditions in contrast to vacuum conditions.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes.

PubMed

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-06

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO 2 , NO, H 2 O, as well as the related fragments during the O 2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO 2 during the complex surface chemical reaction of the ligand and O 2 plasma were monitored using the QCM. The remote PEALD ZrO 2 /zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10 -5  g/m 2 /day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-01

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO2, NO, H2O, as well as the related fragments during the O2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO2 during the complex surface chemical reaction of the ligand and O2 plasma were monitored using the QCM. The remote PEALD ZrO2/zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10-5 g/m2/day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime.

Mesoporous carbon-zirconium oxide nanocomposite derived from carbonized metal organic framework: A coating for solid-phase microextraction.

PubMed

Saraji, Mohammad; Mehrafza, Narges

2016-08-19

In this paper, a mesoporous carbon-ZrO2 nanocomposite was fabricated on a stainless steel wire for the first time and used as the solid-phase microextraction coating. The fiber was synthesized with the direct carbonization of a Zr-based metal organic framework. With the utilization of the metal organic framework as the precursor, no additional carbon source was used for the synthesis of the mesoporous carbon-ZrO2 nanocomposite coating. The fiber was applied for the determination of BTEX compounds (benzene, toluene, ethylbenzene and m, p-xylenes) in different water samples prior to gas chromatography-flame ionization detection. Such important experimental factors as synthesis time and temperature, salt concentration, equilibrium and extraction time, extraction temperature, desorption time and desorption temperature were studied and optimized. Good linearity in the concentration range of 0.2-200μgL(-1) and detection limits in the range of 0.05-0.56μgL(-1) was achieved for BTEX compounds. The intra- and inter-day relative standard deviations were in the range of 3.5-4.8% and 4.9-6.7%, respectively. The prepared fiber showed high capability for the analysis of BTEX compounds in different water and wastewater samples with good relative recoveries in the range of 93-107%. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2018-01-01

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

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

PubMed

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

2018-01-01

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

The Experimental Study of Nuclear Astrophysics Reaction Rate of 93Zr(n,γ)94Zr

NASA Astrophysics Data System (ADS)

Gan, L.; Li, Z. H.; Su, J.; Yan, S. Q.; Guo, B.; Du, X. C.; Wu, Z. D.; Zeng, S.; Jin, S. J.; Wang, Y. B.; Bai, X. X.; Zhang, W. J.; Sun, H. B.; Li, E. T.

The slow neutron capture (s-) process plays a very important role in the nucleosynthesis, which produces about half of the elements heavier than iron. 94Zr is mainly from 93Zr(n,γ)94Zr in the s-process, and the direct component of the 93Zr(n,γ)94Zr capture reaction can be derived from the neutron spectroscopic factor of 94Zr. As the existing neutron spectroscopic factors of 94Zr vary from each other up to 60%, a new work should be adopted to measure it exactly. In the present work, the angular distributions of 94Zr(13C,13C)94Zr, 94Zr(12C,12C)94Zr and 94Zr(12C,13C)93Zr were obtained using the highprecision Q3D magnetic spectrograph. In addition, distorted-wave Born approximation (DWBA) calculations of the transfer differential cross sections were performed. The calculated result displays a good agreement with the experiment data, and a value of 2.60±0.20 for the neutron spectroscopic factor of 94Zr was extracted, and the direct capture cross section versus neutron energy of 93Zr(n,γ)94Zr for the ground state of 94Zr was obtained too.

Zr doped anatase supported reticulated ceramic foams for photocatalytic water purification

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

Plesch, G., E-mail: plesch@fns.uniba.sk; Vargová, M.; Vogt, U.F.

2012-07-15

Highlights: ► Thick photocatalytic anatase films on macroporous reticulated ceramic foams. ► Alumina and alumina–mullite macroporous reticulated foams as photocatalyst support. ► Zr doping significantly improves the TiO{sub 2} film activity in phenol photomineralization. ► Comparison of photocatalytic activity of thick films and powder suspensions. -- Abstract: Titanium dioxide films were deposited on macroporous reticulated Al{sub 2}O{sub 3} and alumina–mullite foams with pore sizes of 15 ppi (pores per inch). Coatings were prepared from suspensions of precursor powders of Aeroxide{sup ®} P25 nanopowder and precipitated TiO{sub 2} by using a dip coating process. The TiO{sub 2} forms films with amore » thickness of ∼2–20 μm. The photocatalytic activity was characterized as the mineralization rate of an aqueous phenol solution under UVA irradiation by the TOC technique. Precipitated TiO{sub 2} films have nearly the same photocatalytic activity as a titania suspension, in which powder aggregates have a size comparable with the thickness of the films. Samples made of Aeroxide{sup ®} P25 nanopowder, in which the size of aggregates is ∼0.1 μm show higher efficiency of photodecomposition in suspensions with films. The doping of precipitated anatase with Zr(IV) in the atomic ratio Zr/Ti = 0.008 significantly improves the photocatalytic activity of the foam supported titania. Zr doped anatase films show better performance as the films prepared only from Aeroxide{sup ®} P25 nanopowder.« less

Surface Modifier-Free Organic-Inorganic Hybridization To Produce Optically Transparent and Highly Refractive Bulk Materials Composed of Epoxy Resins and ZrO2 Nanoparticles.

PubMed

Enomoto, Kazushi; Kikuchi, Moriya; Narumi, Atsushi; Kawaguchi, Seigou

2018-04-25

Surface modifier-free hybridization of ZrO 2 nanoparticles (NPs) with epoxy-based polymers is demonstrated for the first time to afford highly transparent and refractive bulk materials. This is achieved by a unique and versatile hybridization via the one-pot direct phase transfer of ZrO 2 NPs from water to epoxy monomers without any aggregation followed by curing with anhydride. Three types of representative epoxy monomers, bisphenol A diglycidyl ether (BADGE), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (CEL), and 1,3,5-tris(3-(oxiran-2-yl)propyl)-1,3,5-triazinane-2,4,6-trione (TEPIC), are used to produce transparent viscous dispersions. The resulting ZrO 2 NPs are thoroughly characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), and solid-state 13 C CP/MAS NMR measurements. The results from DLS and TEM analyses indicate nanodispersion of ZrO 2 into epoxy monomers as a continuous medium. A surface modification mechanism and the binding fashion during phase transfer are proposed based on the FT-IR and solid-state 13 C CP/MAS NMR measurements. Epoxy-based hybrid materials with high transparency and refractive index are successfully fabricated by heat curing or polymerizing a mixture of monomers containing epoxy-functionalized ZrO 2 NPs and methylhexahydrophthalic anhydride in the presence of a phosphoric catalyst. The TEM and small-angle X-ray scattering measurements of the hybrids show a nanodispersion of ZrO 2 in the epoxy networks. The refractive index at 594 nm ( n 594 ) increases up to 1.765 for BADGE-based hybrids, 1.667 for CEL-based hybrids, and 1.693 for TEPIC-based hybrids. Their refractive indices and Abbe's numbers are quantitatively described by the Lorentz-Lorenz effective medium expansion theory. Their transmissivity is also reasonably explained using Fresnel refraction, Rayleigh scattering, and the Lambert-Beer theories. This surface modifier-free hybridization provides a versatile, fascinating, and promising method for synthesizing a variety of epoxy-based hybrid materials.

Physics of hydride fueled PWR

NASA Astrophysics Data System (ADS)

Ganda, Francesco

The first part of the work presents the neutronic results of a detailed and comprehensive study of the feasibility of using hydride fuel in pressurized water reactors (PWR). The primary hydride fuel examined is U-ZrH1.6 having 45w/o uranium: two acceptable design approaches were identified: (1) use of erbium as a burnable poison; (2) replacement of a fraction of the ZrH1.6 by thorium hydride along with addition of some IFBA. The replacement of 25 v/o of ZrH 1.6 by ThH2 along with use of IFBA was identified as the preferred design approach as it gives a slight cycle length gain whereas use of erbium burnable poison results in a cycle length penalty. The feasibility of a single recycling plutonium in PWR in the form of U-PuH2-ZrH1.6 has also been assessed. This fuel was found superior to MOX in terms of the TRU fractional transmutation---53% for U-PuH2-ZrH1.6 versus 29% for MOX---and proliferation resistance. A thorough investigation of physics characteristics of hydride fuels has been performed to understand the reasons of the trends in the reactivity coefficients. The second part of this work assessed the feasibility of multi-recycling plutonium in PWR using hydride fuel. It was found that the fertile-free hydride fuel PuH2-ZrH1.6, enables multi-recycling of Pu in PWR an unlimited number of times. This unique feature of hydride fuels is due to the incorporation of a significant fraction of the hydrogen moderator in the fuel, thereby mitigating the effect of spectrum hardening due to coolant voiding accidents. An equivalent oxide fuel PuO2-ZrO2 was investigated as well and found to enable up to 10 recycles. The feasibility of recycling Pu and all the TRU using hydride fuels were investigated as well. It was found that hydride fuels allow recycling of Pu+Np at least 6 times. If it was desired to recycle all the TRU in PWR using hydrides, the number of possible recycles is limited to 3; the limit is imposed by positive large void reactivity feedback.

Cooperative electrochemical water oxidation by Zr nodes and Ni–porphyrin linkers of a PCN-224 MOF thin film

DOE PAGES

Usov, P. M.; Ahrenholtz, S. R.; Maza, W. A.; ...

2016-10-06

In this paper, we demonstrate a new strategy for cooperative catalysis and proton abstraction via the incorporation of independent species competent in the desired reactivity into a metal–organic framework (MOF) thin film.

Effects of Polarization on Mechanical Properties of Lead Zirconate Titanate Ceramics Evaluated by Modified Small Punch Tests

NASA Astrophysics Data System (ADS)

Deng, Qihuang; Fan, Yuchi; Wang, Lianjun; Xiong, Zhi; Wang, Hongzhi; Li, Yaogang; Zhang, Qinghong; Kawasaki, Akira; Jiang, Wan

2012-01-01

Pb(Zr,Ti)O3 (PZT) ceramics were prepared by the conventional mixed oxide method, and the strength of the resultant PZT ceramics was evaluated using modified small punch (MSP) tests. Load-displacement curve test results showed that the crack-initiation and fracture strengths of PZT ceramics decreased after polarization. The effect of the polarization accelerated the fatigue properties of PZT ceramics. Scanning electron microscopy (SEM) results showed that microcracks were formed before the maximum load in the MSP test, and the first load drop corresponded to crack initiation.

Synthesis of Zr2WP2O12/ZrO2 Composites with Adjustable Thermal Expansion.

PubMed

Zhang, Zhiping; Sun, Weikang; Liu, Hongfei; Xie, Guanhua; Chen, Xiaobing; Zeng, Xianghua

2017-01-01

Zr 2 WP 2 O 12 /ZrO 2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr 2 WP 2 O 12 /ZrO 2 composites with different mass ratio. Relative densities of all the resulting Zr 2 WP 2 O 12 /ZrO 2 samples were also tested by Archimedes' methods. The obtained Zr 2 WP 2 O 12 /ZrO 2 composites were comprised of orthorhombic Zr 2 WP 2 O 12 and monoclinic ZrO 2 . As the increase of the Zr 2 WP 2 O 12 , the relative densities of Zr 2 WP 2 O 12 /ZrO 2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr 2 WP 2 O 12 /ZrO 2 composites can be tailored from 4.1 × 10 -6 K -1 to -3.3 × 10 -6 K -1 by changing the content of Zr 2 WP 2 O 12 . The 2:1 Zr 2 WP 2 O 12 /ZrO 2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of -0.09 × 10 -6 K -1 . These adjustable and near zero expansion ceramic composites will have great potential application in many fields.

Benzene selectivity in competitive arene hydrogenation: effects of single-site catalyst···acidic oxide surface binding geometry.

PubMed

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P; Bhattacharyya, Alak; Motta, Alessandro; Gallagher, James R; Zhang, Guanghui; Miller, Jeffrey T; Kobayashi, Takeshi; Pruski, Marek; Delferro, Massimiliano; Marks, Tobin J

2015-06-03

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO2 (ZrS), sulfated Al2O3 (AlS), and ZrO2-WO3 (ZrW). Under mild conditions (25 °C, 1 atm H2), the supported Cp*ZrMe3, Cp*ZrBz3, and Cp*ZrPh3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS ≫ AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures, and selectivities for benzene hydrogenation vary with catalyst as ZrBz3(+)/ZrS(-), 83% > Cp*ZrMe2(+)/ZrS(-), 80% > Cp*ZrBz2(+)/ZrS(-), 67% > Cp*ZrPh2(+)/ZrS(-), 57%. For Cp*ZrBz2(+)/ZrS(-), which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe3 and Cp*ZrBz3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz2(+)/AlS(-) vs Cp*ZrMe2(+)/AlS(-). The combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the "cationic" metal center-anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.

Benzene selectivity in competitive arene hydrogenation: Effects of single-site catalyst···acidic oxide surface binding geometry

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

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P.

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO 2 (ZrS), sulfated Al 2O 3 (AlS), and ZrO 2–WO 3 (ZrW). Under mild conditions (25 °C, 1 atm H 2), the supported Cp*ZrMe 3, Cp*ZrBz 3, and Cp*ZrPh 3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS >> AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures,more » and selectivities for benzene hydrogenation vary with catalyst as ZrBz 3 +/ZrS –, 83% > Cp*ZrMe 2 +/ZrS –, 80% > Cp*ZrBz 2 +/ZrS –, 67% > Cp*ZrPh 2 +/ZrS –, 57%. For Cp*ZrBz 2+/ZrS –, which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe 3 and Cp*ZrBz 3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz 2 +/AlS – vs Cp*ZrMe 2 +/AlS –. Furthermore, the combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the “cationic” metal center–anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.« less

Benzene selectivity in competitive arene hydrogenation: Effects of single-site catalyst···acidic oxide surface binding geometry

DOE PAGES

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P.; ...

2015-04-17

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO 2 (ZrS), sulfated Al 2O 3 (AlS), and ZrO 2–WO 3 (ZrW). Under mild conditions (25 °C, 1 atm H 2), the supported Cp*ZrMe 3, Cp*ZrBz 3, and Cp*ZrPh 3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS >> AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures,more » and selectivities for benzene hydrogenation vary with catalyst as ZrBz 3 +/ZrS –, 83% > Cp*ZrMe 2 +/ZrS –, 80% > Cp*ZrBz 2 +/ZrS –, 67% > Cp*ZrPh 2 +/ZrS –, 57%. For Cp*ZrBz 2+/ZrS –, which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe 3 and Cp*ZrBz 3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz 2 +/AlS – vs Cp*ZrMe 2 +/AlS –. Furthermore, the combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the “cationic” metal center–anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.« less

Physiological response to drought in radiata pine: phytohormone implication at leaf level.

PubMed

De Diego, N; Pérez-Alfocea, F; Cantero, E; Lacuesta, M; Moncaleán, P

2012-04-01

Pinus radiata D. Don is one of the most abundant species in the north of Spain. Knowledge of drought response mechanisms is essential to guarantee plantation survival under reduced water supply as predicted in the future. Tolerance mechanisms are being studied in breeding programs, because information on such mechanisms can be used for genotype selection. In this paper, we analyze the changes of leaf water potential, hydraulic conductance (K(leaf)), stomatal conductance and phytohormones under drought in P. radiata breeds (O1, O2, O3, O4, O5 and O6) from different climatology areas, hypothesizing that they could show variable drought tolerance. As a primary signal, drought decreased cytokinin (zeatin and zeatin riboside-Z + ZR) levels in needles parallel to K(leaf) and gas exchange. When Z + ZR decreased by 65%, indole-3-acetic acid (IAA) and abscisic acid (ABA) accumulation started as a second signal and increments were higher for IAA than for ABA. When plants decreased by 80%, Z + ZR and K(leaf) doubled their ABA and IAA levels, the photosystem II yield decreased and the electrolyte leakage increased. At the end of the drought period, less tolerant breeds increased IAA over 10-fold compared with controls. External damage also induced jasmonic acid accumulation in all breeds except in O5 (P. radiata var. radiata × var. cedrosensis), which accumulated salicylic acid as a defense mechanism. After rewatering, only the most tolerant plants recovered their K(leaf,) perhaps due to an IAA decrease and 1-aminocyclopropane-1-carboxylic acid maintenance. From all phytohormones, IAA was the most representative 'water deficit signal' in P. radiata.

Application of thin layer activation technique for surface wear studies in Zr based materials using charged particle induced nuclear reactions

NASA Astrophysics Data System (ADS)

Chowdhury, D. P.; Pal, Sujit; Parthasarathy, R.; Mathur, P. K.; Kohli, A. K.; Limaye, P. K.

1998-09-01

Thin layer activation (TLA) technique has been developed in Zr based alloy materials, e.g., zircaloy II, using 40 MeV α-particles from Variable Energy Cyclotron Centre at Calcutta. A brief description of the methodology of TLA technique is presented to determine the surface wear. The sensitivity of the measurement of surface wear in zircaloy material is found to be 0.22±0.05 μm. The surface wear is determined by TLA technique in zircaloy material which is used in pressurised heavy water reactor and the values have been compared with that obtained by conventional technique for the analytical validation of the TLA technique.

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

NASA Technical Reports Server (NTRS)

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.

Neutronic performance of high-density LEU fuels in water-moderated and water-reflected research reactors

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

Bretscher, M.M.; Matos, J.E.

At the Reduced Enrichment for Research and Test Reactors (RERTR) meeting in September 1994, Durand reported that the maximum uranium loading attainable with U{sub 3}Si{sub 2} fuel is about 6.0 g U/cm{sup 3}. The French Commissariat a l`Energie Atomique (CEA) plan to perform irradiation tests with 5 plates at this loading. Compagnie pour L`Etude et La Realisation de Combustibles Atomiques (CERCA) has also fabricated a few uranium nitride (UN) plates with a uranium density in the fuel meat of 7.0 g/cm{sup 3} and found that UN is compatible with the aluminum matrix at temperatures below 500 C. High density dispersionmore » fuels proposed for development include U-Zr(4 wt%)-Nb(2 wt%), U-Mo(5 wt%), and U-Mo(9 wt%). The purpose of this note is to examine the relative neutronic behavior of these high density fuels in a typical light water-reflected and water-moderated MTR-type research reactor. The results show that a dispersion of the U-Zr-Nb alloy has the most favorable neutronic properties and offers the potential for uranium densities greater than 8.0 g/cm{sup 3}. On the other hand, UN is the least reactive fuel because of the relatively large {sup 14}N(n,p) cross section. For a fixed value of k{sub eff}, the required {sup 235}U loading per fuel element is least for the U-Zr-Nb fuel and steadily increases for the U-Mo(5%), U-Mo(9%), and UN fuels. Because of volume fraction limitations, the UO{sub 2} dispersions are only useful for uranium densities below 5.0 g/cm{sup 3}. In this density range, however, UO{sub 2} is more reactive than U{sub 3}Si{sub 2}.« less

Ceramic Coatings for Clad (The C 3 Project): Advanced Accident-Tolerant Ceramic Coatings for Zr-Alloy Cladding

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

Sickafus, Kurt E.; Wirth, Brian; Miller, Larry

The goal of this NEUP-IRP project is to develop a fuel concept based on an advanced ceramic coating for Zr-alloy cladding. The coated cladding must exhibit demonstrably improved performance compared to conventional Zr-alloy clad in the following respects: During normal service, the ceramic coating should decrease cladding oxidation and hydrogen pickup (the latter leads to hydriding and embrittlement). During a reactor transient (e.g., a loss of coolant accident), the ceramic coating must minimize or at least significantly delay oxidation of the Zr-alloy cladding, thus reducing the amount of hydrogen generated and the oxygen ingress into the cladding. The specific objectivesmore » of this project are as follows: To produce durable ceramic coatings on Zr-alloy clad using two possible routes: (i) MAX phase ceramic coatings or similar nitride or carbide coatings; and (ii) graded interface architecture (multilayer) ceramic coatings, using, for instance, an oxide such as yttria-stabilized zirconia (YSZ) as the outer protective layer. To characterize the structural and physical properties of the coated clad samples produced in 1. above, especially the corrosion properties under simulated normal and transient reactor operating conditions. To perform computational analyses to assess the effects of such coatings on fuel performance and reactor neutronics, and to perform fuel cycle analyses to assess the economic viability of modifying conventional Zr-alloy cladding with ceramic coatings. This project meets a number of the goals outlined in the NEUP-IRP call for proposals, including: Improve the fuel/cladding system through innovative designs (e.g. coatings/liners for zirconium-based cladding) Reduce or eliminate hydrogen generation Increase resistance to bulk steam oxidation Achievement of our goals and objectives, as defined above, will lead to safer light-water reactor (LWR) nuclear fuel assemblies, due to improved cladding properties and built-in accident resistance, as well as the possibilities for enhanced fuel/clad system performance and longevity.« less

Structural and compositional evolution of Al{sub 3}(Zr,Y) precipitates in Al-Zr-Y alloy

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

Gao, Haiyan, E-mail: gaohaiyan@sjtu.edu.cn

Structural and compositional evolution of Al{sub 3}(Zr,Y) precipitates in aged Al-Zr-Y alloy was investigated through atom probe tomography (APT) and transmission electron microscope (TEM) analysis and first principles calculations. The results show that short-bar-shaped D0{sub 19}-Al{sub 3}Y with some Zr atoms dissolved in precipitated at the very beginning of decomposition and worked as heterogeneous nuclei for L1{sub 2}-Al{sub 3}Zr with spherical morphology after being aged at 400 °C for 2 h. Quasi-static coarsening happened as the aging treatment lasted from 2 h to 200 h. However, distribution of Zr and Y atoms in Al{sub 3}(Zr,Y) is nearly uniform and Al{submore » 3}(Zr,Y) do not have the typical “Al{sub 3}RE core-Al{sub 3}Zr shell” structure which observed in other RE containing Al-Zr-RE alloys with L1{sub 2}-Al{sub 3}RE as nuclei. First principles calculations revealed that binding energy between Y and Zr is strong during the growth of Al{sub 3}(Zr,Y), which led to the co-precipitation of Y and Zr atoms and attribute to the evolution of Al{sub 3}(Zr,Y). - Highlights: •Al{sub 3}Y precipitated firstly and then became nuclei for Al{sub 3}Zr during aging of Al-Zr-Y. •Al{sub 3}(Zr,Y) precipitates do not have the typical “Al{sub 3}Y core-Al{sub 3}Zr shell” structure. •Strong binding between Y and Zr led to the co-precipitation of Y and Zr atoms.« less

Simultaneous spectrophotometric determination of trace amounts of uranium, thorium, and zirconium using the partial least squares method after their preconcentration by alpha-benzoin oxime modified Amberlite XAD-2000 resin.

PubMed

Ghasemi, Jahan B; Zolfonoun, E

2010-01-15

A new solid phase extraction method for separation and preconcentration of trace amounts of uranium, thorium, and zirconium in water samples is proposed. The procedure is based on the adsorption of U(VI), Th(IV) and Zr(IV) ions on a column of Amberlite XAD-2000 resin loaded with alpha-benzoin oxime prior to their simultaneous spectrophotometric determination with Arsenazo III using orthogonal signal correction partial least squares method. The enrichment factor for preconcentration of uranium, thorium, and zirconium was found to be 100. The detection limits for U(VI), Th(IV) and Zr(IV) were 0.50, 0.54, and 0.48microgL(-1), respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of 10 replicates, was below 4% for all elements. The practical applicability of the developed sorbent was examined using synthetic seawater, natural waters and ceramic samples.

Zr-ZrO2 cermet solar coatings designed by modelling calculations and deposited by dc magnetron sputtering

NASA Astrophysics Data System (ADS)

Zhang, Qi-Chu; Hadavi, M. S.; Lee, K.-D.; Shen, Y. G.

2003-03-01

High solar performance Zr-ZrO2 cermet solar coatings were designed using a numerical computer model and deposited experimentally. The layer thickness and Zr metal volume fraction for the Zr-ZrO2 cermet solar selective coatings on a Zr or Al reflector with a surface ZrO2 or Al2O3 anti-reflection layer were optimized to achieve maximum photo-thermal conversion efficiency at 80°C under concentration factors of 1-20 using the downhill simplex method in multi-dimensions in the numerical calculation. The dielectric function and the complex refractive index of Zr-ZrO2 cermet materials were calculated using Sheng's approximation. Optimization calculations show that Al2O3/Zr-ZrO2/Al solar coatings with two cermet layers and three cermet layers have nearly identical solar absorptance, emittance and photo-thermal conversion efficiency that are much better than those for films with one cermet layer. The optimized Al2O3/Zr-ZrO2/Al solar coating film with two cermet layers has a high solar absorptance value of 0.97 and low hemispherical emittance value of 0.05 at 80°C for a concentration factor of 2. The Al2O3/Zr-ZrO2/Al solar selective coatings with two cermet layers were deposited using dc magnetron sputtering technology. During the deposition of Zr-ZrO2 cermet layer, a Zr metallic target was run in a gas mixture of argon and oxygen. By control of oxygen flow rate the different metal volume fractions in the cermet layers were achieved using dc reactive sputtering. A solar absorptance of 0.96 and normal emittance of 0.05 at 80°C were achieved.

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

NASA Astrophysics Data System (ADS)

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.

Study on ( n,t) Reactions of Zr, Nb and Ta Nuclei

NASA Astrophysics Data System (ADS)

Tel, E.; Yiğit, M.; Tanır, G.

2012-04-01

The world faces serious energy shortages in the near future. To meet the world energy demand, the nuclear fusion with safety, environmentally acceptability and economic is the best suited. Fusion is attractive as an energy source because of the virtually inexhaustible supply of fuel, the promise of minimal adverse environmental impact, and its inherent safety. Fusion will not produce CO2 or SO2 and thus will not contribute to global warming or acid rain. Furthermore, there are not radioactive nuclear waste problems in the fusion reactors. Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Because, tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. And also, the success of fusion power system is dependent on performance of the first wall, blanket or divertor systems. So, the performance of structural materials for fusion power systems, understanding nuclear properties systematic and working out of ( n,t) reaction cross sections are very important. Zirconium (Zr), Niobium (Nb) and Tantal (Ta) containing alloys are important structural materials for fusion reactors, accelerator-driven systems, and many other fields. In this study, ( n,t) reactions for some structural fusion materials such as 88,90,92,94,96Zr, 93,94,95Nb and 179,181Ta have been investigated. The calculated results are discussed andcompared with the experimental data taken from the literature.

Influence of dosage, pH and contact time in stabilized landfill leachate treatment using ozone/zirconium tetrachloride catalytic oxidation

NASA Astrophysics Data System (ADS)

Zakaria, Siti Nor Farhana; Aziz, Hamidi Abdul

2017-10-01

Leachate is a critical problem of sanitary landfills because it contains high organic matter and hazardous compounds that can generate negative environmental effects. The high chemical oxygen demand (COD) and color of the leachate necessitates its treatment before it can be released to the water body. Thus, an investigation into the performance of advanced oxidation processes (AOPs) was conducted using a combination of ozone (O3) with zirconium tetrachloride (ZrCl4) as catalyst in stabilized landfill leachate treatment. Such leachate was collected from the Alor Pongsu Landfill site (APLS), Perak, Malaysia. COD and color parameter were used as indicators to examine the effect of O3/ZrCl4 dosage, pH, and contact time. The experiment was run under gas flow rate of 1,000 mL/min±10% and temperature below 15 °C. The maximum removal obtained for COD and color were 88% and 100%, respectively. This outcome was achieved at 27 g/m3 ozone dosage, pH 6, 90 min reaction time, and dosage ratio of 1:2 (COD g: ZrCl4 g). The reaction rate constant (k) was 0.2364 min-1 and followed pseudo first order. Thus, given the efficiency of the O3/ZrCl4 mixture for the remediation of stabilized landfill leachate, a new alternative method in leachate industrial treatment was identified.

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

PubMed Central

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

2015-01-01

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

Effect of different Zr contents on properties and microstructure of Cu-Cr-Zr alloys

NASA Astrophysics Data System (ADS)

Jinshui, Chen; Bin, Yang; Junfeng, Wang; Xiangpeng, Xiao; Huiming, Chen; Hang, Wang

2018-02-01

The crystallography and morphology of precipitate particles of Cu-Cr-Zr alloys with varying Zr contents were studied by transmission electron microscopy (TEM) after solution treatments at 950 °C for 1 h and aging treatments at 500 °C for different times ranged from 0.5 h to 24 h. The microhardness and electrical conductivity of Cu-Cr-Zr alloys after various aging process were tested. The results show that the microhardness and electrical conductivity rapidly increased at first, then the microhardness decreased slowly after reaching the peak, while the conductivity continues to increase. Nano-scaled precipitates exhibit two kinds of morphology (coffee bean and ellipse shaped). With increasing Zr content, the Zr-containing precipitation sequence of Cu-Cr-Zr alloys at peak-ageing is Heusler CrCu2Zr → Cu5Zr → Cu4Zr. The Heusler CrCu2Zr phase decomposed into fine and homogeneous Cr and Cu4Zr, resulting in improved alloy properties.

Accelerate Water Quality Improvement

EPA Pesticide Factsheets

EPA is committed to accelerating water quality improvement and minimizing negative impacts to aquatic life from contaminants and other stressors in the Bay Delta Estuary by working with California Water Boards to strengthen water quality improvement plans.

The Impact of Updated Zr Neutron-capture Cross Sections and New Asymptotic Giant Branch Models on our Understanding of the s process and the origin of stardust

DOE PAGES

Lugaro, M.; Tagliente, Giuseppe; Karakas, Amanda I.; ...

2013-12-13

We present model predictions for the Zr isotopic ratios produced by slow neutron captures in C-rich asymptotic giant branch (AGB) stars of masses 1.25-4 M-circle dot and metallicities Z = 0.01-0.03, and compare them to data from single meteoritic stardust silicon carbide (SiC) and high-density graphite grains that condensed in the outflows of these stars. We compare predictions produced using the Zr neutron-capture cross sections from Bao et al. and from n_TOF experiments at CERN, and present a new evaluation for the neutron-capture cross section of the unstable isotope Zr-95, the branching point leading to the production of Zr-96. Themore » new cross sections generally present an improved match with the observational data, except for the Zr-92/Zr-94 ratios, which are on average still substantially higher than predicted. The Zr-96/Zr-94 ratios can be explained using our range of initial stellar masses, with the most Zr-96-depleted grains originating from AGB stars of masses 1.8-3 M-circle dot and the others from either lower or higher masses. The Zr-90,Zr-91/Zr-94 variations measured in the grains are well reproduced by the range of stellar metallicities considered here, which is the same needed to cover the Si composition of the grains produced by the chemical evolution of the Galaxy. The Zr-92/Zr-94 versus Si-29/Si-28 positive correlation observed in the available data suggests that stellar metallicity rather than rotation plays the major role in covering the Zr-90,Zr-91,Zr-92/Zr-94 spread« less

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes

PubMed Central

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-01

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO2, NO, H2O, as well as the related fragments during the O2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO2 during the complex surface chemical reaction of the ligand and O2 plasma were monitored using the QCM. The remote PEALD ZrO2/zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10−5 g/m2/day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime. PMID:28059160

Bone bonding bioactivity of Ti metal and Ti-Zr-Nb-Ta alloys with Ca ions incorporated on their surfaces by simple chemical and heat treatments.

PubMed

Fukuda, A; Takemoto, M; Saito, T; Fujibayashi, S; Neo, M; Yamaguchi, S; Kizuki, T; Matsushita, T; Niinomi, M; Kokubo, T; Nakamura, T

2011-03-01

Ti15Zr4Nb4Ta and Ti29Nb13Ta4.6Zr, which do not contain the potentially cytotoxic elements V and Al, represent a new generation of alloys with improved corrosion resistance, mechanical properties, and cytocompatibility. Recently it has become possible for the apatite forming ability of these alloys to be ascertained by treatment with alkali, CaCl2, heat, and water (ACaHW). In order to confirm the actual in vivo bioactivity of commercially pure titanium (cp-Ti) and these alloys after subjecting them to ACaHW treatment at different temperatures, the bone bonding strength of implants made from these materials was evaluated. The failure load between implant and bone was measured for treated and untreated plates at 4, 8, 16, and 26 weeks after implantation in rabbit tibia. The untreated implants showed almost no bonding, whereas all treated implants showed successful bonding by 4 weeks, and the failure load subsequently increased with time. This suggests that a simple and economical ACaHW treatment could successfully be used to impart bone bonding bioactivity to Ti metal and Ti-Zr-Nb-Ta alloys in vivo. In particular, implants heat treated at 700 °C exhibited significantly greater bone bonding strength, as well as augmented in vitro apatite formation, in comparison with those treated at 600 °C. Thus, with this improved bioactive treatment process these advantageous Ti-Zr-Nb-Ta alloys can serve as useful candidates for orthopedic devices. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Alkaline nanoparticle coatings improve resin bonding of 10-methacryloyloxydecyldihydrogenphosphate-conditioned zirconia.

PubMed

Qian, Mengke; Lu, Zhicen; Chen, Chen; Zhang, Huaiqin; Xie, Haifeng

Creating an alkaline environment prior to 10-methacryloyloxydecyldihydrogenphosphate (MDP) conditioning improves the resin bonding of zirconia. The present study evaluated the effects of four alkaline coatings with different water solubilities and pH values on resin bonding of MDP-conditioned zirconia. Two alkaline nanoparticle coatings were studied in particular. Thermodynamics calculations were performed to evaluate the strengths of MDP-tetragonal phase zirconia chemical bonds at different pH values. Zirconia surfaces with and without alkaline coatings were characterized by scanning electron microscope (SEM)/energy dispersive spectrometer and Fourier transform infrared spectroscopy; alkaline coatings included NaOH, Ca(OH) 2 , nano-MgO, and nano-Zr(OH) 4 . A shear bond strength (SBS) test was performed to evaluate the effects of the four alkaline coatings on bonding; the alkaline coatings were applied to the surfaces prior to conditioning the zirconia with MDP-containing primers. Gibbs free energies of the MDP-tetragonal zirconia crystal model coordination reaction in different pH environments were -583.892 (NaOH), -569.048 [Ca(OH) 2 ], -547.393 (MgO), and -530.279 kJ/mol [Zr(OH) 4 ]. Thermodynamic calculations indicated that the alkaline coatings improved bonding in the following order: NaOH > Ca(OH) 2 > MgO > Zr(OH) 4 . Statistical analysis of SBS tests showed a different result. SBSs were significantly different in groups that had different alkaline coatings, but it was not influenced by different primers. All four alkaline coatings increased SBS compared to control groups. Of the four coatings, nano-Zr(OH) 4 and -MgO showed higher SBS. Therefore, preparing nano-Zr(OH) 4 or -MgO coatings prior to conditioning with MDP-containing primers may potentially improve resin bonding of zirconia in the clinic.

Alkaline nanoparticle coatings improve resin bonding of 10-methacryloyloxydecyldihydrogenphosphate-conditioned zirconia

PubMed Central

Qian, Mengke; Lu, Zhicen; Chen, Chen; Zhang, Huaiqin; Xie, Haifeng

2016-01-01

Creating an alkaline environment prior to 10-methacryloyloxydecyldihydrogenphosphate (MDP) conditioning improves the resin bonding of zirconia. The present study evaluated the effects of four alkaline coatings with different water solubilities and pH values on resin bonding of MDP-conditioned zirconia. Two alkaline nanoparticle coatings were studied in particular. Thermodynamics calculations were performed to evaluate the strengths of MDP-tetragonal phase zirconia chemical bonds at different pH values. Zirconia surfaces with and without alkaline coatings were characterized by scanning electron microscope (SEM)/energy dispersive spectrometer and Fourier transform infrared spectroscopy; alkaline coatings included NaOH, Ca(OH)2, nano-MgO, and nano-Zr(OH)4. A shear bond strength (SBS) test was performed to evaluate the effects of the four alkaline coatings on bonding; the alkaline coatings were applied to the surfaces prior to conditioning the zirconia with MDP-containing primers. Gibbs free energies of the MDP-tetragonal zirconia crystal model coordination reaction in different pH environments were −583.892 (NaOH), −569.048 [Ca(OH)2], −547.393 (MgO), and −530.279 kJ/mol [Zr(OH)4]. Thermodynamic calculations indicated that the alkaline coatings improved bonding in the following order: NaOH > Ca(OH)2 > MgO > Zr(OH)4. Statistical analysis of SBS tests showed a different result. SBSs were significantly different in groups that had different alkaline coatings, but it was not influenced by different primers. All four alkaline coatings increased SBS compared to control groups. Of the four coatings, nano-Zr(OH)4 and -MgO showed higher SBS. Therefore, preparing nano-Zr(OH)4 or -MgO coatings prior to conditioning with MDP-containing primers may potentially improve resin bonding of zirconia in the clinic. PMID:27785013

Effect of humic acid preloading on phosphate adsorption onto zirconium-modified zeolite.

PubMed

Lin, Jianwei; Zhang, Zhe; Zhan, Yanhui

2017-05-01

A zirconium-modified zeolite (ZrMZ) was prepared, and then, humic acid (HA) was immobilized on the ZrMZ surface to prepare HA-loaded ZrMZ (HA-ZrMZ). The obtained ZrMZ and HA-ZrMZ were characterized by energy dispersive X-ray spectroscopy, elemental analyzer, N 2 adsorption/desorption isotherms, pH at the point of zero charge, and X-ray photoelectron spectroscopy. The adsorption characteristics of phosphate on ZrMZ and HA-ZrMZ were comparatively investigated in batch mode. The adsorption mechanism of phosphate on ZrMZ and HA-ZrMZ was investigated by ionic strength effect and 31 P nuclear magnetic resonance. The mechanism for phosphate adsorption onto ZrMZ was the formation of inner-sphere phosphate complexes at the solid/solution interface. The preloading of HA on ZrMZ reduced the phosphate adsorption capacity, and the more the HA loading amount, the lower the phosphate adsorption capacity. However, the preloading of HA on ZrMZ did not change the phosphate adsorption mechanism; i.e., the formation of inner-sphere phosphate surface complexes was still responsible for the adsorption of phosphate on HA-ZrMZ. The decreased phosphate adsorption capacity for ZrMZ after HA coating could be attributed to the fact that the coating of HA on ZrMZ reduced the amount of binding active sites available for phosphate adsorption, changed the adsorbent surface charges, and reduced the specific surface areas and pore volumes of ZrMZ.

Fine Structure in Multi-Phase Zr8Ni21-Zr7Ni10-Zr2Ni7 Alloy Revealed by Transmission Electron Microscope

PubMed Central

Shen, Haoting; Bendersky, Leonid A.; Young, Kwo; Nei, Jean

2015-01-01

The microstructure of an annealed alloy with a Zr8Ni21 composition was studied by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The presence of three phases, Zr8Ni21, Zr2Ni7, and Zr7Ni10, was confirmed by SEM/X-ray energy dispersive spectroscopy compositional mapping and TEM electron diffraction. Distribution of the phases and their morphology can be linked to a multi-phase structure formed by a sequence of reactions: (1) L → Zr2Ni7 + L’; (2) peritectic Zr2Ni7 + L’ → Zr2Ni7 + Zr8Ni21 + L”; (3) eutectic L” → Zr8Ni21 + Zr7Ni10. The effect of annealing at 960 °C, which was intended to convert a cast structure into a single-phase Zr8Ni21 structure, was only moderate and the resulting alloy was still multi-phased. TEM and crystallographic analysis of the Zr2Ni7 phase show a high density of planar (001) defects that were explained as low-energy boundaries between rotational variants and stacking faults. The crystallographic features arise from the pseudo-hexagonal structure of Zr2Ni7. This highly defective Zr2Ni7 phase was identified as the source of the broad X-ray diffraction peaks at around 38.4° and 44.6° when a Cu-K was used as the radiation source. PMID:28793460

Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

DOE PAGES

Nash, Connor P.; Ramanathan, Anand; Ruddy, Daniel A.; ...

2015-12-01

Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C 2–C 4 alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Brønsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporousmore » silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 °C. The zeolite materials exhibited high activity (>98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>10% ethanol conversion) at or above 300 °C. The turnover frequencies for ethanol dehydration at 300 °C decreased in the following order: HZSM-5 > SAPO-34 > Al-MCM-41 > Zr-KIT-6, suggesting that Brønsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 °C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C 3+-alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Brønsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 °C over SAPO-34 (>95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.« less

Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

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

Nash, Connor P.; Ramanathan, Anand; Ruddy, Daniel A.

Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C 2–C 4 alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Brønsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporousmore » silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 °C. The zeolite materials exhibited high activity (>98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>10% ethanol conversion) at or above 300 °C. The turnover frequencies for ethanol dehydration at 300 °C decreased in the following order: HZSM-5 > SAPO-34 > Al-MCM-41 > Zr-KIT-6, suggesting that Brønsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 °C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C 3+-alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Brønsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 °C over SAPO-34 (>95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.« less

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

Structure and Thermodynamical Properties of Zirconium Hydrides from First-Principle

NASA Astrophysics Data System (ADS)

Blomqvist, Jakob; Olofsson, Johan; Alvarez, Anna-Maria; Bjerkén, Christina

Zirconium alloys are used as nuclear fuel cladding material due to their mechanical and corrosion resistant properties together with their favorable cross-section for neutron scattering. At running conditions, however, there will be an increase of hydrogen in the vicinity of the cladding surface at the water side of the fuel. The hydrogen will diffuse into the cladding material and at certain conditions, such as lower temperatures and external load, hydrides will precipitate out in the material and cause well known embrittlement, blistering and other unwanted effects. Using phase-field methods it is now possible to model precipitation buildup in metals, for example as a function of hydrogen concentration, temperature and external load, but the technique relies on input of parameters, such as the formation energy of the hydrides and matrix. To that end, we have computed, using the density functional theory (DFT) code GPAW, the latent heat of fusion as well as solved the crystal structure for three zirconium hydride polymorphs: δ-ZrH1.6, γ-ZrH, and Є-ZrH2.

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

PubMed

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

2018-06-21

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

Ultrastructure Processing of Advanced Materials.

DTIC Science & Technology

1992-11-01

alkoxide) involving the sodium and the other metal [e.g., NaZr 2(OR)9]. The use of anhydrous ammonia usually solves this problem. MCIX + xNH 3 + xROH - M...the formation of pentacoordinate silicic acid complexes with hydroxide and fluoride ions, as well as neutral adducts with hydrogen fluoride, ammonia ...stable than that for any other small neutral adduct such as water, ammonia , and hydrogen chloride. Elimination of water is much easier by internal

Inter-Agency Consultative Group for Space Science (IACG): Handbook of Missions and Payloads

NASA Technical Reports Server (NTRS)

1994-01-01

The ACE spacecraft design is based on the Charge Composition Explorer (CCE) built by Johns Hopkins University (JHU) and the Applied Physics Lab (APL) for the AMPTE program. ACE is designed as a spinning spacecraft with its spin axis aligned to the Earth-Sun axis. The ACE launch weight will be approx. 633 kg, including 105 kg of scientific instruments and 184 kg of propellant. Using a Delta-class expendable launch vehicle, ACE will be launched into an L1 libration point (240 R(sub e)) orbit. Telemetry will be 6.7 kbps average, using tape recorder storage with daily readout to DSN. The experiment power requirement is approximately 76 W nominal and 96 W peak. The prime objective of the ACE mission is: (1) to determine accurate elemental and isotropic abundances including solar matter, local interstellar matter and local galactic matter; (2) to study the origin of elements and evolutionary processing in galactic nucleosynthesis, galactic evolution, origin and evolution of the solar system; (3) to study coronal formation and solar-wind acceleration processes; and (4) to study particle acceleration and transport, including coronal shock acceleration, stochastic flare acceleration, interplanetary shock acceleration, and interstellar acceleration and propagation. To accomplish this objective, ACE will perform comprehensive and coordinated determinations of the elemental and isotopic composition of energetic nuclei accelerated on the Sun, in interplanetary space, and from galactic sources. These observations will span five decades in energy, from solar wind to galactic cosmic ray energies, and will cover the element range from H-1 to Zr-40. Comparison of these samples of matter will be used to study the origin and subsequent evolution of both solar system and galactic material by isolating the effects of fundamental processes that include nucleosynthesis, charged and neutral particle separation, bulk plasma acceleration, and the acceleration of suprathermal and high-energy particles.

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Acceleration induced water removal from ear canals.

NASA Astrophysics Data System (ADS)

Kang, Hosung; Averett, Katelee; Jung, Sunghwan

2017-11-01

Children and adults commonly experience having water trapped in the ear canals after swimming. To remove the water, individuals will shake their head sideways. Since a child's ear canal has a smaller diameter, it requires more acceleration of the head to remove the trapped water. In this study, we theoretically and experimentally investigated the acceleration required to break the surface meniscus of the water in artificial ear canals and hydrophobic-coated glass tubes. In experiments, ear canal models were 3D-printed from a CT-scanned human head. Also, glass tubes were coated with silane to match the hydrophobicity in ear canals. Then, using a linear stage, we measured the acceleration values required to forcefully eject the water from the artificial ear canals and glass tubes. A theoretical model was developed to predict the critical acceleration at a given tube diameter and water volume by using a modified Rayleigh-Taylor instability. Furthermore, this research can shed light on the potential of long-term brain injury and damage by shaking the head to push the water out of the ear canal. This research was supported by National Science Foundation Grant CBET-1604424.

Water bath accelerated curing of concrete.

DOT National Transportation Integrated Search

1970-01-01

Water bath methods for accelerating the strength development of portland cement concrete were investigated in a two phase study as follows. Phase I - Participation in a cooperative accelerated strength testing program sponsored by the American Societ...

Accelerator mass spectrometry of Strontium-90 for homeland security, environmental monitoring, and human health

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

Tumey, S J; Brown, T A; Hamilton, T F

2008-03-03

Strontium-90 is one of the most hazardous materials managed by agencies charged with protecting the public from radiation. Traditional radiometric methods have been limited by low sample throughput and slow turnaround times. Mass spectrometry offers the advantage of shorter analysis times and the ability to measure samples immediately after processing, however conventional mass spectrometric techniques are susceptible to molecular isobaric interferences that limit their overall sensitivity. In contrast, accelerator mass spectrometry is insensitive to molecular interferences and we have therefore begun developing a method for determination of {sup 90}Sr by accelerator mass spectrometry. Despite a pervasive interference from {sup 90}Zr,more » our initial development has yielded an instrumental background of {approx} 10{sup 8} atoms (75 mBq) per sample. Further refinement of our system (e.g., redesign of our detector, use of alternative target materials) is expected to push the background below 10{sup 6} atoms, close to the theoretical limit for AMS. Once we have refined our system and developed suitable sample preparation protocols, we will utilize our capability in applications to homeland security, environmental monitoring, and human health.« less

Additive Manufacturing of Reactive In Situ Zr Based Ultra-High Temperature Ceramic Composites

NASA Astrophysics Data System (ADS)

Sahasrabudhe, Himanshu; Bandyopadhyay, Amit

2016-03-01

Reactive in situ multi-material additive manufacturing of ZrB2-based ultra-high-temperature ceramics in a Zr metal matrix was demonstrated using LENS™. Sound metallurgical bonding was achieved between the Zr metal and Zr-BN composites with Ti6Al4V substrate. Though the feedstock Zr power had α phase, LENS™ processing of the Zr powder and Zr-BN premix powder mixture led to the formation of some β phase of Zr. Microstructure of the Zr-BN composite showed primary grains of zirconium diboride phase in zirconium metal matrix. The presence of ZrB2 ceramic phase was confirmed by X-ray diffraction (XRD) analysis. Hardness of pure Zr was measured as 280 ± 12 HV and, by increasing the BN content in the feedstock, the hardness was found to increase. In Zr-5%BN composite, the hardness was 421 ± 10 HV and the same for Zr-10%BN composite was 562 ± 10 HV. It is envisioned that such multi-materials additive manufacturing will enable products in the future that cannot be manufactured using traditional approaches particularly in the areas of high-temperature metal-ceramic composites with compositional and functional gradation.

Surface thermodynamic stability, electronic and magnetic properties in various (001) surfaces of Zr2CoSn Heusler alloy

NASA Astrophysics Data System (ADS)

Yang, Yan; Feng, Zhong-Ying; Zhang, Jian-Min

2018-05-01

The spin-polarized first-principles are used to study the surface thermodynamic stability, electronic and magnetic properties in various (001) surfaces of Zr2CoSn Heusler alloy, and the bulk Zr2CoSn Heusler alloy are also discussed to make comparison. The conduction band minimum (CBM) of half-metallic (HM) bulk Zr2CoSn alloy is contributed by ZrA, ZrB and Co atoms, while the valence band maximum (VBM) is contributed by ZrB and Co atoms. The SnSn termination is the most stable surface with the highest spin polarizations P = 77.1% among the CoCo, ZrCo, ZrZr, ZrSn and SnSn terminations of the Zr2CoSn (001) surface. In the SnSn termination of the Zr2CoSn (001) surface, the atomic partial density of states (APDOS) of atoms in the surface, subsurface and third layers are much influenced by the surface effect and the total magnetic moment (TMM) is mainly contributed by the atomic magnetic moments of atoms in fourth to ninth layers.

A DFT+U study of Pu immobilization in Gd2Zr2O7

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

On the mechanism of zirconium nitride formation by zirconium, zirconia and yttria burning in air

NASA Astrophysics Data System (ADS)

Malikova, Ekaterina; Pautova, Julia; Gromov, Alexander; Monogarov, Konstantin; Larionov, Kirill; Teipel, Ulrich

2015-10-01

The combustion of Zr and (Zr+ZrO2) powdery mixtures in air was accompanied by major ZrN stabilization. The synthesis of cheap ZrN with the high yield in air was facile and utile. The influence of Y2O3 additive on the content of ZrN the solid combustion products (SCP) was investigated. The reagents and SCP were analyzed by BET, DTA-TGA, XRD, SEM and EDS. Burning temperature was measured by thermal imager. The yield of ZrN in the SCP has been varied by the time regulation of the combustion process. The burning samples were quenched at a certain time to avoid the re-oxidation of the obtained ZrN by oxygen. The quenching of the burned (Zr+ZrO2) samples with the Y2O3 additive was allowed increasing the ZrN yield in SCP up to 66 wt%. The chemical mechanism of ZrN formation in air was discussed and the probable source of ZrN massive formation is suggested.

Effect of zirconia morphology on sulfur-resistant methanation performance of MoO3/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Liu, Chen; Wang, Weihan; Xu, Yan; Li, Zhenhua; Wang, Baowei; Ma, Xinbin

2018-05-01

Two kinds of ZrO2 support with different morphologies were prepared by facile solvothermal method in different solvents. The obtained two supports showed monoclinic zirconia (m-ZrO2) and tetragonal zirconia (t-ZrO2) phase with similar crystalline size. Their supported Mo-based catalysts were prepared by impregnation method and the effect of zirconia morphology on the performance of sulfur-resistant methanation was examined. The results indicated that the MoO3/m-ZrO2 has higher CO conversion than the MoO3/t-ZrO2 catalyst. Characterizations by XRD, Raman, H2-TPR and IR confirmed that the m-ZrO2 is superior to t-ZrO2 for dispersing molybdenum species. In addition, the MoO3/m-ZrO2 catalyst has weaker interaction between support and active Mo speices than the MoO3/t-ZrO2 catalyst, which facilitates to forming active species of nanocrystalline MoS2 layers for sulfur-resistant methanation. The weaker interaction of molybdenum species with m-ZrO2 is related with the more covalent character of the Zrsbnd O bond and more oxygen defective structure of m-ZrO2. A larger number of Lewis acid centers appear on the surface of m-ZrO2, which verified the substantial vacancies on m-ZrO2 exposing coordinately unsaturated Zr3+ and Zr4+ cations. Meanwhile, the less Lewis acid of t-ZrO2 result in stronger interaction between support and molybdenum species and trigger crystalline phase MoO3 and Mosbnd Osbnd Zr linkages.

Influence of free carbon on the characteristics of ZrC and deposition of near-stoichiometric ZrC in TRISO coated particle fuel

NASA Astrophysics Data System (ADS)

Kim, Daejong; Ko, Myeong Jin; Park, Ji Yeon; Cho, Moon Sung; Kim, Weon-Ju

2014-08-01

Advanced TRISO coated particles with a ZrC coating layer as a main pressure boundary were fabricated by a fluidized-bed chemical vapor deposition (FBCVD) method using a chloride process. Experiments were performed to determine the effect of codeposition of graphitic carbon on the hardness and obtain the stoichiometric ZrC phase. The ZrC coating layer was composed of a mixture of ZrC and graphitic carbon phases at a low ZrCl4/CH4 ratio. A near-stoichiometric ZrC without the free carbon can be obtained by employing an impeller-driven ZrCl4 vaporizer. The codeposition of the graphitic carbon significantly lowered the hardness of ZrC while increasing the fraction of the carbon. The hardness reached its maximum when ZrC was in a slight carbon deficit without free carbon. As the graphitic carbon increased up to 12 vol%, the hardness was reduced by approximately 50% compared to the near-stoichiometric ZrC.

Microstructure and mechanical properties of rapidly solidified B2-type Zr–Co alloys containing a second phase of Zr2Co

NASA Astrophysics Data System (ADS)

Li, Peiyou

2018-04-01

Microstructure and mechanical properties of B2-type Zr–Co alloys containing a second phase (Zr2Co) were investigated. Results show that the as-cast Zr52Co48, Zr54Co46, and Zr56Co44 alloys are composed of a eutectic structure of B2 and Zr2Co phases. Relative amounts of Zr2Co phases increase with an increase in Zr content. Zr54Co46 exhibits high yield strength, high Vickers hardness, good ductility, and high toughness values, and thus, Zr54Co46 can be considered to be a novel engineering material. The increase in strength and decrease in plastic strain of the alloys are mainly attributed to the increase in high strength of the brittle Zr2Co phase and to grain refining of the B2 matrix phase.

Oxidation feature and diffusion mechanism of Zr-based metallic glasses near the glass transition point

NASA Astrophysics Data System (ADS)

Hu, Zheng; Lei, Xianqi; Wang, Yang; Zhang, Kun

2018-03-01

The oxidation behaviors of as-cast, pre-deformed, and crystallized Zr47.9Ti0.3Ni3.1Cu39.3Al9.4 metallic glasses (MGs) were studied near the glass transition point. The oxidation kinetics of the crystallized MGs followed a parabolic-rate law, and the as-cast and pre-deformed MGs exerted a typical two-stage behavior above the glass transition temperature (T g). Most interesting, pre-deformed treatment can significantly improve the oxidation rate of MGs, as the initial oxidation appeared earlier than for the as-cast MGs, and was accompanied by much thicker oxide scale. The EDS and XPS results showed that the metal Al acted as the preferred scavenger that absorbed intrinsic oxygen in the near-surface region of as-cast MGs. However, a homogeneous mixed layer without Al was observed in the pre-deformed MGs. We speculated the accelerated diffusion of other elements in the MGs was due to the local increase in the free volume and significant shear-induced dilation of the local structure. The results from this study demonstrate that MGs exhibit controllable atomic diffusion during the oxidation process, which can facilitate use in super-cooled liquid region applications.

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

Ota, S.; Burke, J. T.; Casperson, R. J.

Here, the effect of the production mechanism on the decay of a compound nucleus is investigated. The nucleus 90Zr was produced by three different reactions, namely 90Zr (p,p') 90Zr, 91Zr (p,d) 90Zr, and 92Zr (p,t) 90Zr , which served as surrogate reactions for 89Zr (n,γ). The spin-parity (J π) distributions of the states populated by these reactions were studied to investigate the surrogate reaction approach, which aims at indirectly determining cross sections for compound-nuclear reactions involving unstable targets such as 89Zr. Discrete γ rays, associated with transitions in 90Zr and 89Zr, were measured in coincidence with light ions for scatteringmore » angles of 25°–60° and 90Zr excitation energies extending above the neutron separation energy. The measured transition systematics were used to gain insights into the J π distributions of 90Zr. The 90Zr (p,p') reaction was found to produce fewer γ rays associated with transitions involving high spin states (J = 6–8 ℏ) than the other two reactions, suggesting that inelastic scattering preferentially populates states in 90Zr that have lower spins than those populated in the transfer reactions investigated. The γ-ray production was also observed to vary by factors of 2–3 with the angle at which the outgoing particle was detected. These findings are relevant to the application of the surrogate reaction approach.« less

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

NASA Technical Reports Server (NTRS)

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

1979-01-01

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

Refractory Materials of Zirconate. Part 2: Synthesis and some properties of strontium, zirconate, calcium zirconate and barium zirconate

NASA Technical Reports Server (NTRS)

Okubo, Tsutomo; Yonemochi, Osamu; Nakamura, Kazuo; Maeda, Minoru

1988-01-01

Chemical compounds SrZrO3, CaZrO3, and BaZrO3 were synthesized by solid reaction and arc fusion, and their properties examined. Results were as follows: (1) in the synthesis of CaZrO3 by solid reaction, ZrO2 solid solution with cubic form was produced, which then changed into CaZrO3; (2) the BaZrO3 was a cubic form and did not show any transformation, while SrZrO3 and CaZrO3 with an orthorhombic form transformed to a cubic form at high temperature; and (3) the solubility of BaZrO3 in acid and its vaporization rate at a high temperature were greater than those of zirconates.

High-yield sol-gel synthesis of well-dispersed, colorless ZrO(2) nanocrystals.

PubMed

Mizuno, Mikihisa; Sasaki, Yuichi; Lee, Sungkil; Katakura, Hitoshi

2006-08-15

A 93% high-yield synthesis of well-dispersed, colorless zirconium dioxide (ZrO(2)) nanocrystals is reported. In this synthesis, hydrolysis and condensation reactions of zirconium(IV) tert-butoxide in the presence of oleic acid (100 degrees C) formed ZrO(2) precursors. The ZrO(2) precursors were made of -Zr-O-Zr- networks surrounded by oleic acid molecules. Annealing (280 degrees C) the precursors dispersed in dioctyl ether caused crystallization of the -Zr-O-Zr- networks, thereby generating 4 nm ZrO(2) nanocrystals stabilized with oleic acid. The particles were highly crystalline and tetragonal phase. A dense ZrO(2) nanocrystal dispersion in toluene (280 mg/mL) showed a transmittance of about 90% (3 mm optical path length) in the whole visible region.

Reactions and products in the Cs-Zr-I-O system relevant to fission product chemistry — a review

NASA Astrophysics Data System (ADS)

Chen, T.-M.; Kauzlarich, S. M.; Corbett, J. D.

1988-02-01

Some results and problems associated with the known chemistry of cesium and iodine in the presence of Zr/ZrO 2 at 400-600°C and under anaerobic conditions are described and discussed. These aspects include (1) the recently synthesized cesium zirconates Cs 2ZrO 3 and Cs 4ZrO 4 and some of their thermal and hydrolytic properties (2) the demonstration that the supposedly stable CsI reacts with ZrO 2 at 400-700°C to form Cs 2ZrO 3 and ZrI 4 (as Cs 2ZrI 6) and its implications regarding cesium and iodine distributions (3) present knowledge of binary zirconium iodides, their contamination reactions, and the limited inhibition of the reduction of ZrI 4 by metal provided by static ZrO 2 films (4) newly discovered ternary and quaternary zirconium iodides that are obtained in the presence of many common impurity atoms and, when prsesent, CsI (e.g., Zr 6I 12C, CsZr 6I 14C, Zr 6I 14Fe), the ease with which some of those form at least as low as 450°C, and the complications these and related new phases provide.

Zirconium phosphate nanoplatelets: a biocompatible nanomaterial for drug delivery to cancer

NASA Astrophysics Data System (ADS)

Saxena, Vipin; Diaz, Agustin; Clearfield, Abraham; Batteas, James D.; Hussain, Muhammad Delwar

2013-02-01

The objective of this study was to evaluate the biocompatibility of zirconium phosphate (ZrP) nanoplatelets (NPs), and their use in drug delivery. ZrP and doxorubicin-intercalated ZrP (DOX:ZrP) NPs were characterized by using X-Ray Powder Diffraction (XRPD), Thermogravimetric Analysis (TGA), Transmission Electron Micrography (TEM), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Biocompatibility of ZrP NPs was evaluated in human embryonic kidney (HEK-293), breast cancer (MCF-7), metastatic breast cancer (MDA-MB-231), ovarian cancer (OVCAR-3), resistant cancer (NCI-RES/ADR) cells and mouse macrophage (RAW 264.7) cell lines. Hemocompatibility of ZrP NPs was evaluated with human red blood cells. Simulated body fluid (SBF) of pH 7.4 was used to determine the in vitro release of doxorubicin from DOX:ZrP NPs. Cellular uptake and in vitro cytotoxicity studies of DOX:ZrP NPs were determined in MDA-MB-231. The ZrP nanomaterial can be prepared in the 100-200 nm size range with a platelet-like shape. The ZrP NPs themselves are biocompatible, hemocompatible and showed no toxicity to the macrophage cells. ZrP NPs can intercalate high loads (35% w/w) of doxorubicin between their layers. The release of DOX was sustained for about 2 weeks. DOX:ZrP NPs showed higher cellular uptake and increased cytotoxicity than free DOX in MDA-MB-231 cells. ZrP NPs are highly biocompatible, can intercalate large amounts of drugs and sustain the release of drugs. ZrP NPs improved the cellular uptake and cytotoxicity of DOX to MDA-MB-231 cells. ZrP NPs are promising nanocarriers for drug delivery in cancer therapy.The objective of this study was to evaluate the biocompatibility of zirconium phosphate (ZrP) nanoplatelets (NPs), and their use in drug delivery. ZrP and doxorubicin-intercalated ZrP (DOX:ZrP) NPs were characterized by using X-Ray Powder Diffraction (XRPD), Thermogravimetric Analysis (TGA), Transmission Electron Micrography (TEM), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Biocompatibility of ZrP NPs was evaluated in human embryonic kidney (HEK-293), breast cancer (MCF-7), metastatic breast cancer (MDA-MB-231), ovarian cancer (OVCAR-3), resistant cancer (NCI-RES/ADR) cells and mouse macrophage (RAW 264.7) cell lines. Hemocompatibility of ZrP NPs was evaluated with human red blood cells. Simulated body fluid (SBF) of pH 7.4 was used to determine the in vitro release of doxorubicin from DOX:ZrP NPs. Cellular uptake and in vitro cytotoxicity studies of DOX:ZrP NPs were determined in MDA-MB-231. The ZrP nanomaterial can be prepared in the 100-200 nm size range with a platelet-like shape. The ZrP NPs themselves are biocompatible, hemocompatible and showed no toxicity to the macrophage cells. ZrP NPs can intercalate high loads (35% w/w) of doxorubicin between their layers. The release of DOX was sustained for about 2 weeks. DOX:ZrP NPs showed higher cellular uptake and increased cytotoxicity than free DOX in MDA-MB-231 cells. ZrP NPs are highly biocompatible, can intercalate large amounts of drugs and sustain the release of drugs. ZrP NPs improved the cellular uptake and cytotoxicity of DOX to MDA-MB-231 cells. ZrP NPs are promising nanocarriers for drug delivery in cancer therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr34242e

Structural environments of incompatible elements in silicate glass/melt systems: I. Zirconium at trace levels

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Ponader, Carl W.; Brown, Gordon E., Jr.

1991-06-01

The structural environments of trace levels (2˜000 ppm) of Zr 4+ in several silicate glasses were examined as a function of melt composition and polymerization using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Glass compositions investigated were albite (NaAlSi 3O 8: AB) and a peralkaline composition (Na 3.3AlSi 7O 17: PR)- Zirconium was added to the oxide-carbonate mix prior to melting in the form of ZrO 2 (baddeleyite). A second set of Zr-silicate glasses containing 2000 ppm Zr and 1.0 to 2.4 wt% halogens (F as NaF and Cl as NaCl) was also synthesized. These included the Zr-AB and Zr-PR base-glass compositions as well as Zr-sodium trisilicate composition (Na2Si 3O 7: TS). In all glasses studied, Zr is mainly 6-coordinated by oxygen atoms ( d[Zr-O] ˜2.07 ± 0.01 Å). In the most polymerized glass (AB), a small but significant amount of Zr was also found to occur in 8-coordinated sites ( d[Zr-O] ˜2.22 Å). No clear evidence for F or Cl complexes of Zr was observed in any of the halogen-containing glasses. The regularity of the Zr site increases in the series AB < TS ˜PR. We attribute this change to an increase in the number of non-bridging oxygens in the first-coordination sphere of Zr related to the depolymerizing effects of halogens and/or sodium. Minor but significant interactions of Zr with the tetrahedral network were observed ( d[Zr-{Si, Al}] ˜3.65-3.71 Å ± 0.03 Å), which are consistent with Zr-O-{Si, Al} angles close to 160-170°, as in catapleiite (Na 2ZrSi 3O 9 · 2H 2O). Intermediaterange order, as reflected by the presence and number of second-neighbor {Si, Al} around Zr, increases significantly with increasing melt polymerization. The local environment around Zr is more strongly influenced by bonding requirements than by the network topology of the melt. Stabilization of zirconium in 6-coordinated sites in relatively depolymerized melts should act to decrease the crystal-melt partition coefficients of Zr and may explain the normally incompatible character of Zr during magmatic differentiation. The presence of Zr in sites of higher coordination (ZrO 8) in highly polymerized melts could be a precursor to the crystallization of zircon from such melts and thus may explain why Zr becomes a more compatible element, especially in the latest stages of magmatic differentiation.

PZT thin film actuated elastic fin micromotor.

PubMed

Dubois, M A; Muralt, P

1998-01-01

A piezoelectric elastic fin micromotor based on a PbZr(0.53 )Ti(0.47)O(3) thin film driving a micromachined silicon membrane was fabricated and studied. The stator was characterized by interferometry, and a laser set-up was used to measure the angular velocity and acceleration of the motor. The torque, the output power, and the efficiency of the device were extracted from these measurements. Values up to 1020 rpm and 0.94 microNm were observed for the velocity and the torque, respectively, which would be sufficient for a wristwatch application. The present version exhibited an efficiency of 0.17%, which could theoretically be increased to 4.8%

Self-ion irradiation effects on mechanical properties of nanocrystalline zirconium films

DOE PAGES

Wang, Baoming; Haque, M. A.; Tomar, Vikas; ...

2017-07-13

Zirconium thin films were irradiated at room temperature with an 800 keV Zr + beam using a 6 MV HVE Tandem accelerator to 1.36 displacement per atom damage. Freestanding tensile specimens, 100 nm thick and 10 nm grain size, were tested in-situ inside a transmission electron microscope. Significant grain growth (>300%), texture evolution, and displacement damage defects were observed. Here, stress-strain profiles were mostly linear elastic below 20 nm grain size, but above this limit the samples demonstrated yielding and strain hardening. Experimental results support the hypothesis that grain boundaries in nanocrystalline metals act as very effective defect sinks.

Phase transformations in the hematite-metal system during mechanical alloying

NASA Astrophysics Data System (ADS)

Kozlov, K. A.; Shabashov, V. A.; Litvinov, A. V.; Sagaradze, V. V.

2009-04-01

Mössbauer spectroscopy and X-ray diffraction are used to show that the phase transformations in hematite α-Fe2O3-metal ( M = Fe, Ni, Ti, Zr) powder mixtures induced by severe cold plastic deformation in ball mills occur via the formation of M-Fe-O solid solutions, redox reactions with the reduction of metallic iron, and the formation of secondary M x O y oxides and M x Fe y intermetallics. Mechanical activation in a ball mill is compared to that under high-pressure shear in Bridgman anvils. The transformations that take place in a ball mill are found to have several stages and to be accelerated.

Synthesis, characterization, and photocatalytic application of Pd/ZrO2 and Pt/ZrO2

NASA Astrophysics Data System (ADS)

Saeed, Khalid; Sadiq, Mohammad; Khan, Idrees; Ullah, Saleem; Ali, Nauman; Khan, Adnan

2018-05-01

Zirconia-supported palladium (Pd/ZrO2) and Zirconia-supported platinum (Pt/ZrO2) nanoparticles (NPs) are synthesized from their precursors via impregnation technique. The Pd/ZrO2 and Pt/ZrO2 NPs were analyzed via SEM and EDX, while the study of indigo disulfonate dye degradation was carried out by UV/VIS spectrophotometer. The SEM micrographs illustrated that the Pd and Pt NPs were well placed on ZrO2 surface. The Pd/ZrO2 and Pt/ZrO2 NPs were also employed as photocatalysts for the photodegradation of indigo disulfonate in an aqueous medium under UV-light irradiation. The photodegradation study presented that Pd/ZrO2 and Pt/ZrO2 NPs degraded 96 and 94% of indigo disulfonate in 14 h, respectively. The effect of pH of medium and catalyst dosage and efficiency of recovered Pd/ZrO2 and Pt/ZrO2 NPs on the photocatalytic degradation were also studied. It was also found that the maximum degradation of dye was found at pH 10 (95-97%) and at 0.02 g weight (40.28%).

Nanocrystalline Fe/Zr alloys: preparation by using mechanical alloying and mechanical milling processes

NASA Astrophysics Data System (ADS)

Rodríguez, V. A. Peña; Medina, J. Medina; Marcatoma, J. Quispe; Ayala, Ch. Rojas; Landauro, C. V.; Baggio-Saitovitch, E. M.; Passamani, E. C.

2011-11-01

Nanocrystalline Fe/Zr alloys have been prepared after milling for 9 h the mixture of elemental Fe and Zr powders or the arc-melting produced Fe2Zr alloy by using mechanical alloying and mechanical milling techniques, respectively. X-ray and Mössbauer results of the Fe and Zr powders, mechanically alloyed, suggest that amorphous Fe2Zr phase and \\upalpha-Fe(Zr) nanograins have been produced with relative concentrations of 91% and 9%, respectively. Conversely, the results of the mechanically milled Fe2Zr alloy indicate that nanograins of the Fe2Zr alloy have been formed, surrounded by a magnetic inter-granular phase that are simultaneously dispersed in a paramagnetic amorphous phase.

Composition dependences of crystal structure and electrical properties of epitaxial Pb(Zr,Ti)O3 films grown on Si and SrTiO3 substrates

NASA Astrophysics Data System (ADS)

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.

Spin differences in the Zr 90 compound nucleus induced by ( p , p ' ) , ( p , d ) , and ( p , t ) surrogate reactions

DOE PAGES

Ota, S.; Burke, J. T.; Casperson, R. J.; ...

2015-11-04

Here, the effect of the production mechanism on the decay of a compound nucleus is investigated. The nucleus 90Zr was produced by three different reactions, namely 90Zr (p,p') 90Zr, 91Zr (p,d) 90Zr, and 92Zr (p,t) 90Zr , which served as surrogate reactions for 89Zr (n,γ). The spin-parity (J π) distributions of the states populated by these reactions were studied to investigate the surrogate reaction approach, which aims at indirectly determining cross sections for compound-nuclear reactions involving unstable targets such as 89Zr. Discrete γ rays, associated with transitions in 90Zr and 89Zr, were measured in coincidence with light ions for scatteringmore » angles of 25°–60° and 90Zr excitation energies extending above the neutron separation energy. The measured transition systematics were used to gain insights into the J π distributions of 90Zr. The 90Zr (p,p') reaction was found to produce fewer γ rays associated with transitions involving high spin states (J = 6–8 ℏ) than the other two reactions, suggesting that inelastic scattering preferentially populates states in 90Zr that have lower spins than those populated in the transfer reactions investigated. The γ-ray production was also observed to vary by factors of 2–3 with the angle at which the outgoing particle was detected. These findings are relevant to the application of the surrogate reaction approach.« less

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

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

A First-Principles Study on the Vibrational and Electronic Properties of Zr-C MXenes

NASA Astrophysics Data System (ADS)

Wang, Chang-Ying; Guo, Yong-Liang; Zhao, Yuan-Yuan; Zeng, Guang-Li; Zhang, Wei; Ren, Cui-Lan; Han, Han; Huai, Ping

2018-03-01

Within the framework of density functional theory calculations, the structural, vibrational, and electronic properties of Zr n C n - 1 (n = 2, 3, and 4) and their functionalized MXenes have been investigated. We find that the most stable configurations for Zr-C MXene are the ones that the terminal groups F, O, and OH locate on the common hollow site of the superficial Zr layer and its adjacent C layer. F and OH-terminated Zr 3 C 2 and Zr 4 C 3 have small imaginary acoustic phonon branches around Γ point while the others have no negative phonon modes. The pristine MXenes (Zr 2 C, Zr 3 C 2 and Zr 4 C 3 ) are all metallic with large DOS contributed by the Zr atom at the Fermi energy. When functionalized by F, O and OH, new hybridization states appear and the DOS at the Fermi level are reduced. Moreover, we find that their metallic characteristic increases with an increase in n. For (Zr n C n - 1 )O 2, Zr 2 CO 2 is a semiconductor, Zr 3C2O2 is a semimetal, and Zr 4 C 3O2 becomes a metal. Supported by the National Natural Science Foundation of China under Grant Nos. 11605273, 21571185, U1404111, 11504089, 21501189, 21676291, the Shanghai Municipal Science and Technology Commission 16ZR1443100, the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA02040104)

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

NASA Astrophysics Data System (ADS)

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

2006-07-01

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

Implementation of metal-friendly EAM/FS-type semi-empirical potentials in HOOMD-blue: A GPU-accelerated molecular dynamics software

NASA Astrophysics Data System (ADS)

Yang, Lin; Zhang, Feng; Wang, Cai-Zhuang; Ho, Kai-Ming; Travesset, Alex

2018-04-01

We present an implementation of EAM and FS interatomic potentials, which are widely used in simulating metallic systems, in HOOMD-blue, a software designed to perform classical molecular dynamics simulations using GPU accelerations. We first discuss the details of our implementation and then report extensive benchmark tests. We demonstrate that single-precision floating point operations efficiently implemented on GPUs can produce sufficient accuracy when compared against double-precision codes, as demonstrated in test simulations of calculations of the glass-transition temperature of Cu64.5Zr35.5, and pair correlation function g (r) of liquid Ni3Al. Our code scales well with the size of the simulating system on NVIDIA Tesla M40 and P100 GPUs. Compared with another popular software LAMMPS running on 32 cores of AMD Opteron 6220 processors, the GPU/CPU performance ratio can reach as high as 4.6. The source code can be accessed through the HOOMD-blue web page for free by any interested user.

Signal of Acceleration and Physical Mechanism of Water Cycle in Xinjiang, China

PubMed Central

Feng, Guo-Lin; Wu, Yong-Ping

2016-01-01

Global warming accelerates water cycle with features of regional difference. However, little is known about the physical mechanism behind the phenomenon. To reveal the links between water cycle and climatic environment, we analyzed the changes of water cycle elements and their relationships with climatic and environmental factors. We found that when global warming was significant during the period of 1986-2003, the precipitation in Tarim mountains as well as Xinjiang increased rapidly except for Tarim plains, which indicated that there existed a signal of acceleration for water cycle in Xinjiang. The speed of water cycle is mainly affected by altitude, latitude, longitude, slope direction, and the most fundamental element is temperature. Moreover, according to Clausius-Kela Bai Lung relation, we found that the climate change induced the increase of temperature and accelerated the local water cycle only for the wet places. Our results provide a possible physical mechanisms of water cycle and thus well link the climate change to water circulation. PMID:27907078

Signal of Acceleration and Physical Mechanism of Water Cycle in Xinjiang, China.

PubMed

Feng, Guo-Lin; Wu, Yong-Ping

2016-01-01

Global warming accelerates water cycle with features of regional difference. However, little is known about the physical mechanism behind the phenomenon. To reveal the links between water cycle and climatic environment, we analyzed the changes of water cycle elements and their relationships with climatic and environmental factors. We found that when global warming was significant during the period of 1986-2003, the precipitation in Tarim mountains as well as Xinjiang increased rapidly except for Tarim plains, which indicated that there existed a signal of acceleration for water cycle in Xinjiang. The speed of water cycle is mainly affected by altitude, latitude, longitude, slope direction, and the most fundamental element is temperature. Moreover, according to Clausius-Kela Bai Lung relation, we found that the climate change induced the increase of temperature and accelerated the local water cycle only for the wet places. Our results provide a possible physical mechanisms of water cycle and thus well link the climate change to water circulation.

Thermodynamic Analysis and Growth of Zirconium Carbide by Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Wei, Sun; Hua, Hao Zheng; Xiang, Xiong

Equilibrium calculations were used to optimize conditions for the chemical vapor deposition of zirconium carbide from zirconium halide + CxHy+H2+Ar system. The results show the CVD-ZrC phase diagram is divided into ZrC+C, ZrC and ZrC+Zr zones by C, Zr generating lines. For the same mole of ZrCl4 reactant, it needs higher concentration of CH4 to generate single ZrC phase than that of C3H6. Using these calculations as a guide, single-phase cubic zirconium carbide coatings were deposited onto graphite substrate.

Observations of a Cast Cu-Cr-Zr Alloy

NASA Technical Reports Server (NTRS)

Ellis, David L.

2006-01-01

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

Structure of the intermediate Zr/sub 2/Br/sub 2/H by neutron diffraction and its structural and bonding relationships to other phases

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

Wijeyesekera, S.D.; Corbett, J.D.

1986-12-17

The structures of the isomorphous Zr/sub 2/Br/sub 2/D and Zr/sub 2/Br/sub 2/H have been solved and refined by using Rietveld techniques on pulsed neutron diffraction data obtained from the powdered samples at 14 K (C2/m, a = 19.437 (3) A, b = 3.5253 (4) A, c = 5.9036 (6) A, ..beta.. = 100.98 (1)/sup 0/, R(profile)/R(expected) = 2.44 for the deuteride). The structure consists of layers sequenced Br-Zr-H-H-Zr-Br and arranged such that hydride lies in zigzag chains of distorted metal tetrahedra (or butterflies) (d(Zr-D) = 2.03-2.20 A; d(D-D) = 2.93 A). The structure is intermediate between ZrBr (ccp) and ZrBrHmore » (hcp heavy atoms, double H in trigonal-antiprismatic interstices) and can be generated by concerted intraslab slippage from either. The hemihydride effectively retains most of the strong Zr-Zr bonding of the ZrBr parent while tetrahedral bonding of hydrogen to metal is gained that is absent in ZrBrH. The energetics associated with the contrasting structures of YClH/sub x/ (ZrBr type) and ZrBrH are considered in terms of the results of extended-Hueckel band calculations. 25 references, 7 figures, 3 tables.« less

Effect of the ZrCl4 concentration in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt and the electrolysis current density on the quantitative composition of UO2-ZrO2 cathode deposits. Calculation and experiment

NASA Astrophysics Data System (ADS)

Krotov, V. E.; Filatov, E. C.

2014-08-01

A method is proposed for calculating the ZrO2 content in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt. Based on the known composition of a UO2-ZrO2 cathode deposit, the content is calculated at current densities of 0.08-0.63 A/cm2 and ZrCl4 concentrations of 0-12.3 wt %. The calculated and experimental ZrO2 contents in UO2-ZrO2 cathode deposits are in qualitative and adequate quantitative agreement.

Properties and rapid low-temperature consolidation of nanocrystalline Fe-ZrO2 composite by pulsed current activated sintering

NASA Astrophysics Data System (ADS)

Kang, Hyun-Su; Ko, In-Yong; Yoon, Jin-Kook; Doh, Jung-Mann; Hong, Kyung-Tae; Shon, In-Jin

2011-02-01

Nanopowders of Fe and ZrO2 were synthesized from Fe2O3 and Zr by high-energy ball milling. The powder sizes of Fe and ZrO2 were 70 nm and 12 nm, respectively. Highly dense nanostructured 4/3Fe-ZrO2 composite was consolidated by a pulsed current activated sintering method within 1 minute from the mechanically synthesized powders (Fe-ZrO2) and horizontal milled Fe2O3+Zr powders under the 1 GPa pressure. The grain sizes of Fe and ZrO2 in the composite were calculated. The average hardness and fracture toughness values of nanostuctured 4/3Fe-ZrO2 composite were investigated.

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

PubMed

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

2017-07-01

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

Standardized methods for the production of high specific-activity zirconium-89

PubMed Central

Holland, Jason P.; Sheh, Yiauchung; Lewis, Jason S.

2009-01-01

Zirconium-89 is an attractive metallo-radionuclide for use in immunoPET due to the favorable decay characteristics. Standardized methods for the routine production and isolation of high purity and high specific-activity 89Zr using a small cyclotron are reported. Optimized cyclotron conditions reveal high average yields of 1.52 ± 0.11 mCi/μA·h at a proton beam energy of 15 MeV and current of 15 μA using a solid, commercially available 89Y-foil target (0.1 mm, 100% natural abundance). 89Zr was isolated in high radionuclidic and radiochemical purity (>99.99%) as [89Zr]Zr-oxalate by using a solid-phase hydroxamate resin with >99.5% recovery of the radioactivity. The effective specific-activity of 89Zr was found to be in the range 5.28 – 13.43 mCi/μg (470 – 1195 Ci/mmol) of zirconium. New methods for the facile production of [89Zr]Zr-chloride are reported. Radiolabeling studies using the trihydroxamate ligand desferrioxamine B (DFO) gave 100% radiochemical yields in <15 min. at room temperature and in vitro stability measurements confirmed that [89Zr]Zr-DFO is stable with respect to ligand dissociation in human serum for >7 days. Small-animal PET imaging studies have demonstrated that free 89Zr(IV) ions administered as [89Zr]Zr-chloride accumulate in the liver whilst [89Zr]Zr-DFO is excreted rapidly via the kidneys within <20 min. These results have important implication for the analysis of immunoPET imaging of 89Zr-labeled monoclonal antibodies. The detailed methods described can be easily translated to other radiochemistry facilities and will facilitate the use of 89Zr in both basic science and clinical investigations. PMID:19720285

Effects of pretreatment processes for Zr electrorefining of oxidized Zircaloy-4 cladding tubes

NASA Astrophysics Data System (ADS)

Hwa Lee, Chang; Lee, Yoo Lee; Jeon, Min Ku; Choi, Yong Taek; Kang, Kweon Ho; Park, Geun Il

2014-06-01

The effect of pretreatment processes for the Zr electrorefining of oxidized Zircaloy-4 cladding tubes is examined in LiCl-KCl-ZrCl4 molten salts at 500 °C. The cyclic voltammetries reveal that the Zr dissolution kinetics is highly dependent on the thickness of a Zr oxide layer formed at 500 °C under air atmosphere. For the Zircaloy-4 tube covered with a 1 μm thick oxide layer, the Zr dissolution process is initiated from a non-stoichiometric Zr oxide surface through salt treatment at an open circuit potential in the molten salt electrolyte. The Zr dissolution of the samples in the middle range of oxide layer thickness appears to be more effectively derived by the salt treatment coupled with an anodic potential application at an oxidation potential of Zr. A modification of the process scheme offers an applicability of Zr electrorefining for the treatment of oxidized cladding hull wastes.

Chemical vapor transport of layer structured crystal β-ZrNCl

NASA Astrophysics Data System (ADS)

Ohashi, M.; Yamanaka, S.; Hattori, M.

1988-12-01

A layer structured compound β-ZrNCl is transported to a higher temperature zone with the aid of ammonium chloride as the transporting agent in the temperature range of 823-1173 K. The transport mechanism can be explained by the formation of a volatile compound (NH 4) 2ZrCl 6: β- ZrNCl+5 NH4Cl→( NH4) 2ZrCl6+4 NH3. The measurements of the vapor pressure and the mass spectrum revealed that (NH 4) 2ZrCl 6 decomposed congruently according to the equation: ( NH4) 2ZrCl6( s)→ ZrCl4( g)+2 NH3( g)+2 HCl( g) The enthalpy change for the decomposition was determined to be 533 kJ/mol. By combining the above two equations, a simplified transport equation is derived: β- ZrNCl( s)+3 HCl( g)⇌ ZrCl4( g+ NH3( g) .

Research on self-propagating high temperature synthesis prepared ZrC-ZrB2 composite ceramic

NASA Astrophysics Data System (ADS)

Yong, Cheng; Xunjia, Su; Genliang, Hou; YaKun, Xing

2013-03-01

ZrC-ZrB2 composite ceramic material is prepared by self-propagating high temperature synthesis, using Zr powders, CrO2 powders and Al powders as raw materials. Samples are studied by XRD and SEM, the results show that: ZrC-ZrB2 composite ceramic is attained after self-propagating high-temperature reaction, with Zr+ B4C as the main reactive system, and which is added respectively different content (CrO3 + Al) system. The study finds that the ceramic composite products are mainly composed of ZrC and ZrB2 phase, and other subphase. Compared to the main reactive system composite ceramic, composite ceramic grains grow up obviously, after introduction of the highly exothermic system (CrO3 + Al) in the main reactive system, and with the gradual increase of the content (CrO3 + Al).

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

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

Newnham, I.E.

1959-05-01

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

Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

DOE PAGES

Ma, Wen; Senanayake, Sanjaya D.; Herbert, F. William; ...

2015-03-11

The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+, Zr 2+, and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. As a result, themore » presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.« less

Zirconium phosphate reinforced short side chain perflurosulfonic acid membranes for medium temperature proton exchange membrane fuel cell application

NASA Astrophysics Data System (ADS)

Casciola, Mario; Cojocaru, Paula; Donnadio, Anna; Giancola, Stefano; Merlo, Luca; Nedellec, Yannig; Pica, Monica; Subianto, Surya

2014-09-01

Composite membranes, made of an 830 equivalent weight short-side-chain perfluorosulfonic acid ionomer and containing up to 10 wt% zirconium phosphate (ZrP), are prepared by casting dispersions of ZrP nanoparticles in the ionomer solution. 30 μm thick composite membranes are characterized by transmission electron microscopy, X-ray diffraction, stress-strain tests, conductivity measurements, water uptake and ion-exchange capacity determinations, as well as fuel cell tests in H2/air. In comparison with the neat ionomer, the tensile modulus (E) and the yield stress (Y) of the composite membranes increase with the ZrP content, both at room temperature (ΔE/E up to +75%, ΔY/Y up to +47%) and at 80 °C/70% relative humidity (ΔE/E up to +64%, ΔY/Y up to +103%). Despite their lower hydration, the composite membranes are as conductive as the neat ionomer and the in-plane conductivity at 110 °C ranges from ∼0.005 S cm-1 at 25% RH to 0.14 S cm-1 at 90% RH. The fuel cell performance of a catalyst coated membrane loaded with 10 wt% ZrP is weakly affected by temperature in the range 80-110 °C. The peak power density decreases from 0.36 W cm-2, at 80 °C, to 0.28 W cm-2 at 110 °C, where the composite membrane performs better than the neat ionomer.

Eco-friendly films prepared from plantain flour/PCL blends under reactive extrusion conditions using zirconium octanoate as a catalyst.

PubMed

Gutiérrez, Tomy J; Alvarez, Vera A

2017-12-15

Plantain flour (Musa ssp., group AAB, sub-group clone Harton)/poly(ε-caprolactone) (PCL) blends, containing glycerol as a plasticizer, were prepared by reactive extrusion (REx) in a twin-screw extruder using zirconium octanoate (Zr(Oct) 4 ) as a catalyst, followed by thermo-compression molding for film development. The films were then characterized in terms of their: infrared (FTIR) spectra, water solubility, thermogravimetric (TGA) curves, differential scanning calorimetry (DSC) thermograms, and X-ray diffraction (XDR) diffractograms, as well as their microstructural, mechanical and antimicrobial properties in order to (1) compare the effects of PCLs with two different molecular weights (M w ) on the characteristics of the plantain flour/PCL blends, and (2) determine whether using Zr(Oct) 4 in the production of active composite polymer materials improves their properties. The plantain flour/PCL blends were all developed successfully. The higher M w PCL gave more hydrophobic and thermally stable films with improved mechanical properties. The addition of the Zr(Oct) 4 catalyst to the plantain flour/PCL blends also resulted in films with similar characteristics to those described above, due to the cross-linking of the polymers. In addition, the films containing the catalyst showed antimicrobial activity against Escherichia coli O157:H7 and Staphylococcus aureus indicating a dual effect of Zr(Oct) 4 , and making it an attractive alternative for the development of active films. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fabrication of novel metal ion imprinted xanthan gum-layered double hydroxide nanocomposite for adsorption of rare earth elements.

PubMed

Iftekhar, Sidra; Srivastava, Varsha; Hammouda, Samia Ben; Sillanpää, Mika

2018-08-15

The work focus to enhance the properties of xanthan gum (XG) by anchoring metal ions (Fe, Zr) and encapsulating inorganic matrix (M@XG-ZA). The fabricated nanocomposite was characterized by Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX), Fourier Transform Infrared Spectroscopy (FTIR), surface area (BET) and zeta potential analysis. The adsorption of Sc, Nd, Tm and Yb was investigated after screening of synthesized materials in detail to understand the influence of pH, contact time, temperature and initial REE (rare earth element) concentration both in single and multicomponent system via batch adsorption. The adsorption mechanism was verified by FTIR, SEM and elemental mapping. The SEM images of Zr@XG-ZA demonstrate scutes structure, which disappeared after adsorption of REEs. The maximum adsorption capacities were 132.30, 14.01, 18.15 and 25.73 mg/g for Sc, Nd, Tm and Yb, respectively. The adsorption efficiency over Zr@XG-ZA in multicomponent system was higher than single system and the REEs followed the order: Sc > Yb > Tm > Nd. The Zr@XG-ZA demonstrate good adsorption behavior for REEs up to five cycles and then it can be used as photocatalyst for the degradation of tetracycline. Thus, the work adds a new insight to design and preparation of efficient bifunctional adsorbents from sustainable materials for water purification. Copyright © 2018 Elsevier Ltd. All rights reserved.

A new series of mixed oxalates MM'(C 2O 4) 3(H 2O) 3· nH 2O (M = Cd, Hg, Pb; M' = Zr, Hf) based on eight-fold coordinated metals: Synthesis, crystal structure from single-crystal and powder diffraction data and thermal behaviour

NASA Astrophysics Data System (ADS)

Gavilan, Elisabeth; Audebrand, Nathalie; Jeanneau, Erwann

2007-11-01

A new series of mixed oxalates MM'(C 2O 4) 3(H 2O) 3· nH 2O (M = Cd, Hg, Pb; M' = Zr, Hf) has been prepared. The crystal structures have been solved from single-crystal and powder diffraction data. The isotypical compounds crystallise with space group P2 1/ c (No. 14). The structures consist of honeycomb layers formed by eight-fold coordinated metals, in a distorted square-based antiprismatic conformation, connected together via oxalates which act as bidentate ligands and also as monodentate in a less-common μ3-bridging mode. Sheets are built from two shifted honeycomb layers and linked to each other through a hydrogen network. The resulting frameworks of the series display a compact two-dimensional arrangement of polyhedra MO 8 and M'O 8. Weakly-bonded water molecules are located between and within the sheets. Comparisons with the 3D open-framework structures of related metal oxalates are made. The dehydration processes occur in three or four steps. The final products are MO, M'O 2 and PbZrO 3 resulting from the sublimation of PbO in air. The size of PbZrO 3 crystallites, which are on average isotropic, has been evaluated to be 1055 Å from line-broadening analysis.

Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst.

PubMed

Fang, Guo-Yong; Xu, Li-Na; Wang, Lai-Guo; Cao, Yan-Qiang; Wu, Di; Li, Ai-Dong

2015-01-01

Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst

NASA Astrophysics Data System (ADS)

Fang, Guo-Yong; Xu, Li-Na; Wang, Lai-Guo; Cao, Yan-Qiang; Wu, Di; Li, Ai-Dong

2015-02-01

Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

Homogeneity of Pb(Zr ,Ti)O3 thin films by chemical solution deposition: Extended x-ray absorption fine structure spectroscopy study of zirconium local environment

NASA Astrophysics Data System (ADS)

Malic, Barbara; Arcon, Iztok; Kodre, Alojz; Kosec, Marija

2006-09-01

Sols for Pb(Zr0.53Ti0.47)O3 (PZT) thin films were prepared by 2-methoxyethanol route from lead acetate, titanium n-propoxide, and zirconium n-propoxide, the latter either unmodified or modified with acetylacetone or acetic acid in a 2/1 molar ratio and deposited on sapphire (0001). By Zr K-edge extended x-ray absorption fine structure (EXAFS) spectroscopy, the structural changes in the Zr local environment, induced by the addition of the two modifiers, were followed from the synthesis of the PZT sol to the transition to the amorphous film. In the unmodified PZT sol segregation of Zr species occurs from the original dimers present in the Zr propoxide solution in 2-methoxyethanol. The immediate neighborhood of Zr atoms changes markedly at the transition from the sol to the amorphous film: the local structure around Zr atoms is similar to the one found in tetragonal zirconia particles. The modification of Zr propoxide with acetylacetone in 2-methoxyethanol results in Zr monomers. In PZT sol, clustering of Zr species is observed continuing into the amorphous film. By modification with acetic acid the original dimeric structure of the Zr precursor is retained in the PZT sol and further in the amorphous film. Selective modification of Zr propoxide with acetic acid therefore results in a more homogeneous distribution of Zr atoms in the PZT sol and amorphous film than in both as-received and acetylacetone-modified Zr propoxide.

Examination of Multiphase (Zr,Ti)(V,Cr,Mn,Ni)2 Ni-MH Electrode Alloys: Part II. Solid-State Transformation of the Interdendritic B2 Phase

NASA Astrophysics Data System (ADS)

Bendersky, L. A.; Wang, K.; Boettinger, W. J.; Newbury, D. E.; Young, K.; Chao, B.

2010-08-01

Solidification microstructure of multicomponent (Zr,Ti)-Ni-(V,Cr,Mn,Co) alloys intended for use as negative electrodes in Ni-metal hydride (Ni-MH) batteries was studied in Part I of this series of articles. Part II of the series examines the complex internal structure of the interdendritic grains formed by solid-state transformation and believed to play an important role in the electrochemical charge/discharge characteristics of the overall alloy composition. By studying one alloy, Zr21Ti12.5V10Cr5.5Mn5.1Co5.0Ni40.2Al0.5Sn0.3, it is shown that the interdendritic grains solidify as a B2 (Ti,Zr)44(Ni,TM)56 phase, and then undergo transformation to Zr7Ni10-type, Zr9Ni11-type, and martensitic phases. The transformations obey orientation relationships between the high-temperature B2 phase and the low-temperature Zr-Ni-type intermetallics, and consequently lead to a multivariant structure. The major orientation relationship for the orthorhombic Zr7Ni10 type is [011]Zr7Ni10//[001]B2; (100)Zr7Ni10//(100)B2. The orientation relationship for the tetragonal Zr9Ni11 type is [001]Zr9Ni11//[001]B2; (130)Zr9Ni11//(100)B2. Binary Ni-Zr and ternary Ti-Ni-Zr phase diagrams were used to rationalize the formation of the observed domain structure.

An Assessment of Binary Metallic Glasses: Correlations Between Structure, Glass Forming Ability and Stability (Preprint)

DTIC Science & Technology

2011-07-01

comparisons for the combined influence of R, Fα and chemistry, the Cu- Zr , Zr - Cu, Ni- Zr , Zr -Ni, Cu-Hf, Hf-Cu, Zr -Be and Ni- Nb systems are considered. These... Zr and Cu-Hf have R ≈ 1.248 for ខ> structures; Ni- Nb represents ᝿> structures with R ≈ 1.116 and Zr -Be has a radius ratio near R* = 0.710 for a...similar fits, with regression coefficients from 0.66 to 0.93. The limited data for Cu- Hf, Hf-Cu and Ni- Nb fit within the scatter shown for the Cu- Zr

Study on preferred crystal orientations of Mg-Zr-O composite protective layer in AC-PDP

NASA Astrophysics Data System (ADS)

Bingang, G.; Chunliang, L.; Zhongxiao, S.; Liu, L.; Yufeng, F.; Xing, X.; Duowang, F.

2006-11-01

In order to study the preferred crystal orientations of Mg-Zr-O composite protective layers in PDP, Mg-Zr-O composite protective layers were deposited by Electron-beam Evaporator using (MgO+ZrO{2}) powder mixture as evaporation source material. X-ray diffractometer (XRD) was used to determine preferred crystal orientations of Mg-Zr-O composite protective layers, surface morphologies of films were analyzed by FESEM and voltage characteristics were examined in a testing macroscopic discharge cell of AC-PDP. On the basis of experimental analysis, the influence of oxide addition and deposition conditions on preferred orientations of Mg-Zr-O composite protective layers were investigated. The results showed that the preferred orientations of Mg-Zr-O films were determined by lattice distortion of MgO crystal. The deposition conditions have great effects on the preferred orientations of Mg-Zr-O films. The preferred orientations affect voltage characteristics through affecting surface morphology of Mg-Zr-O films. A small amount of Zr solution in MgO can decrease firing voltage compared with using pure MgO film. Firing voltage is closely related with the [ ZrO{2}/(MgO+ZrO{2})] ratio of evaporation source materials.

Mechanical properties of zirconium alloys and zirconium hydrides predicted from density functional perturbation theory

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Tikare, Veena; ...

2015-10-13

Here, the elastic properties and mechanical stability of zirconium alloys and zirconium hydrides have been investigated within the framework of density functional perturbation theory. Results show that the lowest-energy cubic Pn-3m with combining macron]m polymorph of δ-ZrH 1.5 does not satisfy all the Born requirements for mechanical stability, unlike its nearly degenerate tetragonal P4 2/ mcm polymorph. Elastic moduli predicted with the Voigt–Reuss–Hill approximations suggest that mechanical stability of α-Zr, Zr-alloy and Zr-hydride polycrystalline aggregates is limited by the shear modulus. According to both Pugh's and Poisson's ratios, α-Zr, Zr-alloy and Zr-hydride polycrystalline aggregates can be considered ductile. The Debyemore » temperatures predicted for γ-ZrH, δ-ZrH 1.5 and ε-ZrH 2 are θ D = 299.7, 415.6 and 356.9 K, respectively, while θ D = 273.6, 284.2, 264.1 and 257.1 K for the α-Zr, Zry-4, ZIRLO and M5 matrices, i.e. suggesting that Zry-4 possesses the highest micro-hardness among Zr matrices.« less

Calculation and synthesis of ZrC by CVD from ZrCl4-C3H6-H2-Ar system with high H2 percentage

NASA Astrophysics Data System (ADS)

Zhu, Yan; Cheng, Laifei; Ma, Baisheng; Gao, Shuang; Feng, Wei; Liu, Yongsheng; Zhang, Litong

2015-03-01

A thermodynamic calculation about the synthesis of ZrC from the ZrCl4-C3H6-H2-Ar system with high percentage of H2 was performed using the FactSage thermochemical software. According to the calculation, ZrC coating was synthesized on graphite substrates and carbon fibers by a low pressure chemical vapor deposition (LPCVD) process, and growth rate of the ZrC coating as a function of temperature was investigated. The surface diagrams of condensed-phases in this system were expressed as the functions of the deposition temperature, total pressure and reactant ratios of ZrCl4/(ZrCl4 + C3H6), H2/(ZrCl4 + C3H6), and the yield of the products was determined by the diagrams. A smooth and dense ZrC coating could be synthesized under the instruction of the calculated parameters. The morphologies of the ZrC coatings were significantly affected by temperature and gases flux. The deposition temperature is much lower than that from the ZrCl4-CH4-H2-Ar system.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Cavitation resistance of surface composition "Steel-Ni-TiNi-TiNiZr-cBNCo", formed by High-Velocity Oxygen-Fuel spraying

NASA Astrophysics Data System (ADS)

Blednova, Zh. M.; Dmitrenko, D. V.; Balaev, E. U. O.

2018-01-01

The object of the study is a multilayered surface composition "Steel - a Multicomponent material with Shape Memory Effect - a wear-resistant layer" under conditions of cavitation effects in sea water. Multicomponent TiNi-based coatings with addition of alloying elements such as Zr in an amount up to 10% mass, allow to create a composite material with a gradient of properties at the interface of layers, which gives new properties to coatings and improves their performance significantly. The use of materials with shape memory effect (SME) as surface layers or in the composition of surface layered compositions allows to provide an effective reaction of materials to the influence of external factors and adaptation to external influences. The surface composite layer cBN-10%Co has high hardness and strength, which ensures its resistance to shock cyclic influences of collapsing caverns. The increased roughness of the surface of a solid surface composite in the form of strong columnar structures ensures the crushing of vacuum voids, redistributing their effect on the entire surface, and not concentrating them in certain zones. In addition, the gradient structure of the multilayer composite coating TiNi-Ti33Ni49Zr18-cBN-10%Co Co makes it possible to create conditions for the relaxation of stresses created by the variable impact load of cavitation caverns and the manifestation of compensating internal forces due to thermo-elastic martensitic transformations of SME materials. The cavitation resistance of the coating TiNi-Ti33Ni49Zr18-cBN-10%Co according to the criterion of mass wear is 15-20 times higher than that of the base material without coating and 10-12 times higher than that of the TiNi-TiNiZr coating. The proposed architecture of the multifunctional gradient composition, "steel-Ni-TiNi- Ti33Ni49Zr18-cBN-10%Co", each layer of which has its functional purpose, allows to increase the service life of parts operating under conditions of cavitation-fatigue loading in corrosive environments.

Solvothermal crystallization of nanocrystals of metal oxides

NASA Astrophysics Data System (ADS)

Furukawa, S.; Amino, H.; Iwamoto, S.; Inoue, M.

2008-07-01

Solvothermal crystallization of the hydroxide gels obtained by hydrolysis of alkoxides (Zr, Ta, Nb, ln, Sn, Ti and Al) was examined. Nanocrystals having high surface areas (SBET > 170 m2 g-1) were obtained except for the product derived from indium isopropoxide. The effect of water in organic solvent upon the crystallinity of the product was investigated. The increase in the activity of water by using high concentration of alkoxide or intentional addition of water to the solvothermal medium led to crystal growth of the products. In contrast, decrease in activity of water by adding ethylene glycol before solvothermal treatment caused a decrease in crystallinity of the product.

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

PubMed

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

2008-04-15

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

Characterization of hot-pressed short ZrO{sub 2} fiber toughened ZrB{sub 2}-based ultra-high temperature ceramics

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

Lin, Jia, E-mail: 2013113205@xmut.edu.cn; Huang, Yu; Zhang, Houan

2014-09-15

Two different ZrB{sub 2}-based ultra-high temperature ceramics were produced by hot pressing: ZrB{sub 2} + 20 vol.% SiC particle + 15 vol.% ZrO{sub 2} fiber and ZrB{sub 2} + 20 vol.% SiC whisker + 15 vol.% ZrO{sub 2} fiber. The microstructures were analyzed by using transmission electron microscopy and high-resolution transmission electron microscopy. It was shown that a clean interface without any impurities was identified in ZrB{sub 2}-based hybrid ceramics with SiC whiskers and ZrO{sub 2} fibers, which would significantly improve the toughening mechanism. The results of high-resolution transmission electron microscopy showed that stacking faults in SiC whiskers resulted frommore » an insertion of a (111) layer, which would be one of the main reasons for material anisotropy. However, the interface between the SiC particle and ZrO{sub 2} fiber was found to be ambiguous in ZrB{sub 2}-based hybrid ceramics with SiC particles and ZrO{sub 2} fibers due to the slight reaction. The orientation relationship between t-ZrO{sub 2} and m-ZrO{sub 2} phases obeyed the classical correspondence: (100){sub m}//(100){sub t} and [001]{sub m}//〈001〉{sub t}, which further verified the feasibility of phase transformation toughening mechanism. - Highlights: • ZrB{sub 2}-based ceramics toughened by short ZrO{sub 2} fiber are characterized by TEM and HRTEM. • The orientation relationship of t- and m-ZrO{sub 2} are (100){sub m}//(100){sub t}, [001]{sub m}//〈001〉{sub t} • The clean interface without any impurities leads to improve the toughening mechanism.« less

Archaeological Investigations of Three Sites within the Wipp Core Area, Eddy County, New Mexico.

DTIC Science & Technology

1985-06-01

soils occasionally contain small playas, which hold water, generally quite saline , for short periods of time. Soils of this association are used for...be substituted for rhubarb (Castetter 1935:50). Portulacaceae Po 1*Maca. gZr Small purslane .E. Le Retose purslane Portulaca is a very important

Investigation and Synthesis of High Temperature and Increased Stiffness RSP Aluminum Alloys

DTIC Science & Technology

1988-11-30

under argon atmosphere using a water cooled copper crucible and a non-consumable tungsten electrode. This pro- cedure was followed in previous studies... copper crucible and a non-consum- able tungsten electrode. This procedure was followed in previous studies of Al-Zr-V (5,7). * Presently with National

Synthesis of Carboxylate Cp*Zr(IV) Species: Toward the Formation of Novel Metallocavitands.

PubMed

Daigle, Maxime; Bi, Wenhua; Légaré, Marc-André; Morin, Jean-François; Fontaine, Frédéric-Georges

2015-06-01

With the intent of generating metallocavitands isostructural to species [(CpZr)3(μ(3)-O)(μ(2)-OH)3(κO,O,μ(2)-O2C(R))3](+), the reaction of Cp*2ZrCl2 and Cp*ZrCl3 with phenylcarboxylic acids was carried out. Depending on the reaction conditions, five new complexes were obtained, which consisted of Cp*2ZrCl(κ(2)-OOCPh) (1), (Cp*ZrCl(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2 (2), [(Cp*Zr(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2(μ(2)-OH)2]·Et2O (3·Et2O), [[Cp*ZrCl2](μ-Cl)(μ-OH)(μ-O2CC6H5)[Cp*Zr

Preparation of novel alginate based anion exchanger from Ulva japonica and its application for the removal of trace concentrations of fluoride from water.

PubMed

Paudyal, Hari; Pangeni, Bimala; Inoue, Katsutoshi; Kawakita, Hidetaka; Ohto, Keisuke; Ghimire, Kedar Nath; Alam, Shafiq

2013-11-01

A green seaweed, Ulva japonica, was modified by loading multivalent metal ions such as Zr(IV) and La(III) after CaCl2 cross-linking to produce metal loaded cross-linked seaweed (M-CSW) adsorbents, which were characterized by elemental analysis, functional groups identification, and metal content determination. Maximum sorption potential for fluoride was drastically increased after La(III) and Zr(IV) loading, which were evaluated as 0.58 and 0.95 mmol/g, respectively. Loaded fluoride was quantitatively desorbed by using dilute alkaline solution for its regeneration. Mechanism of fluoride adsorption was inferred in terms of ligand exchange reaction between hydroxyl ion on co-ordination sphere of the loaded metal ions of M-CSW and fluoride ion in aqueous solution. Application of M-CSW for the treatment of actual waste plating solution exhibited successful removal of fluoride to clear the effluent and environmental standards in Japan, suggesting high possibility of its application for the treatment of fluoride rich waste water. Copyright © 2013 Elsevier Ltd. All rights reserved.

Bias polarization study of steam electrolysis by composite oxygen electrode Ba0.5Sr0.5Co0.8Fe0.2O3-δ/BaCe0.4Zr0.4Y0.2O3-δ

NASA Astrophysics Data System (ADS)

Yang, Tao; Shaula, Aliaksandr; Pukazhselvan, D.; Ramasamy, Devaraj; Deng, Jiguang; da Silva, E. L.; Duarte, Ricardo; Saraiva, Jorge A.

2017-12-01

The polarization behavior of Ba0.5Sr0.5Co0.8Fe0.2O3-δ-BaCe0.4Zr0.4Y0.2O3-δ (BSCF-BCZY) electrode under steam electrolysis conditions was studied in detail. The composite oxygen electrode supported by BCZY electrolyzer has been assessed as a function of temperature (T), water vapor partial pressures (pH2O), and bias polarization voltage for electrodes of comparable microstructure. The Electrochemical impedance spectra show two depressed arcs in general without bias polarization. And the electrode resistance became smaller with the increase of the bias polarization under the same water vapor partial pressures. The total resistance of the electrode was shown to be significantly affected by temperature, with the same level of pH2O and bias polarization voltage. This result highlights BSCF-BCZY as an effective oxygen electrode under moderate polarization and pH2O conditions.

Surface Alloying of SUS 321 Chromium-Nickel Steel by an Electron-Plasma Process

NASA Astrophysics Data System (ADS)

Ivanov, Yu. F.; Teresov, A. D.; Petrikova, E. A.; Krysina, O. V.; Ivanova, O. V.; Shugurov, V. V.; Moskvin, P. V.

2017-07-01

The mechanisms of forming nanostructured, nanophase layers are revealed and analyzed in austenitic steel subjected to surface alloying using an electron-plasma process. Nanostructured, nanophase layers up to 30 μm in thickness were formed by melting of the film/substrate system with an electron beam generated by a SOLO facility (Institute of High Current Electronics, SB RAS), Tomsk), which ensured crystallization and subsequent quenching at the cooling rates within the range 105-108 K/s. The surface was modified with structural stainless steel specimens (SUS 321 steel). The film/substrate system (film thickness 0.5 μm) was formed by a plasma-assisted vacuum-arc process by evaporating a cathode made from a sintered pseudoalloy of the following composition: Zr - 6 at.% Ti - 6 at.% Cu. The film deposition was performed in a QUINTA facility equipped with a PINK hot-cathode plasma source and DI-100 arc evaporators with accelerated cooling of the process cathode, which allowed reducing the size and fraction of the droplet phase in the deposited film. It is found that melting of the film/substrate system (Zr-Ti-Cu)/(SUS 321 steel) using a high-intensity pulsed electron beam followed by the high-rate crystallization is accompanied by the formation of α-iron cellular crystallization structure and precipitation of Cr2Zr, Cr3C2 and TiC particles on the cell boundaries, which as a whole allowed increasing microhardness by a factor of 1.3, Young's modulus - by a factor of 1.2, wear resistance - by a factor of 2.7, while achieving a three-fold reduction in the friction coefficient.

Deformation behaviors of Cu29Zr32Ti15Al5Ni19 high entropy bulk metallic glass during nanoindentation

NASA Astrophysics Data System (ADS)

Fang, Qihong; Yi, Ming; Li, Jia; Liu, Bin; Huang, Zaiwang

2018-06-01

The deformation behaviors of Cu29Zr32Ti15Al5Ni19 high entropy bulk metallic glass (HE-BMG) during the nanoindentation are presented via the large-scale molecular dynamics (MD) simulations. The indentation tests are carried out using spherical rigid indenter to investigate the microstructural evolution on the mechanical properties of HE-BMGs in terms of shear strain, indentation force, and surface morphology as well as radial distribution function (RDF). Based on the Hertzian fitting the load-displacement curve, HE-BMG Cu29Zr32Ti15Al5Ni19 has the Young's modulus of 93.1 GPa and hardness of 8.8 GPa. The indentation force requiring for the continual increasing contacted area between the indenter and the substrate goes up with the increasing of indentation depth. In addition, the symmetrical distribution of atomic displacement reveals the isotropic of HE-BMG after the indentation treatment. In the deformation region, the Al element would lead to the serious fluctuation in the first peak of RDF, which is much stronger than the other elements. The severe distortion from the atomic size difference maybe reduce the activation energy to the occurrence of shear deformation in HE-BMG, leading to the transition from brittle to ductile observed by the whole sliding of the local atom group. Through the indentation load-displacement curves at various temperatures, the softening of HE-BMG at high temperatures is in qualitative agreement with the experimental findings. Moreover, this effective strategy is used to accelerate the discovery of excellent mechanical properties of HE-BMGs by means of MD simulation, as well as understand the fundamental nanoindentation response of HE-BMGs.

Effects of Fabrication Parameters on Interface of Zirconia and Ti-6Al-4V Joints Using Zr55Cu30Al10Ni5 Amorphous Filler

NASA Astrophysics Data System (ADS)

Liu, Yuhua; Hu, Jiandong; Shen, Ping; Guo, Zuoxing; Liu, Huijie

2013-09-01

ZrO2 was brazed to Ti-6Al-4V using a Zr55Cu30Al10Ni5 (at.%) amorphous filler in a high vacuum at 1173-1273 K. The influences of brazing temperature, holding time, and cooling rate on the microstructure and shear strength of the joints were investigated. The interfacial microstructures can be characterized as ZrO2/ZrO2- x + TiO/(Zr,Ti)2(Cu,Ni)/(Zr,Ti)2(Cu,Ni,Al)/acicular Widmanstäten structure/Ti-6Al-4V. With the increase in the brazing temperature, both the thickness of the ZrO2- x + TiO layer and the content of the (Zr,Ti)2(Cu,Ni) phase decreased. However, the acicular Widmanstäten structure gradually increased. With the increase in the holding time, the (Zr,Ti)2(Cu,Ni) phase decreased, and the thickness of the (Zr,Ti)2(Cu,Ni) + (Zr,Ti)2(Cu,Ni,Al) layer decreased. In addition, cracks formed adjacent to the ZrO2 side under rapid cooling. The microstructures produced under various fabrication parameters directly influence the shear strength of the joints. When ZrO2 and Ti-6Al-4V couples were brazed at 1173 K for 10 min and then cooled at a rate of 5 K/min, the maximum shear strength of 95 MPa was obtained.

Ab initio molecular dynamics simulations of short-range order in Zr 50Cu 45Al 5 and Cu 50Zr 45Al 5 metallic glasses

DOE PAGES

Huang, Yuxiang; Huang, Li; Wang, C. Z.; ...

2016-02-01

Comparative analysis between Zr-rich Zr 50Cu 45Al 5 and Cu-rich Cu 50Zr 45Al 5 metallic glasses (MGs) is extensively performed to locate the key structural motifs accounting for their difference of glass forming ability. Here we adopt ab initio molecular dynamics simulations to investigate the local atomic structures of Zr 50Cu 45Al 5 and Cu 50Zr 45Al 5 MGs. A high content of icosahedral-related (full and distorted) orders was found in both samples, while in the Zr-rich MG full icosahedrons < 0,0,12,0 > is dominant, and in the Cu-rich one the distorted icosahedral orders, especially < 0,2,8,2 > and , are prominent. And the < 0,2,8,2 > polyhedra in Cu 50Zr 45Al 5 MG mainly originate from Al-centered clusters, while the < 0,0,12,0 > in Zr 50Cu 45Al 5 derives from both Cu-centered clusters and Al-centered clusters. These difference may be ascribed to the atomic size difference and chemical property between Cu and Zr atoms. Lastly, the relatively large size of Zr and large negative heat of mixing between Zr and Al atoms, enhancing the packing density and stability of metallic glass system, may be responsible for the higher glass forming ability of Zr 50Cu 45Al 5.« less

Ab initio molecular dynamics simulations of short-range order in Zr50Cu45Al5 and Cu50Zr45Al5 metallic glasses

NASA Astrophysics Data System (ADS)

Huang, Yuxiang; Huang, Li; Wang, C. Z.; Kramer, M. J.; Ho, K. M.

2016-03-01

Comparative analysis between Zr-rich Zr50Cu45Al5 and Cu-rich Cu50Zr45Al5 metallic glasses (MGs) is extensively performed to locate the key structural motifs accounting for their difference of glass forming ability. Here we adopt ab initio molecular dynamics simulations to investigate the local atomic structures of Zr50Cu45Al5 and Cu50Zr45Al5 MGs. A high content of icosahedral-related (full and distorted) orders was found in both samples, while in the Zr-rich MG full icosahedrons < 0,0,12,0> is dominant, and in the Cu-rich one the distorted icosahedral orders, especially < 0,2,8,2> and < 0,2,8,1> , are prominent. And the < 0,2,8,2> polyhedra in Cu50Zr45Al5 MG mainly originate from Al-centered clusters, while the < 0,0,12,0> in Zr50Cu45Al5 derives from both Cu-centered clusters and Al-centered clusters. These difference may be ascribed to the atomic size difference and chemical property between Cu and Zr atoms. The relatively large size of Zr and large negative heat of mixing between Zr and Al atoms, enhancing the packing density and stability of metallic glass system, may be responsible for the higher glass forming ability of Zr50Cu45Al5.

Biocompatible Ni-free Zr-based bulk metallic glasses with high-Zr-content: compositional optimization for potential biomedical applications.

PubMed

Hua, Nengbin; Huang, Lu; Chen, Wenzhe; He, Wei; Zhang, Tao

2014-11-01

The present study designs and prepares Ni-free Zr60+xTi2.5Al10Fe12.5-xCu10Ag5 (at.%, x=0, 2.5, 5) bulk metallic glasses (BMGs) by copper mold casting for potential biomedical application. The effects of Zr content on the in vitro biocompatibility of the Zr-based BMGs are evaluated by investigating mechanical properties, bio-corrosion behavior, and cellular responses. It is found that increasing the content of Zr is favorable for the mechanical compatibility with a combination of low Young's modulus, large plasticity, and high notch toughness. Electrochemical measurements demonstrate that the Zr-based BMGs are corrosion resistant in a phosphate buffered saline solution. The bio-corrosion resistance of BMGs is improved with the increase in Zr content, which is attributed to the enrichment in Zr and decrease in Al concentration in the surface passive film of alloys. Regular cell responses of mouse MC3T3-E1 cells, including cell adhesion and proliferation, are observed on the Zr-Ti-Al-Fe-Cu-Ag BMGs, which reveals their general biosafety. The high-Zr-based BMGs exhibit a higher cell proliferation activity in comparison with that of pure Zr and Ti-6Al-4V alloy. The effects of Zr content on the in vitro biocompatibility can be used to guide the future design of biocompatible Zr-based BMGs. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of different titanium zirconium implant surfaces on initial supragingival plaque formation.

PubMed

John, Gordon; Becker, Jürgen; Schwarz, Frank

2017-07-01

The aim of the current study was the evaluation of biofilm development on different implant surfaces. Initial biofilm formation was investigated on five different implant surfaces, machined titanium (MTi), modified machined acid-etched titanium (modMATi), machined titanium zirconium (MTiZr), modified machined and acid-etched titanium zirconium (modMATiZr) and sandblasted large grid and acid-etched titanium zirconium surface (SLATiZr) for 24 and 48 h. Biocompatibility was tested after tooth brushing of the samples via cell viability testing with human gingival fibroblasts. After 24 h of biofilm collection, mean plaque surface was detected in the following descending order: After 24 h: MTiZr > MTi > SLATiZr > modMATiZr > modMATi. Both M surfaces showed significant higher biofilm formation than the other groups. After 48 h: MTiZr > MTi > SLATiZr > modMATiZr > modMATi. After tooth brushing: SLATiZr > modMATi > modMATiZr > MTi > MTiZr. All native samples depicted significant higher cell viability than their corresponding surfaces after biofilm removal procedure. The TiZr groups especially the modMATiZr group showed slower and less biofilm formation. In combination with the good biocompatibility, both modMA surfaces seem to be interesting candidates for surfaces in transgingival implant design. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Development of Self-Healing Zirconium-Silicide Coatings for Improved Performance Zirconium-Alloy Fuel Cladding

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

Sridharan, Kumar; Mariani, Robert; Bai, Xianming

Zirconium-alloy fuel claddings have been used successfully in Light Water Reactors (LWR) for over four decades. However, under high temperature accident conditions, zirconium-alloys fuel claddings exhibit profuse exothermic oxidation accompanied by release of hydrogen gas due to the reaction with water/steam. Additionally, the ZrO 2 layer can undergo monoclinic to tetragonal to cubic phase transformations at high temperatures which can induce stresses and cracking. These events were unfortunately borne out in the Fukushima-Daiichi accident in in Japan in 2011. In reaction to such accident, protective oxidation-resistant coatings for zirconium-alloy fuel claddings has been extensively investigated to enhance safety margins inmore » accidents as well as fuel performance under normal operation conditions. Such surface modification could also beneficially affect fuel rod heat transfer characteristics. Zirconium-silicide, a candidate coating material, is particularly attractive because zirconium-silicide coating is expected to bond strongly to zirconium-alloy substrate. Intermetallic compound phases of zirconium-silicide have high melting points and oxidation of zirconium silicide produces highly corrosion resistant glassy zircon (ZrSiO 4) and silica (SiO 2) which possessing self-healing qualities. Given the long-term goal of developing such coatings for use with nuclear reactor fuel cladding, this work describes results of oxidation and corrosion behavior of bulk zirconium-silicide and fabrication of zirconium-silicide coatings on zirconium-alloy test flats, tube configurations, and SiC test flats. In addition, boiling heat transfer of these modified surfaces (including ZrSi 2 coating) during clad quenching experiments is discussed in detail.« less

First-principles study on stability, and growth strategies of small AlnZr (n=1-9) clusters

NASA Astrophysics Data System (ADS)

Li, Zhi; Zhou, Zhonghao; Wang, Hongbin; Li, Shengli; Zhao, Zhen

2016-09-01

The geometries, relative stability as well as growth strategies of the AlnZr (n=1-9) clusters are investigated with spin polarized density functional theory: BLYP. The results reveal that the AlnZr clusters are more likely to form the dense accumulation structures than the AlN (N=1-10) clusters. The average binding energies of AlnZr are higher than those of AlN clusters. The AlnZr (n=3, 5, and 7) clusters are more stable than others by the differences of the total binding energies. Mülliken population analysis for the AlnZr clusters shows that the electron's adsorption ability of Zr is slightly lower than that of Al except for AlZr cluster. Local peaks of the HOMO-LUMO gap curve are found at n=3, 5, and 7. The reaction energies of AlnZr are higher, which means that AlnZr clusters are easier to react with Al clusters. Zr atom preferential reacts with Al2 cluster. Local peaks of the magnetic dipole moments are found at n=2, 5, and 8.

Effect of annealing temperature on the structural, morphological, and mechanical properties of polycrystalline zirconium oxynitride composite films deposited by plasma focus device

NASA Astrophysics Data System (ADS)

Khan, Ijaz A.; Kashif, Muhammad; Farid, Amjad; Rawat, Rajdeep S.; Ahmad, Riaz

2017-12-01

In this article, we reveal the post deposition annealing effect on the structural, morphological, and mechanical properties of polycrystalline zirconium oxynitride (P-ZrON) composite films deposited for 40 focus shots using a plasma focus device. The development of Zr(101), ZrN(111), ZrN(200), Zr3N4(320), ZrN0.28(002), and m-ZrO2(200) diffraction peaks confirms the deposition of P-ZrON composite films. The peak intensity, crystallite size, dislocation density, compressive stress, and texture coefficient of the Zr3N4(320) plane and the microstructural features such as the shape, size and distribution of nanoparticles as well as the film compactness are influenced by the annealing temperature. Elemental analysis confirms the presence of Zr, N, and O in the deposited films. The microhardness of the P-ZrON composite film annealed at 500 °C is found to be 11.87 GPa which is 7.8 times that of virgin zirconium.

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

PubMed

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

2006-07-01

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

Zirconium Phosphate Nanoplatelet Potential for Anticancer Drug Delivery Applications.

PubMed

González, Millie L; Ortiz, Mayra; Hernández, Carmen; Cabán, Jennifer; Rodríguez, Axel; Colón, Jorge L; Báez, Adriana

2016-01-01

Zirconium phosphate (ZrP) nanoplatelets can intercalate anticancer agents via an ion exchange reaction creating an inorganic delivery system with potential for cancer treatment. ZrP delivery of anticancer agents inside tumor cells was explored in vitro. Internalization and cytotoxicity of ZrP nanoplatelets were studied in MCF-7 and MCF-10A cells. DOX-loaded ZrP nanoplatelets (DOX@ZrP) uptake was assessed by confocal (CLSM) and transmission electron microscopy (TEM). Cytotoxicity to MCF-7 and MCF-10A cells was determined by the MTT assay. Reactive Oxy- gen Species (ROS) production was analyzed by fluorometric assay, and cell cycle alterations and induction of apoptosis were analyzed by flow cytometry. ZrP nanoplatelets were localized in the endosomes of MCF-7 cells. DOX and ZrP nanoplatelets were co-internalized into MCF-7 cells as detected by CLSM. While ZrP showed limited toxicity to MCF-7 cells, DOX@ZrP was cytotoxic at an IC₅₀ similar to that of free DOX. Meanwhile, DOX lC₅₀ was significantly lower than the equivalent concentration of DOX@ZrP in MCF-10A cells. ZrP did not induce apoptosis in both cell lines. DOX and DOX@ZrP induced significant oxidative stress in both cell models. Results suggest that ZrP nanoplatelets are promising as carriers of anticancer agents into cancer cells.

Computational thermodynamics aided design of novel ferritic alloys

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

Yang, Ying; Chen, Tianyi; Tan, Lizhen

With the aid of computational thermodynamics, Ni was identified to suppress the liquidus temperature of Fe 2Zr and four Fe-Cr-Ni-Zr alloys were designed to study the Ni effect on the phase stability of Fe 2Zr laves_phase. These alloys were fabricated through traditional arc-metling, followed by annealing at 1000 C for 336 hours and 700 C for 1275 hours. The microstructure were examined and characterized by SEM BSE image, EDS compositional mapping and point scan, XRD and TEM analysis. The major results were summarized below: 1)For investigated alloys with 12wt% Cr, 3~6wt% Zr and 3~9 wt%Ni, the phases in equilibrium withmore » the BCC phase are C15_Laves phase, Fe 23Zr 6 phase. The volume fraction of intermetallic phases increases with Ni and Zr contents. 2)Instead of (Fe,Cr) 2Zr C14_Laves phase, Ni stabilizes the C15_Laves structure in Fe-Cr-Ni-Zr alloys by substituting Fe and Cr atoms with Ni atoms in the first sublattice. 3)Fe 23Zr 6, that is metastable in the Fe-Cr-Zr ternary, is also stabilized by Ni addition. 4)Ni 7Zr 2 phase was observed in samples with high Ni/Zr ratio. Extensive solubility of Fe was identified in the phase. The microstructural and composition results obtained from this study will be incorportated into the the Fe-Cr-Ni-Zr database. The current samples will be subjected to ion irradiaition to be compared with those results for Fe-Cr-Zr alloys. Additional alloys will be designed to form (Fe,Cr,Ni) 2Zr nanoprecipitates for further studies.« less

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

PubMed

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

2015-02-05

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

Role of Al2O3 in Sintering of Submicron Yttria-Stabilized ZrO2 Powders.

DTIC Science & Technology

1983-12-02

and dispersed by milling in a 60 : 40 alcohol : water solution, followed by pressing at 205 MPa. Significantly increased densification was obtained...the range 1100-1350-C, was investigated. The Al󈧘 was added as hydrated A1(OH)l and dispersed by milling in a 60 : 40 alcohol : water solution...124-130 (1975). 24. M. Heughebaert-Therasse, "Contribution a L’etude de L’evolution et du Frittage de la Zircone Stabilisee par Differents Oxydes , a

An infrared band system of the ZrCl molecule

NASA Astrophysics Data System (ADS)

Phillips, J. G.; Davis, S. P.; Galehouse, D. C.

1980-07-01

A series of infrared bands in the 0.97-1.15 micron region which is attributed to ZrCl is analyzed in light of the possibility that the bands may be observable in stellar spectra. Spectra of ZrO and ZrCl were produced by microwave discharge through a mixture of He, O and ZrCl4 and observed by Fourier transform spectrometer, resulting in the observation of 10 bands of the ZrCl system. Rotational quantum number assignments to the lines of the P and R branches observed are obtained and used to derive effective rotational constants for each substate, as well as zero-rotation origins of each subband. Shifts in wave numbers of rotational lines of the isotopes (Zr-92)(Cl-35)(Zr-94)(Cl-35) and (Zr-90)(Cl-37) relative to the more abundant (Zr-90)(Cl-35) are also observed. The observed molecular constants are shown to be in good agreement with those calculated in previous theoretical estimates.

Microstructural analysis of as-processed U-10 wt.%Mo monolithic fuel plate in AA6061 matrix with Zr diffusion barrier

NASA Astrophysics Data System (ADS)

Perez, E.; Yao, B.; Keiser, D. D., Jr.; Sohn, Y. H.

2010-07-01

For higher U-loading in low-enriched U-10 wt.%Mo fuels, monolithic fuel plate clad in AA6061 is being developed as a part of Reduced Enrichment for Research and Test Reactor (RERTR) program. This paper reports the first characterization results from a monolithic U-10 wt.%Mo fuel plate with a Zr diffusion barrier that was fabricated as part of a plate fabrication campaign for irradiation testing in the Advanced Test Reactor (ATR). Both scanning and transmission electron microscopy (SEM and TEM) were employed for analysis. At the interface between the Zr barrier and U-10 wt.%Mo, going from Zr to U(Mo), UZr 2, γ-UZr, Zr solid-solution and Mo 2Zr phases were observed. The interface between AA6061 cladding and Zr barrier plate consisted of four layers, going from Al to Zr, (Al, Si) 2Zr, (Al, Si)Zr 3 (Al, Si) 3Zr, and AlSi 4Zr 5. Irradiation behavior of these intermetallic phases is discussed based on their constituents. Characterization of as-fabricated phase constituents and microstructure would help understand the irradiation behavior of these fuel plates, interpret post-irradiation examination, and optimize the processing parameters of monolithic fuel system.

Synthesis of MAX Phases in the Zr-Ti-Al-C System.

PubMed

Tunca, Bensu; Lapauw, Thomas; Karakulina, Olesia M; Batuk, Maria; Cabioc'h, Thierry; Hadermann, Joke; Delville, Rémi; Lambrinou, Konstantina; Vleugels, Jozef

2017-03-20

This study reports on the synthesis and characterization of MAX phases in the (Zr,Ti) n+1 AlC n system. The MAX phases were synthesized by reactive hot pressing and pressureless sintering in the 1350-1700 °C temperature range. The produced ceramics contained large fractions of 211 and 312 (n = 1, 2) MAX phases, while strong evidence of a 413 (n = 3) stacking was found. Moreover, (Zr,Ti)C, ZrAl 2 , ZrAl 3 , and Zr 2 Al 3 were present as secondary phases. In general, the lattice parameters of the hexagonal 211 and 312 phases followed Vegard's law over the complete Zr-Ti solid solution range, but the 312 phase showed a non-negligible deviation from Vegard's law around the (Zr 0.33 ,Ti 0.67 ) 3 Al 1.2 C 1.6 stoichiometry. High-resolution scanning transmission electron microscopy combined with X-ray diffraction demonstrated ordering of the Zr and Ti atoms in the 312 phase, whereby Zr atoms occupied preferentially the central position in the close-packed M 6 X octahedral layers. The same ordering was also observed in 413 stackings present within the 312 phase. The decomposition of the secondary (Zr,Ti)C phase was attributed to the miscibility gap in the ZrC-TiC system.

Selection by current compliance of negative and positive bipolar resistive switching behaviour in ZrO2-x /ZrO2 bilayer memory

NASA Astrophysics Data System (ADS)

Huang, Ruomeng; Yan, Xingzhao; Morgan, Katrina A.; Charlton, Martin D. B.; (Kees de Groot, C. H.

2017-05-01

We report here a ZrO2-x /ZrO2-based bilayer resistive switching memory with unique properties that enables the selection of the switching mode by applying different electroforming current compliances. Two opposite polarity modes, positive bipolar and negative bipolar, correspond to the switching in the ZrO2 and ZrO2-x layer, respectively. The ZrO2 layer is proved to be responsible for the negative bipolar mode which is also observed in a ZrO2 single layer device. The oxygen deficient ZrO2-x layer plays the dominant role in the positive bipolar mode, which is exclusive to the bilayer memory. A systematic investigation of the ZrO2-x composition in the bilayer memory suggests that ZrO1.8 layer demonstrates optimum switching performance with low switching voltage, narrow switching voltage distribution and good cycling endurance. An excess of oxygen vacancies, beyond this composition, leads to a deterioration of switching properties. The formation and dissolution of the oxygen vacancy filament model has been proposed to explain both polarity switching behaviours and the improved properties in the bilayer positive bipolar mode are attributed to the confined oxygen vacancy filament size within the ZrO2-x layer.

Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces: Implications for catalysis and energy applications

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

Weck, Philippe F.; Juan, Pierre -Alexandre; Dingreville, Remi

The structures and properties of Ce 1–xZr xO 2 (x = 0–1) solid solutions, selected Ce 1–xZr xO 2 surfaces, and Ce 1–xZr xO 2/CeO 2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+ U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O 2 phases, indicating a significant rise in microhardness from CeO 2 to ZrO 2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO 2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energymore » of Ce 1–xZr xO 2(111)/CeO 2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce 1–xZr xO 2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce 1–xZr xO 2/CeO 2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce 0.25Zr 0.75O 2/CeO 2 interfaces.« less

Preparation, chromatographic evaluation and application of adenosine 5'-monophosphate modified ZrO2/SiO2 stationary phase in hydrophilic interaction chromatography.

PubMed

Wang, Qing; Luo, Zhi-Yuan; Ye, Mao; Wang, Yu-Zhuo; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

2015-02-27

The zirconia-coated silica (ZrO2/SiO2) material was obtained by coupling layer-by-layer (LbL) self-assembly method and sol-gel technology, to take dual advantages of the suitable porous structure of SiO2 and basic resistance of ZrO2. Adenosine 5'-monophosphate (5'-AMP) was then self-assembled onto ZrO2/SiO2 via Lewis acid-base interaction, generating 5'-AMP-ZrO2/SiO2. The chromatographic properties of 5'-AMP-ZrO2/SiO2 were systemically studied by evaluating the effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the 5'-AMP-ZrO2/SiO2 possessed hydrophilic interaction chromatographic (HILIC) property comprising hydrophilic, hydrogen-bonding, electrostatic and ion-exchange interactions. For basic analytes, the column efficiency of ZrO2/SiO2 and 5'-AMP-ZrO2/SiO2 was superior to the bare ZrO2, and different selectivity was obtained after the introduction of 5'-AMP. For acidic analytes, good resolution was obtained on 5'-AMP-ZrO2/SiO2 while the analysis failed on the bare ZrO2 column owing to strong adsorption. Hence, the proposed 5'-AMP-ZrO2/SiO2 had great potential in analyzing acidic compounds in HILIC mode. It was an extended application of ZrO2 based SP. Copyright © 2015 Elsevier B.V. All rights reserved.

A combined experimental and theoretical study on ethanol conversion to propylene over Y/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Wang, Fangfang; Xia, Wei; Mu, Xichuan; Chen, Kun; Si, Huimin; Li, Zhihao

2018-05-01

ZrO2-based catalysts doped with Y were prepared by co-precipitation method. The effect of yttrium modification on the selective conversion of bio-ethanol to propylene over ZrO2 catalysts was investigated. The physical and chemical properties of the catalysts were characterized by N2 adsorption-desorption method, temperature programmed desorption and X-ray diffraction. The maximum yield of propylene reached 44.0% over 0.03Y/ZrO2 catalyst. A coordination of acid-base properties accounts for the remarkable improvement of reaction activities over Y-doped ZrO2 catalysts in this investigation. On the basis of calculation results, it can be concluded that significant charge transfer occurs as a result of introduction of Y or O-vacancy. The adsorption of ethanol and propylene on perfect t-ZrO2 (1 0 1), defect t-ZrO2 (1 0 1) and Y/ZrO2 (1 0 1) surfaces were investigated with density functional theory (DFT). The adsorption for ethanol on Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces are more stable than that on perfect t-ZrO2 (1 0 1). On the defect t-ZrO2 (1 0 1) surface, ethanol dominantly absorbs at the O-vacancy site, indicating that O-vacancy becomes the favorable adsorption site. On the Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces, the adsorption energy of propylene decreases, which makes propylene desorb quickly after formation.

Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces: Implications for catalysis and energy applications

DOE PAGES

Weck, Philippe F.; Juan, Pierre -Alexandre; Dingreville, Remi; ...

2017-06-21

The structures and properties of Ce 1–xZr xO 2 (x = 0–1) solid solutions, selected Ce 1–xZr xO 2 surfaces, and Ce 1–xZr xO 2/CeO 2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+ U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O 2 phases, indicating a significant rise in microhardness from CeO 2 to ZrO 2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO 2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energymore » of Ce 1–xZr xO 2(111)/CeO 2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce 1–xZr xO 2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce 1–xZr xO 2/CeO 2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce 0.25Zr 0.75O 2/CeO 2 interfaces.« less

Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr6-Based Metal-Organic Frameworks.

PubMed

Moon, Su-Young; Wagner, George W; Mondloch, Joseph E; Peterson, Gregory W; DeCoste, Jared B; Hupp, Joseph T; Farha, Omar K

2015-11-16

The nerve agent VX is among the most toxic chemicals known to mankind, and robust solutions are needed to rapidly and selectively deactivate it. Herein, we demonstrate that three Zr6-based metal-organic frameworks (MOFs), namely, UiO-67, UiO-67-NH2, and UiO-67-N(Me)2, are selective and highly active catalysts for the hydrolysis of VX. Utilizing UiO-67, UiO-67-NH2, and UiO-67-N(Me)2 in a pH 10 buffered solution of N-ethylmorpholine, selective hydrolysis of the P-S bond in VX was observed. In addition, UiO-67-N(Me)2 was found to catalyze VX hydrolysis with an initial half-life of 1.8 min. This half-life is nearly 3 orders of magnitude shorter than that of the only other MOF tested to date for hydrolysis of VX and rivals the activity of the best nonenzymatic materials. Hydrolysis utilizing Zr-based MOFs is also selective and facile in the absence of pH 10 buffer (just water) and for the destruction of the toxic byproduct EA-2192.

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

PubMed

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

2009-05-18

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

Impact of the oxygen defects and the hydrogen concentration on the surface of tetragonal and monoclinic ZrO2 on the reduction rates of stearic acid on Ni/ZrO2

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

Foraita, Sebastian D.; Fulton, John L.; Chase, Zizwe A.

2015-02-02

The effect of the physicochemical properties of ZrO2 phases on the activity of Ni/ZrO2 catalysts for hydrodeoxygenation of stearic acid are described. A synergistic interaction between Ni and ZrO2 support was found. The effect is greatest for the monoclinic phase of ZrO2.

Radiation damage in cubic ZrO 2 and yttria-stabilized zirconia from molecular dynamics simulations

DOE PAGES

Aidhy, Dilpuneet S.; Zhang, Yanwen; Weber, William J.

2014-11-20

Here, we perform molecular dynamics simulation on cubic ZrO 2 and yttria-stabilized zirconia (YSZ) to elucidate defect cluster formation resulting from radiation damage, and evaluate the impact of Y-dopants. Interstitial clusters composed of split-interstitial building blocks, i.e., Zr-Zr or Y-Zr are formed. Moreover, oxygen vacancies control cation defect migration; in their presence, Zr interstitials aggregate to form split-interstitials whereas in their absence Zr interstitials remain immobile, as isolated single-interstitials. Y-doping prevents interstitial cluster formation due to sequestration of oxygen vacancies.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Al-centered icosahedral ordering in Cu46Zr46Al8 bulk metallic glass

NASA Astrophysics Data System (ADS)

Fang, H. Z.; Hui, X.; Chen, G. L.; Liu, Z. K.

2009-03-01

Icosahedral short-range order, of which Al atoms are caged in the center of icosahedra with Cu and Zr atoms being the vertices, has been evidenced in the Cu46Zr46Al8 glassy structure by ab initio molecular dynamics simulation. These Al-centered clusters distribute irregularly in the three-dimensional space and form a "backbone" structure of the Cu46Zr46Al8 glass alloy. It is suggested that this kind of local structural feature is attributed to the requirement of efficient dense packing and the chemical affinity between Zr-Zr, Zr-Al, and Cu-Zr atoms. Our calculated results are found to be in good agreement with the experimental data.

Predicting the solid state phase diagram for glass-forming alloys of copper and zirconium

NASA Astrophysics Data System (ADS)

Tang, C.; Harrowell, Peter

2012-06-01

The free energies of six crystal structures associated with Cu-Zr alloys—Cu (face centred cubic), Cu2Zr, Cu10Zr7, CuZr, CuZr2 and Zr (hexagonal close packed)—are calculated using the embedded atom potential of Mendelev et al (2009 Phil. Mag. 89 967). We find that the observed low temperature stability of the Cu10Zr7 and CuZr2 phases is not reproduced. Instead, the model predicts that the CuZr phase remains stable down to T = 0 K. This discrepancy is largely removed when the interaction potentials are cut off at a short distance, such as that used by Duan et al (2005 Phys. Rev. B 71 224208). We present evidence, however, that the cut-off distance necessary to achieve the change in phase stability results in pathological artefacts in the energetics of some crystal phases.

In situ ceramic layer growth on coated fuel particles dispersed in a zirconium metal matrix

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

Terrani, Kurt A; Silva, G W Chinthaka M; Kiggans, Jim

2013-01-01

The extent and nature of the chemical interaction between the outermost coating layer of coated fuel particles embedded in zirconium metal during fabrication of metal matrix microencapsulated fuels was examined. Various particles with outermost coating layers of pyrocarbon, SiC, and ZrC have been investigated in this study. ZrC-Zr interaction was least substantial while PyC-Zr reaction can be exploited to produce a ZrC layer at the interface in an in situ manner. The thickness of the ZrC layer in the latter case can be controlled by adjusting the time and temperature during processing. The kinetics of ZrC layer growth is significantlymore » faster from what is predicted using literature carbon diffusivity data in ZrC. SiC-Zr interaction is more complex and results in formation of various chemical phases in a layered aggregate morphology at the interface.« less

Effects of temperature, concentration, and uranium chloride mixture on zirconium electrochemical studies in LiClsbnd KCl eutectic salt

NASA Astrophysics Data System (ADS)

Hoover, Robert O.; Yoon, Dalsung; Phongikaroon, Supathorn

2016-08-01

Experimental studies were performed to provide measurement and analysis of zirconium (Zr) electrochemistry in LiClsbnd KCl eutectic salt at different temperatures and concentrations using cyclic voltammetry (CV). An additional experimental set with uranium chloride added into the system forming UCl3sbnd ZrCl4sbnd LiClsbnd KCl was performed to explore the general behavior of these two species together. Results of CV experiments with ZrCl4 show complicated cathodic and anodic peaks, which were identified along with the Zr reactions. The CV results reveal that diffusion coefficients (D) of ZrCl4 and ZrCl2 as the function of temperature can be expressed as DZr(IV) = 0.00046exp(-3716/T) and DZr(II) = 0.027exp(-5617/T), respectively. The standard rate constants and apparent standard potentials of ZrCl4 at different temperatures were calculated. Furthermore, the results from the mixture of UCl3 and ZrCl4 indicate that high concentrations of UCl3 hide the features of the smaller concentration of ZrCl4 while Zr peaks become prominent as the concentration of ZrCl4 increases.

Alternative Chelator for 89Zr Radiopharmaceuticals: Radiolabeling and Evaluation of 3,4,3-(LI-1,2-HOPO)

PubMed Central

2015-01-01

Zirconium-89 is an effective radionuclide for antibody-based positron emission tomography (PET) imaging because its physical half-life (78.41 h) matches the biological half-life of IgG antibodies. Desferrioxamine (DFO) is currently the preferred chelator for 89Zr4+; however, accumulation of 89Zr in the bones of mice suggests that 89Zr4+ is released from DFO in vivo. An improved chelator for 89Zr4+ could eliminate the release of osteophilic 89Zr4+ and lead to a safer PET tracer with reduced background radiation dose. Herein, we present an octadentate chelator 3,4,3-(LI-1,2-HOPO) (or HOPO) as a potentially superior alternative to DFO. The HOPO ligand formed a 1:1 Zr-HOPO complex that was evaluated experimentally and theoretically. The stability of 89Zr-HOPO matched or surpassed that of 89Zr-DFO in every experiment. In healthy mice, 89Zr-HOPO cleared the body rapidly with no signs of demetalation. Ultimately, HOPO has the potential to replace DFO as the chelator of choice for 89Zr-based PET imaging agents. PMID:24814511

Ca2+-exchange in layered zirconium orthophosphate, α-ZrP: Chemical study and potential application for zinc corrosion inhibition

NASA Astrophysics Data System (ADS)

Bouali, Imane; Rocca, Emmanuel; Veys-Renaux, Delphine; Rhouta, Benaissa; Khalil, Aziza; Aït Aghzzaf, Ahmed

2017-11-01

The control of the corrosion phenomenon occurring at the metal interface requires the development of new non-toxic anticorrosion additives. For this purpose, zirconium orthophosphate compounds (Zr(HPO4)2,H2O noted α-ZrP) were synthesized by both hydrothermal and refluxing methods The Ca2+-cationic exchange in the layered structure is kinetically favoured by low crystallinity of α-ZrP synthesized by refluxing process, and leads to the formation of CaZr(PO4)2,4H2O, noted Ca2+-ZrP. The H+/Ca2+ exchange mechanism is mainly triggered by acid-base considerations, and especially the pKa of α-ZrP/Ca2+-ZrP acid-base couple (evaluated to 2.5). Both compounds are acidic compounds by internal exchangeable H+ for α-ZrP and surface protons for Ca2+-ZrP, and can be used as potential inhibitors of zinc corrosion. Electrochemical measurements show that Ca2+-ZrP compounds dispersed in the NaCl electrolyte buffer the pH value over a long time and therefore allow controlling the corrosion rate of zinc.

Ferroelectricity in Pb 1+δZrO 3 Thin Films

DOE PAGES

Gao, Ran; Reyes-Lillo, Sebastian E.; Xu, Ruijuan; ...

2017-07-16

Antiferroelectric PbZrO 3 is being considered for a wide range of applications where the competition between centrosymmetric and noncentrosymmetric phases is important to the response. Here, we focus on the epitaxial growth of PbZrO 3 thin films and understanding the chemistry structure coupling in Pb 1+δ ZrO 3 (δ = 0, 0.1, 0.2). High-quality, single-phase Pb 1+δZrO 3 films are synthesized via pulsed-laser deposition. Though no significant lattice parameter change is observed in X-ray studies, electrical characterization reveals that while the PbZrO 3 and Pb 1.1ZrO 3 heterostructures remain intrinsically antiferroelectric, the Pb 1.2ZrO 3 heterostructures exhibit a hysteresis loopmore » indicative of ferroelectric response. Furthermore X-ray scattering studies reveal strong quarter-order diffraction peaks in PbZrO 3 and Pb 1.1ZrO 3 heterostructures indicative of antiferroelectricity, while no such peaks are observed for Pb 1.2ZrO 3 heterostructures. Density functional theory calculations suggest the large cation nonstoichiometry is accommodated by incorporation of antisite Pb-Zr defects, which drive the Pb 1.2ZrO 3 heterostructures to a ferroelectric phase with R3c symmetry. In the end, stabilization of metastable phases in materials via chemical nonstoichiometry and defect engineering enables a novel route to manipulate the energy of the ground state of materials and the corresponding material properties.« less

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

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

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

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

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

DOE PAGES

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

2016-08-26

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

Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles.

PubMed

Pan, Yonghe; Gao, Yan; Kong, Dandan; Wang, Guodong; Hou, Jianbo; Hu, Shanwei; Pan, Haibin; Zhu, Junfa

2012-04-10

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures. © 2012 American Chemical Society

Effects of Undercooling and Cooling Rate on Peritectic Phase Crystallization Within Ni-Zr Alloy Melt

NASA Astrophysics Data System (ADS)

Lü, P.; Wang, H. P.

2018-04-01

The liquid Ni-16.75 at. pct Zr peritectic alloy was substantially undercooled and containerlessly solidified by an electromagnetic levitator and a drop tube. The dependence of the peritectic solidification mode on undercooling was established based on the results of the solidified microstructures, crystal growth velocity, as well as X-ray diffraction patterns. Below a critical undercooling of 124 K, the primary Ni7Zr2 phase preferentially nucleates and grows from the undercooled liquid, which is followed by a peritectic reaction of Ni7Zr2+L → Ni5Zr. The corresponding microstructure is composed of the Ni7Zr2 dendrites, peritectic Ni5Zr phase, and inter-dendritic eutectic. Nevertheless, once the liquid undercooling exceeds the critical undercooling, the peritectic Ni5Zr phase directly precipitates from this undercooled liquid. However, a negligible amount of residual Ni7Zr2 phase still appears in the microstructure, indicating that nucleation and growth of the Ni7Zr2 phase are not completely suppressed. The micromechanical property of the peritectic Ni5Zr phase in terms of the Vickers microhardness is enhanced, which is ascribed to the transition of the peritectic solidification mode. To suppress the formation of the primary phase completely, this alloy was also containerlessly solidified in free fall experiments. Typical peritectic solidified microstructure forms in large droplets, while only the peritectic Ni5Zr phase appears in smaller droplets, which gives an indication that the peritectic Ni5Zr phase directly precipitates from the undercooled liquid by completely suppressing the growth of the primary Ni7Zr2 phase and the peritectic reaction due to the combined effects of the large undercooling and high cooling rate.

In-plane orientation and composition dependences of crystal structure and electrical properties of {100}-oriented Pb(Zr,Ti)O3 films grown on (100) Si substrates by metal organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Okamoto, Shoji; Sankara Rama Krishnan, P. S.; Okamoto, Satoshi; Yokoyama, Shintaro; Akiyama, Kensuke; Funakubo, Hiroshi

2017-10-01

In-plane orientation-controlled Pb(Zr x ,Ti1- x )O3 (PZT) films with a thickness of approximately 2 µm and a Zr/(Zr + Ti) ratio of 0.39-0.65 were grown on (100) Si substrates by pulsed metal-organic chemical vapor deposition (MOCVD). In-plane-oriented epitaxial PZT films and in-plane random fiber-textured PZT films with {100} out-of-plane orientation were grown on (100)c SrRuO3//(100)c LaNiO3//(100) CeO2//(100) YSZ//(100) Si and (100)c SrRuO3/(100)c LaNiO3/(111) Pt/TiO2/SiO2/(100) Si substrates, respectively. The effects of Zr/(Zr + Ti) ratio and in-plane orientation on the crystal structure, dielectric, ferroelectric, and piezoelectric properties of the films were systematically investigated. The X-ray diffraction measurement showed that the epitaxial PZT films had a higher volume fraction of (100) orientation than the fiber-textured PZT films in the tetragonal Zr/(Zr + Ti) ratio region. A large difference was not detected between the epitaxial films and the fiber-textured films for Zr/(Zr + Ti) ratio dependence of the dielectric constant, and remanent polarization. However, in the rhombohedral phase region [Zr/(Zr + Ti) = 0.65], coercive field was found to be 1.5-fold different between the epitaxial and fiber-textured PZT films. The maximum field-induced strains measured at 0-100 kV/cm by scanning atomic force microscopy were obtained at approximately Zr/(Zr + Ti) = 0.50 and were about 0.5 and 0.3% for the epitaxial and fiber-textured PZT films, respectively.

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

NASA Astrophysics Data System (ADS)

Atribak, Idriss; Guillén-Hurtado, Noelia; Bueno-López, Agustín; García-García, Avelina

2010-10-01

Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N 2 adsorption at -196 °C and XPS, and were tested for NO oxidation to NO 2. Among the different physico-chemical properties characterised, the surface composition seems to be the most relevant one in order to explain the NO oxidation capacity of these Ce-Zr catalysts. As a general trend, Ce-Zr catalysts with a cerium-rich surface, that is, high XPS-measured Ce/Zr atomic surface ratios, are more active than those with a Zr-enriched surface. The decrease in catalytic activity of the Ce-Zr mixed oxided upon calcinations at 800 °C with regard to 500 °C is mainly attributed to the decrease in Ce/Zr surface ratio, that is, to the surface segregation of Zr. The phase composition (cubic or t'' for Ce-rich compositions) seems not to be a direct effect on the catalytic activity for NO oxidation in the range of compositions tested. However, the formation of a proper solid solution prevents important surface segregation of Zr upon calcinations at high temperature. The effect of the BET surface area in the catalytic activity for NO oxidation of Ce-Zr mixed oxides is minor in comparison with the effect of the Ce/Zr surface ratio.

Microstructure and Mechanical Properties of W-ZrC Composites Synthesized by Reactive Melt Infiltration of Zr2Cu into Porous Preforms from Partially Carburized W Powders

NASA Astrophysics Data System (ADS)

Wang, Dong; Wang, Yu-Jin; Huo, Si-Jia; Zhao, Yan-Wei; Ouyang, Jia-Hu; Song, Gui-Ming; Zhou, Yu

2018-03-01

W-ZrC composites with different W contents from 48 to 73 vol.% have been synthesized by reactive melt infiltration of Zr2Cu melt into porous preforms from partially carburized W powders at 1300 °C for 1 h in vacuum. The influences of carbon content and porosity in the preforms on microstructure and mechanical properties of W-ZrC composites are investigated. Cold isostatic pressing followed by pre-sintering process is used to produce porous preforms with suitable porosities of 53.6-47% under a pressure of 100 MPa to allow sufficient penetration of Zr2Cu melt into the preforms. Small amounts of Cu-rich phases form in the synthesized W-ZrC composites after a complete reaction of y/2xZr2Cu(l) + WC y (s) = y/xZrC x (s) + W(s) + y/2xCu(l). These Cu-rich phases are distributed not only at the phase boundaries of W matrix and ZrC grains, but also in the interior of ZrC x grains. With decreasing W content from 73 to 48 vol.% in the W-ZrC composites, the flexural strength and fracture toughness increase from 519 to 657 MPa and from 9.1 to 10.6 MPa m1/2, respectively.

Influence of ZrO2 addition on the microstructure and discharge properties of Mg-Zr-O protective layers in alternating current plasma display panels

NASA Astrophysics Data System (ADS)

Guo, Bingang; Liu, Chunliang; Song, Zhongxiao; Liu, Liu; Fan, Yufeng; Xia, Xing; Fan, Duowang

2005-08-01

Mg-Zr-O protective layers for alternating current plasma display panels were deposited by e-beam evaporation. The effect of the ZrO2 addition on both the discharge properties [firing voltage Vf, minimum sustaining voltage Vs, and memory coefficient (MC)] and the microstructure of deposited Mg-Zr-O films were investigated. The results show that the film microstructure changes and the electron emission enhancement due to the ZrO2 addition are the main reasons for the improvements of the discharge properties of Mg-Zr-O films. A small amount of Zr solution in MgO under its solid solubility can effectively increase the outer-shell valence electron emission yield so as to decrease Vf and Vs compared with using a pure MgO protective layer. The ZrO2/(MgO +ZrO2) ratio has a great effect on the film surface conditions. Proper surface morphologies make a good contribution to obtain large MC in accordance with lower firing voltage.

Ion-enhanced chemical etching of ZrO2 in a chlorine discharge

NASA Astrophysics Data System (ADS)

Sha, Lin; Cho, Byeong-Ok; Chang, Jane P.

2002-09-01

Chlorine plasma is found to chemically etch ZrO2 thin films in an electron cyclotron resonance reactor, and the etch rate scaled linearly with the square root of ion energy at high ion energies with a threshold energy between 12-20 eV. The etching rate decreased monotonically with increasing chamber pressures, which corresponds to reduced electron temperatures. Optical emission spectroscopy and quadrupole mass spectrometry were used to identify the reaction etching products. No Zr, O, or ZrCl were detected as etching products, but highly chlorinated zirconium compounds (ZrCl2, ZrCl3, and ZrCl4) and ClO were found to be the dominant etching products. ZrCl3 was the dominant etching products at low ion energies, while ZrCl4 became dominant at higher ion energies. This is consistent with greater momentum transfer and enhanced surface chlorination, as determined by x-ray photoelectron spectroscopy, at increased ion energies. Several ion-enhanced chemical reactions are proposed to contribute to the ZrO2 etching. copyright 2002 American Vacuum Society.

Microstructure and mechanical behavior of Zr substrates coated with FeCrAl and Mo by cold-spraying

NASA Astrophysics Data System (ADS)

Park, Dong Jun; Kim, Hyun Gil; Jung, Yang Il; Park, Jung Hwan; Yang, Jae Ho; Koo, Yang Hyun

2018-06-01

FeCrAl and Mo layers were cold-sprayed onto a Zr surface, with the Mo layer introduced between the FeCrAl coating and the Zr matrix preventing high-temperature interdiffusion. Microstructural characterization of the first-deposited Mo layer and the Zr matrix immediately below the Mo/Zr interface was performed using transmission electron microscopy, and near-interface elemental distributions were obtained using energy-dispersive X-ray spectroscopy. The deformation of the coated Mo powder induced the formation of microbands and mechanically interlocked nanoscale structures. The mechanical behavior of Zr with a coating layer was compared with those characteristic of conventional Zr samples. The coated sample showed smaller strength reduction in the test conducted at elevated temperature. The hardness and fracture morphology of the Zr matrix near the interface region were investigated to determine the effect of impacting Mo particles on the matrix microstructure. The enhanced hardness and cleavage fracture morphology of the Zr matrix immediately below the Mo/Zr interface indicated the occurrence of localized deformation owing to Mo particle impact.

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

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

Effects of growth temperature on the properties of atomic layer deposition grown ZrO2 films

NASA Astrophysics Data System (ADS)

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

2003-07-01

Zirconium dioxide films are grown in 200 atomic layer deposition cycles. Zirconium tetrachloride (ZrCl4) and water (H2O) are used as precursors. A relatively high dielectric constant (κ=22), wide band gap, and conduction band offset (5.8 and 1.4 eV, respectively) indicate that zirconium dioxide is a most promising substitute for silicon dioxide as a dielectric gate in complementary metal-oxide-semiconductor devices. However, crystallization and chlorine ions in the films might affect their electrical properties. These ions are produced during atomic layer deposition in which the ZrCl4 precursor reacts with the growth surface. It is desirable to tune the composition, morphology, and structural properties in order to improve their benefit on the electrical ones. To address this issue it is necessary to properly choose the growth parameters. This work focuses on the effects of the growth temperature Tg. ZrO2 films are grown at different substrate temperatures: 160, 200, 250, and 350 °C. Relevant modification of the film structure with a change in substrate temperature during growth is expected because the density of reactive sites [mainly Si+1-(OH)-1 bonds] decreases with an increase in temperature [Y. B. Kim et al., Electrochem. Solid-State Lett. 3, 346 (2000)]. The amorphous film component, for example, that develops at Si+1-(OH)-1 sites on the starting growth surface, is expected to decrease with an increase in growth temperature. The size and consequences of film property modifications with the growth temperature are investigated in this work using x-ray diffraction and reflectivity, and atomic force microscopy. Time of flight-secondary ion mass spectrometry is used to study contaminant species in the films. From capacitance-voltage (CV) and current-voltage (IV) measurements, respectively, the dielectric constant κZrO2 and the leakage current are studied as a function of the film growth temperature.

Assessment of Rainfall Estimates Using a Standard Z-R Relationship and the Probability Matching Method Applied to Composite Radar Data in Central Florida

NASA Technical Reports Server (NTRS)

Crosson, William L.; Duchon, Claude E.; Raghavan, Ravikumar; Goodman, Steven J.

1996-01-01

Precipitation estimates from radar systems are a crucial component of many hydrometeorological applications, from flash flood forecasting to regional water budget studies. For analyses on large spatial scales and long timescales, it is frequently necessary to use composite reflectivities from a network of radar systems. Such composite products are useful for regional or national studies, but introduce a set of difficulties not encountered when using single radars. For instance, each contributing radar has its own calibration and scanning characteristics, but radar identification may not be retained in the compositing procedure. As a result, range effects on signal return cannot be taken into account. This paper assesses the accuracy with which composite radar imagery can be used to estimate precipitation in the convective environment of Florida during the summer of 1991. Results using Z = 30OR(sup 1.4) (WSR-88D default Z-R relationship) are compared with those obtained using the probability matching method (PMM). Rainfall derived from the power law Z-R was found to he highly biased (+90%-l10%) compared to rain gauge measurements for various temporal and spatial integrations. Application of a 36.5-dBZ reflectivity threshold (determined via the PMM) was found to improve the performance of the power law Z-R, reducing the biases substantially to 20%-33%. Correlations between precipitation estimates obtained with either Z-R relationship and mean gauge values are much higher for areal averages than for point locations. Precipitation estimates from the PMM are an improvement over those obtained using the power law in that biases and root-mean-square errors are much lower. The minimum timescale for application of the PMM with the composite radar dataset was found to be several days for area-average precipitation. The minimum spatial scale is harder to quantify, although it is concluded that it is less than 350 sq km. Implications relevant to the WSR-88D system are discussed.

Control water molecules across carbon-based nanochannels

NASA Astrophysics Data System (ADS)

Meng, Xianwen; Huang, Jiping

2018-01-01

Not Available Project supported by the Fundamental Research Funds for the Central Universities of China (Grant No. 2015QNA48), the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20150173), the Science and Technology Commission of Shanghai Municipality, China (Grant No. 16ZR1445100), and the National Natural Science Foudnation of China (Grant Nos. 11725521 and 11605285).

Dual-Function Metal-Organic Framework as a Versatile Catalyst for Detoxifying Chemical Warfare Agent Simulants.

PubMed

Liu, Yangyang; Moon, Su-Young; Hupp, Joseph T; Farha, Omar K

2015-12-22

The nanocrystals of a porphyrin-based zirconium(IV) metal-organic framework (MOF) are used as a dual-function catalyst for the simultaneous detoxification of two chemical warfare agent simulants at room temperature. Simulants of nerve agent (such as GD, VX) and mustard gas, dimethyl 4-nitrophenyl phosphate and 2-chloroethyl ethyl sulfide, have been hydrolyzed and oxidized, respectively, to nontoxic products via a pair of pathways catalyzed by the same MOF. Phosphotriesterase-like activity of the Zr6-containing node combined with photoactivity of the porphyrin linker gives rise to a versatile MOF catalyst. In addition, bringing the MOF crystals down to the nanoregime leads to acceleration of the catalysis.

The Effect of Gas Ion Bombardment on the Secondary Electron Yield of TiN, TiCN and TiZrV Coatings For Suppressing Collective Electron Effects in Storage Rings

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

Le Pimpec, F.; /PSI, Villigen; Kirby, R.E.

In many accelerator storage rings running positively charged beams, ionization of residual gas and secondary electron emission (SEE) in the beam pipe will give rise to an electron cloud which can cause beam blow-up or loss of the circulating beam. A preventative measure that suppresses electron cloud formation is to ensure that the vacuum wall has a low secondary emission yield (SEY). The SEY of thin films of TiN, sputter deposited Non-Evaporable Getters and a novel TiCN alloy were measured under a variety of conditions, including the effect of re-contamination from residual gas.

Influence of polarized PZT on the crystal growth of calcium phosphate

NASA Astrophysics Data System (ADS)

Sun, Xiaodan; Ma, Chunlai; Wang, Yude; Li, Hengde

2002-01-01

The effects of polarization on the crystallization of calcium phosphate are studied in this work. Crystals of calcium phosphate from saturated solution of hydroxyapatite (HA, Ca 10(PO 4) 6(OH) 2) were deposited on the surfaces of ferroelectric ceramics lead zirconate titanium (Pb(Ti,Zr)O 3, PZT). The results of the experiment demonstrated the acceleration effects of polarized PZT on the crystal growth of calcium phosphate. Furthermore, it is indicated that polarization also influenced the orientation of the deposited crystals due to the growth of a layer of (0 0 2) oriented octacalcium phosphate (OCP, Ca 8H 2(PO 4) 6·5H 2O) on the negatively charged surfaces of PZT.

Role of ZrO 2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts

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

Johnson, Gregory R.; Bell, Alexis T.

2015-11-17

The effects of Zr promotion on the structure and performance of Co-based Fischer-Tropsch synthesis (FTS) catalysts were investigated. Inclusion of Zr in the catalysts was found to increase the FTS turnover frequency and the selectivity to C 5+ hydrocarbons and to decrease the selectivity to methane under most operating conditions. These improvements to the catalytic performance are a function of Zr loading up to an atomic ratio of Zr/Co = 1.0, above which the product selectivity is insensitive to higher concentrations of the promoter. Characterization of the Co nanoparticles by different methods demonstrated that the optimal Zr loading corresponds tomore » half monolayer coverage of the Co surface by the promoter. Measurements of the rate of FTS at different pressures and temperatures established that the kinetics data for both the Zr-promoted and unpromoted catalysts are described by a two-parameter Langmuir-Hinshelwood expression. The parameters used to fit this rate law to the experimental data indicate that the apparent rate coefficient and the CO adsorption constant for the Zr-promoted catalysts are higher than those for the unpromoted catalyst. Elemental mapping by means of STEM-EDS provided evidence that Zr is highly dispersed over the catalyst surface and has limited preference for association with the Co nanoparticles. In situ X-ray absorption spectroscopy confirmed the absence of mixing between the Zr and Co in the nanoparticles. Here, these results suggest that Zr exists as a partial layer of ZrO 2 on the surface of the Co metal nanoparticles. Accordingly, it is proposed that Zr promotion effects originate from sites of enhanced activity at the interface between Co and ZrO 2. The possibility that ZrO 2 acts as a Lewis acid to assist in CO dissociation as well as to increase the ratio of CO to H adsorbed on the catalyst surface is discussed.« less

Effect of SiO 2-ZrO 2 supports prepared by a grafting method on hydrogen production by steam reforming of liquefied natural gas over Ni/SiO 2-ZrO 2 catalysts

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Song, In Kyu

SiO 2-ZrO 2 supports with various zirconium contents are prepared by grafting a zirconium precursor onto the surface of commercial Carbosil silica. Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of SiO 2-ZrO 2 supports on the performance of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts is investigated. SiO 2-ZrO 2 prepared by a grafting method serves as an efficient support for the nickel catalyst in the steam reforming of LNG. Zirconia enhances the resistance of silica to steam significantly and increases the interaction between nickel and the support, and furthermore, prevents the growth of nickel oxide species during the calcination process through the formation of a ZrO 2-SiO 2 composite structure. The crystalline structures and catalytic activities of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are strongly influenced by the amount of zirconium grafted. The conversion of LNG and the yield of hydrogen show volcano-shaped curves with respect to zirconium content. Among the catalysts tested, the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) sample shows the best catalytic performance in terms of both LNG conversion and hydrogen yield. The well-developed and pure tetragonal phase of ZrO 2-SiO 2 (Zr/Si = 0.54) appears to play an important role in the adsorption of steam and subsequent spillover of steam from the support to the active nickel. The small particle size of the metallic nickel in the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) catalyst is also responsible for its high performance.

Sulfate-reducing bacteria inhabiting natural corrosion deposits from marine steel structures.

PubMed

Païssé, Sandrine; Ghiglione, Jean-François; Marty, Florence; Abbas, Ben; Gueuné, Hervé; Amaya, José Maria Sanchez; Muyzer, Gerard; Quillet, Laurent

2013-08-01

In the present study, investigations were conducted on natural corrosion deposits to better understand the role of sulfate-reducing bacteria (SRB) in the accelerated corrosion process of carbon steel sheet piles in port environments. We describe the abundance and diversity of total and metabolically active SRB within five natural corrosion deposits located within tidal or low water zone and showing either normal or accelerated corrosion. By using molecular techniques, such as quantitative real-time polymerase chain reaction, denaturing gel gradient electrophoresis, and sequence cloning based on 16S rRNA, dsrB genes, and their transcripts, we demonstrated a clear distinction between SRB population structure inhabiting normal or accelerated low-water corrosion deposits. Although SRB were present in both normal and accelerated low-water corrosion deposits, they dominated and were exclusively active in the inner and intermediate layers of accelerated corrosion deposits. We also highlighted that some of these SRB populations are specific to the accelerated low-water corrosion deposit environment in which they probably play a dominant role in the sulfured corrosion product enrichment.

CuCrZr alloy microstructure and mechanical properties after hot isostatic pressing bonding cycles

NASA Astrophysics Data System (ADS)

Frayssines, P.-E.; Gentzbittel, J.-M.; Guilloud, A.; Bucci, P.; Soreau, T.; Francois, N.; Primaux, F.; Heikkinen, S.; Zacchia, F.; Eaton, R.; Barabash, V.; Mitteau, R.

2014-04-01

ITER first wall (FW) panels are a layered structure made of the three following materials: 316L(N) austenitic stainless steel, CuCrZr alloy and beryllium. Two hot isostatic pressing (HIP) cycles are included in the reference fabrication route to bond these materials together for the normal heat flux design supplied by the European Union (EU). This reference fabrication route ensures sufficiently good mechanical properties for the materials and joints, which fulfil the ITER mechanical specifications, but often results in a coarse grain size for the CuCrZr alloy, which is not favourable, especially, for the thermal creep properties of the FW panels. To limit the abnormal grain growth of CuCrZr and make the ITER FW fabrication route more reliable, a study began in 2010 in the EU in the frame of an ITER task agreement. Two material fabrication approaches have been investigated. The first one was dedicated to the fabrication of solid CuCrZr alloy in close collaboration with an industrial copper alloys manufacturer. The second approach investigated was the manufacturing of CuCrZr alloy using the powder metallurgy (PM) route and HIP consolidation. This paper presents the main mechanical and microstructural results associated with the two CuCrZr approaches mentioned above. The mechanical properties of solid CuCrZr, PM CuCrZr and joints (solid CuCrZr/solid CuCrZr and solid CuCrZr/316L(N) and PM CuCrZr/316L(N)) are also presented.

Impact of the oxygen defects and the hydrogen concentration on the surface of tetragonal and monoclinic ZrO2 on the reduction rates of stearic acid on Ni/ZrO2.

PubMed

Foraita, Sebastian; Fulton, John L; Chase, Zizwe A; Vjunov, Aleksei; Xu, Pinghong; Baráth, Eszter; Camaioni, Donald M; Zhao, Chen; Lercher, Johannes A

2015-02-02

The role of the specific physicochemical properties of ZrO2 phases on Ni/ZrO2 has been explored with respect to the reduction of stearic acid. Conversion on pure m-ZrO2 is 1.3 times more active than on t-ZrO2 , whereas Ni/m-ZrO2 is three times more active than Ni/t-ZrO2 . Although the hydrodeoxygenation of stearic acid can be catalyzed solely by Ni, the synergistic interaction between Ni and the ZrO2 support causes the variations in the reaction rates. Adsorption of the carboxylic acid group on an oxygen vacancy of ZrO2 and the abstraction of the α-hydrogen atom with the elimination of the oxygen atom to produce a ketene is the key to enhance the overall rate. The hydrogenated intermediate 1-octadecanol is in turn decarbonylated to heptadecane with identical rates on all catalysts. Decarbonylation of 1-octadecanol is concluded to be limited by the competitive adsorption of reactants and intermediate. The substantially higher adsorption of propionic acid demonstrated by IR spectroscopy and the higher reactivity to O2 exchange reactions with the more active catalyst indicate that the higher concentration of active oxygen defects on m-ZrO2 compared to t-ZrO2 causes the higher activity of Ni/m-ZrO2 . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of Adsorption and Desorption Performances of Zr-Based Metal-Organic Frameworks Using Paper Spray Mass Spectrometry.

PubMed

Wang, Xiaoting; Chen, Ying; Zheng, Yajun; Zhang, Zhiping

2017-07-08

The dynamic pore systems and high surface areas of flexible metal-organic framework materials make them excellent candidates to be used in different kinds of adsorption processes. However, the adsorption and desorption behaviors of therapeutic drugs on metal-organic frameworks in solution are not fully developed. Here, we systematically investigated the adsorption and desorption behaviors of a typical therapeutic drug, verapamil, over several Zr-based metal-organic frameworks [e.g., Zr-FUM, UiO-66(Zr), UiO-66(Zr)-NH₂ and UiO-66(Zr)-2COOH] as well as ZrO₂ in an acetonitrile solution by using paper spray mass spectrometry. In contrast to other materials, UiO-66(Zr)-2COOH demonstrated a superior adsorption performance to verapamil due to their strong acid-base and/or hydrogen-bond interactions, and the adsorption process fitted well with the pseudo-second-order kinetic model. As verapamil-adsorbed materials were used for desorption experiments, ZrO₂ demonstrated the most favorable desorption performance, whereas UiO-66(Zr)-2COOH yielded the poorest desorption capability. These Zr-based materials had also been coated at the surface with filter papers for the analysis of various drugs and proteins in the process of paper spray mass spectrometry. The results demonstrated that among the studied materials, ZrO₂-coated paper gave the most favorable desorption performance as a pure drug solution, whereas the paper from UiO-66(Zr) demonstrated the optimal capability in the analyses of therapeutic drugs in a complex matrix (e.g., blood) and a protein (e.g., myoglobin).

Electrodeposition and characterization of Ni-Mo-ZrO2 composite coatings

NASA Astrophysics Data System (ADS)

Laszczyńska, A.; Winiarski, J.; Szczygieł, B.; Szczygieł, I.

2016-04-01

Ni-Mo-ZrO2 composite coatings were produced by electrodeposition technique from citrate electrolytes containing dispersed ZrO2 nanopowder. The influence of deposition parameters i.e. concentration of molybdate and ZrO2 nanoparticles in the electrolyte, bath pH and deposition current density on the composition and surface morphology of the coating has been investigated. The structure, microhardness and corrosion properties of Ni-Mo-ZrO2 composites with different molybdenum and ZrO2 content have been also examined. It was found that ZrO2 content in the deposit is increased by rising the nanoparticles concentration in the plating solution up to 20 g dm-3. An increase in molybdate concentration in the electrolyte affects negatively the amount of codeposited ZrO2 nanoparticles. The correlation between the deposition current efficiency and ZrO2 content in the composite coating has been also observed. A decrease in deposition current efficiency leads to deposition of Ni-Mo-ZrO2 composite with low nanoparticles content. This may be explained by formation of higher amounts of gas bubbles on the cathode surface, which prevent the adsorption of ZrO2 nanoparticles on the growing deposit. The XRD analysis revealed that all the studied Ni-Mo-ZrO2 coatings were composed of a single, nanocrystalline phase with FCC structure. It was found that the incorporation of ZrO2 nanoparticles into Ni-Mo alloy matrix affects positively the microhardness and also slightly improves the corrosion properties of Ni-Mo alloy coating.

Effects of pH on heat transfer nanofluids containing ZrO2 and TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Wamkam, Carine Tchamakam; Opoku, Michael Kwabena; Hong, Haiping; Smith, Pauline

2011-01-01

In this paper, pH influences of zeta potential, particle size distribution, rheology, viscosity, and stability on heat transfer nanofluids are studied. Significant enhancement of thermal conductivity (TC) (>20%) containing 3 wt % zirconium dioxide (ZrO2) and titanium dioxide (TiO2) are observed near the isoelectric point (IEP). Meanwhile, at this IEP (pH), particle sizes, and viscosities of these nanofluids demonstrate a significant increase to maximum values. Experimental results also indicate that the stabilities of these nanofluids are influenced by pH values. The reasonable explanation for these interesting phenomena is that at this IEP, the repulsive forces among metal oxides are zero and nanoparticles coagulate together at this pH value. According to the Derjaguin-Landau-Verwey-Overbeek theory, when the pH is equal to or close to the IEP, nanoparticles tend to be unstable, form clusters, and precipitate. The resulting big clusters will trap water and the structures of trapped water are varied due to the strong atomic force among nanoparticles. Water is packed well inside and volume fraction of the nanoparticles will be larger. In addition, shapes of clusters containing trapped water will not be spherical but rather has irregular structure (like chains). Such structure favors thermal transport because they provide a long link. Therefore, overall TC of nanofluids is enhanced. Some literature results and conclusions related to pH effects of nanofluids are discussed and analyzed. Understanding pH effects may enable exploration of fundamental nature of nanofluids.

Oxidation of Ultra High Temperature Ceramics in Water Vapor

NASA Technical Reports Server (NTRS)

Nguyen, QuynhGiao N.; Opila, Elizabeth J.; Robinson, Raymond C.

2004-01-01

Ultra High Temperature Ceramics (UHTCs) including HfB2 + 20v/0 SiC (HS), ZrB2 + 20v/0 SiC (ZS), and ZrB2 + 30v/0 C + 14v/0 SiC (ZCS) have been investigated for use as potential aeropropulsion engine materials. These materials were oxidized in water vapor (90 percent) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 h at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline for comparison. Weight change, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results are compared with tests ran in a stagnant air furnace at temperatures of 1327 C for 100 min, and with high pressure burner rig (HPBR) results at 1100 and 1300 C at 6 atm for 50 h. Low velocity water vapor does not make a significant contribution to the oxidation rates of UHTCs when compared to stagnant air. The parabolic rate constants at 1300 C, range from 0.29 to 16.0 mg(sup 2)cm(sup 4)/h for HS and ZCS, respectively, with ZS results between these two values. Comparison of results for UHTCs tested in the furnace in 90 percent water vapor with HPBR results was difficult due to significant sample loss caused by spallation in the increased velocity of the HPBR. Total recession measurements are also reported for the two test environments.

Fabrication and characterization of polyvinyl alcohol/metal (Ca, Mg, Ti) doped zirconium phosphate nanocomposite films for scaffold-guided tissue engineering application.

PubMed

Kalita, Himani; Pal, Pallabi; Dhara, Santanu; Pathak, Amita

2017-02-01

Nanocomposite films of polyvinyl alcohol (PVA) and zirconium phosphate (ZrP)/doped ZrP (doped with Ca, Mg, Ti) nanoparticles have been developed by solvent casting method to assess their potential as matrix material in scaffold-guided tissue engineering application. The prepared ZrP and doped ZrP nanoparticles as well as the nanocomposite films were characterized by various spectroscopic and microscopic techniques. Nanoindentation studies revealed improved nanomechanical properties in the PVA/doped ZrP nanocomposite films (highest for PVA/Ti doped ZrP: hardness=262.4MPa; elastic modulus=5800MPa) as compared to the PVA/ZrP and neat PVA films. In-vitro cell culture experiments carried out to access the cellular viability, attachment, proliferation, and migration on the substrates, using mouse fibroblast (3T3) cell lines, inferred enhanced bioactivity in the PVA/doped ZrP nanocomposite films (highest for PVA/Ca doped ZrP) in contrast to PVA/ZrP and neat PVA films. Controlled biodegradability as well as swelling behavior, superior bioactivity and improved mechanical properties of the PVA/doped ZrP nanocomposite films make them promising matrix materials for scaffold-guided tissue engineering application. Copyright © 2016 Elsevier B.V. All rights reserved.

Interaction Studies of Ceramic Vacuum Plasma Spraying for the Melting Crucible Materials

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

Jong Hwan Kim; Hyung Tae Kim; Yoon Myung Woo

2013-10-01

Candidate coating materials for re-usable metallic nuclear fuel crucibles, TaC, TiC, ZrC, ZrO2, and Y2O3, were plasmasprayed onto a niobium substrate. The microstructure of the plasma-sprayed coatings and thermal cycling behavior were characterized, and U-Zr melt interaction studies were carried out. The TaC and Y2O3 coating layers had a uniform thickness, and high density with only a few small closed pores showing good consolidation, while the ZrC, TiC, and ZrO2 coatings were not well consolidated with a considerable amount of porosity. Thermal cycling tests showed that the adhesion of the TiC, ZrC, and ZrO2 coating layers with niobium was relativelymore » weak compared to the TaC and Y2O3 coatings. The TaC and Y2O3 coatings had better cycling characteristics with no interconnected cracks. In the interaction studies, ZrC and ZrO2 coated rods showed significant degradations after exposure to U-10 wt.% Zr melt at 1600 degrees C for 15 min., but TaC, TiC, and Y2O3 coatings showed good compatibility with U-Zr melt.« less

Investigation of the fracture mechanics of boride composites

NASA Technical Reports Server (NTRS)

Clougherty, E. V.; Pober, R. L.; Kaufman, L.

1972-01-01

Significant results were obtained in fabrication studies of the role of metallic additives of Zr, Ti, Ni, Fe and Cr on the densification of ZrB2. All elemental additions lower the processing temperatures required to effect full densification of ZrB2. Each addition effects enhanced densification by a clearly distinguishable and different mechanism and the resulting fabricated materials are different. A significant improvement in strength and fracture toughness was obtained for the ZrB2/Ti composition. Mechanical characterization studies for the ZrB2/SiC/C composites and the new ZrB2/Metal materials produced data relevant to the effect of impacting load on measured impact energies, a specimen configuration for which controlled fracture could occur in a suitably hard testing apparatus, and fracture strength data. Controlled fracture--indicative of measurable fracture toughness--was obtained for the ZrB2-SiC-C composite, and a ZrB2/Ti composite fabricated from ZrB2 with an addition of 30 weight per cent Ti. The increased strength and toughness of the ZrB2/Ti composite is consistent with the presence of a significantly large amount of a fine grained acicular phase formed by reaction of Ti with ZrB2 during processing.

Microstructure evolution of a ZrC coating layer in TRISO particles during high-temperature annealing

NASA Astrophysics Data System (ADS)

Kim, Daejong; Chun, Young Bum; Ko, Myeong Jin; Lee, Hyeon-Geun; Cho, Moon-Sung; Park, Ji Yeon; Kim, Weon-Ju

2016-10-01

The influence of high-temperature annealing on the microstructure of zirconium carbide (ZrC) was investigated in relation to its application as a coating layer of a nuclear fuel in a very high temperature gas cooled reactor. ZrC was deposited as a constituent coating layer of TRISO coated particles by a fluidized bed chemical vapor deposition method using a ZrCl4-CH4-Ar-H2 system. The grain growth of ZrC during high-temperature annealing was strongly influenced by the co-deposition of free carbon. Sub-stoichiometric ZrC coatings have experienced a significant grain growth during high-temperature annealing at 1800 °C and 1900 °C for 1 h. On the other hand, a dual phase of stoichiometric ZrC and free carbon experienced little grain growth. It was revealed that the free carbon of the as-deposited ZrC was primarily distributed within the ZrC grains but was redistributed to the grain boundaries after annealing. Consequently, carbon at the grain boundary retarded the grain growth of ZrC. Electron backscatter diffraction (EBSD) results showed that as-deposited ZrC had (001) a preferred orientation that kept its favored direction after significant grain growth during annealing. The hardness slightly decreased as the grain growth progressed.

Thermal expansion of phosphates with the NaZr2(PO4)3 structure containing lanthanides and zirconium: R 0.33Zr2(PO4)3 ( R = Nd, Eu, Er) and Er0.33(1- x) Zr0.25 x Zr2(PO4)3

NASA Astrophysics Data System (ADS)

Volgutov, V. Yu.; Orlova, A. I.

2015-09-01

Phosphates R 0.33Zr2(PO4)3 ( R = Nd, Eu, or Er) and Er0.33(1- х)Zr0.25Zr2(PO4)3 ( х = 0, 0.25, 0.5, 0.75, 1.0) of the NaZr2(PO4)3 family have been synthesized and investigated by high-temperature X-ray diffraction. The crystallochemical approach is used to obtain compounds with expected small and controllable thermal-expansion parameters. Phosphates with close-to-zero thermal-expansion parameters, including those with low thermal-expansion anisotropy, have been obtained: Nd0.33Zr2(PO4)3 with α a =-2.21 × 10-6 °С-1, α c = 0.81 × 10-6 °С-1, and Δα = 3.02 × 10-6 °С-1 and Er0.08Zr0.19Zr2(PO4)3 with α a =-1.86 × 10-6 °С-1, α c = 1.73 × 10-6 °С-1, and Δα = 3.58 × 10-6 °С-1.

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

Qu, Wentao; Sun, Xuguang; Yuan, Bifei

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

High radioactive concentration of 99mTc from a zirconium [99Mo]molybdate gel generator using an acidic alumina column for purification and concentration.

PubMed

Sarkar, S K; Saraswathy, P; Arjun, G; Ramamoorthy, N

2004-06-01

Newer applications of radiopharmaceuticals in nuclear medicine require pertechnetate of moderate to high radioactive concentration. Hence there is a need to develop simple procedures for the concentration of pertechnetate, and such a procedure is given in this paper. Ten to 20 ml of sodium [Tc]pertechnetate eluted in de-ionized water from a zirconium [Mo]molybdate (ZrMo) gel column generator was passed through 2 g of an acidic alumina bed (35 x 8 mm) in order to remove the co-eluted traces of Mo and to retain the pertechnetate. The retained pertechnetate was then re-eluted, quantitatively, in 3 ml of normal saline, from the alumina column. About a 4-fold increase in radioactive concentration of Tc was obtained (cf. approximately 10-12 ml normal saline is required for the elution of Tc from the gel column). Generators containing up to 22.2 GBq (600 mCi) Mo in 6-7 g ZrMo gel column (35 x 13 mm) were prepared and a radioactive concentration of Tc up to 4 GBq x ml (110 mCi x ml) was obtained on the first day of use. The overall recovery of Tc was >90%, Mo breakthrough was 10 to 10% and the duration of concentration was 3-5 min. The chemical impurity in terms of Al, Mo and Zr was <10 ppm each. The same procedure for the concentration of pertechnetate was applied to generators with 12-15 g ZrMo gel beds to obtain a higher capacity Tc gel generator, with similar findings.

Design, R&D and commissioning of EAST tungsten divertor

NASA Astrophysics Data System (ADS)

Yao, D. M.; Luo, G. N.; Zhou, Z. B.; Cao, L.; Li, Q.; Wang, W. J.; Li, L.; Qin, S. G.; Shi, Y. L.; Liu, G. H.; Li, J. G.

2016-02-01

After commissioning in 2005, the EAST superconducting tokamak had been operated with its water cooled divertors for eight campaigns up to 2012, employing graphite as plasma facing material. With increase in heating power over 20 MW in recent years, the heat flux going to the divertors rises rapidly over 10 MW m-2 for steady state operation. To accommodate the rapid increasing heat load in EAST, the bolting graphite tile divertor must be upgraded. An ITER-like tungsten (W) divertor has been designed and developed; and firstly used for the upper divertor of EAST. The EAST upper W divertor is modular structure with 80 modules in total. Eighty sets of W/Cu plasma-facing components (PFC) with each set consisting of an outer vertical target (OVT), an inner vertical target (IVT) and a DOME, are attached to 80 stainless steel cassette bodies (CB) by pins. The monoblock W/Cu-PFCs have been developed for the strike points of both OVT and IVT, and the flat type W/Cu-PFCs for the DOME and the baffle parts of both OVT and IVT, employing so-called hot isostatic pressing (HIP) technology for tungsten to CuCrZr heat sink bonding, and electron beam welding for CuCrZr to CuCrZr and CuCrZr to other material bonding. Both monoblock and flat type PFC mockups passed high heat flux (HHF) testing by means of electron beam facilities. The 80 divertor modules were installed in EAST in 2014 and results of the first commissioning are presented in this paper.

Mechanism of CO 2 hydrogenation over Cu/ZrO 2(2̅12) interface from first-principles kinetics Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Hong, Qi-Jun; Liu, Zhi-Pan

2010-10-01

It has been a goal consistently pursued by chemists to understand and control the catalytic process over composite materials. In order to provide deeper insight on complex interfacial catalysis at the experimental conditions, we performed an extensive analysis on CO 2 hydrogenation over a Cu/ZrO 2 model catalyst by employing density functional theory (DFT) calculations and kinetic Monte Carlo (kMC) simulations based on the continuous stirred tank model. The free energy profiles are determined for the reaction at the oxygen-rich Cu/m-ZrO 2 (2̅12) interface, where all interfacial Zr are six-coordinated since the interface accumulates oxidative species at the reaction conditions. We show that not only methanol but also CO are produced through the formate pathway dominantly, whilst the reverse-water-gas-shift (RWGS) channel has only a minor contribution. H 2CO is a key intermediate species in the reaction pathway, the hydrogenation of which dictates the high temperature of CO 2 hydrogenation. The kinetics simulation shows that the CO 2 conversion is 1.20%, the selectivity towards methanol is 68% at 500 K and the activation energies for methanol and CO formation are 0.79 and 1.79 eV, respectively. The secondary reactions due to the product readsorption lower the overall turnover frequency (TOF) but increase the selectivity towards methanol by 16%. We also show that kMC is a more reliable tool for simulating heterogeneous catalytic processes compared to the microkinetics approach.

Fabrication of low thermal expansion SiC/ZrW2O8 porous ceramics

NASA Astrophysics Data System (ADS)

Poowancum, A.; Matsumaru, K.; Juárez-Ramírez, I.; Torres-Martínez, L. M.; Fu, Z. Y.; Lee, S. W.; Ishizaki, K.

2011-03-01

Low or zero thermal expansion porous ceramics are required for several applications. In this work near zero thermal expansion porous ceramics were fabricated by using SiC and ZrW2O8 as positive and negative thermal expansion materials, respectively, bonded by soda lime glass. The mixture of SiC, ZrW2O8 and soda lime glass was sintered by Pulsed Electric Current Sintering (PECS, or sometimes called Spark Plasma Sintering, SPS) at 700 °C. Sintered samples with ZrW2O8 particle size smaller than 25 μm have high thermal expansion coefficient, because ZrW2O8 has the reaction with soda lime glass to form Na2ZrW3O12 during sintering process. The reaction between soda lime glass and ZrW2O8 is reduced by increasing particle size of ZrW2O8. Sintered sample with ZrW2O8 particle size 45-90 μm shows near zero thermal expansion.

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

NASA Astrophysics Data System (ADS)

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

2011-07-01

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

Experimental Investigation of the 1073 K (800 °C) Isothermal Section of the Al-V-Zr Ternary System

NASA Astrophysics Data System (ADS)

Zhu, Yude; Ouyang, Xuemei; Yin, Fucheng; Zhao, Manxiu; Lou, Jia

2018-03-01

This work is focused on an experimental investigation of the phase equilibria of the Al-V-Zr system at 1073 K (800 °C). The phase equilibria were analyzed using scanning electron microscopy (SEM) coupled with energy-dispersive spectrometry and X-ray diffraction. The results confirmed the presence of twelve three-phase regions and one ternary compound, Τ, which contains 10.0 to 16.5 at. pct Zr, 52.8 to 55.2 at. pct Al, and 29.3 to 36.3 at. pct V. The T phase can be in equilibrium with Al8V5, Al3Zr, Al2Zr, and α-V. The T phase belongs to the tetragonal crystal system with confirmed lattice parameters of a = 0.658531 nm and c = 0.517334 nm. The Al2Zr phase region is extraordinarily large and can be in equilibrium with all the compounds in the Al-Zr and V-Zr systems, with the exception of the AlZr phase.

Effects of Zr Addition on Strengthening Mechanisms of Al-Alloyed High-Cr ODS Steels.

PubMed

Ren, Jian; Yu, Liming; Liu, Yongchang; Liu, Chenxi; Li, Huijun; Wu, Jiefeng

2018-01-12

Oxide dispersion strengthened (ODS) steels with different contents of zirconium (denoted as 16Cr ODS, 16Cr-0.3Zr ODS and 16Cr-0.6Zr ODS) were fabricated to investigate the effects of Zr on strengthening mechanism of Al-alloyed 16Cr ODS steel. Electron backscatter diffraction (EBSD) results show that the mean grain size of ODS steels could be decreased by Zr addition. Transmission electron microscope (TEM) results indicate that Zr addition could increase the number density but decrease the mean diameter and inter-particle spacing of oxide particles. Furthermore, it is also found that in addition to Y-Al-O nanoparticles, Y-Zr-O oxides with finer size were observed in 16Cr-0.3Zr ODS and 16Cr-0.6Zr ODS steels. These changes in microstructure significantly increase the yield strength (YS) and ultimate tensile strength (UTS) of ODS steels through mechanisms of grain boundary strengthening and dispersion strengthening.

Development and fabrication of insulator seals for thermionic diodes

NASA Technical Reports Server (NTRS)

Poirier, V. L.

1972-01-01

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

Effects of Zr Addition on Strengthening Mechanisms of Al-Alloyed High-Cr ODS Steels

PubMed Central

Ren, Jian; Yu, Liming; Liu, Yongchang; Liu, Chenxi; Li, Huijun; Wu, Jiefeng

2018-01-01

Oxide dispersion strengthened (ODS) steels with different contents of zirconium (denoted as 16Cr ODS, 16Cr-0.3Zr ODS and 16Cr-0.6Zr ODS) were fabricated to investigate the effects of Zr on strengthening mechanism of Al-alloyed 16Cr ODS steel. Electron backscatter diffraction (EBSD) results show that the mean grain size of ODS steels could be decreased by Zr addition. Transmission electron microscope (TEM) results indicate that Zr addition could increase the number density but decrease the mean diameter and inter-particle spacing of oxide particles. Furthermore, it is also found that in addition to Y-Al-O nanoparticles, Y-Zr-O oxides with finer size were observed in 16Cr-0.3Zr ODS and 16Cr-0.6Zr ODS steels. These changes in microstructure significantly increase the yield strength (YS) and ultimate tensile strength (UTS) of ODS steels through mechanisms of grain boundary strengthening and dispersion strengthening. PMID:29329260

Mass transport and crystal growth of the mixed ZrS2-ZrSe2 system

NASA Technical Reports Server (NTRS)

Wiedemeier, Heribert; Goldman, Howard

1986-01-01

The solid solubility of the ZrS2-ZrSe2 system was reinvestigated by annealing techniques to establish the relationship between composition and lattice parameters. Mixed crystals of ZrS(2x)Se2(1-x) for selected compositions of the source material were grown by chemical vapor transport and characterized by X-ray diffraction and microscopic methods. The mass transport rates and crystal growth of ZrSSe were investigated and compared with those of other compositions. The mass fluxes of the mixed system showed an increase with increasing selenium content. The transport products were richer in ZrSe2 than the residual source materials when the ZrSe2 content of the starting materials was greater than 50 mol.-pct. The mass transport rates revealed an increasing mass flux with pressure.

Physical properties of molten core materials: Zr-Ni and Zr-Cr alloys measured by electrostatic levitation

NASA Astrophysics Data System (ADS)

Ohishi, Yuji; Kondo, Toshiki; Ishikawa, Takehiko; Okada, Junpei T.; Watanabe, Yuki; Muta, Hiroaki; Kurosaki, Ken; Yamanaka, Shinsuke

2017-03-01

It is important to understand the behaviors of molten core materials to investigate the progression of a core meltdown accident. In the early stages of bundle degradation, low-melting-temperature liquid phases are expected to form via the eutectic reaction between Zircaloy and stainless steel. The main component of Zircaloy is Zr and those of stainless steel are Fe, Ni, and Cr. Our group has previously reported physical property data such as viscosity, density, and surface tension for Zr-Fe liquid alloys using an electrostatic levitation technique. In this study, we report the viscosity, density, and surface tension of Zr-Ni and Zr-Cr liquid alloys (Zr1-xNix (x = 0.12 and 0.24) and Zr0.77Cr0.23) using the electrostatic levitation technique.

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

USGS Publications Warehouse

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

2006-01-01

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

Effect of Zr Doping on Structural and Ferroelectric Properties of Lead-Free Bi0.5(Na0.80K0.20)0.5TiO3 Films

NASA Astrophysics Data System (ADS)

Quan, Ngo Duc; Hung, Vu Ngoc; Dung, Dang Duc

2017-10-01

Environmentally friendly lead-free Bi0.5(Na0.80K0.20)0.5(Ti1- x Zr x )O3 (BNKT- xZr) ferroelectric films with Zr4+ doping concentration x in the range from 0 to 0.05 have been grown on Pt/Ti/SiO2/Si substrates via chemical solution deposition. The effects of Zr4+ substitution on the crystal structure and ferroelectric properties of the films were investigated. X-ray diffraction data revealed that the BNKT- xZr films possessed rhombohedral and tetragonal symmetries at a morphotropic phase boundary when a small amount of Zr4+ doping was added. P- E hysteresis loops typical of ferroelectric materials were observed for all compositions. Zr4+ substituted for Ti4+ in the BNKT- xZr films and remarkably enhanced the ferroelectric properties. The remanent ( P r) and maximum polarization ( P m) reached their highest values of 14.0 μC/cm2 and 35.7 μC/cm2, respectively, at x = 0.02. These values, which are equivalent to the highest P r and P m values in previous reports on lead-free films with different compositions, compare well with those of Pb(Zr,Ti)O3 (PZT) films. Therefore, BNKT- xZr films with optimal Zr4+ concentration could substitute for PZT films in lead-free piezo-microelectromechanical systems (MEMS) devices.

The 95Zr(n, γ)96Zr Cross Section from the Surrogate Ratio Method and Its Effect on s-process Nucleosynthesis

NASA Astrophysics Data System (ADS)

Yan, S. Q.; Li, Z. H.; Wang, Y. B.; Nishio, K.; Lugaro, M.; Karakas, A. I.; Makii, H.; Mohr, P.; Su, J.; Li, Y. J.; Nishinaka, I.; Hirose, K.; Han, Y. L.; Orlandi, R.; Shen, Y. P.; Guo, B.; Zeng, S.; Lian, G.; Chen, Y. S.; Liu, W. P.

2017-10-01

The 95Zr(n, γ)96Zr reaction cross section is crucial in the modeling of s-process nucleosynthesis in asymptotic giant branch stars because it controls the operation of the branching point at the unstable 95Zr and the subsequent production of 96Zr. We have carried out the measurement of the 94Zr(18O, 16O) and 90Zr(18O, 16O) reactions and obtained the γ-decay probability ratio of 96Zr* and 92Zr* to determine the 95Zr(n, γ)96Zr reaction cross sections with the surrogate ratio method. Our deduced Maxwellian-averaged cross section of 66 ± 16 mb at 30 keV is close to the value recommended by Bao et al., but 30% and more than a factor of two larger than the values proposed by Toukan & Käppeler and Lugaro et al., respectively, and routinely used in s-process models. We tested the new rate in stellar models with masses between 2 and 6 M ⊙ and metallicities of 0.014 and 0.03. The largest changes—up to 80% variations in 96Zr—are seen in models of mass 3–4 M ⊙, where the 22Ne neutron source is mildly activated. The new rate can still provide a match to data from meteoritic stardust silicon carbide grains, provided that the maximum mass of the parent stars is below 4 M ⊙, for a metallicity of 0.03.

Zirconium tetrachloride revisited

DOE PAGES

Borjas Nevarez, Rosendo; Balasekaran, Samundeeswari Mariappan; Kim, Eunja; ...

2018-02-19

We present that zirconium tetrachloride, ZrCl 4, is a strategic material with wide-ranging applications. Until now, only one crystallographic study on ZrCl 4has been reported [Krebs (1970).Z. Anorg. Allg. Chem.378, 263–272] and that was more than 40 years ago. The compound used for the previous determination was prepared from ZrO 2 and Cl 2–CCl 4, and single-crystal X-ray diffraction (SCXRD) studies on ZrCl 4 obtained from Zr metal have not yet been reported. In this context, we prepared ZrCl 4 from the reaction of Zr metal and Cl 2 gas in a sealed tube and investigated its structure at 100,more » 150, 200, 250, and 300 K. At 300 K, the SCXRD analysis indicates that ZrCl 4 crystallizes in the orthorhombic space group Pca2 1 [a= 6.262 (9),b= 7.402 (11),c= 12.039 (17) Å, andV= 558.0 (14) Å 3] and consists of infinite zigzag chains of edge-sharing ZrCl 6 octahedra. This chain motif is similar to that observed previously in ZrCl 4, but the structural parameters and space group differ. Finally, in the temperature range 100–300 K, no phase transformation was identified, while elongation of intra-chain Zr...Zr [3.950 (1) Å at 100 K and 3.968 (5) Å at 300 K] and inter-chain Cl...Cl [3.630 (3) Å at 100 K and 3.687 (9) Å at 300 K] distances occurred.« less

Structure, mechanical properties, and grindability of dental Ti-Zr alloys.

PubMed

Ho, Wen-Fu; Chen, Wei-Kai; Wu, Shih-Ching; Hsu, Hsueh-Chuan

2008-10-01

Structure, mechanical properties and grindability of a series of binary Ti-Zr alloys with zirconium contents ranging from 10 to 40 wt% have been investigated. Commercially pure titanium (c.p. Ti) was used as a control. Experimental results indicated that the diffraction peaks of all the Ti-Zr alloys matched those for alpha Ti. No beta-phase peaks were found. The hardness of the Ti-Zr alloys increased as the Zr contents increased, and ranged from 266 HV (Ti-10Zr) to 350 HV (Ti-40Zr). As the concentration of zirconium in the alloys increased, the strength, elastic recovery angles and hardness increased. Moreover, the elastically recoverable angle of Ti-40Zr was higher than of c.p. Ti by as much as 550%. The grindability of each metal was found to be largely dependent on the grinding conditions. The Ti-40Zr alloy had a higher grinding rate and grinding ratio than c.p. Ti at low speed. The grinding rate of the Ti-40Zr alloy at 500 m/min was about 1.8 times larger than that of c.p. Ti, and the grinding ratio was about 1.6 times larger than that of c.p. Ti. Our research suggested that the Ti-40Zr alloy has better mechanical properties, excellent elastic recovery capability and improved grindability at low grinding speed. The Ti-40Zr alloy has a great potential for use as a dental machining alloy.

[Effect of SiO₂-ZrO₂slurry coating on surface performance of zirconia ceramic].

PubMed

Du, Qiao; Niu, Guangliang; Lin, Hong; Jiang, Ruodan

2015-11-01

To evaluate the effect of SiO₂-ZrO₂slurry coating on surface performance of zirconia ceramic. Seventy pre-sintered zirconia discs were randomly divided into seven groups with 10 discs per group. Sample discs in each group received one of the following seven different surface treatments, namely, sintered (group AS), sand blasting after sintered (group SB), coated with slurry of mole ratio of SiO₂to ZrO₂2:1 (group 2SiO₂-1ZrO₂), coated with slurry of mole ratio of SiO₂to ZrO₂1:1 (group 1SiO₂-1ZrO₂), coated with slurry of mole ratio of SiO₂to ZrO₂1:2 (group 1SiO₂-2ZrO₂), coated with slurry of mole ratio of SiO₂to ZrO₂1:3 (group 1SiO₂-3ZrO₂), coated with slurry of mole ratio of SiO₂to ZrO₂1:4 (group 1SiO₂-4ZrO₂). Profilometer, X-ray diffractometer (XRD), energy dispersive spectrometer, scanning electron microscopy (SEM) were used to analyze surface performance. The surface roughness of the discs in group AS was lower than those in the other groups [(0.33 ± 0.03) µm] (P < 0.05), there was no statistically significant difference (P > 0.05) among group 2SiO₂-1ZrO₂[(3.85 ± 0.38) µm], group 1SiO₂-1ZrO₂[(3.78 ± 0.56) µm] and group 1SiO₂-2ZrO₂[(4.06 ± 0.48) µm], and no difference (P > 0.05) was observed between group 1SiO₂-3ZrO₂[(1.02 ± 0.09) µm] and group 1SiO₂-4ZrO₂[(1.53 ± 0.23) µm] either. However, surface roughness in all coating groups was higher than those in group SB [(0.86 ± 0.05) µm] (P < 0.05). According to the XRD pattern, group AS and all coating groups consisted of 100% tetragonal airconia and monoclinic zirconia was detected at surface of group SB. Contents of surface silicon of coating groups increased significantly, however, no silicon was detected at sample surface of group AS and group SB. SEM showed that zirconia grains of coating exposed since part of silicon was etched by hydrofluoric acid, a three-dimensional network of intergrain nano-spaces was created. SiO₂-ZrO₂slurry coating could make surface of zirconia rough and increase Si content without creating monoclinic zirconia.

Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study.

PubMed

Sato, Ryuhei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

2017-08-02

Hydration reactions on a carbonate-terminated cubic ZrO 2 (110) surface were analyzed using ab initio molecular dynamics (AIMD) simulations. After hydration reactions, carbonates were still present on the surface at 500 K. However, these carbonates are very weak conjugate bases and only act as steric hindrance in proton hopping processes between acidic chemisorbed H 2 O molecules (Zr-OH 2 ) and monodentate hydroxyl groups (Zr-OH - ). Similar to a carbonate-free hydrated surface, Zr-OH 2 , Zr-OH - , and polydentate hydroxyl groups ([double bond splayed left]OH + ) were observed, while the ratio of acidic Zr-OH 2 was significantly larger than that on the carbonate-free hydrated surface. A thermodynamic discussion and bond property analysis reveal that CO 2 adsorption significantly decreases the basicity of surface oxide ions ([double bond splayed left]O), whereas the acidity of Zr-OH 2 is not affected. As a result, protons released from [double bond splayed left]OH + react with Zr-OH - to form Zr-OH 2 , leading to a deficiency of proton acceptor sites, which decreases the proton conductivity by the hopping mechanism.

Coverage-dependent amplifiers of vegetation change on global water cycle dynamics

NASA Astrophysics Data System (ADS)

Feng, Huihui; Zou, Bin; Luo, Juhua

2017-07-01

The terrestrial water cycle describes the circulation of water worldwide from one store to another via repeated evapotranspiration (E) from land and precipitation (P) back to the surface. The cycle presents significant spatial variability, which is strongly affected by natural climate and anthropogenic influences. As one of the major anthropogenic influences, vegetation change unavoidably alters surface property and subsequent the terrestrial water cycle, while its contribution is yet difficult to isolate from the mixed influences. Here, we use satellite and in-situ datasets to identify the terrestrial water cycle dynamics in spatial detail and to evaluate the impact of vegetation change. Methodologically, the water cycle is identified by the indicator of difference between evapotranspiration and precipitation (E-P). Then the scalar form of the indicator's trend (ΔE + ΔP) is used for evaluating the dynamics of water cycle, with the positive value means acceleration and negative means deceleration. Then, the contributions of climate and vegetation change are isolated by the trajectory-based method. Our results indicate that 4 accelerating and 4 decelerating water cycles can be identified, affecting 42.11% of global land. The major water cycle type is characterized by non-changing precipitation and increasing evapotranspiration (PNO-EIN), which covers 20.88% of globally land. Vegetation change amplifies both accelerating and decelerating water cycles. It tends to intensify the trend of the decelerating water cycles, while climate change weakens the trend. In the accelerating water cycles, both vegetation and climate change present positive effect to intensify the trend. The effect of plant cover change varies with the coverage. In particular, vegetation change intensifies the water cycle in moderately vegetated regions (0.1 < NDVI < 0.6), but weakens the cycle in sparsely or highly vegetated regions (NDVI < 0.1 or 0.6 < NDVI < 0.8). In extremely vegetated regions (NDVI > 0.85), the water cycle is accelerated because of the significant increase of precipitation. We conclude that vegetation change acts as an amplifier for both accelerating and decelerating terrestrial water cycles, depending on the degree of vegetation coverage.

Local structure in solid solutions of stabilised zirconia with actinide dioxides (UO{sub 2}, NpO{sub 2})

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

Walter, Marcus, E-mail: marcus.walter@vkta.d; Somers, Joseph; Bouexiere, Daniel

2011-04-15

The local structure of (Zr,Lu,U)O{sub 2-x} and (Zr,Y,Np)O{sub 2-x} solid solutions has been investigated by extended X-ray absorption fine structure (EXAFS). Samples were prepared by mixing reactive (Zr,Lu)O{sub 2-x} and (Zr,Y)O{sub 2-x} precursor materials with the actinide oxide powders, respectively. Sintering at 1600 {sup o}C in Ar/H{sub 2} yields a fluorite structure with U(IV) and Np(IV). As typical for stabilised zirconia the metal-oxygen and metal-metal distances are characteristic for the different metal ions. The bond lengths increase with actinide concentration, whereas highest adaptation to the bulk stabilised zirconia structure was observed for U---O and Np---O bonds. The Zr---O bond showsmore » only a slight increase from 2.14 A at 6 mol% actinide to 2.18 A at infinite dilution in UO{sub 2} and NpO{sub 2}. The short interatomic distance between Zr and the surrounding oxygen and metal atoms indicate a low relaxation of Zr with respect to the bulk structure, i.e. a strong Pauling behaviour. -- Graphical abstract: Metal-oxygen bond distances in (Zr,Lu,U)O{sub 2-x} solid solutions with different oxygen vacancy concentrations (Lu/Zr=1 and Lu/Zr=0.5). Display Omitted Research Highlights: {yields} EXAFS indicates high U and Np adaption to the bulk structure of stabilised zirconia. {yields} Zr---O bond length is 2.18 A at infinite Zr dilution in UO{sub 2} and NpO{sub 2}. {yields} Low relaxation (strong Pauling behaviour) of Zr explains its low solubility in UO{sub 2}.« less

Correlative characterization of primary Al{sub 3}(Sc,Zr) phase in an Al–Zn–Mg based alloy

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

Li, J.H., E-mail: jie-hua.li@hotmail.com; Wiessner, M.; Albu, M.

2015-04-15

Three-dimensional electron backscatter diffraction, focused ion beam, transmission electron microscopy and energy filtered transmission electron microscopy were employed to investigate the structural information of primary Al{sub 3}(Sc,Zr) phase, i.e. size, shape, element distribution and orientation relationship with the α-Al matrix. It was found that (i) most primary Al{sub 3}(Sc,Zr) phases have a cubic three-dimensional morphology, with a size of about 6–10 μm, (ii) most primary Al{sub 3}(Sc,Zr) phases are located within the α-Al matrix, and exhibit a cube to cube orientation relationship with the α-Al matrix, and (iii) a layer by layer growth was observed within primary Al{sub 3}(Sc,Zr) phases.more » Al, Cu, Si and Fe are enriched in the α-Al matrix between the layers of cellular eutectic Al{sub 3}(Sc,Zr) phase, while Sc, Ti and Zr are enriched in small Al{sub 3}(Sc,Zr) phases. A peritectic reaction and subsequent eutectic reaction between Al{sub 3}Sc and Al was proposed to interpret the observed layer by layer growth. This paper demonstrates that the presence of impurities (Fe, Si, Cu, Ti) in the diffusion field surrounding the growing Al{sub 3}(Sc,Zr) particle enhances the heterogeneous nucleation of Al{sub 3}(Sc,Zr) phases. - Highlights: • Most fine cubic primary Al{sub 3}(Sc,Zr) phases were observed within the α-Al matrix. • A layer by layer growth within primary Al{sub 3}(Sc,Zr) phase was observed. • A peritectic and subsequent eutectic reaction between Al{sub 3}Sc and Al was proposed. • Impurities in diffusion fields enhance heterogeneous nucleation of Al{sub 3}(Sc,Zr)« less

Study of Adsorption and Desorption Performances of Zr-Based Metal–Organic Frameworks Using Paper Spray Mass Spectrometry

PubMed Central

Wang, Xiaoting; Chen, Ying; Zheng, Yajun

2017-01-01

The dynamic pore systems and high surface areas of flexible metal–organic framework materials make them excellent candidates to be used in different kinds of adsorption processes. However, the adsorption and desorption behaviors of therapeutic drugs on metal–organic frameworks in solution are not fully developed. Here, we systematically investigated the adsorption and desorption behaviors of a typical therapeutic drug, verapamil, over several Zr-based metal–organic frameworks [e.g., Zr-FUM, UiO-66(Zr), UiO-66(Zr)-NH2 and UiO-66(Zr)-2COOH] as well as ZrO2 in an acetonitrile solution by using paper spray mass spectrometry. In contrast to other materials, UiO-66(Zr)-2COOH demonstrated a superior adsorption performance to verapamil due to their strong acid-base and/or hydrogen-bond interactions, and the adsorption process fitted well with the pseudo-second-order kinetic model. As verapamil-adsorbed materials were used for desorption experiments, ZrO2 demonstrated the most favorable desorption performance, whereas UiO-66(Zr)-2COOH yielded the poorest desorption capability. These Zr-based materials had also been coated at the surface with filter papers for the analysis of various drugs and proteins in the process of paper spray mass spectrometry. The results demonstrated that among the studied materials, ZrO2-coated paper gave the most favorable desorption performance as a pure drug solution, whereas the paper from UiO-66(Zr) demonstrated the optimal capability in the analyses of therapeutic drugs in a complex matrix (e.g., blood) and a protein (e.g., myoglobin). PMID:28773131

New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

NASA Astrophysics Data System (ADS)

Mudsainiyan, R. K.; Jassal, A. K.; Chawla, S. K.

2015-10-01

A mesoporous 3D polymeric complex (I) having formula {[Zr(IV)O-μ3-(EDTA)Fe(III)OH]·H2O}n has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of -OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (336·454·530)·(36). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and -OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n-π* transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N2 (SBET=8.7693 m2/g) and a maximum amount of H2 (high surface area=1044.86 m2/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. -7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex.

National Hypersonic Science Center for Materials and Structures

DTIC Science & Technology

2014-08-31

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

Reactivity of Dimeric Tetrazirconium(IV) Wells-Dawson Polyoxometalate toward Dipeptide Hydrolysis Studied by a Combined Experimental and Density Functional Theory Approach.

PubMed

Ly, Hong Giang T; Mihaylov, Tzvetan; Absillis, Gregory; Pierloot, Kristine; Parac-Vogt, Tatjana N

2015-12-07

Detailed kinetic studies on the hydrolysis of glycylglycine (Gly-Gly) in the presence of the dimeric tetrazirconium(IV)-substituted Wells-Dawson-type polyoxometalate Na14[Zr4(P2W16O59)2(μ3-O)2(OH)2(H2O)4] · 57H2O (1) were performed by a combination of (1)H, (13)C, and (31)P NMR spectroscopies. The catalyst was shown to be stable under a broad range of reaction conditions. The effect of pD on the hydrolysis of Gly-Gly showed a bell-shaped profile with the fastest hydrolysis observed at pD 7.4. The observed rate constant for the hydrolysis of Gly-Gly at pD 7.4 and 60 °C was 4.67 × 10(-7) s(-1), representing a significant acceleration as compared to the uncatalyzed reaction. (13)C NMR data were indicative for coordination of Gly-Gly to 1 via its amide oxygen and amine nitrogen atoms, resulting in a hydrolytically active complex. Importantly, the effective hydrolysis of a series of Gly-X dipeptides with different X side chain amino acids in the presence of 1 was achieved, and the observed rate constant was shown to be dependent on the volume, chemical nature, and charge of the X amino acid side chain. To give a mechanistic explanation of the observed catalytic hydrolysis of Gly-Gly, a detailed quantum-chemical study was performed. The theoretical results confirmed the nature of the experimentally suggested binding mode in the hydrolytically active complex formed between Gly-Gly and 1. To elucidate the role of 1 in the hydrolytic process, both the uncatalyzed and the polyoxometalate-catalyzed reactions were examined. In the rate-determining step of the uncatalyzed Gly-Gly hydrolysis, a carboxylic oxygen atom abstracts a proton from a solvent water molecule and the nascent OH nucleophile attacks the peptide carbon atom. Analogous general-base activity of the free carboxylic group was found to take place also in the case of polyoxometalate-catalyzed hydrolysis as the main catalytic effect originates from the -C═O···Zr(IV) binding.

Urchin-like CdS/ZrO2 nanocomposite prepared by microwave-assisted hydrothermal combined with ion-exchange and its multimode photocatalytic activity

NASA Astrophysics Data System (ADS)

Li, Li; Wang, Lili; Zhang, Wenzhi; Zhang, Xiuli; Chen, Xi; Dong, Xue

2014-12-01

A series of urchin-like CdS/ZrO2 nanocomposites with different mole ratios of Cd/Zr were prepared by a two-step method combining the microwave-assisted hydrothermal and ion exchange methods. The products were characterized by X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and N2 adsorption-desorption measurements. The results of the study revealed that the CdS/ZrO2 nanocomposites had mixed phases of tetragonal ZrO2 and hexagonal CdS. Moreover, the samples prepared by the microwave-assisted hydrothermal method possessed the urchin-like structure with a surface composed of protrude-like nanoparticles in large quantities. The absorption in the visible region changed slightly with increasing mole ratio of Cd/Zr. Moreover, compared to the nanocomposites prepared by the conventional heating, the nanocomposites prepared by the microwave-assisted hydrothermal synthesis showed significantly different Brunauer-Emmett-Teller values, and the urchin-like CdS/ZrO2 structures were obtained. The photocatalytic degradation of methyl orange under ultraviolet (UV) light irradiation indicated that the photocatalytic activity of the CdS/ZrO2 nanocomposite with CdS/ZrO2 molar ratio of 30 % was higher than those of CdS, ZrO2, and other different ratios of CdS/ZrO2 nanocomposites. Moreover, under UV light, visible light, and microwave-assisted multimode photocatalytic degradation, the urchin-like CdS/ZrO2 nanocomposites significantly affected the photodegradation of various dyes. To understand the possible reaction mechanism of the photocatalysis by the CdS/ZrO2 nanocomposites, a series of controlled experiments were performed, and the stability and reusability of the CdS/ZrO2 nanocomposites were further investigated by the photocatalytic reaction.

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

NASA Astrophysics Data System (ADS)

Muneshwar, Triratna; Cadien, Ken

2018-03-01

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

Reactive sputtering of δ-ZrH{sub 2} thin films by high power impulse magnetron sputtering and direct current magnetron sputtering

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

Högberg, Hans, E-mail: hans.hogberg@liu.se; Tengdelius, Lina; Eriksson, Fredrik

2014-07-01

Reactive sputtering by high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (DCMS) of a Zr target in Ar/H{sub 2} plasmas was employed to deposit Zr-H films on Si(100) substrates, and with H content up to 61 at. % and O contents typically below 0.2 at. % as determined by elastic recoil detection analysis. X-ray photoelectron spectroscopy reveals a chemical shift of ∼0.7 eV to higher binding energies for the Zr-H films compared to pure Zr films, consistent with a charge transfer from Zr to H in a zirconium hydride. X-ray diffraction shows that the films are single-phase δ-ZrH{sub 2} (CaF{submore » 2} type structure) at H content >∼55 at. % and pole figure measurements give a 111 preferred orientation for these films. Scanning electron microscopy cross-section images show a glasslike microstructure for the HiPIMS films, while the DCMS films are columnar. Nanoindentation yield hardness values of 5.5–7 GPa for the δ-ZrH{sub 2} films that is slightly harder than the ∼5 GPa determined for Zr films and with coefficients of friction in the range of 0.12–0.18 to compare with the range of 0.4–0.6 obtained for Zr films. Wear resistance testing show that phase-pure δ-ZrH{sub 2} films deposited by HiPIMS exhibit up to 50 times lower wear rate compared to those containing a secondary Zr phase. Four-point probe measurements give resistivity values in the range of ∼100–120 μΩ cm for the δ-ZrH{sub 2} films, which is slightly higher compared to Zr films with values in the range 70–80 μΩ cm.« less

Grain Refinement and Mechanical Properties of Cu–Cr–Zr Alloys with Different Nano-Sized TiCp Addition

PubMed Central

Zhang, Dongdong; Bai, Fang; Wang, Yong; Wang, Jinguo; Wang, Wenquan

2017-01-01

The TiCp/Cu master alloy was prepared via thermal explosion reaction. Afterwards, the nano-sized TiCp/Cu master alloy was dispersed by electromagnetic stirring casting into the melting Cu–Cr–Zr alloys to fabricate the nano-sized TiCp-reinforced Cu–Cr–Zr composites. Results show that nano-sized TiCp can effectively refine the grain size of Cu–Cr–Zr alloys. The morphologies of grain in Cu–Cr–Zr composites changed from dendritic grain to equiaxed crystal because of the addition and dispersion of nano-sized TiCp. The grain size decreased from 82 to 28 μm with the nano-sized TiCp content. Compared with Cu–Cr–Zr alloys, the ultimate compressive strength (σUCS) and yield strength (σ0.2) of 4 wt% TiCp-reinforced Cu–Cr–Zr composites increased by 6.7% and 9.4%, respectively. The wear resistance of the nano-sized TiCp-reinforced Cu–Cr–Zr composites increased with the increasing nano-sized TiCp content. The wear loss of the nano-sized TiCp-reinforced Cu–Cr–Zr composites decreased with the increasing TiCp content under abrasive particles. The eletrical conductivity of Cu–Cr–Zr alloys, 2% and 4% nano-sized TiCp-reinforced Cu–Cr–Zr composites are 64.71% IACS, 56.77% IACS and 52.93% IACS, respectively. PMID:28786937

Simulation of Zr content in TiZrCuNi brazing filler metal for Ti6Al4V alloy

NASA Astrophysics Data System (ADS)

Yue, Xishan; Xie, Zonghong; Jing, Yongjuan

2017-07-01

To optimize the Zr content in Ti-based filler metal, the covalent electron on the nearest atoms bond in unit cell ( n A u-v ) with Ti-based BCC structure was calculated, in which the brazing temperature was considered due to its influence on the lattice parameter. Based on EET theory (The Empirical Electron Theory for solid and molecules), n_{{A}}^{{u - v}} represents the strength of the unit cell with defined element composition and structure, which reflects the effect from solid solution strengthening on the strength of the unit cell. For Ti-Zr-15Cu-10Ni wt% filler metal, it kept constant as 0.3476 with Zr as 37.5˜45 wt% and decreased to 0.333 with Zr decreasing from 37.5 to 25 wt%. Finally, it increased up to 0.3406 with Zr as 2˜10 wt%. Thus, Ti-based filler metal with Zr content being 2˜10 wt% is suggested based on the simulation results. Moreover, the calculated covalent electron of n A u-v showed good agreement with the hardness of the joint by filler 37.5Zr and 10Zr. The composition of Ti-10Zr-15Cu-10Ni wt% was verified in this study with higher tensile strength of the brazing joint and uniform microstructure of the interface.

Atom probe tomographic studies of precipitation in Al-0.1Zr-0.1Ti (at.%) alloys.

PubMed

Knipling, Keith E; Dunand, David C; Seidman, David N

2007-12-01

Atom probe tomography was utilized to measure directly the chemical compositions of Al(3)(Zr(1)-(x)Ti(x)) precipitates with a metastable L1(2) structure formed in Al-0.1Zr-0.1Ti (at.%) alloys upon aging at 375 degrees C or 425 degrees C. The alloys exhibit an inhomogeneous distribution of Al(3)(Zr(1)-(x)Ti(x)) precipitates, as a result of a nonuniform dendritic distribution of solute atoms after casting. At these aging temperatures, the Zr:Ti atomic ratio in the precipitates is about 10 and 5, respectively, indicating that Ti remains mainly in solid solution rather than partitioning to the Al(3)(Zr(1)-(x)Ti(x)) precipitates. This is interpreted as being due to the very small diffusivity of Ti in alpha-Al, consistent with prior studies on Al-Sc-Ti and Al-Sc-Zr alloys, where the slower diffusing Zr and Ti atoms make up a small fraction of the Al(3)(Zr(1)-(x)Ti(x)) precipitates. Unlike those alloys, however, the present Al-Zr-Ti alloys exhibit no interfacial segregation of Ti at the matrix/precipitate heterophase interface, a result that may be affected by a significant disparity in the evaporation fields of the alpha-Al matrix and Al(3)(Zr(1)-(x)Ti(x)) precipitates and/or a lack of local thermodynamic equilibrium at the interface.

Bulk Al-Al3Zr composite prepared by mechanical alloying and hot extrusion for high-temperature applications

NASA Astrophysics Data System (ADS)

Pourkhorshid, E.; Enayati, M. H.; Sabooni, S.; Karimzadeh, F.; Paydar, M. H.

2017-08-01

Bulk Al/Al3Zr composite was prepared by a combination of mechanical alloying (MA) and hot extrusion processes. Elemental Al and Zr powders were milled for up to 10 h and heat treated at 600°C for 1 h to form stable Al3Zr. The prepared Al3Zr powder was then mixed with the pure Al powder to produce an Al-Al3Zr composite. The composite powder was finally consolidated by hot extrusion at 550°C. The mechanical properties of consolidated samples were evaluated by hardness and tension tests at room and elevated temperatures. The results show that annealing of the 10-h-milled powder at 600°C for 1 h led to the formation of a stable Al3Zr phase. Differential scanning calorimetry (DSC) results confirmed that the formation of Al3Zr began with the nucleation of a metastable phase, which subsequently transformed to the stable tetragonal Al3Zr structure. The tension yield strength of the Al-10wt%Al3Zr composite was determined to be 103 MPa, which is approximately twice that for pure Al (53 MPa). The yield stress of the Al/Al3Zr composite at 300°C is just 10% lower than that at room temperature, which demonstrates the strong potential for the prepared composite to be used in high-temperature structural applications.

Effects of Al addition on atomic structure of Cu-Zr metallic glass

NASA Astrophysics Data System (ADS)

Li, Feng; Zhang, Huajian; Liu, Xiongjun; Dong, Yuecheng; Yu, Chunyan; Lu, Zhaoping

2018-02-01

The atomic structures of Cu52Zr48 and Cu45Zr48Al7 metallic glasses (MGs) have been studied by molecular dynamic simulations. The results reveal that the molar volume of the Cu45Zr48Al7 MG is smaller than that of the Cu52Zr48 MG, although the size of the Al atom is larger than that of the Cu atom, implying an enhanced atomic packing density achieved by introducing Al into the ternary MG. Bond shortening in unlike atomic pairs Zr-Al and Cu-Al is observed in the Cu45Zr48Al7 MG, which is attributed to strong interactions between Al and (Zr, Cu) atoms. Meanwhile, the atomic packing efficiency is enhanced by the minor addition of Al. Compared with the Cu52Zr48 binary MG, the potential energy of the ternary MG decreases and the glass transition temperature increases. Structural analyses indicate that more Cu- and Al-centered full icosahedral clusters emerge in the Cu45Zr48Al7 MG as some Cu atoms are substituted by Al. Furthermore, the addition of Al leads to more icosahedral medium-range orders in the ternary MG. The increase of full icosahedral clusters and the enhancement of the packing density are responsible for the improved glass-forming ability of Cu45Zr48Al7.

Fabrication and Properties of Plasma-Sprayed Al2O3/ZrO2 Composite Coatings

NASA Astrophysics Data System (ADS)

Dejang, N.; Limpichaipanit, A.; Watcharapasorn, A.; Wirojanupatump, S.; Niranatlumpong, P.; Jiansirisomboon, S.

2011-12-01

Al2O3 /xZrO2 (where x = 0, 3, 13, and 20 wt.%) composite coatings were deposited onto mild steel substrates by atmospheric plasma spraying of mixed α-Al2O3 and nano-sized monoclinic-ZrO2 powders. Microstructural investigation showed that the coatings comprised well-separated Al2O3 and ZrO2 lamellae, pores, and partially molten particles. The coating comprised mainly of metastable γ-Al2O3 and tetragonal-ZrO2 with trace of original α-Al2O3 and monoclinic-ZrO2 phases. The effect of ZrO2 addition on the properties of coatings were investigated in terms of microhardness, fracture toughness, and wear behavior. It was found that ZrO2 improved the fracture toughness, reduced friction coefficient, and wear rate of the coatings.

Investigations on Zr incorporation into Li3V2(PO4)3/C cathode materials for lithium ion batteries.

PubMed

Sun, Hua-Bin; Zhou, Ying-Xian; Zhang, Lu-Lu; Yang, Xue-Lin; Cao, Xing-Zhong; Arave, Hanu; Fang, Hui; Liang, Gan

2017-02-15

Li 3 V 2 (PO 4 ) 3 /C (LVP/C) composites have been modified by different ways of Zr-incorporation via ultrasonic-assisted solid-state reaction. The difference in the effect on the physicochemical properties and the electrochemical performance of LVP between Zr-doping and ZrO 2 -coating has also been investigated. Compared with pristine LVP/C, Zr-incorporated LVP/C composites exhibit better rate capability and cycling stability. In particular, the LVP/C-Zr electrode delivers the highest initial capacity of 150.4 mA h g -1 at 10C with a capacity retention ratio of 88.4% after 100 cycles. The enhanced electrochemical performance of Zr-incorporated LVP/C samples (LVZrP/C and LVP/C-Zr) is attributed to the increased ionic conductivity and electronic conductivity, the improved stability of the LVP structure, and the decreased charge-transfer resistance.

The preparation of Zr-deuteride and phase stability studies of the Zr-D system

NASA Astrophysics Data System (ADS)

Maimaitiyili, T.; Steuwer, A.; Bjerkén, C.; Blomqvist, J.; Hoelzel, M.; Ion, J. C.; Zanellato, O.

2017-03-01

Deuteride phases in the zirconium-deuterium system in the temperature range 25-286 °C have been studied in-situ by high resolution neutron diffraction. The study primarily focused on observations of δ→γ transformation at 180 °C, and the peritectoid reaction α + δ ↔ γ at 255 °C in commercial grade Zr powder that was deuterated to a deuterium/Zr ratio of one to one. A detailed description of the zirconium deuteride preparation route by high temperature gas loading is also described. The lattice parameters of α-Zr, δ-ZrDx and ε-ZrDx were determined by whole pattern crystal structure analysis, using Rietveld and Pawley refinements, and are in good agreement with values reported in the literature. The controversial γ-hydride phase was observed both in-situ and ex-situ in deuterated Zr powder after a heat treatment at 286 °C and slow cooling.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Tracer study of oxygen and hydrogen uptake by Mg alloys in air with water vapor

DOE PAGES

Brady, M. P.; Fayek, M.; Meyer, H. M.; ...

2015-05-15

We studied the pure oxidation of Mg, Mg–3Al–1Zn (AZ31B), and Mg–1Zn–0.25Zr–<0.5Nd (ZE10A) at 85 °C in humid air using sequential exposures with H 2 18O and D 2 16O for water vapor. Incorporation of 18O in the hydroxide/oxide films indicated that oxygen from water vapor participated in the reaction. Moreover, penetration of hydrogen into the underlying metal was observed, particularly for the Zr- and Nd-containing ZE10A. Isotopic tracer profiles suggested a complex mixed inward/outward film growth mechanism.

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

PubMed

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

2018-03-28

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

Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by charge flipping method

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

Chinthaka Silva, G.W., E-mail: chinthaka.silva@gmail.com; Kercher, Andrew A., E-mail: rokparent@comcast.net; Hunn, John D., E-mail: hunnjd@ornl.gov

2012-10-15

Samples with five different zirconium carbide compositions (C/Zr molar ratio=0.84, 0.89, 0.95, 1.05, and 1.17) have been fabricated and studied using a variety of experimental techniques. Each sample was zone refined to ensure that the end product was polycrystalline with a grain size of 10-100 {mu}m. It was found that the lattice parameter was largest for the x=0.89 composition and smallest for the x=1.17 total C/Zr composition, but was not linear; this nonlinearity is possibly explained using electron densities calculated using charge flipping technique. Among the five samples, the unit cell of the ZrC{sub 0.89} sample showed the highest electronmore » density, corresponding to the highest carbon incorporation and the largest lattice parameter. The ZrC{sub 0.84} sample showed the lowest carbon incorporation, resulting in a larger number of carbon vacancies and resultant strain. Samples with larger carbon ratios (x=0.95, 1.05, and 1.17) showed a slight decrease in lattice parameter, due to a decrease in electron density. Optical anisotropy measurements suggest that these three samples contained significant amounts of a graphitic carbon phase, not bonded to the Zr atoms. - Graphical abstract: Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by the charge flipping method. Highlights: Black-Right-Pointing-Pointer The lattice parameter variation: ZrC{sub 0.89}>ZrC{sub 0.84}>ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}. Black-Right-Pointing-Pointer Surface oxygen with no correlation to the lattice parameter variation. Black-Right-Pointing-Pointer ZrC{sub 0.89} had highest electron densities correspond to highest carbon incorporation. Black-Right-Pointing-Pointer Second highest lattice parameter in ZrC{sub 0.84} due to strain. Black-Right-Pointing-Pointer Unit cell electron density order: ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}.« less

Zirconium doped TiO2 thin films deposited by chemical spray pyrolysis

NASA Astrophysics Data System (ADS)

Juma, A.; Oja Acik, I.; Oluwabi, A. T.; Mere, A.; Mikli, V.; Danilson, M.; Krunks, M.

2016-11-01

Chemical spray pyrolysis (CSP) is a flexible deposition technique that allows for mixing of the precursor solutions in different proportions suitable for doping thin films. The CSP method was used to dope TiO2 thin films with Zr by adding zirconium(IV) acetylacetonate into a solution of titanium(IV) isopropoxide in ethanol stabilized by acetylacetone at [Zr]/[Ti] of 0, 5, 10 and 20 at%. The Zr-doped TiO2 thin films were uniform and homogeneous showing much smaller grains than the undoped TiO2 films. Zr stabilized the anatase phase to temperatures above 800 °C depending on Zr concentration in the spray solution. The concentration of Zr determined by XPS was 6.4 at% for the thin film deposited from the 20 at% solution. According to AFM studies, Zr doping decreased the root mean square roughness of TiO2 film from 5.9 to 1.1 nm. An XRD study of samples with the highest Zr amount showed the ZrTiO4 phase started forming after annealing at 800 °C. The optical band gap for TiO2 decreased from 3.3 eV to 3.0 eV after annealing at 800 °C but for the TiO2:Zr(20) film it remained at 3.4 eV. The dielectric constant increased by more than four times with Zr-doping and this was associated with the change in the bond formations caused by substitution of Ti by Zr in the lattice.

Corrosion Performance of Nano-ZrO₂ Modified Coatings in Hot Mixed Acid Solutions.

PubMed

Xu, Wenhua; Wang, Zhenyu; Han, En-Hou; Wang, Shuai; Liu, Qian

2018-06-01

A nano-ZrO₂ modified coating system was prepared by incorporation of nano-ZrO₂ concentrates into phenolic-epoxy resin. The corrosion performance of the coatings was evaluated in hot mixed acid solution, using electrochemical methods combined with surface characterization, and the effects of nano-ZrO₂ content were specially focused on. The results showed that 1% and 3% nano-ZrO₂ addition enhanced the corrosion resistance of the coatings, while 5% nano-ZrO₂ addition declined it. The coating with 3% nano-ZrO₂ presented the minimum amount of species diffusion, the lowest average roughness (5.94 nm), and the highest C/O ratio (4.55) and coating resistance, and it demonstrated the best corrosion performance among the coating specimens.

THERMODYNAMIC PROPERTIES OF Zr AND Hf HALIDES (in Rumanian)

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

Lungu, S.N.

1962-01-01

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

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

NASA Astrophysics Data System (ADS)

Lee, Jinil

In SiC/SiC ceramic matrix composites, toughness is obtained by adding a fiber coating which provides a weak interface for crack deflection and debonding between the fiber and the matrix. However, the most commonly used fiber coatings, carbon and boron nitride, are unstable in oxidative environments. In the present study, the feasibility of using a chemically vapor deposited zirconia (CVD-ZrO 2) fiber coating as an oxidation-resistant interphase for SiC/SiC composites was investigated. The feasibility of the CVD-ZrO2 coating as a useful interphase for SiC/SiC composites was investigated with emphasis on developing critical processing-microstructure relationships. A study of morphological evolution in the CVD-ZrO2 coating suggested that a size-controlled displacive phase transformation from tetragonal ZrO2 (t-ZrO2) to monoclinic ZrO2 (m-ZrO2) was the key mechanism responsible for the weak interface behavior exhibited by the ZrO2 coating. The pre-delamination occurred as a result of (i) continuous formation of t-ZrO2 nuclei on the deposition surface; (ii) martensitic transformation of the tetragonal phase to a monoclinic phase upon reaching a critical grain size; and (iii) development of significant compressive hoop stresses due to the volume dilation associated with the transformation. We also discovered that low oxygen partial pressure in the CVD reactor was required for the nucleation of t-ZrO2 and was ultimately responsible for the delamination behavior. The effects of oxygen partial pressure on the nucleation behavior of the CVD-ZrO2 coating was systematically studied by intentionally adding the controlled amount of O2 into the CVD chamber. Characterization results suggested that the number density of t-ZrO2 nuclei apparently decreased with increasing the oxygen partial pressure from 0.004 to 1.6 Pa. Also, the coating layer became more columnar and contained larger m-ZrO2 grains. The observed relationships between the oxygen partial pressure and the morphological characteristics of the ZrO 2 coating were explained in the context of the grain size and oxygen deficiency effects which have been previously reported to cause the stabilization of the t-ZrO2 phase in bulk ZrO2 specimens.

Preparation and characterization of Mg-Zr mixed oxide aerogels and their application as aldol condensation catalysts.

PubMed

Sádaba, Irantzu; Ojeda, Manuel; Mariscal, Rafael; Richards, Ryan; López Granados, Manuel

2012-10-08

A series of Mg-Zr mixed oxides with different nominal Mg/(Mg+Zr) atomic ratios, namely 0, 0.1, 0.2, 0.4, 0.85, and 1, is prepared by alcogel methodology and fundamental insights into the phases obtained and resulting active sites are studied. Characterization is performed by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N(2) adsorption-desorption isotherms, and thermal and chemical analysis. Cubic Mg(x)Zr(1-x)O(2-x) solid solution, which results from the dissolution of Mg(2+) cations within the cubic ZrO(2) structure, is the main phase detected for the solids with theoretical Mg/(Mg+Zr) atomic ratio ≤0.4. In contrast, the cubic periclase (c-MgO) phase derived from hydroxynitrates or hydroxy precursors predominates in the solid with Mg/(Mg+Zr)=0.85. c-MgO is also incipiently detected in samples with Mg/(Mg+Zr)=0.2 and 0.4, but in these solids the c-MgO phase mostly arises from the segregation of Mg atoms out of the alcogel-derived c-Mg(x)Zr(1-x)O(2-x) phase during the calcination process, and therefore the species c-MgO and c-Mg(x)Zr(1-x)O(2-x) are in close contact. Regarding the intrinsic activity in furfural-acetone aldol condensation in the aqueous phase, these Mg-O-Zr sites located at the interface between c-Mg(x)Zr(1-x)O(2-x) and segregated c-MgO display a much larger intrinsic activity than the other noninterface sites that are present in these catalysts: Mg-O-Mg sites on c-MgO and Mg-O-Zr sites on c-Mg(x)Zr(1-x)O(2-x). The very active Mg-O-Zr sites rapidly deactivate in the furfural-acetone condensation due to the leaching of active phases, deposition of heavy hydrocarbonaceous compounds, and hydration of the c-MgO phase. Nonetheless, these Mg-Zr materials with very high specific surface areas would be suitable solid catalysts for other relevant reactions catalyzed by strong basic sites in nonaqueous environments. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

2014-10-15

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

Application Electrochemical Impedance Spectroscopy Methods to Evaluation Corrosion Behavior of Stainless steels 304 in Nanofluids Media

NASA Astrophysics Data System (ADS)

Hadi Prajitno, Djoko; Umar, Efrizon; Gustaman Syarif, Dani

2017-01-01

Corrosion is a common problem in many engineering metals and alloys. Electrochemical methods are commonly instrument to use as tool to study the corrosion behavior of the metals and alloy. This method was examined interaction between a surface of the metals and alloys in corrosive media. The present paper, the effects of nano particle ZrO2 as an additive to aqua de mineralized on the corrosion behavior of stainless steel were investigated. Electrochemical impedance spectroscopy (EIS) testing was performed in both de mineralized water and demineralized water contain nano particle 0,01% ZrO2 as Nano fluid. Surface morphology examination of the specimens showed that microstructure of stainless steel 304 alloys relatively unchanged after corrosion and EIS testing. According to the corrosion potential examination of the stainless steel 304 in nanofluid media, it showed that stainless steel 304 actively corroded in nanofluida media. The value of anodic Tafel slope stainless steel 304 in nanofluid higher compare with in demineralized water. Tafel polarization examination show that corrosion rate of stainless steel 304 in nanofluid higher compare with corrosin rate in demineralized media.EIS technique show that impedance of stainless steel 304 in nanofluid lower compare with in demineralized media, resulting in an increase in the corrosion rates of these stainless steel 304 specimens in nano fluids

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

PubMed

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

2018-02-06

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

Energy Distributions of Neutrons Scattered from Graphite, Light and Heavy Water, Ice, Zirconium Hydride, Lithium Hydride, Sodium Hydride and Ammonium Chloride by the Beryllium Detector Method

DOE R&D Accomplishments Database

Woods, A. D. B.; Brockhouse, Bertram N.; Sakamoto, M.; Sinclair, R. N.

1960-09-12

Energy distributions of neutrons scattered from various moderators and from several hydrogenous substances were measured at energy transfers of 0.02 to 0.24 ev. Results from experiments on graphite, light and heavy water, ice, ZrH, LiH, NaH, and NH4Cl are included. It is noted that the results are of a preliminary character; however, they are probably the most accurate measurements of high-energy transfers yet made. (J.R.D.)

Method development for the determination of fluorine in water samples via the molecular absorption of strontium monofluoride formed in an electrothermal atomizer

NASA Astrophysics Data System (ADS)

Ozbek, Nil; Akman, Suleyman

The presence of fluorine (F) was detected via the rotational molecular absorption line of diatomic strontium-monofluoride (SrF) generated in the gas phase at 651.187 nm using high-resolution continuum source electrothermal atomic absorption spectrometry. Upon the addition of excess strontium (Sr) as the nitrate, the fluorine in the sample was converted to SrF in the gas phase of a graphite furnace. The effects on the accuracy, precision and sensitivity of variables such as the SrF wavelength, graphite furnace program, amount of Sr, coating of the graphite tube and platform with Zr and Ir and the use of a modifier were investigated and optimized. It was determined that there was no need to use a modifier or to cover the platform/tubes with Zr or Ir. Fluorine concentrations in various water samples (certified waste water, tap water, drinking water and mineral water) were determined using 20 μg of Sr as the molecule-forming reagent and applying a maximum pyrolysis temperature of 800 °C and a molecule-forming temperature of 2200 °C with a heating rate of 2000 °C s- 1. Good linearity was maintained up to 0.1 μg of F. The accuracy and precision of the method were tested by analyzing certified reference wastewater. The results were in good agreement with certified values, and the precision was satisfactory (RSD < 10%). The limit of detection and the characteristic mass for the method were 0.36 ng and 0.55 ng, respectively. Finally, the fluorine concentrations in several drinking water and mineral water samples taken from the market were determined. The results were in good agreement with the values supplied by the producers. No significant differences were found between the results from the linear calibration and standard addition techniques. The method was determined to be simple, fast, accurate and sensitive.

Atomic layer deposition of zirconium silicate films using zirconium tetra-tert-butoxide and silicon tetrachloride

NASA Astrophysics Data System (ADS)

Kim, Won-Kyu; Kang, Sang-Woo; Rhee, Shi-Woo

2003-09-01

A new precursor combination (SiCl4 and Zr(OtC4H9)4) was used to deposit Zr silicate with Zr(OtC4H9)4 as a zirconium source and oxygen source at the same time. SiCl4 and Zr(OtC4H9)4 have higher vapor pressures than their counterpart, ZrCl4 and tetra-n-butyl orthosilicate (TBOS), and it was expected that the cycle time would be shorter. The deposition temperature of the new combination was about 150 °C lower than that of ZrCl4 and TBOS. The film was zirconium rich while it was silicon rich with ZrCl4 and TBOS. Growth rate (nm/cycle), composition ratio [Zr/(Zr+Si)], and chlorine impurity were decreased with increasing deposition temperature from 125 to 225 °C. The composition ratio of the film deposited at 225 °C was 0.53 and the chlorine content was about 0.4 at. %. No carbon was detected by x-ray photoelectron spectroscopy.

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

PubMed

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

2005-09-01

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

Synthesis of zirconium carbide whiskers by a combination of microwave hydrothermal and carbothermal reduction

NASA Astrophysics Data System (ADS)

Li, Kezhi; Zhou, Xuan; Zhao, Zhigang; Chen, Chunyu; Wang, Changcong; Ren, Biyun; Zhang, Leilei

2018-02-01

Zirconium carbide (ZrC) whiskers were successfully synthesized by a combination of microwave hydrothermal (MH) and carbothermal reduction. The precursors of ZrC whiskers were produced by MH, subsequently carbothermally reduced to ZrC whiskers at 1100-1600 °C in an Ar atmosphere. Effects of the reduction temperature and precursors with various carbon/zirconium (C/Zr) molar ratios on the synthesis of ZrC whiskers were investigated. The results showed that the carbothermal reduction occurred at 1100 °C, and terminated at a relatively low temperature (1400 °C). When the reduction temperature was 1500 °C and the C/Zr molar ratio was 5:1, the ZrC whiskers with the largest aspect ratio and the most uniform distribution were produced. The whiskers exhibited the diameters of 0.1-2 μm and the lengths of 5-30 μm. The synthesized ZrC whiskers with a single crystalline phase displayed cylindrical and pagoda-like morphologies. The growth of ZrC whiskers was considered to be governed by the Ostwald ripening and S-L-S mechanism.

Band gap tuning of amorphous Al oxides by Zr alloying

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

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

2016-08-29

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

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

NASA Astrophysics Data System (ADS)

Harte, Allan; Griffiths, Malcolm; Preuss, Michael

2018-07-01

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

Effects of ammonium hydroxide on the structure and gas adsorption of nanosized Zr-MOFs (UiO-66).

PubMed

Abid, Hussein Rasool; Ang, Ha Ming; Wang, Shaobin

2012-05-21

Several zirconium-based metal-organic frameworks (Zr-MOFs) have been synthesized using ammonium hydroxide as an additive in the synthesis process. Their physicochemical properties have been characterized by N(2) adsorption/desorption, XRD, SEM, FTIR, and TGA, and their application in CO(2) adsorption was evaluated. It was found that addition of ammonium hydroxide produced some effects on the structure and adsorption behavior of Zr-MOFs. The pore size and pore volume of Zr-MOFs were enhanced with the additive, however, specific surface area of Zr-MOFs was reduced. Using an ammonium hydroxide additive, the crystal size of Zr-MOF was reduced with increasing amount of the additive. All the samples presented strong thermal stability. Adsorption tests showed that capacity of CO(2) adsorption on the Zr-MOFs under standard conditions was reduced due to decreased micropore fractions. However, modified Zr-MOFs had significantly lower adsorption heat. The adsorption capacity of carbon dioxide was increased at high pressure, reaching 8.63 mmol g(-1) at 987 kPa for Zr-MOF-NH(4)-2.

New Experimental Results on the Interaction of Molten Corium with Reactor Vessel Steel

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

Bechta, S.V.; Khabensky, V.B.; Granovsky, V.S.

In order to justify the concept of in-vessel core melt retention, it is necessary to understand the thermal and physico-chemical phenomena. Especially the interaction of the molten pool with the reactor vessel during outside cooling needs to be understood. These phenomena are very complex, in particular, where interactions with the oxidic melt are concerned. In the early stages of the retention process, the oxidic corium and the vessel steel interact under the conditions of low oxygen potential in the melt. These conditions can be simulated by a molten corium having the composition UO{sub 2}/ZrO{sub 2}/Zr, where the degree of Zr-oxidationmore » is in the range between 30 % (C-30) and 100 % (C-100). Corresponding experiments with prototypic melts at low oxygen potentials are being performed in the ISTC METCOR project 2. phase. These are: - MC 5 of corium composition 71w%UO{sub 2}-29w%ZrO{sub 2} (C-100) in neutral atmosphere (argon), - MC 6 of corium composition 76w%UO{sub 2}-9w%ZrO{sub 2}-15w%Zr (C{approx}30), also in argon. In test MC 5, the interaction of molten C-100 corium with a water-cooled steel specimen was studied for the following maximum temperatures at the specimen surface: 1075 deg. C, 1180 deg. C, 1315 deg. C and 1435 deg. C. The total duration of the experiment was {approx} 36 hours. The MC 5 test serves as a reference test for determining the characteristics of the interaction between oxidic melt and steel specimen under the conditions of minimum chemical interaction potential. To investigate the effect of substoichiometry, test No 6 was then performed with sub-oxidized molten corium C{approx}30. The maximum surface temperature of the cooled steel specimen was held at {approx} 1400 deg. C. The test duration was {approx} 10 hours. The ablation phenomena were found to differ significantly from those observed both in the reference test, as well as in former tests with oxidized melts, as they involved the formation of a low-melting metallic phase at the interface which contains iron, zirconium and uranium. The paper summarizes the results of the experiments and of the performed posttest analysis for tests MC 5 and MC 6. (authors)« less

Sol-gel modification of wood substrates to retard weathering

Treesearch

Mandla A Tshabalala; Sam Williams

2008-01-01

Wood specimens were treated with sol-gel systems based on metalorganic precursors of silicon (Si), iron (Fe), zirconium (Zr), and titanium (Ti). The effect of these sol-gel systems on weathering properties of wood was investigated. These sol-gel systems were found to have a positive effect on surface color stability and water vapor resistance of the specimens. Under...

PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Wilson, A.S.

1958-08-12

An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

Superior removal of arsenic from water with zirconium metal-organic framework UiO-66.

PubMed

Wang, Chenghong; Liu, Xinlei; Chen, J Paul; Li, Kang

2015-11-12

In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5-280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds.

Superior removal of arsenic from water with zirconium metal-organic framework UiO-66

PubMed Central

Wang, Chenghong; Liu, Xinlei; Chen, J. Paul; Li, Kang

2015-01-01

In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5–280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds. PMID:26559001

Accelerated Discovery of Large Electrostrains in BaTiO3 -Based Piezoelectrics Using Active Learning.

PubMed

Yuan, Ruihao; Liu, Zhen; Balachandran, Prasanna V; Xue, Deqing; Zhou, Yumei; Ding, Xiangdong; Sun, Jun; Xue, Dezhen; Lookman, Turab

2018-02-01

A key challenge in guiding experiments toward materials with desired properties is to effectively navigate the vast search space comprising the chemistry and structure of allowed compounds. Here, it is shown how the use of machine learning coupled to optimization methods can accelerate the discovery of new Pb-free BaTiO 3 (BTO-) based piezoelectrics with large electrostrains. By experimentally comparing several design strategies, it is shown that the approach balancing the trade-off between exploration (using uncertainties) and exploitation (using only model predictions) gives the optimal criterion leading to the synthesis of the piezoelectric (Ba 0.84 Ca 0.16 )(Ti 0.90 Zr 0.07 Sn 0.03 )O 3 with the largest electrostrain of 0.23% in the BTO family. Using Landau theory and insights from density functional theory, it is uncovered that the observed large electrostrain is due to the presence of Sn, which allows for the ease of switching of tetragonal domains under an electric field. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Implementation of metal-friendly EAM/FS-type semi-empirical potentials in HOOMD-blue: A GPU-accelerated molecular dynamics software

DOE PAGES

Yang, Lin; Zhang, Feng; Wang, Cai-Zhuang; ...

2018-01-12

We present an implementation of EAM and FS interatomic potentials, which are widely used in simulating metallic systems, in HOOMD-blue, a software designed to perform classical molecular dynamics simulations using GPU accelerations. We first discuss the details of our implementation and then report extensive benchmark tests. We demonstrate that single-precision floating point operations efficiently implemented on GPUs can produce sufficient accuracy when compared against double-precision codes, as demonstrated in test simulations of calculations of the glass-transition temperature of Cu 64.5Zr 35.5, and pair correlation function of liquid Ni 3Al. Our code scales well with the size of the simulating systemmore » on NVIDIA Tesla M40 and P100 GPUs. Compared with another popular software LAMMPS running on 32 cores of AMD Opteron 6220 processors, the GPU/CPU performance ratio can reach as high as 4.6. In conclusion, the source code can be accessed through the HOOMD-blue web page for free by any interested user.« less