Fabrication and magnetic properties of Fe and Co co-doped ZrO2

NASA Astrophysics Data System (ADS)

Okabayashi, J.; Kono, S.; Yamada, Y.; Nomura, K.

2011-12-01

We investigate the effects of Fe and Co co-doping on the magnetic and electronic properties of ZrO2 ceramics prepared by a sol-gel method, and study their dependence on the annealing temperature. Dilute Fe and Co co-doping into ZrO2 exhibits ferromagnetic behavior at room temperature for annealing temperatures above 900 °C, accompanying the phase transition from tetragonal to monoclinic structure in ZrO2. The electronic structures are studied by x-ray absorption spectroscopy and Mössbauer spectroscopy, which suggest that the Fe3+ and Co2+/Co3+ mixing states are dominant in Fe and Co co-doped ZrO2.

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

NASA Astrophysics Data System (ADS)

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

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

The affects of doping Eu 3+ on structures and morphology of ZrO 2 nanocrystals

NASA Astrophysics Data System (ADS)

Yu, Lixin; Liu, Hai; Nogami, Masayuki

2010-07-01

The ZrO 2 and ZrO 2:Eu 3+ nanocrystals (NCs) were prepared by a hydrothermal method. The samples were sintered at different temperatures (500, 800 and 1100 °C). The results indicate that the Eu 3+ ions affect not only the structures of hosts (ZrO 2), but also the morphology of hosts. The shape of ZrO 2:Eu 3+ NCs heated at 1100 °C is the one-dimensional nanorod, while is the zero-dimensional nanoparticle for pure ZrO 2 samples sintered at the same temperature. The excitation and emission spectra of ZrO 2:Eu 3+ NCs were studied. In excitation spectra, the charge transfer band of Eu 3+ in ZrO 2 NCs heated at 1100 °C evidently blue-shifts in comparison with the NCs calcined at 500 and 800 °C. The relative intensity of 5D-7F transitions of Eu 3+ ions and color chromaticity for nanorods are increased in comparison with the nanoparticles.

Intense visible light emission from stress-activated ZrO2:Ti

NASA Astrophysics Data System (ADS)

Akiyama, Morito; Xu, Chao-Nan; Nonaka, Kazuhiro

2002-07-01

We have investigated the luminescence phenomena from stress-activated ZrO2:Ti. The luminescence is clearly visible to the naked eye in the atmosphere. The luminescence center has been identified as the Ti4+ ion from spectra of the mechanoluminescence and also from photoluminescence studies of ZrO2:Ti. The mechanoluminescence intensity decreases on repetitive application of stress but recovers completely on irradiation with ultraviolet light. ZrO2 is an n-type semiconductor and has electron traps. It is suggested that the mechanoluminescence mechanism arises from the movement of dislocations and recombination between electrons and holes released from these traps which are associated with the Ti4+ centers.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

X ray photoelectron spectroscopy (XPS) analysis of Photosensitive ZrO2 array

NASA Astrophysics Data System (ADS)

Li, Y.; Zhao, G.; Zhu, R.; Kou, Z.

2018-03-01

Based on organic zirconium source as the starting material, by adding chemical modifiers which are made up with photosensitive ZrO2 sol. A uniformed ZrO2 array dot was fabricated with a mean diameter of around 800 nm. By using UV-vis spectra and X-ray photoelectron spectroscopy analysis method, studies the photosensitive ZrO2 gel film of photochemical reaction process and the photosensitive mechanism, to determine the zirconium atom centered chelate structure, reaction formed by metal chelate Zr atom for the center, and to establish the molecular model of the chelate. And studied the ultraviolet light in the process of the variation of the XPS spectra, Zr3d5/2 to 184.9 eV corresponding to the binding energy of the as the combination of state peak gradually reduce; By combining with the status of Zr-O peak gradually increase; The strength of the peak is gradually decline. This suggests that in the process of ultraviolet light photo chemical reaction happened. This study is of great significance to the micro fabrication of ZrO2 array not only to the memory devices but also to the optical devices.

Substitutional Cd and Cd-Oxygen Vacancy Complexes in ZrO2 and Ce-doped ZrO_2

NASA Astrophysics Data System (ADS)

Zacate, Matthew O.; Karapetrova, E.; Platzer, R.; Gardner, J. A.; Evenson, W. E.; Sommers, J. A.

1996-03-01

We are using Perturbed Angular Correlation Spectroscopy (PAC) to study oxygen vacancy (V_O) dynamics in tetragonal ZrO2 and Ce-doped ZrO_2. PAC requires a radioactive probe atom, Cd in this study, which sits substitutionally for a Zr ion. Cd is doubly-negatively charged relative to the lattice and attracts doubly-positively charged V_Os. Pure tetragonal zirconia exists only above 950 ^circC and in this temperature range, the V_Os are very mobile. Above 950 ^circC we observe V_Os rapidly hopping about the Cd allowing us to determine the VO concentration and the trapping energy. We have been Ce-doping to stabilize the tetragonal phase to lower temperature to determine the electric field gradient the Cd experiences due to a stationary V_O. As a consequence of the Ce-doping, we observe a local lattice distortion about the Cd which increases with Ce-doping.

Ultrasound-assisted sol-gel synthesis of ZrO2.

PubMed

Guel, Marlene Lariza Andrade; Jiménez, Lourdes Díaz; Hernández, Dora Alicia Cortés

2017-03-01

Synthesis of tetragonal ZrO 2 by both conventional sol-gel and ultrasound-assisted sol-gel methods and using a non-ionic surfactant Tween-20, was performed. A porous microstructure composed of nanometric particles was observed. Tetragonal ZrO 2 was obtained using a low heat treatment temperature of powders, 500°C by both methods. A higher crystallinity and a shorter reaction time were observed when ultrasound was used in the sol-gel method due to the cavitation phenomenon. Copyright © 2016 Elsevier B.V. All rights reserved.

Improved conversion efficiency of dye sensitized solar cell using Zn doped TiO2-ZrO2 nanocomposite

NASA Astrophysics Data System (ADS)

Tomar, Laxmi J.; Bhatt, Piyush J.; Desai, Rahul K.; Chakrabarty, B. S.; Panchal, C. J.

2016-05-01

TiO2-ZrO2 and Zn doped TiO2-ZrO2 nanocomposites were prepared by hydrothermal method for dye sensitized solar cell (DSSC) application. The structural and optical properties were investigated by X -ray diffraction (XRD) and UV-Visible spectroscopy respectively. XRD results revealed the formation of material in nano size. The average crystallite size is 22.32 nm, 17.41 nm and 6.31 nm for TiO2, TiO2-ZrO2 and Zn doped TiO2-ZrO2 nanocomposites respectively. The optical bandgap varies from 2.04 eV to 3.75 eV. Dye sensitized solar cells were fabricated using the prepared material. Pomegranate juice was used as a sensitizer and graphite coated conducting glass plate was used as counter electrode. The I - V characteristics were recorded to measure photo response of DSSC. Photovoltaic parameter like open circuit voltage, power conversion efficiency, and fill factor were evaluated for fabricated solar cell. The power conversion efficiency of DSSC fabricated with TiO2, TiO2-ZrO2 and Zn doped TiO2-ZrO2 nanocomposites were found 0.71%, 1.97% and 4.58% respectively.

Atomic layer deposition and properties of ZrO2/Fe2O3 thin films

PubMed Central

Seemen, Helina; Ritslaid, Peeter; Rähn, Mihkel; Tamm, Aile; Kukli, Kaupo; Kasikov, Aarne; Link, Joosep; Stern, Raivo; Dueñas, Salvador; Castán, Helena; García, Héctor

2018-01-01

Thin solid films consisting of ZrO2 and Fe2O3 were grown by atomic layer deposition (ALD) at 400 °C. Metastable phases of ZrO2 were stabilized by Fe2O3 doping. The number of alternating ZrO2 and Fe2O3 deposition cycles were varied in order to achieve films with different cation ratios. The influence of annealing on the composition and structure of the thin films was investigated. Additionally, the influence of composition and structure on electrical and magnetic properties was studied. Several samples exhibited a measurable saturation magnetization and most of the samples exhibited a charge polarization. Both phenomena were observed in the sample with a Zr/Fe atomic ratio of 2.0. PMID:29441257

Optical and structural characterization of Ge clusters embedded in ZrO2

NASA Astrophysics Data System (ADS)

Agocs, E.; Zolnai, Z.; Rossall, A. K.; van den Berg, J. A.; Fodor, B.; Lehninger, D.; Khomenkova, L.; Ponomaryov, S.; Gudymenko, O.; Yukhymchuk, V.; Kalas, B.; Heitmann, J.; Petrik, P.

2017-11-01

The change of optical and structural properties of Ge nanoclusters in ZrO2 matrix have been investigated by spectroscopic ellipsometry versus annealing temperatures. Radio-frequency top-down magnetron sputtering approach was used to produce the samples of different types, i.e. single-layers of pure Ge, pure ZrO2 and Ge-rich-ZrO2 as well as multi-layers stacked of 40 periods of 5-nm-Ge-rich-ZrO2 layers alternated by 5-nm-ZrO2 ones. Germanium nanoclusters in ZrO2 host were formed by rapid-thermal annealing at 600-800 °C during 30 s in nitrogen atmosphere. Reference optical properties for pure ZrO2 and pure Ge have been extracted using single-layer samples. As-deposited multi-layer structures can be perfectly modeled using the effective medium theory. However, annealed multi-layers demonstrated a significant diffusion of elements that was confirmed by medium energy ion scattering measurements. This fact prevents fitting of such annealed structure either by homogeneous or by periodic multi-layer models.

Surface Modification of Solution-Processed ZrO2 Films through Double Coating for Pentacene Thin-Film Transistors

NASA Astrophysics Data System (ADS)

Kwon, Jin-Hyuk; Bae, Jin-Hyuk; Lee, Hyeonju; Park, Jaehoon

2018-03-01

We report the modification of surface properties of solution-processed zirconium oxide (ZrO2) dielectric films achieved by using double-coating process. It is proven that the surface properties of the ZrO2 film are modified through the double-coating process; the surface roughness decreases and the surface energy increases. The present surface modification of the ZrO2 film contributes to an increase in grain size of the pentacene film, thereby increasing the field-effect mobility and decreasing the threshold voltage of the pentacene thin-film transistors (TFTs) having the ZrO2 gate dielectric. Herein, the molecular orientation of pentacene film is also studied based on the results of contact angle and X-ray diffraction measurements. Pentacene molecules on the double-coated ZrO2 film are found to be more tilted than those on the single-coated ZrO2 film, which is attributed to the surface modification of the ZrO2 film. However, no significant differences are observed in insulating properties between the single-and the double-coated ZrO2 dielectric films. Consequently, the characteristic improvements of the pentacene TFTs with the double-coated ZrO2 gate dielectric film can be understood through the increase in pentacene grain size and the reduction in grain boundary density.

Influence of in situ and ex situ ZrO2 addition on the properties of MgB2

NASA Astrophysics Data System (ADS)

Chen, S. K.; Glowacki, B. A.; MacManus-Driscoll, J. L.; Vickers, M. E.; Majoros, M.

2004-02-01

The effect of ZrO2 addition on the properties of MgB2 has been studied using in situ and ex situ processes. The in situ process was performed by introducing ZrO2 from the milling tools into MgB2 throughout the planetary ball milling, whereas the ex situ process was accomplished by mixing ZrO2 from the milling tools with MgB2 by hand grinding in a mortar. A detectable amount of ZrO2 was present in MgB2 after 4 h of milling during the in situ process and its content increased with milling time as expected. The 400 h milled powder was partially amorphized and showed the formation of a minority ZrB2 phase. For milling up to 100 h, diamagnetism of MgB2 was significantly reduced while Tc remained unchanged. Superconductivity was totally destroyed after 148 h of milling. The loss of superconductivity is attributed to the effect of disordering induced by mechanical milling. As a result of in situ ZrO2 addition, the initial Tc and crystal structure of MgB2 could not be restored upon annealing. With increasing milling time, the expansion of lattice parameters in both the a-axis and c-axis may be due to possible substitution of Mg or B by Zr. The result from the magnetic measurement shows that Jc of MgB2 is deteriorated by in situ ZrO2 addition. On the other hand, ex situ ZrO2 addition with annealing did not degrade the Tc of MgB2.

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.

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

NASA Technical Reports Server (NTRS)

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

2003-01-01

Zirconia (ZrO2) has great technological importance in structural, electrical, and chemical applications. It is the crucial component for state-of-the art thermal barrier coatings and an enabling component as a solid electrolyte for solid-oxide fuel cell systems. Pure ZrO2 is of limited use for industrial applications because of the phase transformations that occur. Upon the addition of stabilizers, cubic (c-ZrO2) and tetragonal (t-ZrO2) forms can be preserved. It is the stabilized and partially stabilized forms of zirconia that function as thermal barrier coatings, solid electrolytes, and oxygen sensors and that have numerous applications in the electrochemical industry. The cubic form of ZrO2 is typically stabilized through Y2O3 additions. However, Y2O3-stabilized zirconia is susceptible to deformation at high temperatures (greater than 900 C) because of the large number of slip systems and the high oxygen diffusion rates, which result in high creep rates at high temperatures. Successful use of ZrO2 at high temperatures requires that new dopant additives be found that will retain or enhance the desirable properties of cubic ZrO2 and yet produce a material with lower creep rates. At the NASA Glenn Research Center, erbium oxide (Er2O3) was identified as a promising dopant for improving the creep resistance of. ZrO2. The selection of Er2O3 was based on the strong interactions of point defects and dislocations. Single crystals of 5 mol% Er2O3- doped ZrO2 rods (4 mm in diameter) and monofilaments (200 to 300 mm in diameter and 30 cm long) were grown using the laser-heated float zone technique, and their creep behavior was measured as a function of temperature. The addition of 5 mol% Er2O3 to single-crystal ZrO2 improved its creep resistance at high temperatures by 2 to 3 orders of magnitude over state-of-the-art Y2O3-doped crystals. Detailed microstructural characterization of ZrO2-Er2O3 single crystals has identified new mechanisms for improving the creep resistance

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

NASA Astrophysics Data System (ADS)

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

2005-11-01

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

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

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

Afterglow based detection and dosimetry of beta particle irradiated ZrO2.

PubMed

Salas-Juárez, Ch J; Cruz-Vázquez, C; Avilés-Monreal, R; Bernal, R

2018-08-01

In this work, we report on the afterglow (AG) response characterization of commercially available ZrO 2 . Pellet shaped samples previously annealed in air at 1000°C during 24h were exposed to beta particle irradiation in the dose range from 0.5 up to 128Gy and their AG decay curves recorded during 600s after irradiation exposure. The characteristic glow curves of beta particle irradiated ZrO 2 show two maxima located around 80°C and 150°C. The first one rapidly vanishes at room temperature, giving rise to AG. The integrated AG signal increases as dose increases from 0.5 to 128Gy, with a linear dependence from 0.5 up to ca. 32Gy. Excellent reproducibility of the AG response was observed in 10 irradiation - AG readout cycles, showing that the studied ZrO 2 samples are reusable. The results here presented show that ZrO 2 is a promising material for use as a radiation dosimeter based on the AG phenomenon. Copyright © 2017 Elsevier Ltd. All rights reserved.

Raman Spectrum of Er-Y-codoped ZrO2 and Fluorescence Properties of Er3+

NASA Astrophysics Data System (ADS)

He, Jun; Luo, Meng-fei; Jin, Ling-yun; He, Mai; Fang, Ping; Xie, Yun-long

2007-02-01

Er-Y-codoped ZrO2 mixed oxides with monoclinic, tetragonal and cubic structures were prepared by a sol-gel method. The crystal structure of ZrO2 matrix and the effect of the ZrO2 phases on the fluorescence properties of Er3+ were studied using Raman spectroscopy. The results indicated that the fluorescence properties of Er3+ depend on its local ZrO2 crystal structures. As ZrO2 matrix transferred from monoclinic to tetragonal and cubic phase, the Raman and fluorescence bands of Er3+ decreased in intensities and tended to form a single peak. With 632.8 nm excitation, the bands between 640 and 680 nm were attributed to the fluorescence of Er3+ in the ZrO2 environment. However, only the fluorescence was observed and no Raman spectra were seen under 514.5 nm excitation, while only Raman spectra were observed under 325 nm excitation. UV Raman spectroscopy was found to be more sensitive in the surface region while the information provided by XRD mainly came from the bulk. The phase with lower symmetry forms more easily on the surface than in the bulk.

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.

Fabrication of SiO2@ZrO2@Y2O3:Eu3+ core-multi-shell structured phosphor.

PubMed

Gao, Xuan; He, Diping; Jiao, Huan; Chen, Juan; Meng, Xin

2011-08-01

ZrO2 interface was designed to block the reaction between SiO2 and Y2O3 in SiO2@Y2O3:Eu coreshell structure phosphor. SiO2@ZrO2@Y2O3:Eu core-multi-shell phosphors were successfully synthesized by combing an LBL method with a Sol-gel process. Based on electron microscopy, X-ray diffraction, and spectroscopy experiments, compelling evidence for the formation of the Y2O3:Eu outer shell on ZrO2 were presented. The presence of ZrO2 layer on SiO2 core can block the reaction of SiO2 core and Y2O3 shell effectively. By this kind of structure, the reaction temperature of the SiO2 core and Y2O3 shell in the SiO2@Y2O3:Eu core-shell structure phosphor can be increased about 200-300 degrees C and the luminescent intensity of this structure phosphor can be improved obviously. Under the excitation of ultraviolet (254 nm), the Eu3+ ion mainly shows its characteristic red (611 nm, 5D0-7F2) emissions in the core-multi-shell particles from Y2O3:Eu3+ shells. The emission intensity of Eu3+ ions can be tuned by the annealing temperatures, the number of coating times, and the thickness of ZrO2 interface, respectively.

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.

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

NASA Technical Reports Server (NTRS)

Farmer, Serene C.; Sayir, Ali

2001-01-01

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

Local epitaxial growth of ZrO2 on Ge (100) substrates by atomic layer epitaxy

NASA Astrophysics Data System (ADS)

Kim, Hyoungsub; Chui, Chi On; Saraswat, Krishna C.; McIntyre, Paul C.

2003-09-01

High-k dielectric deposition processes for gate dielectric preparation on Si surfaces usually result in the unavoidable and uncontrolled formation of a thin interfacial oxide layer. Atomic layer deposition of ˜55-Å ZrO2 film on a Ge (100) substrate using ZrCl4 and H2O at 300 °C was found to produce local epitaxial growth [(001) Ge//(001) ZrO2 and [100] Ge//[100] ZrO2] without a distinct interfacial layer, unlike the situation observed when ZrO2 is deposited using the same method on Si. Relatively large lattice mismatch (˜10%) between ZrO2 and Ge produced a high areal density of interfacial misfit dislocations. Large hysteresis (>200 mV) and high frequency dispersion were observed in capacitance-voltage measurements due to the high density of interface states. However, a low leakage current density, comparable to values obtained on Si substrates, was observed with the same capacitance density regardless of the high defect density.

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

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

Thermodynamic Modeling of the YO(l.5)-ZrO2 System

NASA Technical Reports Server (NTRS)

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

2003-01-01

The YO1.5-ZrO2 system consists of five solid solutions, one liquid solution, and one intermediate compound. A thermodynamic description of this system is developed, which allows calculation of the phase diagram and thermodynamic properties. Two different solution models are used-a neutral species model with YO1.5 and ZrO2 as the components and a charged species model with Y(+3), Zr(+4), O(-2), and vacancies as components. For each model, regular and sub-regular solution parameters are derived fiom selected equilibrium phase and thermodynamic data.

ZrO2 film interfaces with Si and SiO2

NASA Astrophysics Data System (ADS)

Lopez, C. M.; Suvorova, N. A.; Irene, E. A.; Suvorova, A. A.; Saunders, M.

2005-08-01

The interface formed by the thermal oxidation of sputter-deposited Zr metal onto Si(100)- and SiO2-coated Si(100) wafers was studied in situ and in real time using spectroscopic ellipsometry (SE) in the 1.5-4.5 photon energy range and mass spectrometry of recoiled ions (MSRI). SE yielded optical properties for the film and interface and MSRI yielded film and interface composition. An optical model was developed and verified using transmission electron microscopy. Interfacial reaction of the ZrO2 was observed for both substrates, with more interaction for Si substrates. Equivalent oxide thicknesses and interface trap levels were determined on capacitors with lower trap levels found on samples with a thicker SiO2 underlayer. In addition to the optical properties for the intermixed interface layer, the optical properties for Zr metal and unreacted ZrO2 are also reported.

Preparation of magnetron sputtered ZrO2 films on Si for gate dielectric application

NASA Astrophysics Data System (ADS)

Kondaiah, P.; Mohan Rao, G.; Uthanna, S.

2012-11-01

Zirconium oxide (ZrO2) thin films were deposited on to p - Si and quartz substrates by sputtering of zirconium target at an oxygen partial pressure of 4x10-2 Pa and sputter pressure of 0.4 Pa by using DC reactive magnetron sputtering technique. The effect of annealing temperature on structural, optical, electrical and dielectric properties of the ZrO2 films was systematically studied. The as-deposited films were mixed phases of monoclinic and orthorhombic ZrO2. As the annealing temperature increased to 1073 K, the films were transformed in to single phase orthorhombic ZrO2. Fourier transform infrared studies conform the presence of interfacial layer between Si and ZrO2. The optical band gap and refractive index of the as-deposited films were 5.82 eV and 1.81. As the annealing temperature increased to 1073 K the optical band gap and refractive index increased to 5.92 eV and 2.10 respectively. The structural changes were influenced the capacitance-voltage and current-voltage characteristics of Al/ZrO2/p-Si capacitors. The dielectric constant was increased from 11.6 to 24.5 and the leakage current was decreased from 1.65×10-7 to 3.30×10-9 A/ cm2 for the as-deposited and annealed at 1073 K respectively.

Ag nanoparticle effects on the thermoluminescent properties of monoclinic ZrO2 exposed to ultraviolet and gamma radiation

NASA Astrophysics Data System (ADS)

Villa-Sanchéz, G.; Mendoza-Anaya, D.; Gutiérrez-Wing, C.; Pérez-Hernández, R.; González-Martínez, P. R.; Ángeles-Chavez, C.

2007-07-01

The goal of this work was to analyse ZrO2 in the pure state and when doped with Ag nanoparticles, by electron microscopy, x-ray diffraction and thermoluminescence methods. According to the results obtained, Ag nanoparticles did not modify the morphology or the crystalline structure of the ZrO2. The thermoluminescent (TL) response of pure ZrO2 showed two peaks, one at 334 K and the other at 417 K, when it was exposed to ultraviolet (UV) radiation, and at 342 and 397 K when gamma radiation was used. For ZrO2 impregnated with Ag nanoparticles a diminished TL intensity due to nanoparticle shielding was observed, but the glow curve shape was similar. However, when Ag nanoparticles were added during the ZrO2 synthesis, a shift of the TL peaks towards higher temperature values with reference to pure ZrO2 was observed. A linear dependence of the integrated TL signal as a function of the irradiation dose was observed in all analysed samples. It was possible to determine some kinetic parameters, such as activation energy, kinetic order and frequency factor, using the sequential quadratic programming glow curve deconvolution; it was found that these values are highly dependent on the type of radiation used. Ag nanoparticles present in ZrO2 also modified the kinetic parameters, mainly when they were added during the synthesis of ZrO2. Our results reinforce the possibilities of using pure and doped ZrO2 as an appropriate dosimetric material in radiation physics.

Structural and dielectric properties of CTAB modified ZrO2 nanoparticles

NASA Astrophysics Data System (ADS)

Sidhu, Gaganpreet Kaur; Tripathi, S. K.; Kumar, Rajesh

2016-05-01

Zirconia (ZrO2) has been considered as one of the most investigated materials among various metal oxides due its outstanding dielectric properties and ionic conduction properties, which is mainly due to its high oxygen ion conduction. ZrO2 nanoparticles were synthesized using surfactant (CTAB) to study the variation of its dielectric behavior at room temperature. Surfactants form a unique class of chemical compounds, because of their remarkable ability to influence the properties of surfaces and interfaces of nanostructures. The dielectric properties of prepared nanoparticles were studied using LCR meter.

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Improved WO3 photocatalytic efficiency using ZrO2 and Ru for the degradation of carbofuran and ampicillin.

PubMed

Gar Alalm, Mohamed; Ookawara, Shinichi; Fukushi, Daisuke; Sato, Akira; Tawfik, Ahmed

2016-01-25

The photocatalytic degradation of carbofuran (pesticide) and ampicillin (pharmaceutical) using synthesized WO3/ZrO2 nanoparticles under simulated solar light was investigated. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectra analyses were used to characterize the prepared catalysts. The optimum ratio of WO3 to ZrO2 was determined to be 1:1 for the degradation of both contaminants. The degradation of carbofuran and ampicillin by WO3/ZrO2 after 240 min of irradiation was 100% and 96%, respectively. Ruthenium (Ru) was employed as an additive to WO3/ZrO2 to enhance the photocatalytic degradation rate. Ru/WO3/ZrO2 exhibited faster degradation rates than WO3/ZrO2. Furthermore, 100% and 97% degradation of carbofuran and ampicillin, respectively, was achieved using Ru/WO3/ZrO2 after 180 min of irradiation. The durability of the catalyst was investigated by reusing the same suspended catalyst, which achieved 92% of its initial efficiency. The photocatalytic degradation of ampicillin and carbofuran followed pseudo-first order kinetics according to the Langmuir-Hinshelwood model. Copyright © 2015 Elsevier B.V. All rights reserved.

Amorphization of nanocrystalline monoclinic ZrO2 by swift heavy ion irradiation.

PubMed

Lu, Fengyuan; Wang, Jianwei; Lang, Maik; Toulemonde, Marcel; Namavar, Fereydoon; Trautmann, Christina; Zhang, Jiaming; Ewing, Rodney C; Lian, Jie

2012-09-21

Bulk ZrO(2) polymorphs generally have an extremely high amorphization tolerance upon low energy ion and swift heavy ion irradiation in which ballistic interaction and ionization radiation dominate the ion-solid interaction, respectively. However, under very high-energy irradiation by 1.33 GeV U-238, nanocrystalline (40-50 nm) monoclinic ZrO(2) can be amorphized. A computational simulation based on a thermal spike model reveals that the strong ionizing radiation from swift heavy ions with a very high electronic energy loss of 52.2 keV nm(-1) can induce transient zones with temperatures well above the ZrO(2) melting point. The extreme electronic energy loss, coupled with the high energy state of the nanostructured materials and a high thermal confinement due to the less effective heat transport within the transient hot zone, may eventually be responsible for the ionizing radiation-induced amorphization without transforming to the tetragonal polymorph. The amorphization of nanocrystalline zirconia was also confirmed by 1.69 GeV Au ion irradiation with the electronic energy loss of 40 keV nm(-1). These results suggest that highly radiation tolerant materials in bulk forms, such as ZrO(2), may be radiation sensitive with the reduced length scale down to the nano-metered regime upon irradiation above a threshold value of electronic energy loss.

Thermal conductivity of ZrO2-4mol%Y2O3 thin coatings by pulsed thermal imaging method

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

Jang, Byung-Koog; Sun, Jiangang; Kim, Seongwon

Thin ZrO2-4mol% Y2O3 coatings were deposited onto ZrO2 substrates by electron beam-physical vapor deposition. The coated samples revealed a feather-like columnar microstructure. The main phase of the ZrO2-4mol% Y2O3 coatings was the tetragonal phase. To evaluate the influence of the coating’s thickness on the thermal conductivity of thin ZrO2-4mol% Y2O3 coatings, the pulsed thermal imaging method was employed to obtain the thermal conductivity of the coating layer in the two-layer (coating and substrate) samples with thickness between 56 and 337 micrometers. The thermal conductivity of the coating layer was successfully evaluated and compared well with those obtained by the lasermore » flash method for similar coatings. The thermal conductivity of coatings shows an increasing tendency with an increase in the coating’s thickness.« less

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

NASA Astrophysics Data System (ADS)

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

2002-12-01

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

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.

Effect of annealing temperature on microstructural evolution and electrical properties of sol-gel processed ZrO2/Si films

NASA Astrophysics Data System (ADS)

Hwang, Soo Min; Lee, Seung Muk; Park, Kyung; Lee, Myung Soo; Joo, Jinho; Lim, Jun Hyung; Kim, Hyoungsub; Yoon, Jae Jin; Kim, Young Dong

2011-01-01

High-permittivity (k) ZrO2/Si(100) films were fabricated by a sol-gel technique and the microstructural evolution with the annealing temperature (Ta) was correlated with the variation of their electrical performance. With increasing Ta, the ZrO2 films crystallized into a tetragonal (t) phase which was maintained until 700 °C at nanoscale thicknesses. Although the formation of the t-ZrO2 phase obviously enhanced the k value of the ZrO2 dielectric layer, the maximum capacitance in accumulation was decreased by the growth of a low-k interfacial layer (IL) between ZrO2 and Si with increasing Ta. On the other hand, the gate leakage current was remarkably depressed with increasing Ta probably due to the combined effects of the increased IL thickness, optical band gap of ZrO2, and density of ZrO2 and decreased remnant organic components.

Enhanced electrical properties of SrBi4Ti4O15 ceramic with addition of ZrO2

NASA Astrophysics Data System (ADS)

Mamatha, B.; Rani, G. Neeraja; Shankar, J.

2018-04-01

Polycrystalline SrBi4Ti3.95Zr0.05O15 (SBZT) ceramic was prepared by solid-state double sintering method. It was characterized by X-Ray Diffraction (XRD) and Scanning Electron Micrograph (SEM). With the increased addition of ZrO2, the electrical properties as dielectric, ferroelectric and piezoelectric were studied. From XRD, single-phase formation with orthorhombic structure was identified by the increase of ZrO2. The remnant polarization (Pr) and dielectric constant was found to be increased with the increase of ZrO2. With the increase of ZrO2, Curie temperature (Tc) was found to be decreased. The planar electromechanical coupling coefficient (Kp = 0.57) and Piezoelectric coefficient (d33 = 18 pC/N) was found to be increased with the increase of ZrO2.

Single-walled carbon nanotube-facilitated dispersion of particulate TiO2 on ZrO2 ceramic membrane filters.

PubMed

Yao, Yuan; Li, Gonghu; Gray, Kimberly A; Lueptow, Richard M

2008-07-15

We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.

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

NASA Astrophysics Data System (ADS)

Mao, Dongsen; Lu, Guanzhong

2007-02-01

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

Bioactivity and cytocompatibility of zirconia (ZrO(2)) films fabricated by cathodic arc deposition.

PubMed

Liu, Xuanyong; Huang, Anping; Ding, Chuanxian; Chu, Paul K

2006-07-01

Zirconium oxide thin films were fabricated on silicon wafers using a filtered cathodic arc system in concert with oxygen plasma. The structure and phase composition of the zirconium oxide thin films were characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), and transmission electron microscopy (TEM). The bioactivity was assessed by investigating the formation of apatite on the film surface after soaking in simulated body fluids. Bone marrow mesenchymal stem cells (BMMSC) were used to further evaluate the cytocompatibility of the materials. The results indicate that the films are composed of stoichiometric ZrO(2) and the composition is quite uniform throughout the thickness. Bone-like apatite can be formed on the surface of the ZrO(2) thin film in our SBF immersion experiments, suggesting that the surface is bioactive. The outermost layer of the ZrO(2) thin film comprises nano-sized particles that can be identified by AFM images taken on the thin film surface and TEM micrographs obtained from the interface between the ZrO(2) thin film and apatite layer. The nanostructured surface is believed to be the key factor that apatite is induced to precipitate on the surface. Bone marrow mesenchymal stem cells are observed to grow and proliferate in good states on the film surface. Our results show that ZrO(2) thin films fabricated by cathodic arc deposition exhibit favorable bioactivity and cytocompatibility.

Structural, electrical and optical properties of nanostructured ZrO2 thin film deposited by SILAR method

NASA Astrophysics Data System (ADS)

Salodkar, R. V.; Belkhedkar, M. R.; Nemade, S. D.

2018-05-01

Successive Ionic Layer Adsorption and Reaction (SILAR) method has been employed to deposit nanocrystalline ZrO2 thin film of thickness 91 nm onto glass substrates using ZrOCl2.8H2O and NaOH as cationic and anionic precursors respectively. The structural and surface morphological characterizations have been carried out by means of X-ray diffraction and field emission scanning electron microscopy confirms the nanocrystalline nature of ZrO2 thin film. The direct optical band gap and activation energy of the ZrO2 thin film are found to be 4.74 and 0.80eV respectively.

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

DOE PAGES

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

2016-01-18

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

Sintering, thermal stability and mechanical properties of ZrO2-WC composites obtained by pulsed electric current sintering

NASA Astrophysics Data System (ADS)

Huang, Shuigen; Vanmeensel, Kim; van der Biest, Omer; Vleugels, Jozef

2011-03-01

ZrO2-WC composites exhibit comparable mechanical properties as traditional WC-Co materials, which provides an opportunity to partially replace WC-Co for some applications. In this study, 2 mol.% Y2O3 stabilized ZrO2 composites with 40 vol.% WC were consolidated in the 1150°C-1850°C range under a pressure of 60 MPa by pulsed electric current sintering (PECS). The densification behavior, microstructure and phase constitution of the composites were investigated to clarify the role of the sintering temperature on the grain growth, mechanical properties and thermal stability of ZrO2 and WC components. Analysis results indicated that the composites sintered at 1350°C and 1450°C exhibited the highest tetragonal ZrO2 phase transformability, maximum toughness, and hardness and an optimal flexural strength. Chemical reaction of ZrO2 and C, originating from the graphite die, was detected in the composite PECS for 20 min at 1850°C in vacuum.

Chitosan /Zeolite Y/Nano ZrO2 nanocomposite as an adsorbent for the removal of nitrate from the aqueous solution.

PubMed

Teimouri, Abbas; Nasab, Shima Ghanavati; Vahdatpoor, Niaz; Habibollahi, Saeed; Salavati, Hossein; Chermahini, Alireza Najafi

2016-12-01

In the present study, a series of chitosan/Zeolite Y/Nano Zirconium oxide (CTS/ZY/Nano ZrO 2 ) nanocomposites were made by controlling the molar ratio of chitosan (CTS) to Zeolite Y/Nano Zirconium oxide in order to remove nitrate (NO 3 - ) ions in the aqueous solution. The nanocomposite adsorbents were characterized by XRD, FTIR, BET, SEM and TEM. The influence of different molar ratios of CTS to ZY/Nano ZrO 2 , the initial pH value of the nitrate solution, contact time, temperature, the initial concentration of nitrate and adsorbent dose was studied. The adsorption isotherms and kinetics were also analyzed. It was attempted to describe the sorption processes by the Langmuir equation and the theoretical adsorption capacity (Q 0 ) was found to be 23.58mg nitrate per g of the adsorbent. The optimal conditions for nitrate removal were found to be: molar ratio of CTS/ZY/Nano ZrO 2 : 5:1; pH: 3; 0.02g of adsorbent and temperature: 35°C, for 60min. The adsorption capacities of CTS, ZY, Nano ZrO 2 , CTS/Nano ZrO 2 , CTS/ZY and CTS/ZY/Nano ZrO 2 nanocomposites for nitrate removal were compared, showing that the adsorption ability of CTS/ZY/Nano ZrO 2 nanocomposite was higher than the average values of those of CTS (1.95mg/g for nitrate removal), ZY, Nano ZrO 2 , CTS/Nano ZrO 2, and CTS/ZY. Copyright © 2016. Published by Elsevier B.V.

Ultraviolet-assisted direct patterning and low-temperature formation of flexible ZrO2 resistive switching arrays on PET/ITO substrates

NASA Astrophysics Data System (ADS)

Li, Lingwei; Chen, Yuanqing; Yin, Xiaoru; Song, Yang; Li, Na; Niu, Jinfen; Wu, Huimin; Qu, Wenwen

2017-12-01

We demonstrate a low-cost and facile photochemical solution method to prepare the ZrO2 resistive switching arrays as memristive units on flexible PET/ITO substrates. ZrO2 solution sensitive to UV light of 337 nm was synthesized using zirconium n-butyl alcohol as the precursor, and benzoylacetone as the complexing agent. After the dip-coated ZrO2 gel films were irradiated through a mask under the UV lamp (with wavelength of 325-365 nm) at room temperature and rinsed in ethanol, the ZrO2 gel arrays were obtained on PET/ITO substrates. Subsequently, the ZrO2 gel arrays were irradiated by deep UV light of 254 and 185 nm at 150 °C, resulting in the amorphous ZrO2 memristive micro-arrays. The ZrO2 units on flexible PET/ITO substrates exhibited excellent memristive properties. A high ratio of 104 of on-state and off-state resistance was obtained. The resistive switching behavior of the flexible device remained stable after being bent for 103 times. The device showed stable flexibility up to a minimum bending diameter of 1.25 cm.

Dielectric Properties of PMMA and its Composites with ZrO2

NASA Astrophysics Data System (ADS)

Sannakki, Basavaraja; Anita

The polymer films of PMMA with different thickness and its composites with ZrO2 at various weight percentages but of same thickness have been studied. The determination of its dielectric properties, dielectric loss, a.conductivity and dielectric modulus were carried out using capacitance measurements of the above samples as a function of frequency, over the range 50 Hz - 5 MHz at room temperature. The films of PMMA and its composites have been characterized using X-Ray Diffractometer. The dielectric permittivity of films of PMMA behaves nonlinearly as frequency increases over the range 50-300 Hz, where as above 300 Hz the values of dielectric constant remains constant. But it is observed that the dielectric constant of PMMA increases as thickness of the film increases. In case of composite films of PMMA with ZrO2 the values of dielectric permittivity decreases gradually up to frequency of around 1 KHz and at higher frequencies it remains constant for all the weight percentages of ZrO2. The complex form of dielectric modulus of PMMA is obtained from the experimentally measured data of dielectric constant and dielectric loss values. The relaxation time of the orientation of dipoles is obtained from the peak value of angular frequency through the plots of imaginary part of electrical modulus as function of frequency. The impedance of PMMA polymer increases as thickness of the films increases. The a c conductivity of PMMA film remains constant up to frequency of 1 MHz and above. It shows a nonlinear phenomenon with peak values at frequency 4 MHz. Shape and size of the nanoparticles of composite film of PMMA with ZrO2 was analyzed by Field Emission Scanning Electron Microscope (FESEM).

ZrO2:Sm3+ nanophosphor: synthesis, Rietveld refinement, optical and thermoluminescent properties

NASA Astrophysics Data System (ADS)

Ponkumar, S.; Janaki, K.; Prakashbabu, D.; Ramalingam, H. B.; Munirathnam, K.; Sreekanth, T. V. M.; Dhoble, S. J.

2018-02-01

We have synthesized undoped and Sm3+ ions doped ZrO2 nanophosphors by solution combustion method. These nanophosphors crystallized in cubic structure. Rietveld refinement of the samples was performed to estimate lattice parameters. Spherical particles with the sizes of 10-25 nm were observed by transmission electron microscopy. Photoluminescence and thermoluminescence (TL) properties of samples were investigated. Under 400 nm excitation, the nanophosphors have intense red emission at 600 nm. The color coordinates (0.67, 0.33) were located in the red region of CIE diagram. TL properties of nanophosphors were studied by exposing the samples to γ-rays. 5 mol% Sm3+ doped ZrO2 nanophosphor has shown maximum TL intensity after γ-irradiation. To test suitability of the nanophosphors for practical application in dosimetry, the 5 mol% Sm3+ doped ZrO2 sample was irradiated by 14 MeV electron beam in various electron fluence ranging from 100 to 900 Gy and their TL response was recorded.

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.

Optical enhancement of Au doped ZrO2 thin films by sol-gel dip coating method

NASA Astrophysics Data System (ADS)

John Berlin, I.; Joy, K.

2015-01-01

Homogeneous and transparent Au doped ZrO2 thin films were prepared by sol-gel dip coating method. The films have mixed phase of tetragonal, monoclinic and face centered cubic with crack free surface. Due to the increase in Au doping concentration many-body interaction occurs between free carriers and ionized impurities causing decrease in optical band gap from 5.72 to 5.40 eV. Localized surface plasmon resonance peak of the Au doped films appeared at 610 nm. Conversion of photons to surface plasmons allows the sub-wavelength manipulation of electromagnetic radiation. Hence the prepared Au doped ZrO2 thin films can be applied in nanoscale photonic devices such as lenses, switches, waveguides etc. Moreover the photoluminescence (PL) intensity of Au doped ZrO2 thin films decrease due to decrease in the radiative recombination, life time of the excitons and suppression of grain growth of ZrO2 with increasing Au dopant.

Temperature-dependent local structural properties of redox Pt nanoparticles on TiO 2 and ZrO 2 supports

DOE PAGES

Jeong, Eun -Suk; Park, Chang -In; Jin, Zhenlan; ...

2015-01-21

This paper examined the local structural properties of Pt nanoparticles on SiO 2, TiO 2–SiO 2, and ZrO 2–SiO 2 supports to better understand the impact of oxide-support type on the performance of Pt-based catalysts. In situ X-ray absorption fine structure (XAFS) measurements were taken for the Pt L3-edge in a temperature range from 300 to 700 K in He, H 2, and O 2 gas environments. The XAFS measurements demonstrated that Pt atoms were highly dispersed on TiO 2–SiO 2 and ZrO 2–SiO 2 forming pancake-shaped nanoparticles, whereas Pt atoms formed larger particles of hemispherical shapes on SiO 2more » supports. Contrary to the SiO 2 case, the coordination numbers for Pt, Ti, and Zr around Pt atoms on the TiO 2–SiO 2 and ZrO 2–SiO 2 supports were nearly constant from 300 to 700 K under the different gas environments. These results are consistent with the improvements in thermal stability of Pt nanoparticles achieved by incorporating TiO 2 or ZrO 2 on the surface of SiO 2 supports. XAFS analysis further indicated that the enhanced dispersion and stability of Pt were a consequence of the strong metal support interaction via Pt–Ti and Pt–Zr bonds.« less

FAST TRACK COMMUNICATION: Deposition temperature effect on electrical properties and interface of high-k ZrO2 capacitor

NASA Astrophysics Data System (ADS)

Kim, Joo-Hyung; Ignatova, Velislava A.; Heitmann, Johannes; Oberbeck, Lars

2008-09-01

The electrical characteristics, i.e. leakage current and capacitance, of ZrO2 based metal-insulator-metal structures, grown at 225, 250 and 275 °C by atomic layer deposition, were studied. The lowest leakage current was obtained at 250 °C deposition temperature, while the highest dielectric constant (k ~ 43) was measured for the samples grown at 275 °C, most probably due to the formation of tetragonal/cubic phases in the ZrO2 layer. We have shown that the main leakage current of these ZrO2 capacitors is governed by the Poole-Frenkel conduction mechanism. It was observed by x-ray photoelectron spectroscopy depth profiling that at 275 °C deposition temperature the oxygen content at and beyond the ZrO2/TiN interface is higher than at lower deposition temperatures, most probably due to oxygen inter-diffusion towards the electrode layer, forming a mixed TiN-TiOxNy interface layer. At and above 275 °C the ZrO2 layer changes its structure and becomes crystalline as proven by XRD analysis.

(Zr,Ti)O2 interface structure in ZrO2-TiO2 nanolaminates with ultrathin periodicity

NASA Astrophysics Data System (ADS)

Aita, C. R.; DeLoach, J. D.; Yakovlev, V. V.

2002-07-01

A mixed cation interfacial structure in ZrO2-TiO2 nanolaminate films with ultrathin bilayer periodicity grown by sputter deposition at 297 K was identified by x-ray diffraction and nonresonant Raman spectroscopy. This structure consists of an amorphous phase at a ZrO2-on-TiO2 bilayer interface, followed by an extensive crystalline monoclinic (Zr,Ti)O2 solid solution predicted by Vegard's law. Monoclinic (Zr,Ti)O2 has previously been reported only once, in bulk powder of a single composition (ZrTiO4) at high pressure. Its stabilization in the nanolaminates is explained by the Gibbs-Thomson effect. This complex interfacial structure is shown to be a means of accommodating chemical mixing in the absence of a driving force for heteroepitaxy.

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.

Structural, electronic, elastic and thermodynamic properties of Li2ZrO3: A comprehensive study using DFT formalism

NASA Astrophysics Data System (ADS)

Chattaraj, D.

2017-12-01

Lithium zirconate is considered to be potential tritium breeder material for fusion reactors. Here I report a comprehensive study on structural, electronic, elastic, and thermodynamic properties of Li2ZrO3 using plane wave based density functional theory. While the electron-ion interaction term has been described by projected-augmented wave method, the exchange-correlation energy was taken care of through generalized gradient approximation scheme. The optimized lattice and internal parameters of Li2ZrO3 unit cell agree well within ±1-2% from the experimental values. From the electronic structure analysis it is seen that the Fermi energy has significant contribution from the 2s, 2p and 4d orbitals of Li, O and Zr atoms, respectively. Elastic property calculation of Li2ZrO3 showed mechanical stability and anisotropy at ambient pressure. The formation energy (ΔfH) of Li2ZrO3 at 0 K, after zero point energy correction, has been estimated to be -1550 kJ/mol. The temperature dependent thermodynamic functions of Li2ZrO3 have also been calculated from the Debye-Grüneisen quasi-harmonic approximation and reported here.

Improved electrical properties of atomic layer deposited tin disulfide at low temperatures using ZrO2 layer

NASA Astrophysics Data System (ADS)

Lee, Juhyun; Lee, Jeongsu; Ham, Giyul; Shin, Seokyoon; Park, Joohyun; Choi, Hyeongsu; Lee, Seungjin; Kim, Juyoung; Sul, Onejae; Lee, Seungbeck; Jeon, Hyeongtag

2017-02-01

We report the effect of zirconium oxide (ZrO2) layers on the electrical characteristics of multilayered tin disulfide (SnS2) formed by atomic layer deposition (ALD) at low temperatures. SnS2 is a two-dimensional (2D) layered material which exhibits a promising electrical characteristics as a channel material for field-effect transistors (FETs) because of its high mobility, good on/off ratio and low temperature processability. In order to apply these 2D materials to large-scale and flexible electronics, it is essential to develop processes that are compatible with current electronic device manufacturing technology which should be conducted at low temperatures. Here, we deposited a crystalline SnS2 at 150 °C using ALD, and we then annealed at 300 °C. X-ray diffraction (XRD) and Raman spectroscopy measurements before and after the annealing showed that SnS2 had a hexagonal (001) peak at 14.9° and A1g mode at 313 cm-1. The annealed SnS2 exhibited clearly a layered structure confirmed by the high resolution transmission electron microscope (HRTEM) images. Back-gate FETs with SnS2 channel sandwiched by top and bottom ZrO2 on p++Si/SiO2 substrate were suggested to improve electrical characteristics. We used a bottom ZrO2 layer to increase adhesion between the channel and the substrate and a top ZrO2 layer to improve contact property, passivate surface, and protect from process-induced damages to the channel. ZTZ (ZrO2/SnS2/ZrO2) FETs showed improved electrical characteristics with an on/off ratio of from 0.39×103 to 6.39×103 and a mobility of from 0.0076 cm2/Vs to 0.06 cm2/Vs.

Irradiation behavior of LiAlO 2 and Li 2ZrO 3 ceramics in the ALICE 3 experiment

NASA Astrophysics Data System (ADS)

Rasneur, B.; Thevenot, G.; Bouilloux, Y.

1992-09-01

Within the framework of the investigation of ceramic breeders for the DEMO relevant solid blankets developed in Europe, the ALICE 3 experiment was foreseen to study the irradiation behavior of the ceramics. The irradiation was performed in the core of the OSIRIS reactor for 46 FPD (full power days) at 400°C and 600°C. The three ceramics in the configuration contemplated in the BIT and BOT concepts were tested, i.e. LiAlO 2 and Li 2ZrO 3 pellets, Li 4SiO 4 and Li 2ZrO 3 pebbles, respectively. In this paper are reported the results of the post-irradiation examination carried out at CEA on CEA Li 2ZrO 3 and LiAlO 2 specimens: dimensions, X-ray diffraction, ultimate bending strength, diametral compressive strength and residual tritium.

Effect of Er3+ concentration on the luminescence properties of Al2O3-ZrO2 powder

NASA Astrophysics Data System (ADS)

Clabel H., J. L.; Rivera, V. A. G.; Nogueira, I. C.; Leite, E. R.; Siu Li, M.; Marega, E.

2016-12-01

This manuscript reports on the effects of the luminescence properties of Er3+ on Al2O3-ZrO2 powder synthesized by the conventional solid-state method. The best conditions found for the calcinations were 1500 °C and 4 h. The structural dependence of the luminescence on Er3+:Al2O3-ZrO2 is associated with phase transformations of the Al2O3-ZrO2 host and presence of the OH group. Green and red emissions at room temperature from the 2H11/2, 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 levels of Er3+ ions were observed under 482 nm pumping. The green-to-red emission intensity ratios and CIE chromaticity coordinates were determined from emission spectra for the evaluation of light emitted as a function of the Er3+ concentration. The Er3+ luminescence quenching due to group OH and variation in the Er3+ concentration plays an important role in the definition of the luminescent response.

Chemical vapor deposited monolayer MoS2 top-gate MOSFET with atomic-layer-deposited ZrO2 as gate dielectric

NASA Astrophysics Data System (ADS)

Hu, Yaoqiao; Jiang, Huaxing; Lau, Kei May; Li, Qiang

2018-04-01

For the first time, ZrO2 dielectric deposition on pristine monolayer MoS2 by atomic layer deposition (ALD) is demonstrated and ZrO2/MoS2 top-gate MOSFETs have been fabricated. ALD ZrO2 overcoat, like other high-k oxides such as HfO2 and Al2O3, was shown to enhance the MoS2 channel mobility. As a result, an on/off current ratio of over 107, a subthreshold slope of 276 mV dec-1, and a field-effect electron mobility of 12.1 cm2 V-1 s-1 have been achieved. The maximum drain current of the MOSFET with a top-gate length of 4 μm and a source/drain spacing of 9 μm is measured to be 1.4 μA μm-1 at V DS = 5 V. The gate leakage current is below 10-2 A cm-2 under a gate bias of 10 V. A high dielectric breakdown field of 4.9 MV cm-1 is obtained. Gate hysteresis and frequency-dependent capacitance-voltage measurements were also performed to characterize the ZrO2/MoS2 interface quality, which yielded an interface state density of ˜3 × 1012 cm-2 eV-1.

The photoelectronic behaviors of MoO3-loaded ZrO2/carbon cluster nanocomposite materials

NASA Astrophysics Data System (ADS)

Matsui, H.; Ishiko, A.; Karuppuchamy, S.; Hassan, M. A.; Yoshihara, M.

2012-03-01

A novel nano-sized ZrO2/carbon cluster composite materials (Ic's) were successfully obtained by the calcination of ZrCl4/starch complexes I's under an argon atmosphere. Pt- and/or MoO3-loaded ZrO2/carbon clusters composite materials were also prepared by doping Pt and/or MoO3 particles on the surface of Ic's. The surface characterization of the composite materials was carried out using transmission electron microscopy (TEM). The TEM observation of the materials showed the presence of particles with the diameters of a few nanometers, possibly Pt particles, and of 50-100 nm, possibly MoO3 particles, in the matrix. Pt- and/or MoO3-loaded ZrO2/carbon cluster composite materials show the efficient photocatalytic activity under visible light irradiation.

Potential of SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles in achieving integrated magneto-optical isolators

NASA Astrophysics Data System (ADS)

Zamani, Mehdi; Hocini, Abdesselam

2017-05-01

We have investigated the potential of the SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles in order to overcome the problem of integration of the magneto-optical isolators (MOIs). In this way, we have performed a theoretical study for the case of designing perfect and adjustable MOIs based on magnetophotonic crystals (MPCs) containing SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles as a magnetic medium. Despite the existence the attenuation coefficient for SiO2/ZrO2 matrix at wavelength 1550 nm that leads to a non-perfect transmittance, we could introduce an MPC structure having no reflectance; therefore, an ideal MOI for eliminating unwanted back-reflection could be achieved.

Low-temperature CO oxidation over Cu/Pt co-doped ZrO2 nanoparticles synthesized by solution combustion.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2017-01-01

Zirconia (ZrO 2 ) nanoparticles co-doped with Cu and Pt were applied as catalysts for carbon monoxide (CO) oxidation. These materials were prepared through solution combustion in order to obtain highly active and stable catalytic nanomaterials. This method allows Pt 2+ and Cu 2+ ions to dissolve into the ZrO 2 lattice and thus creates oxygen vacancies due to lattice distortion and charge imbalance. High-resolution transmission electron microscopy (HRTEM) results showed Cu/Pt co-doped ZrO 2 nanoparticles with a size of ca. 10 nm. X-ray diffraction (XRD) and Raman spectra confirmed cubic structure and larger oxygen vacancies. The nanoparticles showed excellent activity for CO oxidation. The temperature T 50 (the temperature at which 50% of CO are converted) was lowered by 175 °C in comparison to bare ZrO 2 . Further, they exhibited very high stability for CO reaction (time-on-stream ≈ 70 h). This is due to combined effect of smaller particle size, large oxygen vacancies, high specific surface area and better thermal stability of the Cu/Pt co-doped ZrO 2 nanoparticles. The apparent activation energy for CO oxidation is found to be 45.6 kJ·mol -1 . The CO conversion decreases with increase in gas hourly space velocity (GHSV) and initial CO concentration.

Hydrodeoxygenation of p -Cresol over Pt/Al 2 O 3 Catalyst Promoted by ZrO 2 , CeO 2 , and CeO 2 –ZrO 2

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

Wang, Weiyan; Wu, Kui; Liu, Pengli

2016-07-20

ZrO 2-Al 2O 3 and CeO 2-Al 2O 3 were prepared by a co-precipitation method and selected as supports for Pt catalysts. The effects of CeO 2 and ZrO 2 on the surface area and Brønsted acidity of Pt/Al 2O 3 were studied. In the hydrodeoxygenation (HDO) of p-cresol, the addition of ZrO 2 promoted the direct deoxygenation activity on Pt/ZrOO 2-Al 2O 3 via Caromatic-O bond scission without benzene ring saturation. Pt/CeOO 2-Al 2O 3 exhibited higher deoxygenation extent than Pt/Al 2O 3 due to the fact that Brønsted acid sites on the catalyst surface favored the adsorption ofmore » p-cresol. With the advantages of CeO 2 and ZrO 2 taken into consideration, CeO 2-ZrOO 2-Al 2O 3 was prepared, leading to the highest HDO activity of Pt/CeO 2-ZrOO 2-Al 2O 3. The deoxygenation extent for Pt/CeO 2-ZrOO 2-Al 2O 3 was 48.4% and 14.5% higher than that for Pt/ZrO2O 2-Al 2O 3 and Pt/CeOO 2-Al 2O 3, respectively.« less

Effect of annealing temperature on optical and electrical properties of ZrO2-SnO2 based nanocomposite thin films

NASA Astrophysics Data System (ADS)

Anitha, V. S.; Lekshmy, S. Sujatha; Berlin, I. John; Joy, K.

2014-01-01

Transparent nanocomposite ZrO2-SnO2 thin films were prepared by sol-gel dip-coating technique. Films were annealed at 500°C, 800°C and 1200°C respectively. X-ray diffraction(XRD) spectra showed a mixture of three phases: tetragonal ZrO2 and SnO2 and orthorhombic ZrSnO4. The grain size of all the three phases' increased with annealing temperature. An average transmittance greater than 85%(in UV-Visible region) is observed for all the films. The band gap for the films decreased from 4.79 eV to 4.62 eV with increase in annealing temperature from 500 to 1200 °C. The electrical resistivity increased with increase in annealing temperature. Such composite ZrO2-SnO2 films can be used in many applications and in optoelectronic devices.

The Effect of Microstructure on Mechanical Properties of Directionally Solidified Al2O3/ZrO2(Y2O3) Eutectic

NASA Technical Reports Server (NTRS)

Sayir, Ali; Farmer, Serene C.

1999-01-01

The eutectic architecture of a continuous reinforcing phase within a higher volume fraction phase or matrix can be described as a naturally occurring in-situ composite. Here we report the results of experiments aimed at identifying the sources of high temperature creep resistance and high levels of strength in a two phase Al2O3/ZrO2(Y2O3) system. The mechanical properties of two phase Al2O3/ZrO2(Y2O3) eutectic are superior to those of either constituent alone due to strong constraining effects provided by the coherent interfaces and microstructure. The AlO3/ZrO2(Y2O3) eutectic maintains a low energy interface resulting from directional solidification and can produce strong and stable reinforcing phase/matrix bonding. The phases comprising a eutectic are thermodynamically compatible at higher homologous temperatures than man-made composites and as such offer the potential for superior high temperature properties.

Electronic structure of a laterally graded ZrO2-TiO2 film on Si(100) prepared by metal-organic chemical vapor deposition in ultrahigh vacuum

NASA Astrophysics Data System (ADS)

Richter, J. H.; Karlsson, P. G.; Sandell, A.

2008-05-01

A TiO2-ZrO2 film with laterally graded stoichiometry has been prepared by metal-organic chemical vapor deposition in ultrahigh vacuum. The film was characterized in situ using synchrotron radiation photoelectron spectroscopy (PES) and x-ray absorption spectroscopy. PES depth profiling clearly shows that Ti ions segregate toward the surface region when mixed with ZrO2. The binding energy of the ZrO2 electronic levels is constant with respect to the local vacuum level. The binding energy of the TiO2 electronic levels is aligned to the Fermi level down to a Ti /Zr ratio of about 0.5. At a Ti /Zr ratio between 0.1 and 0.5, the TiO2 related electronic levels become aligned to the local vacuum level. The addition of small amounts of TiO2 to ZrO2 results in a ZrO2 band alignment relative to the Fermi level that is less asymmetric than for pure ZrO2. The band edge positions shift by -0.6eV for a Ti /Zr ratio of 0.03. This is explained in terms of an increase in the work function when adding TiO2, an effect that becomes emphasized by Ti surface segregation.

Impact of nano and bulk ZrO2, TiO2 particles on soil nutrient contents and PGPR.

PubMed

Karunakaran, Gopalu; Suriyaprabha, Rangaraj; Manivasakan, Palanisamy; Yuvakkumar, Rathinam; Rajendran, Venkatachalam; Kannan, Narayanasamy

2013-01-01

Currently, nanometal oxides are used extensively in different industries such as medicine, cosmetics and food. The increased consumption of nanoparticles (NPs) leads the necessity to understand the fate of the nanoparticles in the environment. The present study focused on the ecotoxicological behaviour of bulk and nano ZrO2 (Zirconia) and TiO2 (Titania) particles on PGPR (plant growth promoting rhizobacteria), soil and its nutrient contents. The microbial susceptibility study showed that nano TiO2 had 13 +/- 0.9 mm (B. megaterium), 15 +/- 0.2 mm (P. fluorescens), 16 +/- 0.2 mm (A. vinelandii) and 12 +/- 0.3 mm (B. brevis) zones of inhibition. However, nano and bulk ZrO2 particles were non-toxic to PGPR. In addition, it was found that toxicity varied depends on the medium of reaction. The soil study showed that nano TiO2 was found to be highly toxic, whereas bulk TiO2 was less toxic towards soil bacterial populations at 1000 mg L(-1). In contrast, nano and bulk ZrO2 were found to be inert at 1000 mg L(-1). The observed zeta potential and hydrophobicity of TiO2 particles causes more toxic than ZrO2 in parallel with particle size. However, nano TiO2 decreases the microbial population as well as nutrient level of the soil but not zirconia. Our finding shows that the mechanism of toxicity depends on size, hydrophobic potential and zeta potential of the metal oxide particles. Thus, it is necessary to take safety measures during the disposal and use of such toxic nanoparticles in the soil to prevent their hazardous effects.

ZrO2/bamboo leaves ash (BLA) Catalyst in Biodiesel Conversion of Rice Bran Oil

NASA Astrophysics Data System (ADS)

Fatimah, Is; Taushiyah, Ana; Badriatun Najah, Fitri; Azmi, Ulil

2018-04-01

Preparation, characterization and catalytic activity of ZrO2/bamboo leaves ash (BLA) catalyst for conversion of rice bran oil to biodiesel have been investigated. The catalyst was prepared by impregnation method of ZrOCl2 as ZrO2 precursor with BLA at a theoretical content of 20% wt. followed by calcination. The physicochemical properties of the catalyst material were characterized by x-ray diffraction (XRD), FTIR and surface acidity measurement. Activity test of materials in biodiesel conversion of rice bran oil was used by reflux method and microwave (MW) assisted method. Reaction variables studied in the investigation were the effect of catalyst weight and time of MW irradiation compared with the use reflux method. The results showed that ZrO2/BLA catalyst exhibited competitively effective and efficient processes for the production of biodiesel. The reflux method demonstrated an higher conversion (%) compared to MW method, however MW method showed the better reusable properties.

Ethanol dehydrogenation on copper catalysts with ytterbium stabilized tetragonal ZrO2 support

NASA Astrophysics Data System (ADS)

Chuklina, S. G.; Pylinina, A. I.; Podzorova, L. I.; Mikhailina, N. A.; Mikhalenko, I. I.

2016-12-01

The physicochemical and catalytic properties of Cu-containing crystalline zirconia, obtained via sol-gel synthesis in the presence of Yb3+ ions and polyvinylpyrrolidone, are studied. DTG/DSC, TEM, XRD and BET methods are used to analyze the crystallization, texture, phase uniformity, surface and porosity of ZrO2 nanopowders. It is shown that increasing the copper content (1, 3, and 5 wt % from ZrO2) raises the dehydrogenation activity in the temperature range of 100-400°C and lowers the activation energy of acetaldehyde formation. It is found that the activity of all Cu/ t-ZrO2 catalysts grows under the effects of the reaction medium, due to the migration and redispersion of copper.

Low-temperature, solution-processed ZrO2:B thin film: a bifunctional inorganic/organic interfacial glue for flexible thin-film transistors.

PubMed

Park, Jee Ho; Oh, Jin Young; Han, Sun Woong; Lee, Tae Il; Baik, Hong Koo

2015-03-04

A solution-processed boron-doped peroxo-zirconium oxide (ZrO2:B) thin film has been found to have multifunctional characteristics, providing both hydrophobic surface modification and a chemical glue layer. Specifically, a ZrO2:B thin film deposited on a hydrophobic layer becomes superhydrophilic following ultraviolet-ozone (UVO) treatment, whereas the same treatment has no effect on the hydrophobicity of the hydrophobic layer alone. Investigation of the ZrO2:B/hydrophobic interface layer using angle-resolved X-ray photoelectron spectroscopy (AR XPS) confirmed it to be chemically bonded like glue. Using the multifunctional nature of the ZrO2:B thin film, flexible amorphous indium oxide (In2O3) thin-film transistors (TFTs) were subsequently fabricated on a polyimide substrate along with a ZrO2:B/poly-4-vinylphenol (PVP) dielectric. An aqueous In2O3 solution was successfully coated onto the ZrO2:B/PVP dielectric, and the surface and chemical properties of the PVP and ZrO2:B thin films were analyzed by contact angle measurement, atomic force microscopy (AFM), Fourier transform infrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The surface-engineered PVP dielectric was found to have a lower leakage current density (Jleak) of 4.38 × 10(-8) A/cm(2) at 1 MV/cm, with no breakdown behavior observed up to a bending radius of 5 mm. In contrast, the electrical characteristics of the flexible amorphous In2O3 TFT such as on/off current ratio (Ion/off) and electron mobility remained similar up to 10 mm of bending without degradation, with the device being nonactivated at a bending radius of 5 mm. These results suggest that ZrO2:B thin films could be used for low-temperature, solution-processed surface-modified flexible devices.

Improved photocatalytic degradation rates of phenol achieved using novel porous ZrO2-doped TiO2 nanoparticulate powders.

PubMed

McManamon, Colm; Holmes, Justin D; Morris, Michael A

2011-10-15

This paper studies the photocatalytic degradation of phenol using zirconia-doped TiO(2) nanoparticles. ZrO(2) was chosen due to its promising results during preliminary studies. Particles smaller than 10nm were synthesised and doped with quantities of ZrO(2) ranging from 0.5 to 4% (molar metal content). Particles were calcined at different temperatures to alter the TiO(2) structure, from anatase to rutile, in order to provide an ideal ratio of the two phases. Powder X-ray diffraction (PXRD) analysis was used to examine the transformation between anatase and rutile. Degradation of phenol was carried out using a 40 W UV bulb at 365 nm and results were measured by UV-vis spectrometry. TEM images were obtained and show the particles exhibit a highly ordered structure. TiO(2) doped with 1% ZrO(2) (molar metal content) calcined at 700 °C proved to be the most efficient catalyst. This is due to an ideal anatase:rutlie ratio of 80:20, a large surface area and the existence of stable electron-hole pairs. ZrO(2) doping above the optimum loading acted as an electron-hole recombination centre for electron-hole pairs and reduced photocatalytic degradation. Synthesised photocatalysts compared favourably to the commercially available photocatalyst P25. The materials also demonstrated the ability to be recycled with similar results to those achieved on fresh material after 5 uses. Copyright © 2011 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Zalnezhad, E.

2016-05-01

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

Effect of ZrO2 on the sintering behavior, strength and high-frequency dielectric properties of electrical ceramic porcelain insulator

NASA Astrophysics Data System (ADS)

Singh Mehta, Niraj; Sahu, Praveen Kumar; Ershad, Md; Saxena, Vipul; Pyare, Ram; Ranjan Majhi, Manas

2018-01-01

In the present study, the effect of ZrO2 on the sintering, strength and dielectric behavior of electrical ceramic porcelain insulator with substituting alumina content by zirconia (in weight percentage from 0% to 30%) is investigated. The different composition of samples containing different zirconia (ZrO2) contents of 0, 10, 20, and 30 wt% are prepared using the uniaxial pressure technique applying 160 MPa pressure. Further, the prepared samples are also analyzed for sintering temperatures (1350 °C), and effects are observed on mechanical and electric properties of porcelain insulator. Different characterizations such as Dilatometer, x-ray diffraction, scanning electron microscopy and differential thermal analysis/thermo gravimetric analysis were used to evaluate the thermal, phase detection, micro structural and weight loss changes by increasing concentration of ZrO2 on base porcelain composition. At 1350 °C, for the composition having 20 wt% ZrO2 with 10 wt% alumina, the maximum density was observed 2.81 g cm-3 with a porosity of 2.23%. The highest tensile strength of 41 ± 3 MPa is observed for the same sample composition. The minimum value of thermal expansion coefficient is found to be in the range of 10-6 for the sample with 30 wt% ZrO2 content sintered at 1350 °C compared to other prepared samples. Similarly, the highest dielectric value (5.1-4.4) having dielectric loss (0.08-0.12) is achieved for the sample with 30 wt% ZrO2 content sintered at 1350 °C in the frequency range of 4-20 GHz at room temperature. According to the mechanical properties, the composition having 20 wt% ZrO2 on base ceramic porcelain composition has enormous potential to serve as a high strength refractory material. For dielectric properties, the composition having 30 wt% ZrO2 is more suitable for the electrical application.

Microstructural Evolution of Al2O3-ZrO2 (Y2O3) Composites and its Correlation with Toughness

NASA Astrophysics Data System (ADS)

Kim, Hee Seung; Seo, Mi Young; Kim, Ik Jin

2008-02-01

The microstructure of zirconia (ZrO2) toughened alumina (Al2O3) ceramics was carefully controlled so as to obtain dense and fine-grained ceramics, thereby improving the properties and reliability of the ceramics for capillary applications in semiconductor bonding technology. Al2O3-ZrO2(Y2O3) composite was produced via Ceramic Injection Molding (CIM) technology, followed by Sinter-HIP process. Room temperature strength, hardness, Young's modulus, thermal expansion coefficient and toughness were determined, as well as surface strengthening induced by the fine grained homogenous microstructure and the thermal treatment. The changes in alumina/zirconia grain size, sintering condition and HIP treatment were found to be correlated.

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%.

Interface investigation of solution processed high- κ ZrO2/Si MOS structure by DLTS

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, Ksr Koteswara

The interfacial region is dominating due to the continuous downscaling and integration of high- k oxides in CMOS applications. The accurate characterization of high- k oxides/semiconductor interface has the significant importance towards its usage in memory and thin film devices. The interface traps at the high - k /semiconductor interface can be quantified by deep level transient spectroscopy (DLTS) with better accuracy in contrast to capacitance-voltage (CV) and conductance technique. We report the fabrication of high- k ZrO2 films on p-Si substrate by a simple and inexpensive sol-gel spin-coating technique. Further, the ZrO2/Si interface is characterized through DLTS. The flat-band voltage (VFB) and the density of slow interface states (oxide trapped charges) extracted from CV characteristics are 0.37 V and 2x10- 11 C/cm2, respectively. The activation energy, interface state density and capture cross-section quantified by DLTS are EV + 0.42 eV, 3.4x1011 eV- 1 cm- 2 and 5.8x10- 18 cm2, respectively. The high quality ZrO2 films own high dielectric constant 15 with low leakage current density might be an appropriate insulating layer in future electronic application. The low value of interface state density and capture cross-section are the indication of high quality interface and the defect present at the interface may not affect the device performance to a great extent. The DLTS study provides a broad understanding about the traps present at the interface of spin-coated ZrO2/Si.

A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization

NASA Astrophysics Data System (ADS)

Dzhikiya, O. V.; Smolikov, M. D.; Kazantsev, K. V.; Yablokova, S. S.; Kireeva, T. V.; Paukshtis, E. A.; Gulyaeva, T. I.; Belyi, A. S.

2017-08-01

The effect of palladium concentration in a range from 0.02 to 1.6 wt.% on characteristics of n-hexane isomerization was studied. The (O2-Hchem) titration and O2 chemisorption study revealed that palladium in Pd/SO4/ZrO2/Al2O3 systems adsorbs hydrogen in a ratio H/Pds = 1.13-1.65 at./at. Investigation of the charge state of the metal by IR spectroscopy of adsorbed CO showed the presence of both the metallic (Pd0) and charged palladium species. Pd/SO4/ZrO2/Al2O3 catalysts with charged palladium atoms exhibit high activity and selectivity in n-hexane isomerization.

About properties of ZrO2 thermal protective coatings obtained from spherical powder mixtures

NASA Astrophysics Data System (ADS)

Berdnik, O. B.; Tsareva, I. N.; Tarasenko, Yu P.

2017-05-01

It is developed the technology of high-energy plasma spraying of the zirconium dioxide (ZrO2) thermal protective coating on the basis of ZrO2 tetragonal and cubic phases with the spheroidal grain shape and the columnar substructure, with the total porosity P = 4 %, the hardness HV = 12 GPa, the roughness parameter R a ˜ 6 μm, the thickness 0.3-3 mm. As a sublayer it is used the heat-resistant coating of “Ni-Co-Cr-Al-Y” system with an intermetallic phase composition and the layered microstructure of the grains.

Promotional effect of Al2O3 on WO3/CeO2-ZrO2 monolithic catalyst for selective catalytic reduction of nitrogen oxides with ammonia after hydrothermal aging treatment

NASA Astrophysics Data System (ADS)

Xu, Haidi; Liu, Shuang; Wang, Yun; Lin, Qingjin; Lin, Chenlu; Lan, Li; Wang, Qin; Chen, Yaoqiang

2018-01-01

Hydrothermal stability of catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) has always been recognized as a challenge in development of candidate catalysts for applications in diesel engine emissions. In this study, Al2O3 was introduced into CeO2-ZrO2 to improve the NH3-SCR activity of WO3/CeO2-ZrO2 after hydrothermal aging (HA) treatment at 800 °C for 12 h. The activity results indicated that the NH3-SCR activity of WO3/CeO2-ZrO2-HA was obviously improved in the whole reaction temperature range after doping Al2O3 into CeO2-ZrO2, for example, the average and maximum NOx conversion were separately increased by ca. 20% and 25% after HA treatment. XRD, Raman, TEM and EDX results revealed that the introduction of Al2O3 inhibited the sintering and agglomeration of CeO2-ZrO2 and WO3 and the formation of Ce2(WO4)3 after HA treatment. Accordingly, WO3/CeO2-ZrO2-Al2O3-HA showed remarkably improved structural stability and reducibility, increased surface acidity, and facilitated the reactivity between adsorbed NH3 and nitrate species, which together contributed to its better catalytic performance after hydrothermal aging treatment.

The Effect of ZrO2 Nanoparticles on the Microstructure and Properties of Sintered WC–Bronze-Based Diamond Composites

PubMed Central

Sun, Youhong; Wu, Haidong; Li, Meng; Meng, Qingnan; Gao, Ke; Lü, Xiaoshu; Liu, Baochang

2016-01-01

Metal matrix-impregnated diamond composites are widely used in diamond tool manufacturing. In order to satisfy the increasing engineering requirements, researchers have paid more and more attention to enhancing conventional metal matrices by applying novel methods. In this work, ZrO2 nanoparticles were introduced into the WC–bronze matrix with and without diamond grits via hot pressing to improve the performance of conventional diamond composites. The effects of ZrO2 nanoparticles on the microstructure, density, hardness, bending strength, and wear resistance of diamond composites were investigated. The results indicated that the hardness and relative density increased, while the bending strength decreased when the content of ZrO2 nanoparticles increased. The grinding ratio of diamond composites increased significantly by 60% as a result of nano-ZrO2 addition. The enhancement mechanism was discussed. Diamond composites showed the best overall properties with the addition of 1 wt % ZrO2 nanoparticles, thus paving the way for further applications. PMID:28773469

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

ZrO2-modified mesoporous nanocrystalline TiO2-xNx as efficient visible light photocatalysts.

PubMed

Wang, Xinchen; Yu, Jimmy C; Chen, Yilin; Wu, Ling; Fu, Xianzhi

2006-04-01

Mesoporous nanocrystalline TiO2-xNx and TiO2-xNx/ZrO2 visible-light photocatalysts have been prepared by a sol-gel method. The photocatalysts were characterized by XRD, N2 adsorption-desorption, TEM, XPS, UV/Vis, and IR spectroscopy. The photocatalytic activity of the samples was evaluated by the decomposition of ethylene in air under visible light (lambda > 450 nm) illumination. Results revealed that nitrogen was doped into the lattice of TiO2 by the thermal treatment of NH3-adsorbed TiO2 hydrous gels, converting the TiO2 into a visible-light responsive catalyst. The introduction of ZrO2 into TiO2-xNx considerably inhibits the undesirable crystal growth during calcination. Consequently, the ZrO2-modified TiO2-xNx displays higher porosity, higher specific surface area, and an improved thermal stability over the corresponding unmodified TiO2-xNx samples.

A composite material with CeO2-ZrO2 nanocrystallines embedded in SiO2 matrices and its enhanced thermal stability and oxygen storage capacity

NASA Astrophysics Data System (ADS)

Yang, Runnong; Liu, Yumei; Yu, Lin; Zhao, Xiangyun; Yang, Xiaobo; Sun, Ming; Luo, Junyin; Fan, Qun; Xiao, Jianming; Zhao, Yuzhong

2018-06-01

A simple hydrothermal procedure is introduced, which leads to the successful synthesis of a new composite material with fine CeO2-ZrO2 nanocrystallites embedded in amorphous and porous SiO2 matrices. The composite material possesses an extraordinary high thermal stability. After being calcined at 1000 °C, it retains CeO2-ZrO2 nanocrystallites of the size around 5 nm, a BET-specific surface area of 165 m2/g, and an oxygen storage capacity of 468 μmol/g. No phase segregation for CeO2-ZrO2 nanocrystallites is detected and the SiO2 matrices remain not crystallized. The composite material shows a great potential as a support of three-way catalyst, as evidenced in catalytic tests with supported Pt.

Hydroxyaptite nanorods patterned ZrO2 bilayer coating on zirconium for the application of percutaneous implants.

PubMed

Zhang, Lan; Han, Yong; Tan, Guoxin

2015-03-01

Percutaneous implant requires a tight bond between the underlying dermis of skin and implant surface to prevent epithelial down-growth and infection, while fibroblasts play a key role in the skin-implant integration. In this work, nanorod-shaped hydroxyaptite (HA) with a mean diameter of 70 nm and length of 400 nm was hydrothermally grown on micro-arc oxidized (MAOed) Ca- and P-doped ZrO2 to form a bilayer coating. The hydrothermal formation mechanism of HA nanorods was explored, and the adsorption of total protein on the coating from α-MEM medium containing 10% fetal bovine serum was examined. Employing L-929 cells, the behaviors of fibroblasts on the bilayer coating, including adhesion and proliferation were evaluated together the polished Zr and as-MAOed ZrO2. The obtained results show that the HA nanorods nucleated on ZrO2 and grew at the expense of the doped Ca and P ions during the hydrothermal treatment (HT). The HA nanorods patterned coating enhanced protein absorption, and significantly improved the adhesion and proliferation of fibroblasts compared to the as-MAOed ZrO2 and polished Zr. It suggests that the HA nanorods/ZrO2 coated zirconium has a potential application for percutaneous implants to enhance the attachment of skin. Copyright © 2015 Elsevier B.V. All rights reserved.

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).

Theoretical study of the promotional effect of ZrO2 on In2O3 catalyzed methanol synthesis from CO2 hydrogenation

NASA Astrophysics Data System (ADS)

Zhang, Minhua; Dou, Maobin; Yu, Yingzhe

2018-03-01

Methanol synthesis from CO2 hydrogenation on the ZrO2 doped In2O3(110) surface (Zr-In2O3(110)) with oxygen vacancy has been studied using the density functional theory calculations. The calculated results show that the doped ZrO2 species prohibits the excessive formation of oxygen vacancies and dissociation of H2 on In2O3 surface slightly, but enhances the adsorption of CO2 on both perfect and defective Zr-In2O3(110) surface. Methanol is formed via the HCOO route. The hydrogenation of CO2 to HCOO is both energetically and kinetically facile. The HCOO hydrogenates to polydentate H2CO (p-H2CO) species with an activation barrier of 0.75 eV. H3CO is produced from the hydrogenation of monodentate H2CO (mono-H2CO), transformation from p-H2CO with 0.82 eV reaction energy, with no barrier whether there is hydroxyl group between the mono-H2CO and the neighboring hydride or not. Methanol is the product of H3CO protonation with 0.75 eV barrier. The dissociation and protonation of CO2 are both energetically and kinetically prohibited on Zr-In2O3(110) surface. The doped ZrO2 species can further enhance the adsorption of all the intermediates involved in CO2 hydrogenation to methanol, activate the adsorbed CO2 and H2CO, and stabilize the HCOO, H2CO and H3CO, especially prohibit the dissociation of H2CO or the reaction of H2CO with neighboring hydride to form HCOO and gas phase H2. All these effects make the ZrO2 supported In2O3 catalyst exhibit higher activity and selectivity on methanol synthesis from CO2 hydrogenation.

Stress analysis of ZrO2/SiO2 multilayers deposited on different substrates with different thickness periods

NASA Astrophysics Data System (ADS)

Shao, Shuying; Shao, Jianda; He, Hongbo; Fan, Zhengxiu

2005-08-01

The effects of repeating thickness periods on stress are studied in ZrO2/SiO2 multilayers deposited by electron-beam evaporation on BK7 glass and fused-silica substrates. The results show that the residual stress is compressive and decreases with an increase of the periods of repeating thickness in the ZrO2/SiO2 multilayers. At the same time, the residual stress in multilayers deposited on BK7 glass is less than that of samples deposited on fused silica. The variation of the microstructure examined by x-ray diffraction shows that microscopic deformation does not correspond to macroscopic stress, which may be due to variation of the interface stress.

Defect-Rich Dopant-Free ZrO2 Nanostructures with Superior Dilute Ferromagnetic Semiconductor Properties.

PubMed

Rahman, Md Anisur; Rout, S; Thomas, Joseph P; McGillivray, Donald; Leung, Kam Tong

2016-09-14

Control of the spin degree of freedom of an electron has brought about a new era in spin-based applications, particularly spin-based electronics, with the potential to outperform the traditional charge-based semiconductor technology for data storage and information processing. However, the realization of functional spin-based devices for information processing remains elusive due to several fundamental challenges such as the low Curie temperature of group III-V and II-VI semiconductors (<200 K), and the low spin-injection efficiencies of existing III-V, II-VI, and transparent conductive oxide semiconductors in a multilayer device structure, which are caused by precipitation and migration of dopants from the host layer to the adjacent layers. Here, we use catalyst-assisted pulsed laser deposition to grow, for the first time, oxygen vacancy defect-rich, dopant-free ZrO2 nanostructures with high TC (700 K) and high magnetization (5.9 emu/g). The observed magnetization is significantly greater than both doped and defect-rich transparent conductive oxide nanomaterials reported to date. We also provide the first experimental evidence that it is the amounts and types of oxygen vacancy defects in, and not the phase of ZrO2 that control the ferromagnetic order in undoped ZrO2 nanostructures. To explain the origin of ferromagnetism in these ZrO2 nanostructures, we hypothesize a new defect-induced bound polaron model, which is generally applicable to other defect-rich, dopant-free transparent conductive oxide nanostructures. These results provide new insights into magnetic ordering in undoped dilute ferromagnetic semiconductor oxides and contribute to the design of exotic magnetic and novel multifunctional materials.

Comparing the Thermodynamic Behaviour of Al(1)+ZrO2(s) to Al(1)+Al2O3(s)

NASA Technical Reports Server (NTRS)

Copland, Evan

2004-01-01

In an effort to better determine the thermodynamic properties of Al(g) and Al2O(g). the vapor in equilibrium with Al(l)+ZrO2(s) was compared to the vapor in equilibrium with Al(l)+Al2O3(s) over temperature range 1197-to-1509K. The comparison was made directly by Knudsen effusion-cell mass spectrometry with an instrument configured for a multiple effusion-cell vapor source (multi-cell KEMS). Second law enthalpies of vaporization of Al(g) and Al2O(g) together with activity measurements show that Al(l)+ZrO2(s) is thermodynamically equivalent to Al(l)+Al2O3(s), indicating Al(l) remained pure and Al2O3(s) was present in the ZrO2-cell. Subsequent observation of the Al(l)/ZrO2 and vapor/ZrO2 interfaces revealed a thin Al2O3-layer had formed, separating the ZrO2-cell from Al(l) and Al(g)+Al2O(g), effectively transforming it into an Al2O3 effusion-cell. This behavior agrees with recent observations made for Beta-NiAl(Pt) alloys measured in ZrO2 effusion-cell.

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.

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.

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.

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.

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.

Labeling of HeLa cells using ZrO2:Yb3+-Er3+ nanoparticles with upconversion emission

NASA Astrophysics Data System (ADS)

Ceja-Fdez, Andrea; López-Luke, Tzarara; Oliva, Jorge; Vivero-Escoto, Juan; Gonzalez-Yebra, Ana Lilia; Rojas, Ruben A. Rodriguez; Martínez-Pérez, Andrea; de la Rosa, Elder

2015-04-01

This work reports the synthesis, structural characterization, and optical properties of ZrO2:Yb3+-Er3+ (2-1 mol%) nanocrystals. The nanoparticles were coated with 3-aminopropyl triethoxysilane (APTES) and further modified with biomolecules, such as Biotin-Anti-rabbit (mouse IgG) and rabbit antibody-AntiKi-67, through a conjugation method. The conjugation was successfully confirmed by Fourier transform infrared, zeta potential, and dynamic light scattering. The internalization of the conjugated nanoparticles in human cervical cancer (HeLa) cells was followed by two-photon confocal microscopy. The ZrO2:Yb3+-Er3+ nanocrystals exhibited strong red emission under 970-nm excitation. Moreover, the luminescence change due to the addition of APTES molecules and biomolecules on the nanocrystals was also studied. These results demonstrate that ZrO2:Yb3+-Er3+ nanocrystals can be successfully functionalized with biomolecules to develop platforms for biolabeling and bioimaging.

SPS-RS technique for solid-phase “in situ” synthesis of biocompatible ZrO2 porous ceramics

NASA Astrophysics Data System (ADS)

Shichalin, O. O.; Medkov, M. A.; Grishchenko, D. N.; Mayorov, V. Yu; Fedorets, A. N.; Belov, A. A.; Golub, A. V.; Gridasova, E. A.; Papynov, E. K.

2018-02-01

The prospective method of spark plasma sintering-reaction synthesis (SPS-RS) for fabrication of ceramics based on ZrO2 and biocompatible with living tissue is presented. Nanostructured ceramics has high mechanical strength (more than 400 MPa) and controlled porosity depending on specified sintering conditions. Biocompatible phases Ca10(PO4)6(OH)2 are formed “in situ” during SPS sintering of ZrO2 powder due to chemical interaction of phosphate precursors preliminary introduced into the mixture. The effective method to improve (to develop) porous structure of bioceramics obtained by SPS or SPS-RS techniques using poreforming agent (carbon black) is proposed. Suggested original SPS-RS “in situ” technique provides fabrication of new ZrO2 ceramics containing biocompatible phosphate components and possessing unique structural and mechanical characteristics. Such ceramics is indispensable for bone-ceramic implants that are able to activate processes of osteogenesis during bone tissue recovery.

Influence of deposition temperature on mechanical properties of plasma-sprayed hydroxyapatite coating on titanium alloy with ZrO2 intermediate layer

NASA Astrophysics Data System (ADS)

Chou, Bang-Yen; Chang, Edward

2003-06-01

Hydroxyapatite coatings were plasma sprayed on the Ti6A14V substrate with and without an intermediate ZrO2 layer; meanwhile the temperatures of substrates were varied at 90, 140, and 200 °C. The coatings were subjected to the standard adhesion test per ASTM C633-79. The purpose of the investigation was to study the effects of those processing variables on the bonding strength and failure behavior of the system. It is found that the bonding strengths of HA/ZrO2 and HA coatings generally decrease with increasing substrate temperature, except for the HA/ZrO2 coating deposited at 200 °C. The rationale of the results is attributed to the residual stress reported in the literature. Introducing ZrO2 bond coat is found to significantly promote the bonding strength of HA coating. The possible strengthening mechanism is the rougher surface of ZrO2 bond coat and the higher toughness of ZrO2, which provide the mechanical strengthening effects. The slightly denser HA in 200 °C deposited HA coating cannot explain the high bonding strength of the HA/ZrO2 coating, nor the mechanical strengthening effect of ZrO2 intermediate layer should apply. It is believed that a stronger diffusion bonding is formed at the interface of HA and ZrO2, which increases the bonding between them chemically. The bonding strengths of HA/ZrO2 and HA coatings are correlated with the area fraction of adhesive failure of the coatings. The correlation explains the findings in this study.

Synthesis of ZrO 2 thin films by atomic layer deposition: growth kinetics, structural and electrical properties

NASA Astrophysics Data System (ADS)

Cassir, Michel; Goubin, Fabrice; Bernay, Cécile; Vernoux, Philippe; Lincot, Daniel

2002-06-01

Ultra thin films of ZrO 2 were synthesized on soda lime glass and SnO 2-coated glass, using ZrCl 4 and H 2O precursors by atomic layer deposition (ALD), a sequential CVD technique allowing the formation of dense and homogeneous films. The effect of temperature on the film growth kinetics shows a first temperature window for ALD processing between 280 and 350 °C and a second regime or "pseudo-window" between 380 and 400 °C, with a growth speed of about one monolayer per cycle. The structure and morphology of films of less than 1 μm were characterized by XRD and SEM. From 275 °C, the ZrO 2 film is crystallized in a tetragonal form while a mixture of tetragonal and monoclinic phases appears at 375 °C. Impedance spectroscopy measurements confirmed the electrical properties of ZrO 2 and the very low porosity of the deposited layer.

Microstructural Evolution of Nanocrystalline ZrO2 in a Fe Matrix During High-Temperature Exposure

NASA Astrophysics Data System (ADS)

Raghavendra, K. G.; Dasgupta, Arup; Athreya, C. N.; Jayasankar, K.; Saroja, S.; Subramanya Sarma, V.

2018-06-01

The current study examines the evolution of nanocrystallites of ZrO2 with time and temperature in a Fe-ZrO2 composite. The crystallite sizes were determined through X-ray peak broadening analysis by the Williamson-Hall method together with dark field transmission electron microscopy. The ZrO2 crystallites were found to be stable and retained their sizes at 973 K and 1073 K for hold durations up to 600 minutes. On the other hand, the crystallites were seen to grow at 1173 K and reached up to 200 nm for a hold time of 600 minutes. The Ostwald ripening model was adopted to understand crystallite growth while a dislocation-driven pipe diffusion was adopted for understanding the kinetics of grain growth. The activation energy of grain growth was calculated as 379 kJ mol-1. The modeled and experimentally calculated size evolutions with time and temperature were shown to be in good agreement with each other. A detailed discussion on the kinetics and activation energy of grain growth of ZrO2 crystallites in a Fe matrix is presented in this manuscript.

Bioactivity and cell proliferation in radiopaque gel-derived CaO-P2O5-SiO2-ZrO2 glass and glass-ceramic powders.

PubMed

Montazerian, Maziar; Yekta, Bijan Eftekhari; Marghussian, Vahak Kaspari; Bellani, Caroline Faria; Siqueira, Renato Luiz; Zanotto, Edgar Dutra

2015-10-01

In this study, 10 mol% ZrO2 was added to a 27CaO-5P2O5-68SiO2 (mol%) base composition synthesized via a simple sol-gel method. This composition is similar to that of a frequently investigated bioactive gel-glass. The effects of ZrO2 on the in vitro bioactivity and MG-63 cell proliferation of the glass and its derivative polycrystalline (glass-ceramic) powder were investigated. The samples were characterized using thermo-gravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectroscopy (EDS). Release of Si, Ca, P and Zr into simulated body fluid (SBF) was determined by inductively coupled plasma (ICP). Upon heat treatment at 1000 °C, the glass powder crystallized into an apatite-wollastonite-zirconia glass-ceramic powder. Hydroxycarbonate apatite (HCA) formation on the surface of the glass and glass-ceramic particles containing ZrO2 was confirmed by FTIR and SEM. Addition of ZrO2 to the base glass composition decreased the rate of HCA formation in vitro from one day to three days, and hence, ZrO2 could be employed to control the rate of apatite formation. However, the rate of HCA formation on the glass-ceramic powder containing ZrO2 crystal was equal to that in the base glassy powder. Tests with a cultured human osteoblast-like MG-63 cells revealed that the glass and glass-ceramic materials stimulated cell proliferation, indicating that they are biocompatible and are not cytotoxic in vitro. Moreover, zirconia clearly increased osteoblast proliferation over that of the Zr-free samples. This increase is likely associated with the lower solubility of these samples and, consequently, a smaller variation in the media pH. Despite the low solubility of these materials, bioactivity was maintained, indicating that these glassy and polycrystalline powders are potential candidates for bone graft substitutes and bone cements with

Effect of thermal cycling on ZrO2-Y2O3 thermal barrier coatings

NASA Technical Reports Server (NTRS)

Mcdonald, G.; Hendricks, R. C.

1980-01-01

The paper studies the comparative life of plasma-sprayed ZrO2-Y2O3 thermal barrier coatings on NiCrAlY bond coats on Rene 41 in short (4 min) and long (57 min) thermal cycles at 1040 C in a 0.3-Mach flame. Attention is given to determining the effect of short- and long-duration cycles on ZrO2-Y2O3 coatings, the cause of any cycle frequency effects, and methods to improve tolerance to thermal stress. Short cycles greatly reduced the life of the ceramic coating in terms of time at temperatures as compared to longer cycles, the failed coating indicating compressive failure. The experiments and stress calculations show that repeatedly subjecting a ceramic coating to high rates of initial heating has a more destructive influence on the coating than sustained operation at temperature. The effect of such thermal compressive stresses might be minimized through coating deposition and thickness control and by turbine cycle measurement to keep starting heating rates below critical values.

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Electrochemical corrosion, wear and cell behavior of ZrO2/TiO2 alloyed layer on Ti-6Al-4V.

PubMed

Li, Jianfang; He, Xiaojing; Zhang, Guannan; Hang, Ruiqiang; Huang, Xiaobo; Tang, Bin; Zhang, Xiangyu

2018-06-01

Ti-6Al-4V (TC4) has received increasing attention as biomaterial but also raised concerns about the long-term safety of releasing of metal ions and poor wear resistance. In this work, an ZrO 2 /TiO 2 alloyed layer was prepared on TC4 by plasma surface alloying with Zr and subsequently annealed in the air for improved corrosion and wear resistant. To assess the corrosion performance of the alloyed layer, the specimens were measured by open circuit potential, electrochemical impedance spectroscopy and potentiodynamic polarization in simulated body fluid solution. The result shows that the ZrO 2 /TiO 2 alloyed layer exhibits strikingly high polarization resistance, wide passive region and very low current density, indicating the excellent corrosion resistance. The layer also displays significant improvement of wear resistance. Furthermore, the alloyed layer restricts cell adhesion and spreading. We infer that the ZrO 2 /TiO 2 alloyed layer might be potentially useful implanted devices such as biosensors, bioelectronics or drug delivery devices. Copyright © 2018 Elsevier B.V. All rights reserved.

Assessment of solid/liquid equilibria in the (U, Zr)O2+y system

NASA Astrophysics Data System (ADS)

Mastromarino, S.; Seibert, A.; Hashem, E.; Ciccioli, A.; Prieur, D.; Scheinost, A.; Stohr, S.; Lajarge, P.; Boshoven, J.; Robba, D.; Ernstberger, M.; Bottomley, D.; Manara, D.

2017-10-01

Solid/liquid equilibria in the system UO2sbnd ZrO2 are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the only study available in the literature on the whole pseudo-binary system. In addition, a minimum melting point is identified here for compositions near (U0.6Zr0.4)O2+y, around 2800 K. The solidus line is rather flat on a broad range of compositions around the minimum. It increases for compositions closer to the pure end members, up to the melting point of pure UO2 (3130 K) on one side and pure ZrO2 (2970 K) on the other. Solid state phase transitions (cubic-tetragonal-monoclinic) have also been observed in the ZrO2-rich compositions X-ray diffraction. Investigations under 0.3 MPa air (0.063 MPa O2) revealed a significant decrease in the melting points down to 2500 K-2600 K for increasing uranium content (x(UO2)> 0.2). This was found to be related to further oxidation of uranium dioxide, confirmed by X-ray absorption spectroscopy. For example, a typical oxidised corium composition U0.6Zr0.4O2.13 was observed to solidify at a temperature as low as 2493 K. The current results are important for assessing the thermal stability of the system fuel - cladding in an oxide based nuclear reactor, and for simulating the system behaviour during a hypothetical severe accident.

Thermophysical properties of liquid UO2, ZrO2 and corium by molecular dynamics and predictive models

NASA Astrophysics Data System (ADS)

Kim, Woong Kee; Shim, Ji Hoon; Kaviany, Massoud

2017-08-01

Predicting the fate of accident-melted nuclear fuel-cladding requires the understanding of the thermophysical properties which are lacking or have large scatter due to high-temperature experimental challenges. Using equilibrium classical molecular dynamics (MD), we predict the properties of melted UO2 and ZrO2 and compare them with the available experimental data and the predictive models. The existing interatomic potential models have been developed mainly for the polymorphic solid phases of these oxides, so they cannot be used to predict all the properties accurately. We compare and decipher the distinctions of those MD predictions using the specific property-related autocorrelation decays. The predicted properties are density, specific heat, heat of fusion, compressibility, viscosity, surface tension, and the molecular and electronic thermal conductivities. After the comparisons, we provide readily usable temperature-dependent correlations (including UO2-ZrO2 compounds, i.e. corium melt).

Room Temperature Magnetic Behavior In Nanocrystalline Ni-Doped Zro2 By Microwave-Assisted Polyol Synthesis

NASA Astrophysics Data System (ADS)

Parimita Rath, Pragyan; Parhi, Pankaj Kumar; Ranjan Panda, Sirish; Priyadarshini, Barsharani; Ranjan Sahoo, Tapas

2017-08-01

This article, deals with a microwave-assisted polyol method to demonstrate a low temperature route < 250°C, to prepare a high temperature cubic zirconia phase. Powder XRD pattern shows broad diffraction peaks suggesting nanometric size of the particles. Magnetic behavior of 1-5 at% Ni doped samples show a threshold for substitutional induced room temperature ferromagnetism up to 3 at% of Ni. TGA data reveals that Ni-doped ZrO2 polyol precursors decompose exothermically below 300°C. IR data confirms the reduction of Zr(OH)4 precipitates to ZrO2, in agreement with the conclusions drawn from the TGA analysis.

The glass-like thermal conductivity in ZrO2-Dy3TaO7 ceramic for promising thermal barrier coating application

NASA Astrophysics Data System (ADS)

Wu, Peng; Hu, Ming Yu; Chong, Xiao Yu; Feng, Jing

2018-03-01

Using the solid-state reaction method, the (ZrO2)x-(Dy3TaO7)1-x (x = 0, 0.02, 0.04, 0.06, 0.08, and 0.1) ceramics are synthesized in this work. The identification of the crystal structures indicates that the (ZrO2)x-(Dy3TaO7)1-x ceramics belong to the orthorhombic system, and the space group is C2221 in spite of the value of x increasing to 0.1. The thermal conductivities of the (ZrO2)x-(Dy3TaO7)1-x ceramics range from 1.3 W/(m K) to 1.8 W/(m K), and this value is much lower than that of 7-8 YSZ (yttria-stabilized zirconia). Besides, the (ZrO2)x-(Dy3TaO7)1-x ceramics possess the glass-like thermal conductivity caused by intrinsic oxygen vacancies existing in the lattice of Dy3TaO7. Moreover, the results of thermal expansion rates demonstrate that the (ZrO2)x-(Dy3TaO7)1-x ceramics possess excellent high temperature phase stability, and the thermal expansion coefficients [(9.7-11) × 10-6 K-1] are comparable to that of 7-8 YSZ.

Defects versus grain size effects on the ferromagnetism of ZrO2 nanocrystals clarified by positron annihilation

NASA Astrophysics Data System (ADS)

Wang, D. D.; Qi, N.; Jiang, M.; Chen, Z. Q.

2013-01-01

Undoped ZrO2 nanocrystals were annealed in open air from 100 °C to 1300 °C. X-ray diffraction and transmission electron microscope were used to study the structure change and grain growth. Both the methods reveal that the ZrO2 grain size has very slight increase after annealing up to 900 °C. Positron annihilation measurements reveal a high concentration of vacancy defects which most probably exist in the grain boundary region. Thermal annealing above 500 °C causes recovery of these defects, and after annealing at 1200 °C, most of them are removed. Room temperature ferromagnetism is observed for the sample annealed at 100 °C and 500 °C. The magnetization becomes very weak after the nanocrystals are annealed at 700 °C, and it almost disappears at 1000 °C. It is clear that the intrinsic ferromagnetism in our ZrO2 nanocrystals is mostly related with the interfacial defects instead of grain size effects.

Develop Roll-to-Roll Manufacturing Process of ZrO 2 Nanocrystals/Acrylic Nanocomposites for High Refractive Index Applications

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

Joshi, Pooran C.; Compton, Brett G.; Li, Jianlin

2015-04-01

The purpose of this Cooperative Research and Development Agreement (CRADA) was to develop and evaluate ZrO 2/acrylic nanocomposite coatings for integrated optoelectronic applications. The formulations engineered to be compatible with roll-to-roll process were evaluated in terms of optical and dielectric properties. The uniform distribution of the ZrO 2 nanocrystals in the polymer matrix resulted in highly tunable refractive index and dielectric response suitable for advanced photonic and electronic device applications.

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.

Investigation of phase transition properties of ZrO2 thin films

NASA Astrophysics Data System (ADS)

Kumar, Davinder; Singh, Avtar; Kaur, Manpreet; Rana, Vikrant Singh; Kaur, Raminder

2018-05-01

This paper presents the synthesis of transparent thin films of zirconium oxide (ZrO2) deposited on glass substrates by sol-gel dip coating technique. Synthesized films were characterized for different annealing time and withdrawal speed. Change in crystallographic properties of thin films was investigated by using X-ray diffraction. Surface morphology of transparent thin films was estimated by using scanning electron microscope.

Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

NASA Astrophysics Data System (ADS)

Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

2018-06-01

The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.

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

PubMed

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

2009-06-01

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

Thermodynamic Database for the NdO(1.5)-YO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Copland, Evan H.; Kaufman, Larry

2001-01-01

A database for YO(1.5)-NdO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 for ThermoCalc (ThermoCalc AB, Stockholm, Sweden) has been developed. The basis of this work is the YO(1.5)-ZrO2 assessment by Y. Du, Z. Jin, and P. Huang, 'Thermodynamic Assessment of the ZrO2-YO(1.5) System'. Experimentally only the YO(1.5)-ZrO2 system has been well-studied. All other systems are only approximately known. The major simplification in this work is the treatment of each single cation unit as a component. The pure liquid oxides are taken as reference states and two term lattice stability descriptions are used for each of the components. The limited experimental phase diagrams are reproduced.

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

PubMed

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

2018-01-01

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

Characterisation of well-adhered ZrO2 layers produced on structured reactors using the sonochemical sol-gel method

NASA Astrophysics Data System (ADS)

Jodłowski, Przemysław J.; Chlebda, Damian K.; Jędrzejczyk, Roman J.; Dziedzicka, Anna; Kuterasiński, Łukasz; Sitarz, Maciej

2018-01-01

The aim of this study was to obtain thin zirconium dioxide coatings on structured reactors using the sonochemical sol-gel method. The preparation method of metal oxide layers on metallic structures was based on the synergistic combination of three approaches: the application of ultrasonic irradiation during the synthesis of Zr sol-gel based on a precursor solution containing zirconium(IV) n-propoxide, the addition of stabilszing agents, and the deposition of ZrO2 on the metallic structures using the dip-coating method. As a result, dense, uniform zirconium dioxide films were obtained on the FeCrAlloy supports. The structured reactors were characterised by various physicochemical methods, such as BET, AFM, EDX, XRF, XRD, XPS and in situ Raman spectroscopy. The results of the structural analysis by Raman and XPS spectroscopy confirmed that the metallic surface was covered by a ZrO2 layer without any impurities. SEM/EDX mapping revealed that the deposited ZrO2 covered the metallic support uniformly. The mechanical and high temperature tests showed that the developed ultrasound assisted sol-gel method is an efficient way to obtain thin, well-adhered zirconium dioxide layers on the structured reactors. The prepared metallic supports covered with thin ZrO2 layers may be a good alternative to layered structured reactors in several dynamics flow processes, for example for gas exhaust abatement.

Surface Crystallization of a MgO/Y2O3/SiO2/Al2O3/ZrO2 Glass: Growth of an Oriented β-Y2Si2O7 Layer and Epitaxial ZrO2

PubMed Central

Wisniewski, Wolfgang; Seidel, Sabrina; Patzig, Christian; Rüssel, Christian

2017-01-01

The crystallization behavior of a glass with the composition 54.7 SiO2·10.9 Al2O3·15.0 MgO·3.4 ZrO2·16.0 Y2O3 is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) including electron backscatter diffraction (EBSD) and (scanning) transmission electron microscopy [(S)TEM] including energy-dispersive X-ray spectrometry (EDXS). This glass shows the sole surface crystallization of four different yttrium silicates of the composition Y2Si2O7 (YS). The almost simultaneous but independent nucleation of α-, β-, δ-, and ε-YS at the surface is followed by growth into the bulk, where ε-YS quickly dominates a first crystallized layer. An accumulation of Mg at the growth front probably triggers a secondary nucleation of β-YS, which forms a thin compact layer before fragmenting into a highly oriented layer of fine grained crystals occupying the remaining bulk. The residual glass between the YS growth structures allows the crystallization of indialite, yttrium stabilized ZrO2 (Y-ZrO2) and very probably μ-cordierite during cooling. Hence, this glass basically shows the inverted order of crystallization observed in other magnesium yttrium alumosilicate glasses containing less Y2O3. An epitaxial relationship between Y-ZrO2 and ε-YS is proven and multiple twinning relationships occur in the YS phases. PMID:28281661

Effects of SnO2, WO3, and ZrO2 addition on the magnetic and mechanical properties of NiCuZn ferrites

NASA Astrophysics Data System (ADS)

Wang, Sea-Fue; Yang, Hsiao-Ching; Hsu, Yung-Fu; Hsieh, Chung-Kai

2015-01-01

In this study, the effects of SnO2, WO3 and ZrO2 addition at levels up to 5 wt% on the magnetic and mechanical properties of Ni0.5Cu0.3Zn0.2Fe2O4 ceramics were investigated. Only Ni0.5Cu0.3Zn0.2Fe2O4 ceramic with a SnO2 addition of ≥3.5 wt% required a densification temperature of 1150 °C, while the others reached maximum densification at 1075 °C. All samples revealed a pure spinel phase and a uniform microstructure, except for the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic with the WO3 addition, which showed an exaggerated grain growth accompanied with a small amount of needle-shaped Cu0.85Zn0.15WO4 second phase. The fracture mode in the pure Ni0.5Cu0.3Zn0.2Fe2O4 ceramic revealed a transgranular phase, as the CuO second phase increased the grain boundary strength; the Ni0.5Cu0.3Zn0.2Fe2O4 ceramics sintered with 5 wt% additives showed an intergranular phase. The Vickers hardness and the bending strength of the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic were 733.6 and 62.0 MPa, respectively. The Vickers hardness of the ferrite with added SnO2 or ZrO2 showed only a slight improvement, while an apparent change (832.7) was observed with the addition of 5.0 wt% WO3. The bending strength of the ferrite was optimized at 75.7 MPa with 2.0 wt% SnO2 and at 90.5 MPa with 3.5 wt% ZrO2, while that of the ferrite sintered with WO3 added dropped gradually from 62.0 to 47.7 MPa as the amount of WO3 was increased from 0 to 5.0 wt% due to the non-uniform microstructure. The pure Ni0.5Cu0.3Zn0.2Fe2O4 ceramic sintered at 1075 °C had an initial permeability of 356.9 and a quality factor of 71.2. The addition of ZrO2 led to a significant increase in the initial permeability (588.4 at 5.0 wt% ZrO2), but a slight decline in the quality factor (56.6 at 5.0 wt% ZrO2).

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure.

PubMed

Wang, Bo; Zhu, Jianpeng; Ma, Hongzhu

2009-05-15

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.

Structural and morphological study of ZrO2 thin films

NASA Astrophysics Data System (ADS)

Kumar, Davinder; Singh, Avtar; Kaur, Manpreet; Rana, Vikrant Singh; Kaur, Raminder

2018-05-01

In this paper we discuss the fabrication of transparent thin films of Zirconium Oxide (ZrO2) deposited on glass substrates by sol-gel dip coating technique. Further these fabricated films were characterized for different annealing temperatures and withdrawal speed. X-ray diffraction is used to study the structural properties of deposited thin films and it reveals the change in crystallographic properties with the change in annealing temperature. Thickness of thin films is estimated by using scanning electron microscope.

Ceramic composite separators coated with moisturized ZrO(2) nanoparticles for improving the electrochemical performance and thermal stability of lithium ion batteries.

PubMed

Kim, Ki Jae; Kwon, Hyuk Kwon; Park, Min-Sik; Yim, Taeeun; Yu, Ji-Sang; Kim, Young-Jun

2014-05-28

We introduce a ceramic composite separator prepared by coating moisturized ZrO2 nanoparticles with a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-12wt%HFP) copolymer on a polyethylene separator. The effect of moisturized ZrO2 nanoparticles on the morphology and the microstructure of the polymeric coating layer is investigated. A large number of micropores formed around the embedded ZrO2 nanoparticles in the coating layer as a result of the phase inversion caused by the adsorbed moisture. The formation of micropores highly affects the ionic conductivity and electrolyte uptake of the ceramic composite separator and, by extension, the rate discharge properties of lithium ion batteries. In particular, thermal stability of the ceramic composite separators coated with the highly moisturized ZrO2 nanoparticles (a moisture content of 16 000 ppm) is dramatically improved without any degradation in electrochemical performance compared to the performance of pristine polyethylene separators.

Conductive atomic force microscopy study of the photoexcitation effect on resistive switching in ZrO2(Y) films with Au nanoparticles

NASA Astrophysics Data System (ADS)

Novikov, A. S.; Filatov, D. O.; Antonov, D. A.; Antonov, I. N.; Shenina, M. E.; Gorshkov, O. N.

2018-03-01

We report on the experimental observation of the effect of optical excitation on resistive switching in ultrathin ZrO2(Y) films with single-layered arrays of Au nanoparticles. The samples were prepared by depositing nanometer-thick Au films sandwiched between two ZrO2(Y) layers by magnetron sputtering followed by annealing. Resistive switching was studied by conductive atomic force microscopy by measuring cyclic current-voltage curves of a probe-to-sample contact. The contact area was illuminated by radiation of a semiconductor laser diode with the wavelength corresponding to the plasmon resonance in an Au nanoparticle array. The enhancement of the hysteresis in cyclic current-voltage curves due to bipolar resistive switching under illumination was observed. The effect was attributed to heating of Au nanoparticles due to plasmonic optical absorption and a plasmon resonance, which enhances internal photoemission of electrons from the Fermi level in Au nanoparticles into the conduction band of ZrO2(Y). Both factors promote resistive switching in a ZrO2(Y) matrix.

Modeling of methanol decomposition on Pt/CeO2/ZrO2 catalyst in a packed bed microreactor

NASA Astrophysics Data System (ADS)

Pohar, Andrej; Belavič, Darko; Dolanc, Gregor; Hočevar, Stanko

2014-06-01

Methanol decomposition on Pt/CeO2/ZrO2 catalyst is studied inside a packed bed microreactor in the temperature range of 300-380 °C. The microreactor is fabricated using low-temperature co-fired ceramic (LTCC) technology, which is well suited for the production of relatively complex three-dimensional structures. It is packed with 2 wt% Pt-CeO2 catalyst, which is deposited onto ZrO2 spherical particles. A 1D mathematical model, which incorporates diffusion, convection and mass transfer through the boundary layer to the catalyst particles, as well as a 3D computational fluid dynamics model, are developed to describe the methanol decomposition process inside the packed bed. The microreactor exhibits reliable operation and no catalyst deactivation was observed during three months of experimentation. A comparison between the 1D mathematical model and the 3D model, considering the full 3D geometry of the microreactor is made and the differences between the models are identified and evaluated.

In situ NAP-XPS spectroscopy during methane dry reforming on ZrO2/Pt(1 1 1) inverse model catalyst

NASA Astrophysics Data System (ADS)

Rameshan, C.; Li, H.; Anic, K.; Roiaz, M.; Pramhaas, V.; Rameshan, R.; Blume, R.; Hävecker, M.; Knudsen, J.; Knop-Gericke, A.; Rupprechter, G.

2018-07-01

Due to the need of sustainable energy sources, methane dry reforming is a useful reaction for conversion of the greenhouse gases CH4 and CO2 to synthesis gas (CO  +  H2). Syngas is the basis for a wide range of commodity chemicals and can be utilized for fuel production via Fischer–Tropsch synthesis. The current study focuses on spectroscopic investigations of the surface and reaction properties of a ZrO2/Pt inverse model catalyst, i.e. ZrO2 particles (islands) grown on a Pt(1 1 1) single crystal, with emphasis on in situ near ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) during MDR reaction. In comparison to technological systems, model catalysts facilitate characterization of the surface (oxidation) state, surface adsorbates, and the role of the metal-support interface. Using XPS and infrared reflection absorption spectroscopy we demonstrated that under reducing conditions (UHV or CH4) the ZrO2 particles transformed to an ultrathin ZrO2 film that started to cover (wet) the Pt surface in an SMSI-like fashion, paralleled by a decrease in surface/interface oxygen. In contrast, (more oxidizing) dry reforming conditions with a 1:1 ratio of CH4 and CO2 were stabilizing the ZrO2 particles on the model catalyst surface (or were even reversing the strong metal support interaction (SMSI) effect), as revealed by in situ XPS. Carbon deposits resulting from CH4 dissociation were easily removed by CO2 or by switching to dry reforming conditions (673–873 K). Thus, at these temperatures the active Pt surface remained free of carbon deposits, also preserving the ZrO2/Pt interface.

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

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

Demonstration of motion control of ZrO2 microparticles in uniform/non-uniform electric field

NASA Astrophysics Data System (ADS)

Onishi, Genki; Trung, Ngo Nguyen Chi; Matsutani, Naoto; Nakayama, Tadachika; Suzuki, Tsuneo; Suematsu, Hisayuki; Niihara, Koichi

2018-02-01

This study aims to elucidate the mechanism that drives dielectric microparticles under an electric field. The driving of microstructures is affected by various electrical phenomena occurring at the same time such as surface potential, polarization, and electrostatic force. It makes the clarification of the driving mechanism challenging. A simple experimental system was used to observe the behavior of spherical ZrO2 microparticles in a nonaqueous solution under an electric field. The results suggest that the mechanism that drives the ZrO2 microparticles under an electric field involved the combination of an electric image force, a gradient force, and the contact charging phenomenon. A method is proposed to control the motion of micro- and nanostructures in further study and applications.

Characterization of ZrO2 buffer layers for sequentially evaporated Y-Ba-CuO on Si and Al2O3 substrates

NASA Technical Reports Server (NTRS)

Valco, George J.; Rohrer, Norman J.; Pouch, John J.; Warner, Joseph D.; Bhasin, Kul B.

1988-01-01

Thin film high temperature superconductors have the potential to change the microwave technology for space communications systems. For such applications it is desirable that the films be formed on substrates such as Al2O3 which have good microwave properties. The use of ZrO2 buffer layers between Y-Ba-Cu-O and the substrate has been investigated. These superconducting films have been formed by multilayer sequential electron beam evaporation of Cu, BaF2 and Y with subsequent annealing. The three layer sequence of Y/BaF2/Cu is repeated four times for a total of twelve layers. Such a multilayer film, approximately 1 micron thick, deposited directly on SrTiO3 and annealed at 900 C for 45 min produces a film with a superconducting onset of 93 K and critical temperature of 85 K. Auger electron spectroscopy in conjunction with argon ion sputtering was used to obtain the distribution of each element as a function of depth for an unannealed film, the annealed film on SrTiO3 and annealed films on ZrO2 buffer layers. The individual layers were apparent. After annealing, the bulk of the film on SrTiO3 is observed to be fairly uniform while films on the substrates with buffer layers are less uniform. The Y-Ba-Cu-O/ZrO2 interface is broad with a long Ba tail into the ZrO2, suggesting interaction between the film and the buffer layer. The underlying ZrO2/Si interface is sharper. The detailed Auger results are presented and compared with samples annealed at different temperatures and durations.

Electron-hole pairs generated in ZrO2 nanoparticle resist upon exposure to extreme ultraviolet radiation

NASA Astrophysics Data System (ADS)

Kozawa, Takahiro; Santillan, Julius Joseph; Itani, Toshiro

2018-02-01

Metal oxide nanoparticle resists have attracted much attention as the next-generation resist used for the high-volume production of semiconductor devices. However, the sensitization mechanism of the metal oxide nanoparticle resists is unknown. Understanding the sensitization mechanism is important for the efficient development of resist materials. In this study, the energy deposition in a zirconium oxide (ZrO2) nanoparticle resist was investigated. The numbers of electron-hole pairs generated in a ZrO2 core and an methacrylic acid (MAA) ligand shell upon exposure to 1 mJ cm-2 (exposure dose) extreme ultraviolet (EUV) radiations were theoretically estimated to be 0.16 at most and 0.04-0.17 cm2 mJ-1, respectively. By comparing the calculated distribution of electron-hole pairs with the line-and-space patterns of the ZrO2 nanoparticle resist fabricated by an EUV exposure tool, the number of electron-hole pairs required for the solubility change of the resist films was estimated to be 1.3-2.2 per NP. NP denotes a nanoparticle consisting of a metal oxide core with a ligand shell. In the material design of metal oxide nanoparticle resists, it is important to efficiently use the electron-hole pairs generated in the metal oxide core for the chemical change of ligand molecules.

Combinatorial Investigation of ZrO2-Based Dielectric Materials for Dynamic Random-Access Memory Capacitors

NASA Astrophysics Data System (ADS)

Kiyota, Yuji; Itaka, Kenji; Iwashita, Yuta; Adachi, Tetsuya; Chikyow, Toyohiro; Ogura, Atsushi

2011-06-01

We investigated zirconia (ZrO2)-based material libraries in search of new dielectric materials for dynamic random-access memory (DRAM) by combinatorial-pulsed laser deposition (combi-PLD). We found that the substitution of yttrium (Y) to Zr sites in the ZrO2 system suppressed the leakage current effectively. The metal-insulator-metal (MIM) capacitor property of this system showed a leakage current density of less than 5×10-7 A/cm2 and the dielectric constant was 20. Moreover, the addition of titanium (Ti) or tantalum (Ta) to this system caused the dielectric constant to increase to ˜25 within the allowed leakage level of 5×10-7 A/cm2. Therefore, Zr-Y-Ti-O and Zr-Y-Ta-O systems have good potentials for use as new materials with high dielectric constants of DRAM capacitors instead of silicon dioxides (SiO2).

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

PubMed

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

2017-02-01

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

Study of fracture toughness of ZrO2 ceramics

NASA Astrophysics Data System (ADS)

Deryugin, Yevgeny; Narkevich, Natalya; Vlasov, Ilya; Panin, Victor; Danilenko, Igor; Schmauder, Siegfried

2017-12-01

The fracture toughness characteristics of ZrO2ceramics were determined experimentally using an original technique of wedging small-sized chevron notch specimens developed at the Institute of Strength Physics and Materials Science SB RAS (Russia) in the laboratory of physical mesomechanics of materials and non-destructive testing. Measurements have shown that inelastic displacements can be more than 22% of the total displacement of the consoles by the time of the specimen failure. The effect of the Y2O3 stabilizer on the critical stress intensity factor KIc was verified. It was shown that an increase in the Y2O3 stabilizer content from 3 to 8% significantly decreases the fracture toughness. The stress intensity factor KIc falls within the range from 5.7 to 2.35 MPa m1/2.

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.

Gadolinium-doped hollow CeO2-ZrO2 nanoplatform as multifunctional MRI/CT dual-modal imaging agent and drug delivery vehicle.

PubMed

Wei, Zuwu; Wu, Ming; Li, Zuanfang; Lin, Zhan; Zeng, Jinhua; Sun, Haiyan; Liu, Xiaolong; Liu, Jingfeng; Li, Buhong; Zeng, Yongyi

2018-11-01

Developing multifunctional nanoparticle-based theranostic platform for cancer diagnosis and treatment is highly desirable, however, most of the present theranostic platforms are fabricated via complicated structure/composition design and time-consuming synthesis procedures. Herein, the multifunctional Gd/CeO 2 -ZrO 2 /DOX-PEG nanoplatform with single nano-structure was fabricated through a facile route, which possessed MR/CT dual-model imaging and chemotherapy ability. The nanoplatform not only exhibited well-defined shapes, tunable compositions and narrow size distributions, but also presented a well anti-cancer effect and MR/CT imaging ability. Therefore, the Gd/CeO 2 -ZrO 2 /DOX-PEG nanoplatform could be applied for chemotherapy as well as dual-model MR/CT imaging.

Hydrothermal-precipitation preparation of CdS@(Er3+:Y3Al5O12/ZrO2) coated composite and sonocatalytic degradation of caffeine.

PubMed

Huang, Yingying; Wang, Guowei; Zhang, Hongbo; Li, Guanshu; Fang, Dawei; Wang, Jun; Song, Youtao

2017-07-01

Here, we reported a novel method to dispose caffeine by means of ultrasound irradiation combinated with CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) coated composite as sonocatalyst. The CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) was synthesized via hydrothermal-precipitation method and then characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and UV-vis diffuse reflectance spectra (DRS). After that, the sonocatalytic degradation of caffeine in aqueous solution was conducted adopting CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) and CdS@ZrO 2 coated composites as sonocatalysts. In addition, some influencing factors such as CdS and ZrO 2 molar proportion, caffeine concentration, ultrasonic irradiation time, sonocatalyst dosage and addition of several inorganic oxidants on sonocatalytic degradation of caffeine were investigated by using UV-vis spectra and gas chromatograph. The experimental results showed that the presence of Er 3+ :Y 3 Al 5 O 12 could effectively improve the sonocatalytic degradation activity of CdS@ZrO 2 . To a certain extent some inorganic oxidants can also enhance sonocatalytic degradation of caffeine in the presence of CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ). The best sonocatalytic degradation ratio (94.00%) of caffeine could be obtained when the conditions of 5.00mg/L caffeine, 1.00g/L prepared CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ), 10.00mmol/LK 2 S 2 O 8 , 180min ultrasonic irradiation (40kHz frequency and 50W output power), 100mL total volume and 25-28°C temperature were adopted. It seems that the method of sonocatalytic degradation caused by CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) displayspotentialadvantages in disposing caffeine. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrochemical Corrosion and In Vitro Bioactivity of SiO2:ZrO2-Coated 316L Stainless Steel in Simulated Body Fluid

NASA Astrophysics Data System (ADS)

Srinivasan, A.; Rajendran, N.

2015-08-01

The effect of Si:Zr ratio on the in vitro bioactivity and electrochemical corrosion behavior of SiO2:ZrO2-mixed oxide-coated 316L stainless steel (SS) was evaluated in simulated body fluid (SBF) solution for 72, 120, and 168 h. Growth of Hydroxyapatite (HAp) was accelerated when Si content in the coating was increased. The Zr content in the coating improved the corrosion resistance of 316L SS rather than accelerating the HAp growth. When the Si:Zr ratio was 50:50, the coating exhibited significant improvement in corrosion resistance as well as HAp growth. The mechanism of HAp growth was proposed based on the change in surface zeta potential values of the coatings. Potentiodynamic polarization studies revealed about 10 and 5 times reduction in corrosion current density ( i corr) values for SiO2:ZrO2 (50:50)-coated 316L SS after 168 h of immersion compared to SiO2, ZrO2, and Si:Zr (70:30) coatings in SBF solutions thus confirming the superior corrosion resistance. The equivalent circuit parameters derived from electrochemical impedance spectroscopy studies further confirmed significant improvement in charge transfer resistance value even after 168 h of exposure.

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.

Mechanical Properties of Plasma-Sprayed ZrO2-8 wt% Y2O3 Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Zhu, Dongming; Miller, Robert A.

2004-01-01

Mechanical behavior of free standing, plasma-sprayed ZrO2-8 wt% Y2O3 thermal barrier coatings, including strength, fracture toughness, fatigue, constitutive relation, elastic modulus, and directionality, has been determined under various loading-specimen configurations. This report presents and describes a summary of mechanical properties of the plasma-sprayed coating material to provide them as a design database.

Surface Characterization of ZrO2/Zr Coating on Ti6Al4V and IN VITRO Evaluation of Corrosion Behavior and Biocompatibility

NASA Astrophysics Data System (ADS)

Wang, Ruoyun; Sun, Yonghua; He, Xiaojing; Gao, Yuee; Yao, Xiaohong

Biocompatibility is crucial for implants. In recent years, numerous researches were conducted aiming to modify titanium alloys, which are the most extensively used materials in orthopedic fields. The application of zirconia in the biomedical field has recently been explored. In this study, the biological ZrO2 coating was synthesized on titaniumalloy (Ti6Al4V) substrates by a duplex-treatment technique combining magnetron sputtering with micro-arc oxidation (MAO) in order to further improve the corrosion resistance and biocompatibility of Ti6Al4V alloys. The microstructures and phase constituents of the coatings were characterized by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD), the surface wettability was evaluated by contact angle measurements. The results show that ZrO2 coatings are porous with pore sizes less than 2μm and consist predominantly of the tetragonal ZrO2 (t-ZrO2) and cubic ZrO2(c-ZrO2) phase. Electrochemical tests indicate that the corrosion rate of Ti6Al4V substrates is appreciably reduced after surface treatment in the phosphate buffer saline (PBS). In addition, significantly improved cell adhesion and growth were observed from the ZrO2/Zr surface. Therefore, the hybrid approach of magnetron sputtering and MAO provides a surface modification for Ti6Al4V to achieve acceptable corrosion resistance and biocompatibility.

Porous Ceramic Composite ZrO2(MgO)-MgO for Osteoimplantology

NASA Astrophysics Data System (ADS)

Buyakov, A. S.; Kulkov, S. N.

2017-02-01

Pore and crystalline structure, biocompatibility of ceramic composite ZrO2(MgO)-MgO were studied. The main mechanical characteristics were determined and it has been shown that compression strength directly depends on microstresses obtained from X-ray data. In-vitro studies of mesenchymal stromal stem cells (MMSC), cultivated on material surface are shown that cell proliferation and differentiation of MMSC goes throw osteogenic type.

Low temperature solution processed high-κ ZrO2 gate dielectrics for nanoelectonics

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, K. S. R. Koteswara

2016-05-01

The high-κ gate dielectrics, specifically amorphous films offer salient features such as exceptional mechanical flexibility, smooth surfaces and better uniformity associated with low leakage current density. In this work, ∼35 nm thick amorphous ZrO2 films were deposited on silicon substrate at low temperature (300 °C, 1 h) from facile spin-coating method and characterized by various analytical techniques. The X-ray diffraction and X-ray photoelectron spectroscopy reveal the formation of amorphous phase ZrO2, while ellipsometry analysis together with the Atomic Force Microscope suggest the formation of dense film with surface roughness of 1.5 Å, respectively. The fabricated films were integrated in metal-oxide-semiconductor (MOS) structures to check the electrical capabilities. The oxide capacitance (Cox), flat band capacitance (CFB), flat band voltage (VFB), dielectric constant (κ) and oxide trapped charges (Qot) extracted from high frequency (1 MHz) C-V curve are 186 pF, 104 pF, 0.37 V, 15 and 2 × 10-11 C, respectively. The small flat band voltage 0.37 V, narrow hysteresis and very little frequency dispersion between 10 kHz-1 MHz suggest an excellent a-ZrO2/Si interface with very less trapped charges in the oxide. The films exhibit a low leakage current density 4.7 × 10-9 A/cm2 at 1 V. In addition, the charge transport mechanism across the MOSC is analyzed and found to have a strong bias dependence. The space charge limited conduction mechanism is dominant in the high electric field region (1.3-5 V) due to the presence of traps, while the trap-supported tunneling is prevailed in the intermediate region (0.35-1.3 V). Low temperature solution processed ZrO2 thin films obtained are of high quality and find their importance as a potential dielectric layer on Si and polymer based flexible electronics.

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.

Enhanced thermoelectric figure-of-merit in Bi-Sb-Te nanocomposites with homogenously dispersed oxide ceramic ZrO2 nanoparticles

NASA Astrophysics Data System (ADS)

Madavali, B.; Kim, H. S.; Lee, K. H.; Hong, S. J.

2017-06-01

In this research, p-type BiSbTe/ZrO2 nanocomposite powders were fabricated by high-energy ball milling. Different weight percentages of ZrO2 (2, 4, and 6 wt. %) nanoparticles were incorporated into the bulk (BiSbTe) matrix by consolidation of as-synthesized nanocomposites (NCs) powder by spark plasma sintering at 673 K. The phase and existence of ZrO2 nano-inclusions was confirmed by X-ray diffraction and transmission electron microscopy-selected area electron diffraction analysis. The Seebeck coefficient of the BiSbTe/ZrO2 NCs was significantly improved (˜36% for 4 wt. % added NCs) by a decrease in the carrier concentration and energy filtering effect, whereas the thermal conductivity was much reduced via strong scattering of carriers/phonons. The peak thermoelectric figure-of-merit (1.34 ± 0.06) was obtained for BiSbTe into which 2 wt. % ZrO2 was dispersed, which was approximately 20% greater than that of the undispersed sample. The hardness of the nanocomposites was significantly improved (˜27%) due to grain-boundary hardening and a dispersion strengthening mechanism.

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.

TiO2, SiO2 and ZrO2 Nanoparticles Synergistically Provoke Cellular Oxidative Damage in Freshwater Microalgae

PubMed Central

Liu, Yinghan; Ye, Nan; Fang, Hao; Wang, Degao

2018-01-01

Metal-based nanoparticles (NPs) are the most widely used engineered nanomaterials. The individual toxicities of metal-based NPs have been plentifully studied. However, the mixture toxicity of multiple NP systems (n ≥ 3) remains much less understood. Herein, the toxicity of titanium dioxide (TiO2) nanoparticles (NPs), silicon dioxide (SiO2) NPs and zirconium dioxide (ZrO2) NPs to unicellular freshwater algae Scenedesmus obliquus was investigated individually and in binary and ternary combination. Results show that the ternary combination systems of TiO2, SiO2 and ZrO2 NPs at a mixture concentration of 1 mg/L significantly enhanced mitochondrial membrane potential and intracellular reactive oxygen species level in the algae. Moreover, the ternary NP systems remarkably increased the activity of the antioxidant defense enzymes superoxide dismutase and catalase, together with an increase in lipid peroxidation products and small molecule metabolites. Furthermore, the observation of superficial structures of S. obliquus revealed obvious oxidative damage induced by the ternary mixtures. Taken together, the ternary NP systems exerted more severe oxidative stress in the algae than the individual and the binary NP systems. Thus, our findings highlight the importance of the assessment of the synergistic toxicity of multi-nanomaterial systems. PMID:29419775

Facile synthesis of highly stable and well-dispersed mesoporous ZrO(2)/carbon composites with high performance in oxidative dehydrogenation of ethylbenzene.

PubMed

Li, Qiang; Xu, Jie; Wu, Zhangxiong; Feng, Dan; Yang, Jianping; Wei, Jing; Wu, Qingling; Tu, Bo; Cao, Yong; Zhao, Dongyuan

2010-09-28

Highly ordered mesoporous ZrO(2)/carbon (FDU-15) composites have been synthesized via a facile evaporation induced triconstituent co-assembly (EISA) approach by using Pluronic F127 as a template and zirconium oxychloride octahydrate and resol as Zr and carbon sources. The synthesized mesoporous composites exhibit a highly ordered two-dimensional (2-D) hexagonal mesostructure with relatively high specific surface areas (up to 947 m(2) g(-1)), pore sizes around 3.8 nm and high pore volumes (up to 0.71 cm(3) g(-1)). The results clearly show that the crystalline zirconia nanoparticles (ca. 1.9-3.9 nm) are well-dispersed in amorphous matrices of the ordered mesoporous carbon FDU-15 materials, which construct the nanocomposites. The ordered mesostructures of the obtained ZrO(2)/FDU-15 composites can be well-retained even at the high pyrolysis temperature (up to 900 degrees C), suggesting a high thermal stability. The zirconia content of the ZrO(2)/FDU-15 composites can be tunable in a wide range (up to 47%). Moreover, the resultant mesoporous ZrO(2)/FDU-15 composites exhibit high catalytic activity in oxidative dehydrogenation (ODH) of ethylbenzene (EB) to styrene (ST), with high ethylbenzene conversion (59.6%) and styrene selectivity (90.4%), which is mainly attributed to the synergistic catalytic effect between the oxygen-containing groups located on the carbon pore walls and weakly basic sites of the nanocrystalline ZrO(2). Furthermore, the high specific surface areas and opening pore channels are also responsible for their high catalytic activity. Therefore, it is a very promising catalyst material in styrene production on an industrial scale.

Effect of ZrO2 Powders on the Pyrolysis of Polycarbosilanes Coating Under Laser Ablation

NASA Astrophysics Data System (ADS)

Cheng, Han; Chen, Zhaofeng; Tao, Jie; Yan, Bo; Li, Cong; Wang, Liangbing; Zhang, Ying; Fang, Dan; Wan, Shuicheng; Wu, Wangping

Aircrafts hold the outstanding mastery of the sky in modern wars, however the laser beam weapons can carry out laser attacking to aircrafts. The purpose of the present paper is to research on a new type laser protective material. Polycarbosilanes (PCS)/divinylbenzene mixtures containing ZrO2 powders were brushed to the surface of the aluminum alloy plates and then cured at 150°C for 6 h. The PCS-coated plates were ablated by laser for 3 s. The phase identification of as-ablated powders was examined by X-ray diffraction. The results indicated that the as-ablated powders of cured PCS were composed of major phase β-SiC and smaller amounts of free carbon. The PCS composite coating played a certain role of laser ablation resistance. The effect of added ZrO2 powders on the pyrolysis of PCS-coating under laser ablation is conspicuous.

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

PubMed Central

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

2017-01-01

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

New ZrO2/Al2O3 Nanocomposite Fabricated from Hybrid Nanoparticles Prepared by CO2 Laser Co-Vaporization

PubMed Central

Bartolomé, José F.; Smirnov, Anton; Kurland, Heinz-Dieter; Grabow, Janet; Müller, Frank A.

2016-01-01

Alumina toughened zirconia (ATZ) and zirconia toughened alumina (ZTA) are currently the materials of choice to meet the need for tough, strong, and bioinert ceramics for medical devices. However, the mechanical properties of ZrO2/Al2O3 dispersion ceramics could be considerably increased by reducing the corresponding grain sizes and by improving the homogeneity of the phase dispersion. Here, we prepare nanoparticles with an intraparticular phase distribution of Zr(1−x)AlxO(2−x/2) and (γ-, δ-)Al2O3 by the simultaneous gas phase condensation of laser co-vaporized zirconia and alumina raw powders. During subsequent spark plasma sintering the zirconia defect structures and transition alumina phases transform to a homogeneously distributed dispersion of tetragonal ZrO2 (52.4 vol%) and α-Al2O3 (47.6 vol%). Ceramics sintered by spark plasma sintering are completely dense with average grain sizes in the range around 250 nm. Outstanding mechanical properties (flexural strength σf = 1500 MPa, fracture toughness KIc = 6.8 MPa m1/2) together with a high resistance against low temperature degradation make these materials promising candidates for next generation bioceramics in total hip replacements and for dental implants. PMID:26846310

New ZrO2/Al2O3 Nanocomposite Fabricated from Hybrid Nanoparticles Prepared by CO2 Laser Co-Vaporization

NASA Astrophysics Data System (ADS)

Bartolomé, José F.; Smirnov, Anton; Kurland, Heinz-Dieter; Grabow, Janet; Müller, Frank A.

2016-02-01

Alumina toughened zirconia (ATZ) and zirconia toughened alumina (ZTA) are currently the materials of choice to meet the need for tough, strong, and bioinert ceramics for medical devices. However, the mechanical properties of ZrO2/Al2O3 dispersion ceramics could be considerably increased by reducing the corresponding grain sizes and by improving the homogeneity of the phase dispersion. Here, we prepare nanoparticles with an intraparticular phase distribution of Zr(1-x)AlxO(2-x/2) and (γ-, δ-)Al2O3 by the simultaneous gas phase condensation of laser co-vaporized zirconia and alumina raw powders. During subsequent spark plasma sintering the zirconia defect structures and transition alumina phases transform to a homogeneously distributed dispersion of tetragonal ZrO2 (52.4 vol%) and α-Al2O3 (47.6 vol%). Ceramics sintered by spark plasma sintering are completely dense with average grain sizes in the range around 250 nm. Outstanding mechanical properties (flexural strength σf = 1500 MPa, fracture toughness KIc = 6.8 MPa m1/2) together with a high resistance against low temperature degradation make these materials promising candidates for next generation bioceramics in total hip replacements and for dental implants.

A thermal study on the structural changes of bimetallic ZrO2-modified TiO2 nanotubes synthesized using supercritical CO2.

PubMed

Lucky, R A; Charpentier, P A

2009-05-13

In this study the thermal behavior of bimetallic ZrO(2)-TiO(2) (10/90 mol/mol) nanotubes are discussed which were synthesized via a sol-gel process in supercritical carbon dioxide (scCO(2)). The effects of calcination temperature on the morphology, phase structure, mean crystallite size, specific surface area and pore volume of the nanotubes were investigated by using a variety of physiochemical techniques. We report that SEM and TEM images showed that the nanotubular structure was preserved at up to 800 degrees C calcination temperature. When exposed to higher temperatures (900-1000 degrees C) the ZrO(2)-TiO(2) tubes deformed and the crystallites fused together, forming larger crystallites, and a bimetallic ZrTiO(4) species was detected. These results were further examined using TGA, FTIR, XRD and HRTEM analysis. The BET textural properties demonstrated that the presence of a small amount of Zr in the TiO(2) matrix inhibited the grain growth, stabilized the anatase phase and increased the thermal stability.

A high performance transparent resistive switching memory made from ZrO2/AlON bilayer structure

NASA Astrophysics Data System (ADS)

Tsai, Tsung-Ling; Chang, Hsiang-Yu; Lou, Jesse Jen-Chung; Tseng, Tseung-Yuen

2016-04-01

In this study, the switching properties of an indium tin oxide (ITO)/zirconium oxide (ZrO2)/ITO single layer device and those of a device with an aluminum oxynitride (AlON) layer were investigated. The devices with highly transparent characteristics were fabricated. Compared with the ITO/ZrO2/ITO single layer device, the ITO/ZrO2/AlON/ITO bilayer device exhibited a larger ON/OFF ratio, higher endurance performance, and superior retention properties by using a simple two-step forming process. These substantial improvements in the resistive switching properties were attributed to the minimized influence of oxygen migration through the ITO top electrode (TE), which can be realized by forming an asymmetrical conductive filament with the weakest part at the ZrO2/AlON interface. Therefore, in the ITO/ZrO2/AlON/ITO bilayer device, the regions where conductive filament formation and rupture occur can be effectively moved from the TE interface to the interior of the device.

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.

Dip-coated ZrO2-Y2O3 coatings tested in molten salts for CSP applications

NASA Astrophysics Data System (ADS)

Pérez, Francisco Javier; Encinas-Sánchez, Víctor; Lasanta, María Isabel; de Miguel, María Teresa; García-Martín, Gustavo

2017-06-01

In the present work, the behaviour of ZrO2 - Y2O3 coatings in contact with molten salts at 500 °C has been studied. The coatings were prepared by sol-gel and deposited by dip-coating on AISI 304 specimens previously prepared by sanding and polishing. The behaviour in contact with molten salt was studied through static corrosion tests by the immersion of the coated samples in an alkali-nitrate mixture with a composition of 60 wt.% NaNO3/40 wt.% KNO3 (commonly known as Solar Salt). Prior to test, the deposited coatings were characterized using Scanning Electron Microscopy and X-Ray Diffraction, showing a compacted, homogeneous and uniform aspect and t-YSZ as main component. After corrosion tests, the samples were characterized via gravimetric, Scanning Electron Microscopy and X-Ray Diffraction. The results show a good behaviour of the coated samples compared with the bare coupon samples. However after 1000 h of testing m-ZrO2 appears in the composition,. At this preliminary study, results confirm the suitability of ZrO2 - Y2O3 coatings in solar applications after those working hours, although it is necessary to optimize the coating and study its behaviour at longer times.

Mechanical Properties and Plasma Erosion Resistance of ZrO2p(3Y)/BN-SiO2 Ceramic Composites under Different Sintering Temperature

NASA Astrophysics Data System (ADS)

Zhou, Yu; Duan1, Xiaoming; Jia, Dechang; Yang, Zhihua; Meng, Qingchang; Yu, Yang; Yu, Daren; Ding, Yongjie

2011-10-01

ZrO2p(3Y)/BN-SiO2 ceramic composites were hot pressed under different sintering temperature. The ceramic composites were composed by BN, m-ZrO2, t-ZrO2 and SiO2. The relative density, bending strength, elastic modulus and fracture toughness increase with the sintering temperature increasing, the maximum value of which at the sintering temperature of 1800°C are 97.5%, 229.9MPa, 60.8GPa and 3.55MPam1/2, respectively. The erosion resistance ability of ZrO2p(3Y)/BN-SiO2 ceramic composites rise gradually with the sintering temperature increasing, and the erosion rate of the ceramic composite sintered at 1800°C is 8.03×10-3mm/h.

Electrical characteristics and step coverage of ZrO2 films deposited by atomic layer deposition for through-silicon via and metal-insulator-metal applications

NASA Astrophysics Data System (ADS)

Choi, Kyeong-Keun; Park, Chan-Gyung; Kim, Deok-kee

2016-01-01

The electrical characteristics and step coverage of ZrO2 films deposited by atomic layer deposition were investigated for through-silicon via (TSV) and metal-insulator-metal applications at temperatures below 300 °C. ZrO2 films were able to be conformally deposited on the scallops of 50-µm-diameter, 100-µm-deep TSV holes. The mean breakdown field of 30-nm-thick ZrO2 films on 30-nm-thick Ta(N) increased about 41% (from 2.7 to 3.8 MV/cm) upon H2 plasma treatment. With the plasma treatment, the breakdown field of the film increased and the temperature coefficient of capacitance decreased significantly, probably as a result of the decreased carbon concentration in the film.

Effects of Post-Deposition Annealing on ZrO2/n-GaN MOS Capacitors with H2O and O3 as the Oxidizers

NASA Astrophysics Data System (ADS)

Zheng, Meijuan; Zhang, Guozhen; Wang, Xiao; Wan, Jiaxian; Wu, Hao; Liu, Chang

2017-04-01

GaN-based metal-oxide-semiconductor capacitors with ZrO2 as the dielectric layer have been prepared by atomic layer deposition. The accumulation and depletion regions can be clearly distinguished when the voltage was swept from -4 to 4 V. Post-annealing results suggested that the capacitance in accumulation region went up gradually as the annealing temperature increased from 300 to 500 °C. A minimum leakage current density of 3 × 10-9 A/cm2 at 1 V was obtained when O3 was used for the growth of ZrO2. Leakage analysis revealed that Schottky emission and Fowler-Nordheim tunneling were the main leakage mechanisms.

Annealing Behavior of 57Fe Implanted in ZrO2(Y)

NASA Astrophysics Data System (ADS)

Zhang, G. L.; Yu, F. H.; Weng, H. M.; Zhang, H. H.

1998-12-01

Using conversion electron Mossbauer spectroscopy(CEMS) and slow positron beam, the chemical states of the implanted 57Fe (100KeV,3 × 10 16 ions/cm 2) in ZrO2 containing 3 mol% Y 2O 3( ZY 3) and its thermodynamic behavior during annealing process with the temperature from 200 to 500°C were studied. After annealing at 400°C the complex of Fe3+-V has been mostly dissolved, and the prior phase to α-Fe and α-Fe nano-crystalline cluster were present in the sample. Meanwhile the mixed conducting of oxygen-ions and electrons in the ZY3 containing Fe sample appeared.

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

PubMed

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

2013-05-11

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

Researches on Tie Rod Ends Lubricated by Grease with TiO2 and ZrO2 Nanoparticles

NASA Astrophysics Data System (ADS)

Wozniak, Marek; Siczek, Krzysztof; Kubiak, Przemysław; Jozwiak, Piotr; Siczek, Krystian

2018-05-01

The nanoparticles of some materials can be used successfully to improve tribological properties through decreasing both wear and friction borne out of contact between the contact surfaces of elements in different devices, particularly vehicles. Nanoparticles of TiO2 and ZrO2 were chosen as additives to the lithium grease lubricating the contact surfaces in tie rod ends. The object of study was the steel ball – the component of the tie rod end – mating with the polymer insert and lubricated with the pure lithium grease or containing the addition of pure TiO2, pure ZrO2 nanoparticles, with a 1%wt. Studies on friction were carried out using the tester allowing cyclical rotational motion and different loading of contact. Wear was investigated by driving a car, whose tie rod ends were analysed, on a fixed ‘eight’-shape track and with a fixed velocity pattern. The aim of the study was to obtain the values and waveforms of friction moment and wear versus cycles, loading and composition of lubricating grease. The waveforms of friction coefficient were obtained using the FEM model of the analysed contact zone. Based on the obtained waveforms, recommendations for the composition of additives for lithium grease were made.

Doping Li and K into Na2ZrO3 Sorbent to Improve Its CO2 Capture Capability

NASA Astrophysics Data System (ADS)

Duan, Yuhua

Carbon dioxide is one of the major combustion products which once released into the air can contribute to global climate change. Solid sorbents have been reported in several previous studies to be promising candidates for CO2 sorbent applications due to their high CO2 absorption capacities at moderate working temperatures. However, at a given CO2 pressure, the turnover temperature (Tt) of an individual solid capture CO2 reaction is fixed and may be outside the operating temperature range (ΔTo) for a particularly capture technology. In order to shift such Tt for a solid into the range of ΔTo, its corresponding thermodynamic property must be changed by changing its structure by reacting (mixing) with other materials or doping with other elements. As an example, by combining thermodynamic database searching with ab initio thermodynamics calculations, in this work, we explored the Li- and K-doping effects on the Tt shifts of Na2ZrO3 at different doping levels. The obtained results showed that compared to pure Na2ZrO3, the Li- and K-doped mixtures Na2-αMαZrO3 (M =Li, K) have lower Tt and higher CO2 capture capacities.

A Simple Method for High-Performance, Solution-Processed, Amorphous ZrO2 Gate Insulator TFT with a High Concentration Precursor

PubMed Central

Cai, Wei; Zhu, Zhennan; Wei, Jinglin; Fang, Zhiqiang; Zheng, Zeke; Zhou, Shangxiong; Peng, Junbiao; Lu, Xubing

2017-01-01

Solution-processed high-k dielectric TFTs attract much attention since they cost relatively little and have a simple fabrication process. However, it is still a challenge to reduce the leakage of the current density of solution-processed dielectric TFTs. Here, a simple solution method is presented towards enhanced performance of ZrO2 films by intentionally increasing the concentration of precursor. The ZrO2 films not only exhibit a low leakage current density of 10−6 A/cm2 at 10 V and a breakdown field of 2.5 MV/cm, but also demonstrate a saturation mobility of 12.6 cm2·V−1·s−1 and a Ion/Ioff ratio of 106 in DC pulse sputtering IGZO-TFTs based on these films. Moreover, the underlying mechanism of influence of precursor concentration on film formation is presented. Higher concentration precursor results in a thicker film within same coating times with reduced ZrO2/IGZO interface defects and roughness. It shows the importance of thickness, roughness, and annealing temperature in solution-processed dielectric oxide TFT and provides an approach to precisely control solution-processed oxide films thickness. PMID:28825652

Structural effects due to the incorporation of Ar atoms in the lattice of ZrO 2 thin films prepared by ion beam assisted deposition

NASA Astrophysics Data System (ADS)

Holgado, J. P.; Escobar Galindo, R.; van Veen, A.; Schut, H.; de Hosson, J. Th. M.; González-Elipe, A. R.

2002-09-01

Two sets of ZrO 2 thin films have been prepared at room temperature by ion beam induced chemical vapour deposition and subsequently annealed up to 1323 K. The two sets of samples have been prepared by using either O 2+ or mixtures of (O 2++Ar +) ions for the decomposition of a volatile metallorganic precursor of zirconium. The structure and microstructure of these two sets of samples have been determined by means of X-ray diffraction, Fourier transform infrared spectroscopy and positron beam analysis (PBA). The samples were very compact and dense and had a very low-surface roughness. After annealing in air at T⩾573 K both sets of films were transparent and showed similar refraction indexes. For the (O 2++Ar +)-ZrO 2 thin films it is shown by X-ray photoelectron spectroscopy and Rutherford back scattering that a certain amount of incorporated Ar (5-6 at.%) remains incorporated within the oxide lattice. No changes were detected in the amount of incorporated Ar even after annealing at T=773 K. For higher annealing temperatures ( T>1073 K), the amount of Ar starts to decrease, and at T=1223 K only residual amounts of Ar (<0.4%) remain within the lattice. It has been found that as far as Ar atoms remain incorporated within the ZrO 2 network, the (O 2+-Ar +)-ZrO 2 films present a cubic/tetragonal phase. When the amount of "embedded" Ar decreases, the crystalline phase reverts to monoclinic, the majority phase observed for the (O 2+)-ZrO 2 films after any annealing treatments. The microstructure of the films after different annealing treatments has been investigated by PBA. The presence of Ar ions and the initial amorphous state of the layers were detected by this technique. An increase of the open volume was observed after annealing up to 773 K in both sets of samples. For higher annealing temperatures the samples showed a progressive crystallisation resulting in a decrease of the open volume. During this sintering the samples without embedded Ar present a higher

Effect of ambient oxygen on the photoluminescence of sol-gel-derived nanocrystalline ZrO2:Eu,Nb

NASA Astrophysics Data System (ADS)

Puust, Laurits; Kiisk, Valter; Eltermann, Marko; Mändar, Hugo; Saar, Rando; Lange, Sven; Sildos, Ilmo; Dolgov, Leonid; Matisen, Leonard; Jaaniso, Raivo

2017-06-01

The development of inorganic nanophosphors is an active research field due to many applications, including optical gas sensing materials. We found a systematic dependence of the photoluminescence (PL) of europium (Eu3+) impurity ions in zirconia (ZrO2) nanocrystals on the ambient oxygen concentration in a O2/N2 mixture at normal pressure. Europium-doped ZrO2 powders were synthesized via a sol-gel route. Heat-treatment at 1200 °C resulted in a well-developed monoclinic phase (XRD crystallite size of ~50 nm) and an intense PL of Eu3+ ions residing in the dominant phase (Eu3+ was excited directly at 395 or 464 nm). Co-doping with niobium resulted in a narrowing of the PL emission lines. Only Nb5+ was detected by XPS and is believed to charge-compensate Eu3+ activators throughout the material leading to a more regular crystal lattice. At room temperature, the exposure to oxygen suppressed the Eu3+ fluorescence, whereas, at elevated temperatures (300 °C), the effect was reversed. At 300 °C and under a focused continuous laser beam, a substantial PL response (>50%) was achieved when switching 100% of N2 for 100% of O2. PL decay kinetics clearly showed that at 300 °C fluorescence quenching centers were induced within the material by oxygen desorption. The relatively fast (<5 min) and sub-linear PL response to the changes of oxygen concentration shows that ZrO2:Eu,Nb is a promising PL-based oxygen sensing material over a wide-range of oxygen pressures.

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

Effects of Post-Deposition Annealing on ZrO2/n-GaN MOS Capacitors with H2O and O3 as the Oxidizers.

PubMed

Zheng, Meijuan; Zhang, Guozhen; Wang, Xiao; Wan, Jiaxian; Wu, Hao; Liu, Chang

2017-12-01

GaN-based metal-oxide-semiconductor capacitors with ZrO 2 as the dielectric layer have been prepared by atomic layer deposition. The accumulation and depletion regions can be clearly distinguished when the voltage was swept from -4 to 4 V. Post-annealing results suggested that the capacitance in accumulation region went up gradually as the annealing temperature increased from 300 to 500 °C. A minimum leakage current density of 3 × 10 -9  A/cm 2 at 1 V was obtained when O 3 was used for the growth of ZrO 2 . Leakage analysis revealed that Schottky emission and Fowler-Nordheim tunneling were the main leakage mechanisms.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode

PubMed Central

Shinde, Pravin S.; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-01-01

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes. PMID:27577967

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode.

PubMed

Shinde, Pravin S; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-31

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr(4+) ions from ZrO2 UL and Sn(4+) ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode

NASA Astrophysics Data System (ADS)

Shinde, Pravin S.; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-01

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

Application of the method of images on electrostatic phenomena in aqueous Al2O3 and ZrO2 suspensions.

PubMed

Cordelair, Jens; Greil, Peter

2003-09-15

A new solution for the Poisson equation for the diffuse part of the double layer around spherical particles will be presented. The numerical results are compared with the solution of the well-known DLVO theory. The range of the diffuse layer differs considerably in the two theories. Also, the inconsistent representation of the surface and diffuse layer charge in the DLVO theory do not occur in the new theory. Experimental zeta potential measurements were used to determine the charge of colloidal Al2O3 and ZrO2 particles. It is shown that the calculated charge can be interpreted as a superposition of independent H+ and OH- adsorption isotherms. The corresponding Langmuir adsorption isotherms are taken to model the zeta potential dependence on pH. In the vicinity of the isoelectric point the model fits well with the experimental data, but at higher ion concentrations considerable deviations occur. The deviations are discussed. Furthermore, the numerical results for the run of the potential in the diffuse part of the double layer were used to determine the electrostatic interaction potential between the particles in correlation with the zeta potential measurements. The corresponding total interaction potentials, including the van der Waals attraction, were taken to calculate the coagulation half-life for a suspension with a particle loading of 2 vol%. It is shown that stability against coagulation is maintained for Al2O3 particles in the pH region between 3.3 and 7 and for ZrO2 only around pH 5. Stability against flocculation can be achieved in the pH regime between 4.5 and 7 for Al2O3, while the examined ZrO2 particles are not stable against flocculation in aqueous suspensions.

Phase study of SiO2-ZrO2 composites prepared from polymorphic combination of starting powders via a ball-milling followed by calcination

NASA Astrophysics Data System (ADS)

Musyarofah; Nurlaila, R.; Muwwaqor, N. F.; Saukani, M.; Kuswoyo, A.; Triwikantoro; Pratapa, S.

2017-04-01

The effects of SiO2-ZrO2 polymorphic combinations as starting powders and calcination temperature on phase composition of the SiO2-ZrO2 composites were studied. Stoichiometric (1:1 mol%) mixtures of the SiO2-ZrO2 composites were mechanically activated using a ball-milling for 5 h followed by calcinations at 1000, 1100 and 1200 °C for 3 h. The composites used in the present study were a-SiO2+ a-ZrO2, a-SiO2+ t-ZrO2, c-SiO2+ a-ZrO2 and c-SiO2+ t-ZrO2 which were symbolized by AA, AT, CA and CT, respectively. Prefixes a, t and c denote amorphous, tetragonal and cristobalite, respectively. The phase composition was determined by Rietveld analysis of X-ray diffraction (XRD) data using Rietica software. The identified phases for all calcined samples were a combination among t-ZrO2, c-SiO2, m-ZrO2 and zircon (ZrSiO4). Amorphous zirconia formed a transient tetragonal zirconia phase during heating, which reacted with silica to form zircon. The zircon phase was not found to form even at 1200 °C in the AT and CT mixtures and at 1100 °C in the CA mixture. The AA mixture in particular crystallized to form zircon at a lower temperature with more composition fraction than the others, ca 82.9 (14) mol%.

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.

Atomic layer deposited ZrO2 nanofilm on Mg-Sr alloy for enhanced corrosion resistance and biocompatibility.

PubMed

Yang, Qiuyue; Yuan, Wei; Liu, Xiangmei; Zheng, Yufeng; Cui, Zhenduo; Yang, Xianjin; Pan, Haobo; Wu, Shuilin

2017-08-01

The biodegradability and good mechanical property of magnesium alloys make them potential biomedical materials. However, their rapid corrosion rate in the human body's environment impairs these advantages and limits their clinical use. In this work, a compact zirconia (ZrO 2 ) nanofilm was fabricated on the surface of a magnesium-strontium (Mg-Sr) alloy by the atomic layer deposition (ALD) method, which can regulate the thickness of the film precisely and thus also control the corrosion rate. Corrosion tests reveal that the ZrO 2 film can effectively reduce the corrosion rate of Mg-Sr alloys that is closely related to the thickness of the film. The cell culture test shows that this kind of ZrO 2 film can also enhance the activity and adhesion of osteoblasts on the surfaces of Mg-Sr alloys. The significance of the current work is to develop a zirconia nanofilm on biomedical MgSr alloy with controllable thickness precisely through atomic layer deposition technique. By adjusting the thickness of nanofilm, the corrosion rate of Mg-Sr alloy can be modulated, thereafter, the degradation rate of Mg-based alloys can be controlled precisely according to actual clinical requirement. In addition, this zirconia nanofilm modified Mg-Sr alloys show excellent biocompatibility than the bare samples. Hence, this work provides a new surface strategy to control the degradation rate while improving the biocompatibility of substrates. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A stable solid acid material: Sulfated ZrO2 dispersed on alumina nanotubes

NASA Astrophysics Data System (ADS)

Feng, Yu; Jiaqi, Chen; Xu, Wang; Rui-Feng, Li

2017-02-01

A tubular solid acid catalyst was designed by loading sulfated zirconia into γ-Al2O3 nanotubes using the method of stepwise deposition. The XRD, N2 adsorption-desorption characterization demonstrated that introducing alumina nanotube and SO4 2- anions have played an important role in stabilizing the metastable tetragonal ZrO2 phase, and the sulfated zirconia on the surface of the γ-Al2O3 nanotube has high dispersion and stability. The catalyst reused repeatedly possesses large amounts of acid sites and good acidity, exhibiting high catalytic activity and stability for isopropylbenzene cracking.

Platinum catalytic effect on oxygen fugacity of CO 2H 2 gas mixtures measured with ZrO 2 oxygen sensor at 105 Pa from 1300 to 700°C

NASA Astrophysics Data System (ADS)

Miyamoto, M.; Mikouchi, T.

1996-08-01

The oxygen fugacity of CO 2H 2 gas mixtures were measured with a ZrO 2 oxygen sensor at high temperatures in a furnace. We confirmed that the oxygen fugacity values measured by the ZrO 2 cell are more reducing than those of the CO 2H 2 gas mixtures calculated by using JANAF data at temperatures below 1150°C as was previously reported by Huebner (1975). We successfully decreased the deviation of the measured oxygen-fugacity value from the calculated one down to temperature of 800°C by using a Pt catalyst. Our results suggest that the deviation is probably due to incomplete equilibration of the gases.

Terbium content affects the luminescence properties of ZrO2:Tb nanoparticles for mammary cancer imaging in mice

NASA Astrophysics Data System (ADS)

Kaszewski, Jarosław; Borgstrom, Emanuel; Witkowski, Bartłomiej S.; Wachnicki, Łukasz; Kiełbik, Paula; Slonska, Anna; Domino, Malgorzata A.; Narkiewicz, Urszula; Gajewski, Zdzislaw; Hochepied, Jean-François; Godlewski, Michał M.; Godlewski, Marek

2017-12-01

The use of nanoparticles in medicine is a rapidly growing research field with numerous potential applications, especially in the field of cancer diagnosis and therapy. Nanoparticles can be intrinsically diagnostic of therapeutic, or they can be conjugated with diagnostic or therapeutic compounds. Nanoparticles may also passively or actively target tumor cells specifically using the enhanced permeation and retention (EPR) effect, or the addition of targeting ligands to their surface. This may provide a diagnostic or/and therapeutic tools to target primary as well as metastatic tumors. The transport, distribution and toxicity of nanoparticles depends greatly on their size and composition, thus every new formulation needs to be extensively researched. This work was focused on the development of Tb-doped ZrO2 nanoparticles (NPs) for application in cancer imaging. Obtained nanoparticles were below 10 nm with very low influence of Tb concentration on size. Terbium stabilization of ZrO2 had influence on the luminescence properties of obtained material. Partially stabilized zirconium dioxide exhibited broad host related emission peaking at 500 nm, disappearing with the terbium content. We confirmed alimentary absorption and wide distribution of luminescent ZrO2:Tb nanoparticles in mice with their gradual accumulation in the experimentally induced mammary cancers. Furthermore, a high concentration of NPs was found within the lung metastases as opposed to healthy lung tissue, where no NPs-related signal was observed.

Physicochemical properties of precursors of Al2O3-ZrO2 oxide ceramics prepared by electrochemical method

NASA Astrophysics Data System (ADS)

Petrova, E. V.; Dresvyannikov, A. F.; Ahmadi Daryakenari, M.; Khairullina, A. I.

2016-05-01

Scanning electron microscopy, X-ray, and thermal analysis are used to examine the structure and properties of dispersive systems based on aluminum and zirconium oxides prepared electrochemically. The effect the conditions of synthesis have on the structure and morphology of Al2O3-ZrO2 particles is studied. It is shown that the effect of an electric field on the reaction medium allows us to adjust the physicochemical properties and morphology.

ZrO2 nanoparticles labeled via a native protein corona: detection by fluorescence microscopy and Raman microspectroscopy in rat lungs.

PubMed

Silge, Anja; Bräutigam, Katharina; Bocklitz, Thomas; Rösch, Petra; Vennemann, Antje; Schmitz, Inge; Popp, Jürgen; Wiemann, Martin

2015-08-07

ZrO2 nanoparticles are frequently used in composite materials such as dental fillers from where they may be released and inhaled upon polishing and grinding. Since the overall distribution of ZrO2 NP inside the lung parenchyma can hardly be observed by routine histology, here a labeling with a fluorphore was used secondary to the adsorption of serum proteins. Particles were then intratracheally instilled into rat lungs. After 3 h fluorescent structures consisted of agglomerates scattered throughout the lung parenchyma, which were mainly concentrated in alveolar macrophages after 3 d. A detection method based on Raman microspectroscopy was established to investigate the chemical composition of those fluorescent structures in detail. Raman measurements were arranged such that no spectral interference with the protein-bound fluorescence label was evident. Applying chemometrical methods, Raman signals of the ZrO2 nanomaterial were co-localized with the fluorescence label, indicating the stability of the nanomaterial-protein-dye complex inside the rat lung. The combination of Raman microspectroscopy and adsorptive fluorescence labeling may, therefore, become a useful tool for studying the localization of protein-coated nanomaterials in cells and tissues.

Conduction mechanism of leakage current due to the traps in ZrO2 thin film

NASA Astrophysics Data System (ADS)

Seo, Yohan; Lee, Sangyouk; An, Ilsin; Song, Chulgi; Jeong, Heejun

2009-11-01

In this work, a metal-oxide-semiconductor capacitor with zirconium oxide (ZrO2) gate dielectric was fabricated by an atomic layer deposition (ALD) technique and the leakage current characteristics under negative bias were studied. From the result of current-voltage curves there are two possible conduction mechanisms to explain the leakage current in the ZrO2 thin film. The dominant mechanism is the space charge limited conduction in the high-electric field region (1.5-5.0 MV cm-1) while the trap-assisted tunneling due to the existence of traps is prevailed in the low-electric field region (0.8-1.5 MV cm-1). Conduction caused by the trap-assisted tunneling is found from the experimental results of a weak temperature dependence of current, and the trap barrier height is obtained. The space charge limited conduction is evidenced, for different temperatures, by Child's law dependence of current density versus voltage. Child's law dependence can be explained by considering a single discrete trapping level and we can obtain the activation energy of 0.22 eV.

Electronic structural studies on the improved thermal stability of Li(Ni0.8Co0.15Al0.05)O2 by ZrO2 coating for lithium ion batteries

DOE PAGES

Kim, Ji-Young; Kim, Sang Hoon; Kim, Dong Hyun; ...

2017-03-21

The electronic structures of bare and ZrO 2-coated Li(Ni 0.8Co 0.15Al 0.05)O 2 electrode systems were investigated using a combination of time-resolved X-ray diffraction and soft X-ray absorption spectroscopy (XAS) techniques. The ZrO 2 coating on the surface of Li(Ni 0.8Co 0.15Al 0.05)O 2 was effective in elevating the onset temperature of the dissociation of charged Li 0.33(Ni 0.8Co 0.15Al 0.05)O 2, which will enhance the safety of Li-ion cells. Lastly, soft XAS spectra of the Ni LII,III-edge in the partial electron yield mode were obtained, which showed that the enhanced electrochemical properties and thermal stability of the cathode materialsmore » by ZrO 2 coating can be attributed to the suppression of unwanted Ni oxidation state changes at the surface.« less

Co nanoparticle effects on the thermoluminescent signal induced by UV and gamma radiation in ZrO2 powders

NASA Astrophysics Data System (ADS)

Villa-Sánchez, G.; Mendoza-Anaya, D.; Eufemia Fernández-García, M.; Escobar-Alarcón, L.; Olea-Mejía, O.; González-Martínez, P. R.

2014-05-01

Zirconia powders, both pure and doped with Co nanoparticles were prepared by the sol-gel method followed by thermal treatment at 1000 °C. The morphological and crystallographic characteristics were studied by scanning and transmission electron microscopy, X-ray diffraction and the Rietveld refinements method. Analysis of the thermoluminescent (TL) signal induced by UV and gamma radiation was also conducted. According to the results, Co nanoparticles have a strong influence on the growth of ZrO2 particles and favor the formation of monoclinic zirconia. Moreover, an important influence of the added Co nanoparticles was observed on the position of the TL peaks of ZrO2, inducing a shift in the luminescence towards higher temperatures as well as the presence of more TL peaks at higher temperatures.

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.

Effect of ZrO2 film thickness on the photoelectric properties of mixed-cation perovskite solar cells

NASA Astrophysics Data System (ADS)

Li, Yanyan; Zhao, Li; Wei, Shoubin; Xiao, Meng; Dong, Binghai; Wan, Li; Wang, Shimin

2018-05-01

In this work, perovskite solar cells (PSCs) were fabricated in the ambient air, with a scaffold layer composed of TiO2/ZrO2 double layer as the mesoscopic layer and carbon as the counter electrode. The effect of ZrO2 thin film thickness on the photovoltaic performances of PSCs was also studied in detail. Results showed that the photoelectric properties of as-prepared PSCs largely depend on the thin film thickness due to a series of factors, including surface roughness, charge transport resistance, and electron-hole recombination rate. The power conversion efficiency of PSCs increased from 8.37% to 11.33% by varying the thin film thickness from 75 nm to 305 nm, and the optimal power conversion efficiency was realized up to the 11.33% with a thin film thickness of 167 nm. This research demonstrates a promising route for the high-efficiency and low-cost photovoltaic technology.

Al2O3/ZrO2/Y3Al5O12 Composites: A High-Temperature Mechanical Characterization

PubMed Central

Palmero, Paola; Pulci, Giovanni; Marra, Francesco; Valente, Teodoro; Montanaro, Laura

2015-01-01

An Al2O3/5 vol%·ZrO2/5 vol%·Y3Al5O12 (YAG) tri-phase composite was manufactured by surface modification of an alumina powder with inorganic precursors of the second phases. The bulk materials were produced by die-pressing and pressureless sintering at 1500 °C, obtaining fully dense, homogenous samples, with ultra-fine ZrO2 and YAG grains dispersed in a sub-micronic alumina matrix. The high temperature mechanical properties were investigated by four-point bending tests up to 1500 °C, and the grain size stability was assessed by observing the microstructural evolution of the samples heat treated up to 1700 °C. Dynamic indentation measures were performed on as-sintered and heat-treated Al2O3/ZrO2/YAG samples in order to evaluate the micro-hardness and elastic modulus as a function of re-heating temperature. The high temperature bending tests highlighted a transition from brittle to plastic behavior comprised between 1350 and 1400 °C and a considerable flexural strength reduction at temperatures higher than 1400 °C; moreover, the microstructural investigations carried out on the re-heated samples showed a very limited grain growth up to 1650 °C. PMID:28787961

Dimensional stability and electrochemical behaviour of ZrO2 incorporated electrospun PVdF-HFP based nanocomposite polymer membrane electrolyte for Li-ion capacitors.

PubMed

Solarajan, Arun Kumar; Murugadoss, Vignesh; Angaiah, Subramania

2017-04-11

Different weight percentages of ZrO 2 (0, 3, 5, 7 and 10 wt%) incorporated electrospun PVDF-HFP nanocomposite polymer membranes (esCPMs) were prepared by electrospinning technique. They were activated by soaking in 1 M LiPF 6 containing 1:1 volume ratio of EC : DMC (ethylene carbonate:dimethyl carbonate) to get electrospun nanocomposite polymer membrane electrolytes (esCPMEs). The influence of ZrO 2 on the physical, mechanical and electrochemical properties of esCPM was studied in detail. Finally, coin type Li-ion capacitor cell was assembled using LiCo 0.2 Mn 1.8 O 4 as the cathode, Activated carbon as the anode and the esCPME containing 7 wt% of ZrO 2 as the separator, which delivered a discharge capacitance of 182.5 Fg -1 at the current density of 1Ag -1 and retained 92% of its initial discharge capacitance even after 2,000 cycles. It revealed that the electrospun PVdF-HFP/ZrO 2 based nanocomposite membrane electrolyte could be used as a good candidate for high performance Li-ion capacitors.

Preparation of Si nano-crystals with controlled oxidation state from SiO disproportionated by ZrO2 ball-milling

NASA Astrophysics Data System (ADS)

Okamoto, Yuji; Harada, Yoshitomo; Ohta, Narumi; Takada, Kazunori; Sumiya, Masatomo

2016-09-01

We demonstrate that a SiO disproportionation reaction can be achieved simply by high energy mechanochemical milling. The planetary ball-milling of ZrO2 for a few minutes generated Si nano-crystals. Milling conditions including rotation speed, ball number, milling time, and type of ball material were able to control the oxidation states of Si. The ball-milled SiO powder was tested as an anode of a lithium battery. ZrO2 contamination from the vial and balls was eliminated by dipping the ball-milled SiO powder in (NH4)HSO4 molten salt and heating for 5 min. The disproportionated SiO powder showed characteristics comparable to those of a powder prepared by a conventional heating process taking several hours.

The improvement of retention time of metal-ferroelectric (PbZr0.53Ti0.47O3)-insulator (ZrO2)-semiconductor transistors and capacitors by leakage current reduction using surface treatment

NASA Astrophysics Data System (ADS)

Shih, Wen-Chieh; Kang, Kun-Yung; Lee, Joseph Ya-Min

2007-11-01

Metal-ferroelectric-insulator-semiconductor transistors (MFISFETs) and capacitors with the structure of Al /Pb (Zr0.53,Ti0.47) O3/ZrO2/Si were fabricated. The wafers were pretreated with H2O2 before ZrO2 deposition and/or post-treated with HCl after ZrO2 deposition. The leakage current density at 5V is reduced from 10-1to5×10-6A /cm2. The subthreshold slope was improved to 91mV/decade. The MFISFETs maintain a threshold voltage window of about 1.1V after an elapsed time of 3000s. The mobility is 267cm2/Vs. The improvements are most likely due to the reduction of interfacial layer thickness and the interface states at the ZrO2/Si interface.

Compressive Strength Evaluation in Brazed ZrO2/Ti6Al4V Joints Using Finite Element Analysis

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Kee, Se Ho; Jung, Flora; Heo, Yongku; Jung, Jae Pil

2016-05-01

This study aims to synthesize and evaluate the compressive strength of the ZrO2/Ti-6Al-4V joint brazed using an active metal filler Ag-Cu-Sn-Ti, and its application to dental implants assuring its reliability to resist the compressive failure in the actual oral environment. The brazing was performed at a temperature of 750 °C for 30 min in a vacuum furnace under 5 × 10-6 Torr atmosphere. The microstructure of the brazed joint showed the presence of an Ag-rich matrix and a Cu-rich phase, and Cu-Ti intermetallic compounds were observed along the Ti-6Al-4V bonded interface. The compressive strength of the brazed ZrO2/Ti-6Al-4V joint was measured by EN ISO 14801 standard test method. The measured compressive strength of the joint was ~1477 MPa—a value almost five times that of existing dental cements. Finite element analysis also confirmed the high von Mises stress values. The compressive strains in the samples were found concentrated near the Ti-6Al-4V position, matching with the position of the real fractured sample. These results suggest extremely significant compressive strength in ZrO2/Ti-6Al-4V joints using the Ag-Cu-Sn-Ti filler. It is believed that a highly reliable dental implant can be processed and designed using the results of this study.

Effects of TiO2 and ZrO2 nanofillers in LiBOB based PVdF/PVC composite polymer electrolytes (CPE)

NASA Astrophysics Data System (ADS)

Aravindan, V.; Vickraman, P.

2007-11-01

A novel type of lithium bis(oxalato)borate (LiBOB) synthesized by the solid-state reaction method has been presented. LiBOB composite polymer electrolytes (CPE) prepared with dispersions of TIO2/ZrO2with various concentrations into the host blend matrices of poly(vinylidenefluoride) (PVdF)-poly(vinylchloride) (PVC) are investigated by scanning electron microscopy, x-ray diffraction (XRD) and ac impedance measurements. The plasticizing agent selected for the present study is a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) for the phase separated morphology of the studied polymers. The impedance studies on CPE membranes identify that membranes, with 2.5 wt% of fillers, have enhanced conductivities of 5.43 × 10-4 S cm-1 and 4.38 × 10-4 S cm-1, respectively, for TiO2 and ZrO2 at ambient temperature. The XRD investigations confirm that the membranes with filler levels exceeding the limit of 2.5 wt% show a gradual increase in the degree of crystallinity, rendering them less conducting. The activation energy calculations also highlight variations in conductivities of all the membranes.

Chemical reaction mechanisms between Y2O3 stabilized ZrO2 and Gd doped CeO2 with PH3 in coal syngas

NASA Astrophysics Data System (ADS)

Chen, Gang; Kishimoto, Haruo; Yamaji, Katsuhiko; Kuramoto, Koji; Gong, Mingyang; Liu, Xingbo; Hackett, Gregory; Gerdes, Kirk; Horita, Teruhisa

2014-12-01

To clarify the chemical stability of the key materials exposed to coal syngas (CSG) containing PH3 contaminant atmosphere, exposure tests of Y2O3 8 mol.% stabilized ZrO2 (YSZ) and Gd doped CeO2 (GDC) are carried out in simulated CSG with different concentrations of PH3. Significant reaction between YSZ and 10 ppm PH3 in CSG atmosphere is confirmed, and no obvious reaction is detected on the surface of YSZ after exposed in CSG with 1 ppm PH3. YPO4, Zr2.25(PO4)3 and monoclinic Y partial stabilized ZrO2 (m-PSZ) are identified on the YSZ pellet surface after exposed in CSG with 10 ppm PH3. GDC reacted with PH3 even at 1 ppm concentration. A (Ce0.9Gd0.1)PO4 layer is formed on the surface of GDC pellet after exposure in CSG with 10 ppm PH3. Possible reaction mechanisms between YSZ and GDC with PH3 in CSG are clarified. Compared with GDC, YSZ exhibits sufficient phosphorus resistance for devices directly exposed to a coal syngas atmosphere containing low concentration of PH3.

Influence of ZrO2, SiO2, Al2O3 and TiO2 nanoparticles on maize seed germination under different growth conditions.

PubMed

Karunakaran, Gopalu; Suriyaprabha, Rangaraj; Rajendran, Venkatachalam; Kannan, Narayanasamy

2016-08-01

The focus of this investigation is to evaluate the phytotoxicity of selected metal oxide nanoparticles and microparticles as a function of maize seed germination and root elongation under different growth conditions (Petri plate, cotton and soil). The results of seed germination and root elongation experiments reveal that all the growth conditions show almost similar results. Alumina (Al2O3) and titania (TiO2) nanoparticles significantly reduce the germination percentage, whereas silica (SiO2) nanoparticles and microparticles enhance the same. The results of nanoparticles and microparticles of zirconia (ZrO2) are found to be same as those of controls. Root elongation is enhanced by SiO2 nanoparticles and microparticles treatment, whereas inhibition is observed with Al2O3 and TiO2 nanoparticles and microparticles. The X-ray fluorescence spectrometry data of the treated and control seed samples show that seeds uptake SiO2 particles to a greater extent followed by TiO2, Al2O3 and ZrO2. In addition, the uptake of nanoparticles is found to be greater than that of microparticles. Thus, the tested metal oxides penetrated seeds at the nanoscale as compared with the microscale. This study clarifies phytotoxicity of nanoparticles treated in different growth substrates and highlights the impact of nanoparticles on environment and agricultural systems.

Dimensional stability and electrochemical behaviour of ZrO2 incorporated electrospun PVdF-HFP based nanocomposite polymer membrane electrolyte for Li-ion capacitors

PubMed Central

Solarajan, Arun Kumar; Murugadoss, Vignesh; Angaiah, Subramania

2017-01-01

Different weight percentages of ZrO2 (0, 3, 5, 7 and 10 wt%) incorporated electrospun PVDF-HFP nanocomposite polymer membranes (esCPMs) were prepared by electrospinning technique. They were activated by soaking in 1 M LiPF6 containing 1:1 volume ratio of EC : DMC (ethylene carbonate:dimethyl carbonate) to get electrospun nanocomposite polymer membrane electrolytes (esCPMEs). The influence of ZrO2 on the physical, mechanical and electrochemical properties of esCPM was studied in detail. Finally, coin type Li-ion capacitor cell was assembled using LiCo0.2Mn1.8O4 as the cathode, Activated carbon as the anode and the esCPME containing 7 wt% of ZrO2 as the separator, which delivered a discharge capacitance of 182.5 Fg−1 at the current density of 1Ag−1 and retained 92% of its initial discharge capacitance even after 2,000 cycles. It revealed that the electrospun PVdF-HFP/ZrO2 based nanocomposite membrane electrolyte could be used as a good candidate for high performance Li-ion capacitors. PMID:28397783

Continuous electron stimulated desorption using a ZrO2/Ag permeation membrane

NASA Technical Reports Server (NTRS)

Outlaw, R. A.; Hoflund, Gar B.; Davidson, M. R.

1989-01-01

During the development of an atomic oxygen beam generator for laboratory simulation of the atmospheric conditions in low earth orbit, a new technique for performing electron stimulated desorption (ESD) in a continuous manner has been developed. In this technique, oxygen permeates through an Ag membrane at elevated temperature thereby providing a continuous supply of oxygen atoms to the 1000-A ZrO2 coating at the vacuum interface. ESD then results in a large peak of neutral O2 molecules which ultimately decay into steady-state desorption. The ESD signal is linear with respect to primary beam flux (0.035 O2 molecules per electron at a primary beam energy of 1 keV) but nonlinear with respect to primary beam energy.

Photo-, sono- and sonophotocatalytic degradation of methylene blue using Fe3O4/ZrO2 composites catalysts

NASA Astrophysics Data System (ADS)

Kristianto, Y.; Taufik, A.; Saleh, R.

2017-07-01

In the present work, magnetite material Fe3O4/ZrO2 with various molar ratios was prepared by the two-step method (sol-gel followed by the ultrasonic-assisted method). The as-prepared samples were fairly characterized by various characterization methods, such as X-ray Diffraction (XRD), Vibrating Sample Magnetometer (VSM), Fourier Transform Infrared (FT-IR) and Thermal Gravimetric Analysis (TGA). The catalytic performance of the as-prepared samples was evaluated based on the degradation of methylene blue under UV light, ultrasound and combination of UV and ultrasound irradiation. The results revealed that the sample with Fe3O4:ZrO2 molar ratio of 0.5:1 showed the best catalytic performance under UV, ultrasound and UV + ultrasound irradiation. The degradation of methylene blue follows the order: sonophotocatalytic > sonocatalytic > photocatalytic. In addition, the effect of various scavengers has also been studied. Furthermore, all prepared samples could be used as a convenient recyclable catalyst.

Characterizing the residual glass in a MgO/Al2O3/SiO2/ZrO2/Y2O3 glass-ceramic

PubMed Central

Seidel, Sabrina; Patzig, Christian; Wisniewski, Wolfgang; Gawronski, Antje; Hu, Yongfeng; Höche, Thomas; Rüssel, Christian

2016-01-01

The non-isochemical crystallization of glasses leads to glass-ceramics in which the chemical composition of the amorphous matrix differs from that of the parent glass. It is challenging to solely analyse the properties of these residual glassy phases because they frequently contain finely dispersed crystals. In this study, the composition of the residual glass matrix after the crystallization of a glass with the mol% composition 50.6 SiO2 · 20.7 MgO · 20.7 Al2O3 · 5.6 ZrO2 · 2.4 Y2O3 is analysed by scanning transmission electron microscopy (STEM) including energy dispersive X-ray analysis (EDXS). A batch of the residual glass with the determined composition is subsequently melted and selected properties are analysed. Furthermore, the crystallization behaviour of this residual glass is studied by X-ray diffraction, scanning electron microscopy including electron backscatter diffraction and STEM-EDXS analyses. The residual glass shows sole surface crystallization of indialite and multiple yttrium silicates while bulk nucleation does not occur. This is in contrast to the crystallization behaviour of the parent glass, in which a predominant bulk nucleation of spinel and ZrO2 is observed. The crystallization of the residual glass probably leads to different crystalline phases when it is in contact to air, rather than when it is enclosed within the microstructure of the parent glass-ceramics. PMID:27734918

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.

The Performance Improvement of N2 Plasma Treatment on ZrO2 Gate Dielectric Thin-Film Transistors with Atmospheric Pressure Plasma-Enhanced Chemical Vapor Deposition IGZO Channel.

PubMed

Wu, Chien-Hung; Huang, Bo-Wen; Chang, Kow-Ming; Wang, Shui-Jinn; Lin, Jian-Hong; Hsu, Jui-Mei

2016-06-01

The aim of this paper is to illustrate the N2 plasma treatment for high-κ ZrO2 gate dielectric stack (30 nm) with indium-gallium-zinc-oxide (IGZO) thin-film transistors (TFTs). Experimental results reveal that a suitable incorporation of nitrogen atoms could enhance the device performance by eliminating the oxygen vacancies and provide an amorphous surface with better surface roughness. With N2 plasma treated ZrO2 gate, IGZO channel is fabricated by atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) technique. The best performance of the AP-PECVD IGZO TFTs are obtained with 20 W-90 sec N2 plasma treatment with field-effect mobility (μ(FET)) of 22.5 cm2/V-s, subthreshold swing (SS) of 155 mV/dec, and on/off current ratio (I(on)/I(off)) of 1.49 x 10(7).

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.

Evolution of zirconyl-stearate Langmuir monolayers and the synthesized ZrO2 thin films with pH

NASA Astrophysics Data System (ADS)

Choudhary, Raveena; Sharma, Rajni; Brar, Loveleen K.

2018-04-01

ZrO2 thin films have a wide range of applications ranging from photonics, antireflection coatings, and resistive oxygen gas sensors, as a gate dielectric and in high temperature fuel cells. We have used the deposition of zirconyl stearate monolayers followed by their oxidation as a method for the synthesis of zirconium oxide thin films. The zirconyl stearate films have been studied and deposited for first time to the best of our knowledge. The Langmuir monolayers are studied using pressure-Area (π-A) isotherms and oscillatory barrier method. The morphology of the films for limited number of layers was studied with FE-SEM to determine the effect of pH on the final ZrO2 film. The 200 layer deposition films show pure monoclinic phase. The films have a band gap ˜6.0eV with a strong PL emission peak is at 490 nm and a weak peak is at 423 nm. So the films formed by this deposition method are suitable for luminescent applications

Mass-Mobility Characterization of Flame-made ZrO2 Aerosols: Primary Particle Diameter & Extent of Aggregation

PubMed Central

Eggersdorfer, M.L.; Gröhn, A.J.; Sorensen, C.M.; McMurry, P.H.; Pratsinis, S.E.

2013-01-01

Gas-borne nanoparticles undergoing coagulation and sintering form irregular or fractal-like structures affecting their transport, light scattering, effective surface area and density. Here, zirconia (ZrO2) nanoparticles are generated by scalable spray combustion, and their mobility diameter and mass are obtained nearly in-situ by differential mobility analyzer (DMA) and aerosol particle mass (APM) measurements. Using these data, the density of ZrO2 and a power law between mobility and primary particle diameters, the structure of fractal-like particles is determined (mass-mobility exponent, prefactor and average number and surface area mean diameter of primary particles, dva). The dva determined by DMA-APM measurements and this power law is in good agreement with the dva obtained by ex-situ nitrogen adsorption and microscopic analysis. Using this combination of measurements and above power law, the effect of flame spray process parameters (e.g. precursor solution and oxygen flow rate as well as zirconium concentration) on fractal-like particle structure characteristics is investigated in detail. This reveals that predominantly agglomerates (physically-bonded particles) and aggregates (chemically- or sinter-bonded particles) of nanoparticles are formed at low and high particle concentrations, respectively. PMID:22959835

A novel electrochemical sensor for detecting hyperin with a nanocomposite of ZrO2-SDS-SWCNTs as decoration.

PubMed

Li, Shuo; Lei, Sheng; Yu, Qian; Zou, Lina; Ye, Baoxian

2018-08-01

A novel high-sensitive electrochemical sensor with glassy carbon electrode (GCE) as support for hyperin determination is successfully designed and constructed, and the well-shaped nano-meter modified material is synthesized via a one-step and facile route. Functionalized with surfactant sodium dodecyl sulfate (SDS), Single-Walled Carbon Nanotubes (SWCNTs) are synchronously grafted with ZrO 2 nanoparticles to develop into the as-prepared nano-composite (ZrO 2 -SDS-SWCNTs). Compared to the previous reports related with hyperin detection, the linear range gets wider and detection limit (LOD) becomes lower with the aid of this novel nano-composite modified glassy carbon electrode (ZrO 2 -SDS-SWCNTs/GCE). The crystalline phases and functionalization of the preparation process has been investigated by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) instrument analysis, respectively, and the micro-morphology of related modified materials is also visibly characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). In addition, electrochemical properties of the modified materials are comparably explored by means of impedance spectroscopy (EIS) and cyclic voltammograms (CV). According to the established calibration curve under optimized condition, the peak current (Differential pulse voltammetry (DPV) signal) keeps a linear relationship with hyperin concentration in the ranges of 1.0 × 10 -9 - 3.0 × 10 -7 mol L -1 , meanwhile detection limit reaches as low as 5 × 10 -10 mol L -1 (S/N = 3). As for practical applications, the proposed sensor has also worked well on sensitive hyperin determination in real species Abelmoschus manihot. Copyright © 2018 Elsevier B.V. All rights reserved.

Novel ZrO2 based ceramics stabilized by Fe2O3, SiO2 and Y2O3

NASA Astrophysics Data System (ADS)

Rada, S.; Culea, E.; Rada, M.

2018-03-01

Samples in the 5Fe2O3·10SiO2·xY2O3·(85-x)ZrO2 composition where x = 5, 10 and 15 mol% Y2O3 were synthesized and investigated by XRD, SEM, density measurements, FTIR, UV-Vis, EPR and PL spectroscopies. X-ray diffraction patterns confirm the presence of the tetragonal and cubic ZrO2 crystalline phases in all samples. The IR data show the overlaps of absorption bands assigned to Zrsbnd Osbnd Zr and Sisbnd Osbnd linkages in samples. UV-Vis and PL data indicate higher concentrations of intrinsic defects by doping with Y2O3 concentrations. The EPR spectra are characterized by two resonance lines situated at about g ∼ 4.3 and g ∼ 2 for lower Y2O3 contents.

Lu2O3-SiO2-ZrO2 Coatings for Environmental Barrier Application by Solution Precursor Plasma Spraying and Influence of Precursor Chemistry

NASA Astrophysics Data System (ADS)

Darthout, Émilien; Quet, Aurélie; Braidy, Nadi; Gitzhofer, François

2014-02-01

As environmental barrier coatings are subjected to thermal stress in gas turbine engines, the introduction of a secondary phase as zircon (ZrSiO4) is likely to increase the stress resistance of Lu2Si2O7 coatings generated by induction plasma spraying using liquid precursors. In a first step, precursor chemistry effect is investigated by the synthesis of ZrO2-SiO2 nanopowders by induction plasma nanopowder synthesis technique. Tetraethyl orthosilicate (TEOS) as silicon precursor and zirconium oxynitrate and zirconium ethoxide as zirconium precursors are mixed in ethanol and produce a mixture of tetragonal zirconia and amorphous silica nanoparticles. The use of zirconium ethoxide precursor results in zirconia particles with diameter below 50 nm because of exothermic thermal decomposition of the ethoxide and its high boiling point with respect to solvent, while larger particles are formed when zirconium oxynitrate is employed. The formation temperature of zircon from zirconia and silica oxides is found at 1425 °C. Second, coatings are synthesized in Lu2O3-ZrO2-SiO2 system. After heat treatment, the doping effect of lutetium on zirconia grains totally inhibits the zircon formation. Dense coatings are obtained with the use of zirconium ethoxide because denser particles with a homogeneous diameter distribution constitute the coating.

Schottky barrier SOI-MOSFETs with high-k La2O3/ZrO2 gate dielectrics

PubMed Central

Henkel, C.; Abermann, S.; Bethge, O.; Pozzovivo, G.; Klang, P.; Stöger-Pollach, M.; Bertagnolli, E.

2011-01-01

Schottky barrier SOI-MOSFETs incorporating a La2O3/ZrO2 high-k dielectric stack deposited by atomic layer deposition are investigated. As the La precursor tris(N,N′-diisopropylformamidinato) lanthanum is used. As a mid-gap metal gate electrode TiN capped with W is applied. Processing parameters are optimized to issue a minimal overall thermal budget and an improved device performance. As a result, the overall thermal load was kept as low as 350, 400 or 500 °C. Excellent drive current properties, low interface trap densities of 1.9 × 1011 eV−1 cm−2, a low subthreshold slope of 70-80 mV/decade, and an ION/IOFF current ratio greater than 2 × 106 are obtained. PMID:21461054

The effect of preliminary hydrolysis on the properties of ZrO2-7% Y2O3 powders prepared by hydroxide precipitation

NASA Astrophysics Data System (ADS)

Zhirenkina, Nina V.; Mashkovtsev, Maxim A.; Bereskina, Polina A.; Zakirov, Ilsur F.; Baksheev, Evgenie O.; Bujnachev, Sergey V.; Vereshchagin, Artem O.

2017-09-01

In this study, the effect of preliminary hydrolysis of zirconyl oxysulfate on the properties of ZrO2-7 % Y2O3 powders prepared by hydroxides precipitation at a constant pH of 5 was studied. X-ray diffraction analysis showed the monophasic nature of the samples and the insignificant difference between CSR (coherent scattering regions). Samples differed in particle size distribution, porosity and morphology.

Effect of thermal cycling on ZrO2-Y2O3 thermal barrier coatings

NASA Technical Reports Server (NTRS)

Mcdonald, G.; Hendricks, R. C.

1980-01-01

A study was made of the comparative life of plasma sprayed ZrO2-Y2O3 thermal barrier coatings on NiCrAlY bond coats on Rene 41 in short (4 min) and long (57 min) thermal cycles to 1040 C in a 0.3 Mach flame. Short cycles greatly reduced the life of the ceramic coating in terms of time at temperature as compared to longer cycles. Appearance of the failed coating indicated compressive failure. Failure occurred at the bond coat-ceramic coat junction. At heating rates greater than 550 kw/sq m, the calculated coating detachment stress was in the range of literature values of coating adhesive/cohesive strength. Methods are discussed for decreasing the effect of high heating rate by avoiding compressive stress.

Improving Corrosion Resistance of 316L Austenitic Stainless Steel Using ZrO2 Sol-Gel Coating in Nitric Acid Solution

NASA Astrophysics Data System (ADS)

Kazazi, Mahdi; Haghighi, Milad; Yarali, Davood; Zaynolabedini, Masoomeh H.

2018-03-01

In this study, thin-film coating of zirconium oxide (ZrO2) was prepared by sol-gel method and subsequent heat treatment process. The sol was prepared by controlled hydrolysis of zirconium tetrapropoxide using acetic acid and ethanol/acetylacetone mixture as catalyst and chelating agent, respectively, and finally deposited onto the 316L austenitic stainless steel (316L SS) using dip coating method in order to improve its corrosion resistance in nitric acid medium. The composition, structure, and morphology of the coated surface were investigated by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The obtained results from XRD and FTIR state the formation of tetragonal and monoclinic ZrO2 phase. Also, the obtained results from surface morphology investigation by SEM and AFM indicate the formation of smooth, homogeneous and uniform coatings on the steel substrate. Then, the corrosion behavior of stainless steel was investigated in a 1 and 10 M nitric acid solutions using electrochemical impedance spectroscopy and linear polarization test. The obtained results from these tests for ZrO2-coated specimens indicated a considerable improvement in the corrosion resistance of 316L stainless steel by an increase in corrosion potential and transpassive potential, and a decrease in passive current density and corrosion current density. The decrease in passive current density in both the concentration of solutions was two orders of magnitude from bare to coated specimens.

Incorporation of ZrO2 particles in the oxide layer formed on Mg by anodizing: Influence of electrolyte concentration and current modes.

PubMed

Sankara Narayanan, T S N; Lee, Min Ho

2016-02-15

The objectives of the present study are to ascertain, particle incorporation during the initial stages of microarc oxidation (MAO), feasibility of increasing the level of particle incorporation through manipulation of process variables and, the use of MgO-ZrO2 composite coatings either as a pre-treatment or as a post-treatment for MAO coated Mg. Anodic oxide coatings were prepared using 0.3M NaOH+15g/l ZrO2 and 3M NaOH+15g/l ZrO2 at 10V under direct current, pulsed current (PC) unipolar and PC bipolar modes. MAO coatings were prepared using 5g/l NaOH+15g/l Na2SiO3 at 250V under direct current mode for 2min. The study reveals that it is possible to incorporate ZrO2 particles in the anodic oxide layer, suggesting such a possibility during the initial stages of MAO. When the MgO-ZrO2 composite coating is used as a pre-treatment, it helps to reduce the size and density of the pores of the MAO coatings and increased the corrosion resistance. When it is used as a post-treatment, lamellar shaped Mg(OH)2 with a very high surface area is formed on the surface, which would be beneficial to impart a better bioactivity and to facilitate immobilization of biomolecules. Copyright © 2015. Published by Elsevier Inc.

Luminescent properties of ZrO2:Tb nanoparticles for applications in neuroscience

NASA Astrophysics Data System (ADS)

Słońska, A.; Kaszewski, J.; Wolska-Kornio, E.; Witkowski, B.; Wachnicki, Ł.; Mijowska, E.; Karakitsou, V.; Gajewski, Z.; Godlewski, M.; Godlewski, M. M.

2016-09-01

In this paper a new generation of non-toxic nanoparticles based on the zirconium oxide doped with 0.5%Tb and co-doped by the range of 0-70% with Y was evaluated for the use as a fluorescent biomarker of neuronal trafficking. The ZrO2:Tb nanoparticles were created by microwave driven hydrothermal method. Influence of the yttrium content and thermal processing on the Tb3+ related luminescence emission was discussed. The higher intensities were achieved, when host was cubic and for the nanoparticles with 33 nm. Presence of yttrium was associated with the energy coupling of the host and dopant, wide excitation band is present at 309 and 322 nm before and after calcination respectively.

Preparation of Nanocrystalline Powders of ZrO2, Stabilized by Y2O3 Dobs for Ceramics

NASA Astrophysics Data System (ADS)

Petrunin, V. F.; Korovin, S. A.

The purpose of this study was to develop a synthesis conditions and produce samples of nanocrystalline zirconia powder in a high-temperature phase state. To increase the stability of this state at room temperature, Y2O3 was used as a dop in the two-stages chemical method including coprecipitation mixture of the corresponding hydroxides and air drying. To reduce agglomeration of nanoparticles during heat treatment of precursors the microwave oven instead of a muffle was used. Different characterisation methods have been used to determine that the obtained powders are nano-scale corresponds to a high-temperature tetragonal phase of ZrO2. It is shown that such nanocrystalline powders may be used to produce highly-dense nanoceramics.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

MgO-Al2O3-ZrO2 Amorphous Ternary Composite: A Dense and Stable Optical Coating

NASA Technical Reports Server (NTRS)

Shaoo, Naba K.; Shapiro, Alan P.

1998-01-01

The process-parameter-dependent optical and structural properties of MgO-Al2O3-ZrO2 ternary mixed-composite material were investigated. Optical properties were derived from spectrophotometric measurements. The surface morphology, grain size distributions, crystallographic phases, and process- dependent material composition of films were investigated through the use of atomic force microscopy, x-ray diffraction analysis, and energy-dispersive x-ray analysis. Energy-dispersive x-ray analysis made evident the correlation between the optical constants and the process-dependent compositions in the films. It is possible to achieve environmentally stable amorphous films with high packing density under certain optimized process conditions.

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

The visible spectrum of zirconium dioxide, ZrO2

NASA Astrophysics Data System (ADS)

Le, Anh; Steimle, Timothy C.; Gupta, Varun; Rice, Corey A.; Maier, John P.; Lin, Sheng H.; Lin, Chih-Kai

2011-09-01

The electronic spectrum of a cold molecular beam of zirconium dioxide, ZrO2, has been investigated using laser induced fluorescence (LIF) in the region from 17 000 cm-1 to 18 800 cm-1 and by mass-resolved resonance enhanced multi-photon ionization (REMPI) spectroscopy from 17 000 cm-1-21 000 cm-1. The LIF and REMPI spectra are assigned to progressions in the tilde A{^1}B_2(ν1, ν2, ν3) ← tilde X{^1}A_1(0, 0, 0) transitions. Dispersed fluorescence from 13 bands was recorded and analyzed to produce harmonic vibrational parameters for the tilde X{^1}A_1 state of ω1 = 898(1) cm-1, ω2 = 287(2) cm-1, and ω3 = 808(3) cm-1. The observed transition frequencies of 45 bands in the LIF and REMPI spectra produce origin and harmonic vibrational parameters for the tilde A{^1}B_2 state of Te = 16 307(8) cm-1, ω1 = 819(3) cm-1, ω2 = 149(3) cm-1, and ω3 = 518(4) cm-1. The spectra were modeled using a normal coordinate analysis and Franck-Condon factor predictions. The structures, harmonic vibrational frequencies, and the potential energies as a function of bending angle for the tilde A{^1}B_2 and tilde X{^1}A_1 states are predicted using time-dependent density functional theory, complete active space self-consistent field, and related first-principle calculations. A comparison with isovalent TiO2 is made.

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.

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.

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.

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

The Composition of Intermediate Products of the Thermal Decomposition of (NH4)2ZrF6 to ZrO2 from Vibrational-Spectroscopy Data

NASA Astrophysics Data System (ADS)

Voit, E. I.; Didenko, N. A.; Gaivoronskaya, K. A.

2018-03-01

Thermal decomposition of (NH4)2ZrF6 resulting in ZrO2 formation within the temperature range of 20°-750°C has been investigated by means of thermal and X-ray diffraction analysis and IR and Raman spectroscopy. It has been established that thermolysis proceeds in six stages. The vibrational-spectroscopy data for the intermediate products of thermal decomposition have been obtained, systematized, and summarized.

Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

PubMed

Zhang, Xinghua; Zhang, Qi; Wang, Tiejun; Ma, Longlong; Yu, Yuxiao; Chen, Lungang

2013-04-01

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel. Copyright © 2013 Elsevier Ltd. All rights reserved.

Deconvolution Method on OSL Curves from ZrO2 Irradiated by Beta and UV Radiations

NASA Astrophysics Data System (ADS)

Rivera, T.; Kitis, G.; Azorín, J.; Furetta, C.

This paper reports the optically stimulated luminescent (OSL) response of ZrO2 to beta and ultraviolet radiations in order to investigate the potential use of this material as a radiation dosimeter. The experimentally obtained OSL decay curves were analyzed using the computerized curve de-convolution (CCD) method. It was found that the OSL curve structure, for the short (practical) illumination time used, consists of three first order components. The individual OSL dose response behavior of each component was found. The values of the time at the OSL peak maximum and the decay constant of each component were also estimated.

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.

Paramagnetic defects and charge trapping behavior of ZrO2 films deposited on germanium by plasma-enhanced CVD

NASA Astrophysics Data System (ADS)

Mahata, C.; Bera, M. K.; Bose, P. K.; Maiti, C. K.

2009-02-01

Internal photoemission and magnetic resonance studies have been performed to investigate the charge trapping behavior and chemical nature of defects in ultrathin (~14 nm) high-k ZrO2 dielectric films deposited on p-Ge (1 0 0) substrates at low temperature (<200 °C) by plasma-enhanced chemical vapor deposition (PECVD) in a microwave (700 W, 2.45 GHz) plasma at a pressure of ~65 Pa. Both the band and defect-related electron states have been characterized using electron paramagnetic resonance, internal photoemission, capacitance-voltage and current-voltage measurements under UV illumination. Capacitance-voltage and photocurrent-voltage measurements were used to determine the centroid of oxide charge within the high-k gate stack. The observed shifts in photocurrent response of the Al/ZrO2/GeO2/p-Ge metal-insulator-semiconductor (MIS) capacitors indicate the location of the centroids to be within the ZrO2 dielectric near to the gate electrode. Moreover, the measured flat band voltage and photocurrent shifts also indicate a large density of traps in the dielectric. The impact of plasma nitridation on the interfacial quality of the oxides has been investigated. Different N sources, such as NO and NH3, have been used for nitrogen engineering. Oxynitride samples show a lower defect density and trapping over the non-nitrided samples. The charge trapping and detrapping properties of MIS capacitors under stressing in constant current and voltage modes have been investigated in detail.

The effect of ZrO2 and TiO 2 on solubility and strength of apatite-mullite glass-ceramics for dental applications.

PubMed

Fathi, Hawa M; Miller, Cheryl; Stokes, Christopher; Johnson, Anthony

2014-03-01

The effect of ZrO2 and TiO2 on the chemical and mechanical properties of apatite-mullite glass-ceramics was investigated after sample preparation according to the ISO (2768:2008) recommendations for dental ceramics. All materials were characterized using differential thermal analysis, X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. X-ray fluorescence spectroscopy was used to determine the concentrations of elements present in all materials produced. The chemical solubility test and the biaxial flexural strength (BFS) test were then carried out on all the samples. The best solubility value of 242 ± 61 μg/cm(2) was obtained when HG1T was heat-treated for 1 h at the glass transition temperature plus 20 °C (Tg + 20 °C) followed by 5 h at 1200 °C. The highest BFS value of 174 ± 38 MPa was achieved when HG1Z and HG1Z+T were heat-treated for 1 h at the Tg + 20 °C followed by 7 h at 1200 °C. The present study has demonstrated that the addition of TiO2 to the reference composition showed promise in both the glass and heat-treated samples. However, ZrO2 is an effective agent for developing the solubility or the mechanical properties of an apatite-mullite glass-ceramic separately but does not improve the solubility and the BFS simultaneously.

Spectroscopic properties of Sm3+ and V4+ ions in Na2O-SiO2-ZrO2 glasses

NASA Astrophysics Data System (ADS)

Neeraja, K.; Rao, T. G. V. M.; Kumar, A. Rupesh; Uma Lakshmi, V.; Veeraiah, N.; Rami Reddy, M.

2013-12-01

Na2O-SiO2-ZrO2 glasses of Sm3+ ions with and without V2O5 are characterized by spectroscopic and optical properties. The XRD and EDS spectra of the glass samples reveal an amorphous nature with different compositions within the glass matrix. The Infrared and Raman spectral studies are carried out and the existence of conventional structural units are analyzed in the glass network. The ESR spectra of the glass samples have indicating that a considerable proportion of vanadium ion exists in V4+ state. The optical absorption spectra of these glasses are recorded at room temperature, from the measured intensities of various absorption bands the Judd-Ofelt parameters Ω2, Ω4 and Ω6 are calculated. The photo-luminescence spectra recorded with excited wavelength 400 nm, five emission bands are observed; in this the energy transfer probability takes place between Sm3+ and V4+ ions.

Sunlight activated anodic freestanding ZrO2 nanotube arrays for Cr(VI) photoreduction.

PubMed

Bashirom, Nurulhuda; Tan, Wai Kian; Go, Kawamura; Matsuda, Atsunori; Abdul Razak, Khairunisak; Lockman, Zainovia

2018-06-14

Visible-light-active freestanding zirconia (ZrO2) nanotube (FSZNT) arrays were fabricated by a facile electrochemical anodization method in fluoride containing ethylene glycol electrolyte added to it 1 vol.% of potassium carbonate (K2CO3) at 60 V for 1 h. Poor adhesion at metal|oxide interface was induced by K2CO3 leading to formation of the FSZNT flakes. The effect of crystal structures of FSZNTs e.g., amorphous, amorphous/tetragonal, and tetragonal/monoclinic was investigated towards the photocatalytic reduction of 10 ppm hexavalent chromium, Cr(VI) at pH 2 under sunlight. The results demonstrate the amorphous FSZNTs exhibited the highest Cr(VI) removal efficiency than the crystalline FSZNTs (95 % versus 33 % after 5 h). The high photocatalytic activity of the amorphous FSZNTs can be attributed to enhanced Cr(VI) adsorption, high visible light absorption, and better charge carriers separation. The low photocatalytic activity of the crystalline FSZNTs annealed at 500 °C was mainly attributed to poor Cr(VI) adsorption, low visible light absorption, and less photoactive monoclinic-ZrO2. © 2018 IOP Publishing Ltd.

Electronic structure and electron energy-loss spectroscopy of ZrO2 zirconia

NASA Astrophysics Data System (ADS)

Dash, L. K.; Vast, Nathalie; Baranek, Philippe; Cheynet, Marie-Claude; Reining, Lucia

2004-12-01

The atomic and electronic structures of zirconia are calculated within density functional theory, and their evolution is analyzed as the crystal-field symmetry changes from tetrahedral [cubic (c-ZrO2) and tetragonal (t-ZrO2) phases] to octahedral (hypothetical rutile ZrO2 ), to a mixing of these symmetries (monoclinic phase, m-ZrO2 ). We find that the theoretical bulk modulus in c-ZrO2 is 30% larger than the experimental value, showing that the introduction of yttria in zirconia has a significant effect. Electronic structure fingerprints which characterize each phase from their electronic spectra are identified. We have carried out electron energy-loss spectroscopy experiments at low momentum transfer and compared these results to the theoretical spectra calculated within the random phase approximation. We show a dependence of the valence and 4p ( N2,3 edge) plasmons on the crystal structure, the dependence of the latter being brought into the spectra by local-field effects. Last, we attribute low energy excitations observed in EELS of m-ZrO2 to defect states 2eV above the top of the intrinsic valence band, and the EELS fundamental band gap value is reconciled with the 5.2 or 5.8eV gaps determined by vacuum ultraviolet spectroscopy.

[Preparing of Al2O3/ZrO2 composite dental ceramics through isostatic pressing technology].

PubMed

Liang, Xiao-Feng; Yin, Guang-Fu; Yang, Shi-Yuan; Wang, Jun-Xia

2006-08-01

To find out how to prepare high-density dental ceramics through isostatic pressing so that sintering shrinkage will be reduced. To prepare Al2O3/ZrO2 composite powder first, then to mold through dry-pressing, and to shape the green-body through isostatic pressing. The green-bodies were sintered at the temperature of 1 400 degrees C and kept at the temperature for different period of time (2 h, 3 h, 4 h). After that, the density and fracture strength were measured and the microstructure observed by scanning electron microscope (SEM). The sample product's density, line-shrinkage, and fracture strength of ceramics was rising with the sintering time lengthened. The sample product kept under the temperature of 1 400 degrees C for 4 hours, the fracture strength was (497.27 +/- 78.45) MPa and glass phase distributed evenly in the ceramics and the grains were integrated owing to the glass phase. The longer the sintering time, the more even the microstructure was. The sintering quality and the efficiency were improved through isostatic pressing.

Structural and chemical degradation mechanisms of pure YSZ and its components ZrO2 and Y2O3 in carbon-rich fuel gases.

PubMed

Köck, Eva-Maria; Kogler, Michaela; Götsch, Thomas; Klötzer, Bernhard; Penner, Simon

2016-05-25

Structural and chemical degradation mechanisms of metal-free yttria stabilized zirconia (YSZ-8, 8 mol% Y2O3 in ZrO2) in comparison to its pure oxidic components ZrO2 and Y2O3 have been studied in carbon-rich fuel gases with respect to coking/graphitization and (oxy)carbide formation. By combining operando electrochemical impedance spectroscopy (EIS), operando Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS), the removal and suppression of CH4- and CO-induced carbon deposits and of those generated in more realistic fuel gas mixtures (syngas, mixtures of CH4 or CO with CO2 and H2O) was examined under SOFC-relevant conditions up to 1273 K and ambient pressures. Surface-near carbidization is a major problem already on the "isolated" (i.e. Nickel-free) cermet components, leading to irreversible changes of the conduction properties. Graphitic carbon deposition takes place already on the "isolated" oxides under sufficiently fuel-rich conditions, most pronounced in the pure gases CH4 and CO, but also significantly in fuel gas mixtures containing H2O and CO2. For YSZ, a comparative quantification of the total amount of deposited carbon in all gases and mixtures is provided and thus yields favorable and detrimental experimental approaches to suppress the carbon formation. In addition, the effectivity and reversibility of removal of the coke/graphite layers was comparably studied in the pure oxidants O2, CO2 and H2O and their effective contribution upon addition to the pure fuel gases CO and CH4 verified.

Reproducibility of ZrO2-based freeze casting for biomaterials.

PubMed

Naleway, Steven E; Fickas, Kate C; Maker, Yajur N; Meyers, Marc A; McKittrick, Joanna

2016-04-01

The processing technique of freeze casting has been intensely researched for its potential to create porous scaffold and infiltrated composite materials for biomedical implants and structural materials. However, in order for this technique to be employed medically or commercially, it must be able to reliably produce materials in great quantities with similar microstructures and properties. Here we investigate the reproducibility of the freeze casting process by independently fabricating three sets of eight ZrO2-epoxy composite scaffolds with the same processing conditions but varying solid loading (10, 15 and 20 vol.%). Statistical analyses (One-way ANOVA and Tukey's HSD tests) run upon measurements of the microstructural dimensions of these composite scaffold sets show that, while the majority of microstructures are similar, in all cases the composite scaffolds display statistically significant variability. In addition, composite scaffolds where mechanically compressed and statistically analyzed. Similar to the microstructures, almost all of their resultant properties displayed significant variability though most composite scaffolds were similar. These results suggest that additional research to improve control of the freeze casting technique is required before scaffolds and composite scaffolds can reliably be reproduced for commercial or medical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

The effect of feed rate and recycle rate variable on leaching process of Na2Zro3 with HCl in continuous stirred tank reactor (CSTR) series

NASA Astrophysics Data System (ADS)

Palupi, Bekti; Supranto, Sediawan, Wahyudi Budi; Setyadji, Moch.

2017-05-01

This time, the natural resources of zircon sand is processed into several zirconium products which is utilized for various industries, such as ceramics, glass industry, metal industry and nuclear industry. The process of zircon sand into zirconium products through several stages, one of them is leaching process of Na2ZrO3 with HCl. In this research, several variations of recycle-rate/feed-rate had been done to determine the effect on leaching process. The leaching was processed at temperature of 90°C, ratio of Na2ZrO3:HCl = 1g:30mL, and 142 rotary per minute of stirring speed for 30 minutes with variation of recycle-rate/feed-rate such as 0.478, 0.299, 0.218, 0.171 and 0.141. The diameter size of Na2ZrO3 powder that used are 0.088 to 0.149 mm. This process was carried out in Continuous Stirred Tank Reactor (CSTR) series with recycle. Based on this research, the greater of the recycle-rate/feed-rate variable, the obtained Zr recovery decreased. The correlation between recycle-rate/feed-rate and Zr recovery is shown by the equation y = -146.91x + 103.51, where y is the Zr recovery and x is the recycle-rate/feed-rate. The highest Zr recovery was 90.52% obtained at recycle-rate/feed-rate 0.141. The mathematical modeling involving the probability model P(r) = 2β2r2 exp(-βr2) can be applied to this leaching process with Sum of Squared Errors (SSE) values in the range of 6×10-7 - 7×10-6.

Effect of the CTAB concentration on the upconversion emission of ZrO 2:Er 3+ nanocrystals

NASA Astrophysics Data System (ADS)

López-Luke, T.; De la Rosa, E.; Sólis, D.; Salas, P.; Angeles-Chavez, C.; Montoya, A.; Díaz-Torres, L. A.; Bribiesca, S.

2006-10-01

Upconversion emission of ZrO 2:Er 3+ (0.2 mol%) nanophosphor were studied as function of surfactant concentration after excitation at 968 nm. The strong green emission was produced by the transition 2H 11/2 + 4S 3/2 → 4I 15/2 and was explained in terms of cooperative energy transfer between neighboring ions. The upconverted signal was enhanced but the fluorescence decay time was reduced as either the surfactant concentration increases or the annealing time reduces. Experimental results show that surfactant concentration controls the particle size and morphology while annealing time control the phase composition and crystallite size. The highest intensity was obtained for a sample composed of a mixture of tetragonal (33 wt.%) and monoclinic (67 wt.%) phase with crystallite size of 31 and 59 nm, respectively. This result suggests that tetragonal crystalline structure and small crystallite size are more favorable for the upconversion emission.

Fabrication of nano ZrO2 dispersed novel W79Ni10Ti5Nb5 alloy by mechanical alloying and pressureless sintering

NASA Astrophysics Data System (ADS)

Sahoo, R. R.; Patra, A.; Karak, S. K.

2017-02-01

A high energy planetary ball-mill was employed to synthesize tungsten (W) based alloy with nominal composition of W79Ni10Ti5Nb5(ZrO2)1 (in wt. %) for 20 h with chrome steel as grinding media, toluene as process control agent (PCA) along with compaction at 500 MPa pressure for 5 mins and sintering at 1500°C for 2 h using Ar atmosphere. X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS), elemental mapping and Transmission electron microscopy (TEM) was used to study the phase formation, microstructure of both milled powder and consolidated alloy. The crystallite size of W in W79Ni10Ti5Nb5(ZrO2)1 powder was 37 nm, 14.7 nm at 10 h and 20 h of milling respectively and lattice strain enhances to 0.54% at 20 h of milling. The crystallite size reduction is more at 10 h of milling and the rate drop beyond 10 to 20 h of milling. The intense improvement in dislocation density was evident upto 10 h of milling and the rate decreases between 10 to 20 h of milling. Increase in the lattice parameter of tungsten in W79Ni10Ti5Nb5(ZrO2)1 alloy upto 0.09% was observed at 10 h of milling owing to severe stress assisted deformation followed by contraction upto 0.07% at 20 h of milling due to formation of solid solution. The large spherical particles at 0 h of milling transformed to elongated shape at 10 h of milling and finer morphology at 20 h of milling. The average particle size reduced from 100 µm to 4.5 µm with the progress of milling from 0 to 20 h. Formation of fine polycrystallites of W was revealed by bright field TEM analysis and the observed crystallite size from TEM study was well supported by the evaluated crystallite size from XRD. XRD pattern and SEM micrograph of sintered alloy revealed the formation of NbNi, Ni3Ti intermetallic phases. Densification of 91.5% was attained in the 20 h milled and sintered alloy. Mechanical behaviour of the sintered product was evaluated by hardness and wear study. W79Ni10Ti5Nb5(ZrO2)1 alloy

Evaluation of fracture toughness of ZrO 2 and Si 3N 4 engineering ceramics following CO 2 and fibre laser surface treatment

NASA Astrophysics Data System (ADS)

Shukla, P. P.; Lawrence, J.

2011-02-01

The fracture toughness property ( K1C) of Si 3N 4 and ZrO 2 engineering ceramics was investigated by means of CO 2 and a fibre laser surface treatment. Near surface modifications in the hardness were investigated by employing the Vickers indentation method. Crack lengths and the crack geometry were then measured by using the optical microscopy. A co-ordinate measuring machine was used to investigate the diamond indentations and to measure the lengths of the cracks. Thereafter, computational and analytical methods were employed to determine the K1C. An increase in the K1C of both ceramics was found by the CO 2 and the fibre laser surface treatment in comparison to the as-received surfaces. The K1C of the CO 2 laser radiated surface of the Si 3N 4 was over 3% higher in comparison to that of the fibre laser treated surface. This was by softening of the near surface layer of the Si 3N 4 which comprised of lowering of hardness, which in turn increased the crack resistance. The effects were not similar in ZrO 2 ceramic to that of the Si 3N 4 as the fibre laser radiation in this case had produced an increase of 34% compared to that of the CO 2 laser radiation. This occurred due to propagation of lower crack resulting from the Vickers indentation test during the fibre laser surface treatment which inherently affected the end K1C through an induced compressive stress layer. The K1C modification of the two ceramics treated by the CO 2 and the fibre laser was also believed to be influenced by the different laser wavelength and its absorption co-efficient, the beam delivery system as well as the differences in the brightness of the two lasers used.

Y-doped Li 8ZrO 6: A Li-Ion Battery Cathode Material with High Capacity

DOE PAGES

Huang, Shuping; Wilson, Benjamin E.; Wang, Bo; ...

2015-08-11

We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li 8ZrO 6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li + for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/dischargemore » cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO 2, and O 2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li 6ZrO 6 and Li 5ZrO 6 delithiation products can be thermodynamically metastable to release of O 2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole.« less

Y-doped Li 8ZrO 6: A Li-Ion Battery Cathode Material with High Capacity

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

Huang, Shuping; Wilson, Benjamin E.; Wang, Bo

We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li 8ZrO 6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li + for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/dischargemore » cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO 2, and O 2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li 6ZrO 6 and Li 5ZrO 6 delithiation products can be thermodynamically metastable to release of O 2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole.« less

Aqueous phase hydrogenation of phenol catalyzed by Pd and PdAg on ZrO 2

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

Resende, Karen A.; Hori, Carla E.; Noronha, Fabio B.

The impact of particle size of ZrO 2-supported Pd and of alloying with Ag was explored for hydrogenation of phenol in aqueous phase. Kinetic assessments were performed in a batch reactor, on monometallic Pd/ZrO 2 samples with different Pd loadings (0.5%, 1% and 2%), as well as on a 1% PdAg/ZrO 2 sample. The catalytic activity normalized to accessible Pd (turnover frequency, TOF) increased with the particle size of Pd. Reaction orders in phenol and H 2 and lower activation energies suggest that smaller particles bind the reacting substrates more strongly, leading to higher surface coverages by phenol. But, surprisingly,more » smaller Pd particles exhibited lower TOFs. The lower activity of the small Pd particles is attributed to lower activation entropies for the strongly bound species. Furthermore, the presence of Ag increased the catalyst activity by decreasing the apparent energy of activation and increasing the coverages of phenol and H 2, without negatively affecting the activation entropy.« less

Aqueous phase hydrogenation of phenol catalyzed by Pd and PdAg on ZrO 2

DOE PAGES

Resende, Karen A.; Hori, Carla E.; Noronha, Fabio B.; ...

2017-08-05

The impact of particle size of ZrO 2-supported Pd and of alloying with Ag was explored for hydrogenation of phenol in aqueous phase. Kinetic assessments were performed in a batch reactor, on monometallic Pd/ZrO 2 samples with different Pd loadings (0.5%, 1% and 2%), as well as on a 1% PdAg/ZrO 2 sample. The catalytic activity normalized to accessible Pd (turnover frequency, TOF) increased with the particle size of Pd. Reaction orders in phenol and H 2 and lower activation energies suggest that smaller particles bind the reacting substrates more strongly, leading to higher surface coverages by phenol. But, surprisingly,more » smaller Pd particles exhibited lower TOFs. The lower activity of the small Pd particles is attributed to lower activation entropies for the strongly bound species. Furthermore, the presence of Ag increased the catalyst activity by decreasing the apparent energy of activation and increasing the coverages of phenol and H 2, without negatively affecting the activation entropy.« less

[Pollution prevention and control of aqueous extract of astragali radix processed with ZrO2 inorganic ceramic membrane micro-filtration].

PubMed

Pan, Lin-Men; Huang, Min-Yan; Guo, Li-Wei

2012-11-01

To study the measures for preventing and controlling the pollution of aqueous extract of Astragali Radix proceeded with inorganic ceramic membrane micro-filtration, in order to find effective measures for preventing and controlling the membrane pollution. The resistance distribution, polymer removal and changes in physical and chemical parameters of the zirconium oxide film of different pore diameters were determined to analyze the state or location of pollutants as well as the regularity of formation. Meanwhile, recoil and ultrasonic physical measures were adopted to strengthen the membrane process, in order to explore the methods for preventing and controlling the membrane pollution. When 0.2 microm of ZrO2 micro-filtrated aqueous extract of Astragali Radix, the rate of pollution was as high as 44.9%. The hole blocking resistance and the concentration polarization resistance were the main filtration resistances, while the surface deposit resistance decreased with the increase in the membrane's hold diameter; after micro-filtration, the liquid turbidity significantly reduced, with slight changes in both pH and viscosity. The 0.2 microm ZrO2 micro-filtration membrane performed better than the 0.05 microm pore size membrane in terms of conductivity. The 0. 2 microm and 0.05 microm pore diameter membranes showed better performance in the removal of pectin. The ultrasonic measure to strengthen membranes is more suitable to this system, with a flux rate up by 41.7%. The membrane optimization process adopts appropriate measures for preventing and controlling the membrane pollution, in order to reduce the membrane pollution, recover membrane performance and increase filtration efficiency.

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

NASA Astrophysics Data System (ADS)

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

2012-07-01

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

Study of thin film production of ceramic ZrO2 on silicon wafer using second harmonic Nd-Yag laser with pulsed laser deposition technique

NASA Astrophysics Data System (ADS)

Suliyanti, Maria M.; Hidayah, Affi Nur; Kurniawan, K. H.

2012-06-01

Study about thin film production using technique pulsed laser deposition have been done. The Pulsed Laser Deposition (PLD) method has been used for growing thin film of ZrO2 on silicon wafer substrate (111 single crystal, thickness 400μm and diameter 7.5 cm). The target made from Zirconia oxide powder mixing with PVA and press using pressure 100kgN. The laser beam was focused by a lens (f = 100mm) through a quartz window onto the sample surface and the substrate was placed in parallel line with target. The distance between the target and the substrate is about 1 cm. The early results of this synthesis using 75 mJ Nd-YAG second harmonic laser pulse (532 nm Nd-YAG) and low pressure chamber surrounding gas 5 Torr. The irradiation of laser take around 6000 shoots or 10 minutes using frequencies laser 10 Hz. The micro thickness of film can be produced on silicon wafer using this technique. The results of ZrO2 thin film on substrate about 26.92%.

MOCVD of HfO2 and ZrO2 high-k gate dielectrics for InAlN/AlN/GaN MOS-HEMTs

NASA Astrophysics Data System (ADS)

Abermann, S.; Pozzovivo, G.; Kuzmik, J.; Strasser, G.; Pogany, D.; Carlin, J.-F.; Grandjean, N.; Bertagnolli, E.

2007-12-01

We apply metal organic chemical vapour deposition (MOCVD) of HfO2 and of ZrO2 from β-diketonate precursors to grow high-k gate dielectrics for InAlN/AlN/GaN metal oxide semiconductor (MOS)-high electron mobility transistors (HEMTs). High-k oxides of about 12 nm-14 nm are deposited for the MOS-HEMTs incorporating Ni/Au gates, whereas as a reference, Ni-contact-based 'conventional' Schottky-barrier (SB)-HEMTs are processed. The processed dielectrics decrease the gate current leakage of the HEMTs by about four orders of magnitude if compared with the SB-gated HEMTs and show superior device characteristics in terms of IDS and breakdown.

Transformations to granular zircon revealed: Twinning, reidite, and ZrO2 in shocked zircon from Meteor Crater (Arizona, USA)

USGS Publications Warehouse

Cavosie, Aaron; Timms, Nicholas E.; Erickson, Timmons M.; Hagerty, Justin J.; Hörz, Friedrich

2016-01-01

Granular zircon in impact environments has long been recognized but remains poorly understood due to lack of experimental data to identify mechanisms involved in its genesis. Meteor Crater in Arizona (United States) contains abundant evidence of shock metamorphism, including shocked quartz, the high pressure polymorphs coesite and stishovite, diaplectic SiO2 glass, and lechatelierite (fused SiO2). Here we report the presence of granular zircon, a new shocked mineral discovery at Meteor Crater, that preserve critical orientation evidence of specific transformations that occurred during its formation at extreme impact conditions. The zircon grains occur as aggregates of sub-µm neoblasts in highly shocked Coconino Formation Sandstone (CFS) comprised of lechatelierite. Electron backscatter diffraction shows that each grain consists of multiple domains, some with boundaries disoriented by 65°, a known {112} shock-twin orientation. Other domains have crystallographic c-axes in alignment with {110} of neighboring domains, consistent with the former presence of the high pressure ZrSiO4 polymorph reidite. Additionally, nearly all zircon preserve ZrO2 + SiO2, providing evidence of partial dissociation. The genesis of CFS granular zircon started with detrital zircon that experienced shock-twinning and reidite formation from 20 to 30 GPa, ultimately yielding a phase that retained crystallographic memory; this phase subsequently recrystallized to systematically oriented zircon neoblasts, and in some areas partially dissociated to ZrO2. The lechatelierite matrix, experimentally constrained to form at >2000 °C, provided an ultra high-temperature environment for zircon dissociation (~1670 °C) and neoblast formation. The capacity of granular zircon to preserve a cumulative P-T record has not been recognized previously, and provides a new method for retrieving histories of impact-related mineral transformations in the crust at conditions far beyond which most rocks melt.

Chemical Stability and Biological Properties of Plasma-Sprayed CaO-SiO2-ZrO2 Coatings

NASA Astrophysics Data System (ADS)

Liang, Ying; Xie, Youtao; Ji, Heng; Huang, Liping; Zheng, Xuebin

2010-12-01

In this work, calcia-stabilized zirconia powders were coated by silica derived from tetraethoxysilane (TEOS) hydrolysis. After calcining at 1400 °C, decalcification of calcia-stabilized zirconia by silica occurred and powders composed of Ca2SiO4, ZrO2, and CaZrO3 were prepared. We produced three kinds of powders with different Ca2SiO4 contents [20 wt.% (denoted as CZS2), 40 wt.% (denoted as CZS4), and 60 wt.% (denoted as CZS6)]. The obtained powders were sprayed onto Ti-6Al-4V substrates using atmospheric plasma spraying. The microstructure of the powders and coatings were analyzed. The dissolution rates of the coatings were assessed by monitoring the ions release and mass losses after immersion in Tris-HCl buffer solution. Results showed that the chemical stability of the coatings were significantly improved compared with pure calcium silicate coatings, and increased with the increase of Zr contents. The CZS4 coating showed not only good apatite-formation ability in simulated body fluid, but also well attachment and proliferation capability for the canine bone marrow stem cells. Results presented here indicate that plasma-sprayed CZS4 coating has medium dissolution rate and good biological properties, suggesting its potential use as bone implants.

Visible upconversion emission and non-radiative direct Yb 3+ to Er 3+ energy transfer processes in nanocrystalline ZrO 2:Yb 3+,Er 3+

NASA Astrophysics Data System (ADS)

Diaz-Torres, L. A.; Meza, O.; Solis, D.; Salas, P.; De la Rosa, E.

2011-06-01

Wide band gap Yb 3+ and Er 3+ codoped ZrO 2 nanocrystals have been synthesized by a modified sol-gel method. Under 967 nm excitation strong green and red upconversion emission is observed for several Er 3+ to Yb 3+ ions concentration ratios. A simple microscopic rate equation model is used to study the effects of non-radiative direct Yb 3+ to Er 3+ energy transfer processes on the visible and near infrared fluorescence decay trends of both Er 3+ and Yb 3+ ions. The microscopic rate equation model takes into account the crystalline phase as well as the size of nanocrystals. Nanocrystals phase and size were estimated from XRD patterns. The rate equation model succeeds to fit simultaneously all visible and near infrared fluorescence decay profiles. The dipole-dipole interaction parameters that drive the non-radiative energy transfer processes depend on doping concentration due to crystallite phase changes. In addition the non-radiative relaxation rate ( 4I11/2→ 4I13/2) is found to be greater than that estimated by the Judd-Ofelt parameters due to the action of surface impurities. Results suggest that non-radiative direct Yb 3+ to Er 3+ energy transfer processes in ZrO 2:Yb,Er are extremely efficient.

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

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.

Surface Passivation of ZrO2 Artificial Dentures by Magnetized Coaxial Plasma deposition

NASA Astrophysics Data System (ADS)

Arai, Soya; Kurumi, Satoshi; Matsuda, Ken-Ichi; Suzuki, Kaoru; Hara, Katsuya; Kato, Tatsuya; Asai, Tomohiko; Hirose, Hideharu; Masutani, Shigeyuki; Nihon University Team

2015-09-01

Recent growth and fabrication technologies for functional materials have been greatly contributed to drastic development of oral surgery field. Zirconia based ceramics is expected to utilize artificial dentures because these ceramics have good biocompatibility, high hardness and aesthetic attractively. However, to apply these ceramics to artificial dentures, this denture is removed from a dental plate because of weakly bond. For improving this problem, synthesis an Al passivation-layer on the ceramics for bonding with these dental items is suitable. In order to deposit the passivation layer, we focused on a magnetized coaxial plasma deposition (MCPD). The greatest characteristic of MCPD is that high-melting point metal can be deposited on various substrates. Additionally, adhesion force between substrate and films deposited by the MCPD is superior to it of general deposition methods. In this study, we have reported on the growth techniques of Al films on ZrO2 for contributing to oral surgery by the MCPD. Surface of deposited films shows there were some droplets and thickness of it is about 200 nm. Thickness is increased to 500 nm with increasing applied voltage.

Methane Decomposition and Carbon Growth on Y2O3, Yttria-Stabilized Zirconia, and ZrO2

PubMed Central

2014-01-01

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents. PMID:24587591

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.

Aqueous phase hydrogenation of phenol catalyzed by Pd and PdAg on ZrO 2

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

Resende, Karen A.; Hori, Carla E.; Noronha, Fabio B.

Hydrogenation of phenol in aqueous phase was studied over a series of ZrO2-supported Pd catalysts in order to explore the effects of particle size and of Ag addition on the activity of Pd. Kinetic assessments were performed in a batch reactor, on monometallic Pd/ZrO2 samples with different Pd loadings (0.5%, 1% and 2%), as well as on a 1% PdAg/ZrO2 sample. The turnover frequency (TOF) increases with the Pd particle size. The reaction orders in phenol and H2 indicate that the surface coverages by phenol, H2 and their derived intermediates are higher on 0.5% Pd/ZrO2 than on other samples. Themore » activation energy was the lowest on the least active sample (0.5% Pd/ZrO2), while being identical on 1% and 2% Pd/ZrO2 catalysts. Thus, the significantly lower activity of the small Pd particles (1-2 nm on average) in 0.5%Pd/ZrO2 is explained by the unfavorable activation entropies for the strongly bound species. The presence of Ag increases considerably the TOF of the reaction by decreasing the Ea and increasing the coverages of phenol and H2.« less

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.

Doping effects of Yb 3+ on the crystal structures, nanoparticle properties and electrical behaviors of ZrO 2 derived from a facile urea-based hydrothermal route

NASA Astrophysics Data System (ADS)

Zhang, Ya-Wen; Sun, Xiao; Xu, Gang; Yan, Chun-Hua

2004-06-01

Weakly-agglomerated nanocrystalline (ZrO 2) 1- x(Yb 2O 3) x ( x=0.02-0.2) powders with high surface area (109-151 m 2 g -1) were synthesized by a two-step hydrothermal process in the presence of urea: a stock solution of metal nitrates and urea was heated at 80 °C for 24 h and then at 180 °C for 48 h. For x=0.04-0.2, the as-derived powders were an assembly of uniform nanoparticles with well-defined edges in the size between 6.1-8.4 nm. Before and after calcination at 800 °C, the lattice parameters, microstrain and surface area of the (ZrO 2) 1- x(Yb 2O 3) x samples tended to increase with Yb 3+ concentration; while, the average crystallite size decreased correspondingly. In the Arrhenius plots over the measurement temperature range of 400-800 °C, the bulk ionic conductivity of the compacts sintered at 1400 °C for 24 h showed a maximum value at the composition of x=0.08 in cubic structure, with an activation energy of 0.89 eV. At 800 °C, σb=0.049 S cm -1 for x=0.08.

The synthesis of ZrO2-Y2O3 ceramic fibers by the method of impregnation of viscous threads

NASA Astrophysics Data System (ADS)

Titova, S. M.; Obabkov, N. V.; Zakirova, A. F.; Zakirov, I. F.; Dokuchaev, V. S.; Shak, A. V.

2017-09-01

The possibility of synthesis of ZrO2-Y2O3 oxide fibers and their applicatiuon for reinforcing porous ceramics of the same composition was investigated. Ceramic fibers were obtained by impregnating viscose strings with solutions of zirconyl and yttrium nitrates. The method allows synthesis of the fibers with a diameter of 400 µm and length of 5 to 20 mm. The strength of the synthesized fibers was determined. The maximum tensile strength (132.45 MPa) was demonstrated by fibers obtained with a working solution concentration of 500 g oxides/L. Repeated impregnation of the viscose yarn led to an increase in the strength of the fibers to 205 MPa. Ceramic fibers can be used as reinforcing elements of oxide ceramics. The bending strength of the reinforced ceramics was 3 MPa. After 10 cycles of thermal cycling (heating to 1100 °C and cooling in water) the bending strength was reduced to 1 MPa.

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

NASA Technical Reports Server (NTRS)

Klettlinger, Jennifer Lindsey Suder

2012-01-01

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

Catalytic ethanolysis and gasification of kraft lignin into aromatic alcohols and H2-rich gas over Rh supported on La2O3/CeO2-ZrO2.

PubMed

Yang, Jing; Zhao, Liang; Liu, Chunze; Wang, Yuanyuan; Dai, Liyi

2016-10-01

Efficient catalytic ethanolysis and gasification of kraft lignin were conducted over a versatile supported catalyst Rh/La2O3/CeO2-ZrO2 to give high-value aromatic alcohols and H2-rich gas. The removal of phenolic hydroxyl group was the most prevalent reaction, and importantly, almost no phenols, undesired char and saturating the aromatic ring were detected. Meanwhile, the feedstock and solvent both played key roles in H2 generation that contributed to the hydrodeoxygenation of liquid components and made the whole catalytic process out of H2 supply. Reusability tests of catalyst indicated that the crystalline phase transition and agglomeration of support, the loss of noble metal Rh and carbon deposition were the possible reasons for its deactivation in supercritical ethanol. Comparing with water, methanol and isopropanol system, ethanol was the only effective solvent for the depolymerization process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Al2O3-ZrO2 Finely Structured Multilayer Architectures from Suspension Plasma Spraying

NASA Astrophysics Data System (ADS)

Tingaud, Olivier; Montavon, Ghislain; Denoirjean, Alain; Coudert, Jean-François; Rat, Vincent; Fauchais, Pierre

2010-01-01

Suspension plasma spraying (SPS) is an alternative to conventional atmospheric plasma spraying (APS) aiming at manufacturing thinner layers (i.e., 10-100 μm) due to the specific size of the feedstock particles, from a few tens of nanometers to a few micrometers. The staking of lamellae and particles, which present a diameter ranging from 0.1 to 2.0 μm and an average thickness from 20 to 300 nm, permits to manufacture finely structured layers. Moreover, it appears as a versatile process able to manufacture different coating architectures according to the operating parameters (suspension properties, injection configuration, plasma properties, spray distance, torch scan velocity, scanning step, etc.). However, the different parameters controlling the properties of the coating, and their interdependences, are not yet fully identified. Thus, the aim of this paper is, on the one hand, to better understand the influence of operating parameters on the coating manufacturing mechanisms (in particular, the plasma gas mixture effect) and, on the other hand, to produce Al2O3-ZrO2 finely structured layers with large varieties of architectures. For this purpose, a simple theoretical model was used to describe the plasma torch operating conditions at the nozzle exit, based on experimental data (mass enthalpy, arc current intensity, thermophysical properties of plasma forming gases, etc.) and the influences of the spray parameters were determined by mean of the study of sizes and shapes of spray beads. The results enabled then to reach a better understanding of involved phenomena and their interactions on the final coating architectures permitting to manufacture several types of microstructures.

Influence of hot isostatic pressing on ZrO2-CaO dental ceramics properties.

PubMed

Gionea, Alin; Andronescu, Ecaterina; Voicu, Georgeta; Bleotu, Coralia; Surdu, Vasile-Adrian

2016-08-30

Different hot isostatic pressing conditions were used to obtain zirconia ceramics, in order to assess the influence of HIP on phase transformation, compressive strength, Young's modulus and density. First, CaO stabilized zirconia powder was synthesized through sol-gel method, using zirconium propoxide, calcium isopropoxide and 2-metoxiethanol as precursors, then HIP treatment was applied to obtain final dense ceramics. Ceramics were morphologically and structurally characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Density measurements, compressive strength and Young's modulus tests were also performed in order to evaluate the effect of HIP treatment. The zirconia powders heat treated at 500°C for 2h showed a pure cubic phase with average particle dimension about 70nm. The samples that were hot isostatic pressed presented a mixture of monoclinic-tetragonal or monoclinic-cubic phases, while for pre-sintered samples, cubic zirconia was the single crystalline form. Final dense ceramics were obtained after HIP treatment, with relative density values higher than 94%. ZrO2-CaO ceramics presented high compressive strength, with values in the range of 500-708.9MPa and elastic behavior with Young's modulus between 1739MPa and 4372MPa. Finally zirconia ceramics were tested for biocompatibility allowing the normal development of MG63 cells in vitro. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of firing schedule on solubility limits and transport properties of ZrO 2-TiO 2-Y 2O 3 fluorites

NASA Astrophysics Data System (ADS)

Fagg, D. P.; Frade, J. R.; Mogensen, M.; Irvine, J. T. S.

2007-08-01

The low Y/high Zr edge of the cubic defect fluorite solid solution in the system ZrO 2-TiO 2-Y 2O 3 in air is reassessed, as it is these compositions which have been suggested to offer the highest levels of mixed conductivity. Vegard's law is obeyed for values of x which lie within the cubic defect fluorite phase in Zr 1-x-yY yTi xO 2-δ for values of y=0.2 and 0.25. Measured lattice parameters show good agreement with those calculated from the Kim relation. Deviation from Vegard's law places the limit of the solid solution at x=0.18 and 0.20 for values of y=0.2 and 0.25, respectively, at 1500 °C. Discrepancies in current literature data can be shown to be due to differences in firing schedule such as slight temperature fluctuations and/or different cooling rates. A high level of care of sintering temperature and cooling profile is essential to form the most promising single-phase materials which contain maximum Ti-contents with low Y-contents. Contraction of the phase limit as a result of poor synthesis control leads to erroneously high values of bulk ionic conductivity while values of electronic conductivity are shown to be less affected.

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.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO2 nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant; Gong, Kai; White, Claire E.

Conventional drying of colloidal materials and gels (including cement) can lead to detrimental effects due to the buildup of internal stresses as water evaporates from the nano/microscopic pores. However, the underlying nanoscopic alterations in these gel materials that are, in part, responsible for macroscopically-measured strain values, especially at low relative humidity, remain a topic of open debate in the literature. In this study, sodium-based calcium-alumino-silicate-hydrate (C-(N)-A-S-H) gel, the major binding phase of silicate-activated blast furnace slag (one type of low-CO$_2$ cement), is investigated from a drying perspective, since it is known to suffer extensively from drying-induced microcracking. By employing in situ synchrotron X-ray total scattering measurements and pair distribution function (PDF) analysis we show that the significant contributing factor to the strain development in this material at extremely low relative humidity (0%) is the local atomic structural rearrangement of the C-(N)-A-S-H gel, including collapse of interlayer spacing and slight disintegration of the gel. Moreover, analysis of the medium range (1.0 - 2.2 nm) ordering in the PDF data reveals that the PDF-derived strain values are in much closer agreement (same order of magnitude) with the macroscopically measured strain data, compared to previous results based on reciprocal space X-ray diffraction data. From a mitigation standpoint, we show that small amounts of ZrO$_2$ nanoparticles are able to actively reinforce the structure of silicate-activated slag during drying, preventing atomic level strains from developing. Mechanistically, these nanoparticles induce growth of a silica-rich gel during drying, which, via density functional theory calculations, we show is attributed to the high surface reactivity of tetragonal ZrO$_2$.

Mechanical properties investigation on single-wall ZrO2 nanotubes: A finite element method with equivalent Poisson's ratio for chemical bonds

NASA Astrophysics Data System (ADS)

Yang, Xiao; Li, Huijian; Hu, Minzheng; Liu, Zeliang; Wärnå, John; Cao, Yuying; Ahuja, Rajeev; Luo, Wei

2018-04-01

A method to obtain the equivalent Poisson's ratio in chemical bonds as classical beams with finite element method was proposed from experimental data. The UFF (Universal Force Field) method was employed to calculate the elastic force constants of Zrsbnd O bonds. By applying the equivalent Poisson's ratio, the mechanical properties of single-wall ZrNTs (ZrO2 nanotubes) were investigated by finite element analysis. The nanotubes' Young's modulus (Y), Poisson's ratio (ν) of ZrNTs as function of diameters, length and chirality have been discussed, respectively. We found that the Young's modulus of single-wall ZrNTs is calculated to be between 350 and 420 GPa.

Magnetic properties of nitrogen-doped ZrO2: Theoretical evidence of absence of room temperature ferromagnetism

PubMed Central

Albanese, Elisa; Leccese, Mirko; Di Valentin, Cristiana; Pacchioni, Gianfranco

2016-01-01

N-dopants in bulk monoclinic ZrO2 and their magnetic interactions have been investigated by DFT calculations, using the B3LYP hybrid functional. The electronic and magnetic properties of the paramagnetic N species, substitutionals and interstitials, are discussed. Their thermodynamic stability has been estimated as a function of the oxygen partial pressure. At 300 K, N prefers interstitial sites at any range of oxygen pressure, while at higher temperatures (700–1000 K), oxygen poor-conditions facilitate substitutional dopants. We have considered the interaction of two N defects in various positions in order to investigate the possible occurrence of ferromagnetic ordering. A very small magnetic coupling constant has been calculated for several 2N-ZrO2 configurations, thus demonstrating that magnetic ordering can be achieved only at very low temperatures, well below liquid nitrogen. Furthermore, when N atoms replace O at different sites, resulting in slightly different positions of the corresponding N 2p levels, a direct charge transfer can occur between the two dopants with consequent quenching of the magnetic moment. Another mechanism that contributes to the quenching of the N magnetic moments is the interplay with oxygen vacancies. These effects contribute to reduce the concentration of magnetic impurities, thus limiting the possibility to establish magnetic ordering. PMID:27527493

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.

Influence of Heat Treatment on Fracture Toughness and Wear Resistance of Nicral-Zro2 Multilayered Thermal Barrier Coating

NASA Astrophysics Data System (ADS)

Ye, Zibo; Wang, Guanghong

2018-04-01

The chemical composition and fracture toughness of thermal barrier coatings (TBCs) before and after heat treatment were characterized, and the cracks around the interface between the coating and the substrate could be successfully eliminated and meanwhile the porosity of the coatings tended to reduce. The XRD analysis revealed the coatings were composed of non-transformable tetragonal t' phase of ZrO2 and γ -(Ni, Cr) with minor Ni3Al (γ') precipitates. Additionally, the relationship between the heat treatment and wear resistance was systematically studied. The results indicated that both the hardness and fracture toughness increased after quenching process. The oxidation wear became more prominent after heat treatment, which probably resulted from the better bonding strength of coatings. Dense and homogeneous microstructure introduced by vacuum oil-quenching improved stabilization of the weight gain during thermal cycle test.

Behaviour of Li 2ZrO 3 and Li 2TiO 3 pebbles relevant to their utilization as ceramic breeder for the HCPB blanket

NASA Astrophysics Data System (ADS)

Lulewicz, J. D.; Roux, N.; Piazza, G.; Reimann, J.; van der Laan, J.

2000-12-01

Li 2ZrO 3 and Li 2TiO 3 pebbles are being investigated at Commissariat à l'Energie Atomique as candidate alternative ceramics for the European helium-cooled pebble bed (HCPB) blanket. The pebbles are fabricated using the extrusion-spheronization-sintering process and are optimized regarding composition, geometrical characteristics, microstructural characteristics, and material purity. Tests were designed and are being performed with other organizations so as to check the functional performance of the pebbles and pebble beds with respect to the HCPB blanket requirements, and, finally, to make the selection of the most appropriate ceramic for the HCPB blanket. Tests include high temperature long-term annealing, thermal shock, thermal cycling, thermal mechanical behaviour of pebble beds, thermal conductivity of pebble beds, and tritium extraction. Current results indicate the attractiveness of these ceramics pebbles for the HCPB blanket.

Kinetics of nitric oxide and oxygen gases on porous Y-stabilized ZrO2-based sensors.

PubMed

Killa, Sajin; Cui, Ling; Murray, Erica P; Mainardi, Daniela S

2013-08-16

Using impedance spectroscopy the electrical response of sensors with various porous Y-stabilized ZrO2 (YSZ) microstructures was measured for gas concentrations containing 0-100 ppm NO with 10.5%O2 at temperatures ranging from 600-700 °C. The impedance response increased substantially as the sensor porosity increased from 46%-50%. Activation energies calculated based on data from the impedance measurements increased in magnitude (97.4-104.9 kJ/mol for 100 ppm NO) with respect to increasing YSZ porosity. Analysis of the oxygen partial pressure dependence of the sensors suggested that dissociative adsorption was the dominant rate limiting. The PWC/DNP theory level was used to investigate the gas-phase energy barrier of the 2NO+O2 → 2NO2 reaction on a 56-atom YSZ/Au model cluster using Density Functional Theory and Linear Synchronous Transit/Quadratic Synchronous Transit calculations. The reaction path shows oxygen surface reactions that begin with NO association with adsorbed O2 on a Zr surface site, followed by O2 dissociative adsorption, atomic oxygen diffusion, and further NO2 formation. The free energy barrier was calculated to be 181.7 kJ/mol at PWC/DNP. A qualitative comparison with the extrapolated data at 62% ± 2% porosity representing the YSZ model cluster indicates that the calculated barriers are in reasonable agreement with experiments, especially when the RPBE functional is used.

Corrosion and wear properties of laser surface modified NiTi with Mo and ZrO 2

NASA Astrophysics Data System (ADS)

Ng, K. W.; Man, H. C.; Yue, T. M.

2008-08-01

Because of its biocompatibility, superelasticity and shape memory characteristics, NiTi alloys have been gaining immense interest in the medical field. However, there is still concern on the corrosion resistance of this alloy if it is going to be implanted in the human body for a long time. Titanium is not toxic but nickel is carcinogenic and is implicated in various reactions including allergic response and degeneration of muscle tissue. Debris from wear and the subsequent release of Ni + ions due to corrosion in the body system are fatal issues for long-term application of this alloy in the human body. This paper reports the corrosion and wear properties of laser surface modified NiTi using Mo and ZrO 2 as surface alloying elements, respectively. The modified layers which are free from microcracks and porosity, act as both physical barrier to nickel release and enhance the bulk properties, such as hardness, wear resistance, and corrosion resistance. The electrochemical performance of the surface modified alloy was studied in Hanks' solution. Electrochemical impedance spectroscopy was measured.

High-Temperature Particulate Matter Filtration with Resilient Yttria-Stabilized ZrO2 Nanofiber Sponge.

PubMed

Wang, Haolun; Lin, Sen; Yang, Shen; Yang, Xudong; Song, Jianan; Wang, Dong; Wang, Haiyang; Liu, Zhenglian; Li, Bo; Fang, Minghao; Wang, Ning; Wu, Hui

2018-05-01

Particulate matter (PM) is a major air pollutant in many regions, jeopardizing ecosystems and public health. Filtration at pollutant source is one of the most important ways to protect the environment, however, considering the high-temperature exhaust gas emissions, effective removal of PM and related pollutants from their sources remains a major challenge. In this study, a resilient, heat-resisting, and high-efficiency PM filter based on yttria-stabilized ZrO 2 (YSZ) nanofiber sponge produced with a scalable solution blow spinning process is reported. The porous 3D sponge composed of YSZ nanofibers is lightweight (density of 20 mg cm -3 ) and resilient at both room temperature and high temperatures. At room-temperature conditions, the YSZ nanofiber sponge exhibits 99.4% filtration efficiency for aerosol particles with size in the range of 20-600 nm, associated with a low pressure drop of only 57 Pa under an airflow velocity of 4.8 cm s -1 . At a high temperature of 750 °C, the ceramic sponge maintains a high filtration efficiency of 99.97% for PM 0.3-2.5 under a high airflow velocity of 10 cm s -1 . A practical vehicle exhaust filter to capture particles with filtration efficiency of >98.3% is also assembled. Hence, the YSZ nanofiber sponge has enormous potential to be applied in industry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser Direct Writing Process for Making Electrodes and High-k Sol-Gel ZrO2 for Boosting Performances of MoS2 Transistors.

PubMed

Kwon, Hyuk-Jun; Jang, Jaewon; Grigoropoulos, Costas P

2016-04-13

A series of two-dimensional (2D) transition metal dichalcogenides (TMDCs), including molybdenum disulfide (MoS2), can be attractive materials for photonic and electronic applications due to their exceptional properties. Among these unique properties, high mobility of 2D TMDCs enables realization of high-performance nanoelectronics based on a thin film transistor (TFT) platform. In this contribution, we report highly enhanced field effect mobility (μ(eff) = 50.1 cm(2)/(V s), ∼2.5 times) of MoS2 TFTs through the sol-gel processed high-k ZrO2 (∼22.0) insulator, compared to those of typical MoS2/SiO2/Si structures (μ(eff) = 19.4 cm(2)/(V s)) because a high-k dielectric layer can suppress Coulomb electron scattering and reduce interface trap concentration. Additionally, in order to avoid costly conventional mask based photolithography and define the patterns, we employ a simple laser direct writing (LDW) process. This process allows precise and flexible control with reasonable resolution (up to ∼10 nm), depending on the system, and enables fabrication of arbitrarily patterned devices. Taking advantage of continuing developments in laser technology offers a substantial cost decrease, and LDW may emerge as a promising technology.

Ultrathin ZnO interfacial passivation layer for atomic layer deposited ZrO2 dielectric on the p-In0.2Ga0.8As substrate

NASA Astrophysics Data System (ADS)

Liu, Chen; Lü, Hongliang; Yang, Tong; Zhang, Yuming; Zhang, Yimen; Liu, Dong; Ma, Zhenqiang; Yu, Weijian; Guo, Lixin

2018-06-01

Interfacial and electrical properties were investigated on metal-oxidesemiconductor capacitors (MOSCAPs) fabricated with bilayer ZnO/ZrO2 films by atomic layer deposition (ALD) on p-In0.2Ga0.8As substrates. The ZnO passivated In0.2Ga0.8As MOSCAPs have exhibited significantly improved capacitance-voltage (C-V) characteristics with the suppressed "stretched out" effect, increased accumulation capacitance and reduced accumulation frequency dispersion as well as the lower gate leakage current. In addition, the interface trap density (Dit) estimated by the Terman method was decreased dramatically for ZnO passivated p-In0.2Ga0.8As. The inherent mechanism is attributed to the fact that an ultrathin ZnO IPL employed by ALD prior to ZrO2 dielectric deposition can effectively suppress the formation of defect-related low-k oxides and As-As dimers at the interface, thus effectively improving the interface quality by largely removing the border traps aligned near the valence band edge of the p-In0.2Ga0.8As substrate.

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.

Effect of variable cerium concentration on photoluminescence behaviour in ZrO2 phosphor synthesized by combustion synthesis method

NASA Astrophysics Data System (ADS)

Dubey, Vikas; Kaur, Jagjeet

2016-05-01

Present paper reports synthesis and characterization of trivalent cerium (Ce3+) doped zirconium dioxide (ZrO2) phosphors. Effect of variable concentration of cerium on photoluminescence (PL) is studied. Samples were prepared by combustion synthesis technique which is suitable for less time taking techniques also for large scale production for phosphors. Starting material used for sample preparation are Zr(NO3)3 and Ce(NO3)3 and urea used as a fuel. All prepared phosphor with variable concentration of Ce3+ (0.1 to 2mol%) was studied by photoluminescence analysis it is found that the excitation spectra of prepared phosphor shows broad excitation centred at 390nm. The excitation spectra with variable concentration of Ce3+ show strong peaks at 447nm. Spectrophotometric determinations of peaks are evaluated by Commission Internationale de I'Eclairage technique. Using this phosphor, the desired CIE values including emissions throughout the violet (390 nm) and blue (427 nm) of the spectra were achieved. Efficient blue light emitting diodes were fabricated using Ce3+ doped phosphor based on near ultraviolet (NUV) excited LED lights.

Porous TiO2-ZrO2 thin film formed by electrochemical technique to improve the biocompatibility of titanium alloy in physiological environment

NASA Astrophysics Data System (ADS)

Benea, L.; Dănăilă, E.; Ponthiaux, P.

2017-02-01

Porous Ti and Ti alloys have received increasing research interest for bone tissue engineering, especially for dental and orthopaedic implants because they provide cell ingrowths and vascularization, improving of adhesion and osseointegration. The tribocorrosion process is encountered in orthopaedic and dentistry applications, since it is known that the implants are often exposed to simultaneous chemical/electrochemical and mechanical stresses. The purpose of this study was to carry out a systematic investigation of the tribo-electrochemical performance of porous TiO2-ZrO2 thin film formed by anodization of Ti-10Zr alloy surface in an artificial saliva solution and to compare the resulted performance with that of the untreated Ti-10Zr alloy surface in order to be applied for biomedical use. The in situ electrochemical technique used for investigation of tribo-electrochemical degradation was the open circuit potential (OCP) measurement performed before, during and after sliding tests. The results presented herein show that controlled anodic oxidation method can significantly improve the tribocorrosion and friction performances of Ti-10Zr alloy surface intended for biomedical applications.

Enhancement of oxidative electrocatalytic properties of platinum nanoparticles by supporting onto mixed WO3/ZrO2 matrix

NASA Astrophysics Data System (ADS)

Rutkowska, Iwona A.; Wadas, Anna; Kulesza, Pawel J.

2016-12-01

Nanostructured mixed metal (W, Zr) oxide matrices (in a form of layered intercalated films of WO3 and ZrO2) are considered here for supporting and activating catalytic platinum nanoparticles toward electrooxidation of ethanol. Remarkable increases of electrocatalytic (voltammetric, chronoamperometric) currents measured in 0.5 mol dm-3 H2SO4 (containing 0.5 mol dm-3 ethanol) have been observed. Comparison has been made to the behavior of methanol and acetaldehyde under analogous conditions. The enhancement effects are interpreted in terms of specific interactions between platinum nanoparticles and the metal oxide species, high acidity of the mixed oxide sites, as well as high population of surface hydroxyl groups and high mobility of protons existing in close vicinity of Pt catalytic sites. The metal oxide nanostructures are expected to interact competitively (via the surface hydroxyl groups) with adsorbates of the undesirable reaction intermediates, including CO, facilitating their desorption ("third body effect"), or even oxidative removal (e.g., of CO to CO2). The fact that the partially reduced tungsten oxide (HxWO3) component is characterized by fast electron transfers coupled to proton displacements tends to improve the overall charge propagation at the electrocatalytic interface.

CeO2-Y2O3-ZrO2 Membrane with Enhanced Molten Salt Corrosion Resistance for Solid Oxide Membrane (SOM) Electrolysis Process

NASA Astrophysics Data System (ADS)

Zou, Xingli; Li, Xin; Shen, Bin; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu; Ding, Weizhong

2017-02-01

Innovative CeO2-Y2O3-ZrO2 membrane has been successfully developed and used in the solid oxide membrane (SOM) electrolysis process for green metallic materials production. The x mol pct ceria/(8- x) mol pct yttria-costabilized zirconia ( xCe(8- x)YSZ, x = 0, 1, 4, or 7) membranes have been fabricated and investigated as the membrane-based inert anodes to control the SOM electroreduction process in molten salt. The characteristics of these fabricated xCe(8- x)YSZ membranes including their corrosion resistances in molten salt and their degradation mechanisms have been systematically investigated and compared. The results show that the addition of ceria in the YSZ-based membrane can inhibit the depletion of yttrium during the SOM electrolysis, which thus makes the ceria-reinforced YSZ-based membranes possess enhanced corrosion resistances to molten salt. The ceria/yttria-costabilized zirconia membranes can also provide reasonable oxygen ion conductivity during electrolysis. Further investigation shows that the newly modified 4Ce4YSZ ceramic membrane has the potential to be used as novel inert SOM anode for the facile and sustainable production of metals/alloys/composites materials such as Si, Ti5Si3, TiC, and Ti5Si3/TiC from their metal oxides precursors in molten CaCl2.

Synthesis, characterization and biological study on Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide and bis(3-hydroxyimino)butan-2-ylidene)-oxalohydrazide.

PubMed

El-Asmy, A A; El-Gammal, O A; Radwan, H A

2010-09-01

Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide (H(2)L(1)) and oxalyl bis(diacetylmonoxime hydrazone) [its IUPAC name is oxalyl bis(3-hydroxyimino)butan-2-ylidene)oxalohydrazide] (H(4)L(2)) have been synthesized and characterized by partial elemental analysis, spectral (IR; electronic), thermal and magnetic measurements. [Cr(L(1))(H(2)O)(3)(Cl)].H(2)O, [ZrO(HL(1))(2)].C(2)H(5)OH, [UO(2)(L(1))(H(2)O)(2)] [ZrO(H(3)L(2))(Cl)](2).2H(2)O, [HfO(H(3)L(2))(Cl)](2).2H(2)O and [UO(2)(H(2)L(2))].2H(2)O have been suggested. H(2)L(1) behaves as a monobasic or dibasic bidentate ligand while H(4)L(2) acts as a tetrabasic octadentate with the two metal centers. The molecular modeling of the two ligands have been drawn and their molecular parameters were calculated. Examination of the DNA degradation of H(2)L(1) and H(4)L(2) as well as their complexes revealed that direct contact of [ZrO(H(3)L(2))(Cl)](2).2H(2)O or [HfO(H(3)L(2))(Cl)](2).2H(2)O degrading the DNA of Eukaryotic subject. The ligands and their metal complexes were tested against Gram's positive Bacillus thuringiensis (BT) and Gram's negative (Escherichia coli) bacteria. All compounds have small inhibitory effects. Copyright 2010 Elsevier B.V. All rights reserved.

The effect of micro-structure on upconversion luminescence of Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glass-ceramics

NASA Astrophysics Data System (ADS)

Zhang, Minghui; Wen, Haiqin; Pan, Xiuhong; Yu, Jianding; Jiang, Meng; Yu, Huimei; Tang, Meibo; Gai, Lijun; Ai, Fei

2018-03-01

Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glasses have been prepared by aerodynamic levitation method. The glasses show high refractive index of 2.28 and Abbe number of 18.3. Glass-ceramics heated at 880 °C for 50 min perform the strongest upconversion luminescence. X-ray diffraction patterns of glass-ceramics with different depths indicate that rare earth ions restrain crystallization. Body crystallization mechanism mixed with surface crystallization is confirmed in the heat treatment. Surface crystals achieve priority to grow, resulting in important effects on upconversion luminescence. The results of atomic force microscope and scanning electron microscope indicate that crystal particles with uniform size distribute densely and homogenously on the surface and large amount of glass matrix exists in the glass ceramics heated at 880 °C for 50 min. Crystals in the glass-ceramics present dense structure and strong boundaries, which can reduce the mutual nonradiative relaxation rate among rare earth ions and then improve upconversion luminescence effectively. Based on micro-structural study, the mechanism that upconversion luminescence can be improved by heat treatment has been revealed. The results of micro-structural analysis agree well with the spectra.

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

PubMed

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

2017-10-01

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

The behavior of ZrO2/20%Y2O3 and Al2O3 coatings deposited on aluminum alloys at high temperature regime

NASA Astrophysics Data System (ADS)

Pintilei, G. L.; Crismaru, V. I.; Abrudeanu, M.; Munteanu, C.; Baciu, E. R.; Istrate, B.; Basescu, N.

2015-10-01

Aluminum alloy present numerous advantages like lightness, high specific strength and diversity which recommend them to a high number of applications from different fields. In extreme environments the protection of aluminum alloys is difficult and requires a high number of requirements like high temperature resistance, thermal fatigue resistance, corrosion fatigue resistance and galvanic corrosion resistance. To obtain these characteristics coatings can be applied to the surfaces so they can enhance the mechanical and chemical properties of the parts. In this paper two coatings were considered for deposition on an AA2024 aluminum alloy, ZrO2/20%Y2O3 and Al2O3. To obtain a better adherence of the coating to the base material an additional bond layer of NiCr is used. Both the coatings and bond layer were deposited by atmospheric plasma spraying on the samples. The samples were subjected to a temperature of 500 °C and after that slowly cooled to room temperature. The samples were analyzed by electron microscopy and X-ray diffraction to determine the morphological and phase changes that occurred during the temperature exposure. To determine the stress level in the parts due to thermal expansion a finite element analysis was performed in the same conditions as the tests.

Nanocomposite membranes based on polybenzimidazole and ZrO2 for high-temperature proton exchange membrane fuel cells.

PubMed

Nawn, Graeme; Pace, Giuseppe; Lavina, Sandra; Vezzù, Keti; Negro, Enrico; Bertasi, Federico; Polizzi, Stefano; Di Noto, Vito

2015-04-24

Owing to the numerous benefits obtained when operating proton exchange membrane fuel cells at elevated temperature (>100 °C), the development of thermally stable proton exchange membranes that demonstrate conductivity under anhydrous conditions remains a significant goal for fuel cell technology. This paper presents composite membranes consisting of poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI4N) impregnated with a ZrO2 nanofiller of varying content (ranging from 0 to 22 wt %). The structure-property relationships of the acid-doped and undoped composite membranes have been studied using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, wide-angle X-ray scattering, infrared spectroscopy, and broadband electrical spectroscopy. Results indicate that the level of nanofiller has a significant effect on the membrane properties. From 0 to 8 wt %, the acid uptake as well as the thermal and mechanical properties of the membrane increase. As the nanofiller level is increased from 8 to 22 wt % the opposite effect is observed. At 185 °C, the ionic conductivity of [PBI4N(ZrO2 )0.231 ](H3 PO4 )13 is found to be 1.04×10(-1)  S cm(-1) . This renders membranes of this type promising candidates for use in high-temperature proton exchange membrane fuel cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insights on the High-Temperature Operational Limits of ZrO2-Y2O3 TBCs Manufactured via Air Plasma Spray

NASA Astrophysics Data System (ADS)

Lima, Rogerio S.; Marple, Basil R.

2017-03-01

The effective high-temperature operation limit of a ZrO2-7-8 wt.%Y2O3 (YSZ) thermal barrier coating (TBC) manufactured via air plasma spray (APS) is considered to be 1300 °C. This is related to the metastable tetragonal t'-phase formed during the rapid quenching of the YSZ particles during spraying. The t'-phase transforms into the equilibrium tetragonal and cubic phases at temperatures ≥ 1300 °C, which can lead to the formation of the monoclinic phase of YSZ upon cooling to room temperature. This formation of the monoclinic phase is accompanied by a volume expansion that leads to TBC failure due to extensive micro-cracking. To further investigate this limitation, an APS YSZ TBC was sprayed on a CMSX-4 substrate. By using a thermal (laser) gradient cyclic testing, a temperature gradient was generated across the TBC/substrate system. The YSZ T- front and substrate backside T- back temperature levels were 1500 and 1000 °C, respectively. In cycle conditions (5-min or 1-h hot and 2-min cool), no TBC failure has been observed. This behavior was partially attributed to the unexpected absence of the monoclinic phase of the YSZ in the cycled coatings. Although preliminary, these results are promising regarding increasing the effective high-temperature operational limits of APS YSZ TBCs.

Process-Parameter-Dependent Optical and Structural Properties of ZrO2MgO Mixed-Composite Films Evaporated from the solid Solution

NASA Technical Reports Server (NTRS)

Sahoo, N. K.; Shapiro, A. P.

1998-01-01

The process-parameter-dependent optical and structural properties of ZrO2MgO mixed-composite material have been investigated. Optical properties were derived from spectrophotometric measurements. By use of atomic force microscopy, x-ray diffraction analysis, and energy-dispersive x-ray (EDX) analysis, the surface morphology, grain size distributions, crystallographic phases, and process-dependent material composition of films have been investigated. EDX analysis made evident the correlation between the oxygen enrichment in the films prepared at a high level of oxygen pressure and the very low refractive index. Since oxygen pressure can be dynamically varied during a deposition process, coatings constructed of suitable mixed-composite thin films can benefit from continuous modulation of the index of refraction. A step modulation approach is used to develop various multilayer-equivalent thin-film devices.

The influence of ZrO2/20%Y2O3 and Al2O3 deposited coatings to the behavior of an aluminum alloy subjected to mechanical shock

NASA Astrophysics Data System (ADS)

Pintilei, G. L.; Crismaru, V. I.; Abrudeanu, M.; Munteanu, C.; Luca, D.; Istrate, B.

2015-10-01

Aluminum alloys are used in the aerospace industry due to their good mechanical properties and their low density compared with the density of steels. Usually the parts made of aluminum alloys contribute to the structural frame of aircrafts and they must withstand static and variable mechanical loads and also mechanical loads applied in a very short time which determine different phenomenon's in the material behavior then static or fatigue loads. This paper analysis the resilience of a 2024 aluminum alloy subjected to shock loads and the way how a coating can improve its behavior. For improving the behavior two coatings were considered: Al2O3 with 99.5% purity and ZrO2/20%Y2O3. The coatings were deposited on the base material by plasma spraying. The samples with and without coating were subject to mechanical shock to determine the resilience of the materials and the cracks propagation was investigated using SEM analysis. To highlight the physical phenomenon's that appear in the samples during the mechanical shock, explicit finite element analysis were done using Ansys 14.5 software.

Ball-in-ball ZrO2 nanostructure for simultaneous CT imaging and highly efficient synergic microwave ablation and tri-stimuli-responsive chemotherapy of tumors.

PubMed

Long, Dan; Niu, Meng; Tan, Longfei; Fu, Changhui; Ren, Xiangling; Xu, Ke; Zhong, Hongshan; Wang, Jingzhuo; Li, Laifeng; Meng, Xianwei

2017-06-29

Combined thermo-chemotherapy displays outstanding synergically therapeutic efficiency when compared with standalone thermotherapy and chemotherapy. Herein, we developed a smart tri-stimuli-responsive drug delivery system involving X@BB-ZrO 2 NPs (X represents loaded IL, DOX, keratin and tetradecanol) based on novel ball-in-ball-structured ZrO 2 nanoparticles (BB-ZrO 2 NPs). The microwave energy conversion efficiency of BB-ZrO 2 NPs was 41.2% higher than that of traditional single-layer NPs due to the cooperative action of self-reflection and spatial confinement effect of the special two-layer hollow nanostructure. The tri-stimuli-responsive controlled release strategy indicate that integrated pH, redox and microwaves in single NPs based on keratin and tetradecanol could effectively enhance the specific controlled release of DOX. The release of DOX was only 8.1% in PBS with pH = 7.2 and GSH = 20 μM. However, the release could reach about 50% at the tumor site (pH = 5.5, GSH = 13 mM) under microwave ablation. The as-made X@BB-ZrO 2 NPs exhibited perfect synergic therapy effect of chemotherapy and microwave ablation both in subcutaneous tumors (H22 tumor-bearing mice) and deep tumors (liver transplantation VX2 tumor-bearing rabbit model). There was no recurrence and death in the X@BB-ZrO 2 + MW group during the therapy of subcutaneous tumors even on the 42 nd day. The growth rates in the deep tumor of the control, MW and X@BB-ZrO 2 + MW groups were 290.1%, 14.1% and -42% 6 days after ablation, respectively. Dual-source CT was used to monitor the metabolism behavior of the as-made BB-ZrO 2 NPs and traditional CT was utilized to monitor the tumor growth in rabbits. Frozen section examination and ICP results indicated the precise control of drug delivery and enhanced cytotoxicity by the tri-stimuli-responsive controlled release strategy. The ball-in-ball ZrO 2 NPs with high microwave energy conversion efficiency were first developed for synergic microwave ablation and

Synthesis and Characterization of Yttria-Stabilized Zirconia Nanoparticles Doped with Ytterbium and Gadolinium: ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3

NASA Astrophysics Data System (ADS)

Bahamirian, M.; Hadavi, S. M. M.; Rahimipour, M. R.; Farvizi, M.; Keyvani, A.

2018-03-01

Defect cluster thermal barrier coatings (TBCs) are attractive alternatives to Yttria-stabilized zirconia (YSZ) in advanced applications. In this study, YSZ nanoparticles doped with ytterbium and gadolinium (ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3 (ZGYbY)) were synthesized through a chemical co-precipitation and calcination method, and characterized by in situ high-temperature X-ray diffraction analysis in the temperature range of 25 °C to 1000 °C (HTK-XRD), thermogravimetric analysis, differential thermal analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM). Precise cell parameters of t-prime phase and the best zirconia phase for TBC applications were calculated by Cohen's and Rietveld refinement methods. Optimum crystallization temperature of the precursor powder was found to be 1000 °C. Furthermore, FE-SEM results for the calcined ZGYbY powders indicated orderly particles of uniform shape and size with a small tendency toward agglomeration. Average lattice thermal expansion coefficient in the temperature range of 25 °C to 1000 °C was determined to be 31.71 × 10-6 K-1.

Synthesis and Characterization of Yttria-Stabilized Zirconia Nanoparticles Doped with Ytterbium and Gadolinium: ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3

NASA Astrophysics Data System (ADS)

Bahamirian, M.; Hadavi, S. M. M.; Rahimipour, M. R.; Farvizi, M.; Keyvani, A.

2018-06-01

Defect cluster thermal barrier coatings (TBCs) are attractive alternatives to Yttria-stabilized zirconia (YSZ) in advanced applications. In this study, YSZ nanoparticles doped with ytterbium and gadolinium (ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3 (ZGYbY)) were synthesized through a chemical co-precipitation and calcination method, and characterized by in situ high-temperature X-ray diffraction analysis in the temperature range of 25 °C to 1000 °C (HTK-XRD), thermogravimetric analysis, differential thermal analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM). Precise cell parameters of t-prime phase and the best zirconia phase for TBC applications were calculated by Cohen's and Rietveld refinement methods. Optimum crystallization temperature of the precursor powder was found to be 1000 °C. Furthermore, FE-SEM results for the calcined ZGYbY powders indicated orderly particles of uniform shape and size with a small tendency toward agglomeration. Average lattice thermal expansion coefficient in the temperature range of 25 °C to 1000 °C was determined to be 31.71 × 10-6 K-1.

Crystallisation of Ba1-xSrxZn2Si2O7 from BaO/SrO/ZnO/SiO2 glass with different ZrO2 and TiO2 concentrations

NASA Astrophysics Data System (ADS)

Vladislavova, Liliya; Kracker, Michael; Zscheckel, Tilman; Thieme, Christian; Rüssel, Christian

2018-04-01

The effect of different nucleation agents such as ZrO2 and TiO2 was investigated for a first time with respect to their crystallisation behaviour in the glass system BaO-SrO-ZnO-SiO2. In all studied glasses, a Ba1-xSrxZn2Si2O7 (0.1 ≤ x ≤ 0.9) solid solution crystallized. This phase was first described in 2015 to possess a similar structure as the high temperature phase of BaZn2Si2O7 and a thermal expansion close to zero or even negative. It may find applications e.g. as cook panels, telescope mirrors, and furnace windows. Kinetic parameters of the crystallisation process were determined by supplying different heating rates in a differential scanning calorimeter (DSC). The results were evaluated using the equations of Ozawa and Kissinger with respect to the activation energies. Furthermore, the Ozawa method was used for the determination of Avrami parameters, which provides further information on the nucleation and crystallisation processes. Scanning electron microscopy including electron backscatter diffraction (EBSD) was used to characterise the microstructure, to determine the crystallite size and the crystal orientation. For the characterisation of the occurring crystalline phases, X-ray diffraction was used.

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.

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.

Mechanically reliable thermoelectric (TE) nanocomposites by dispersing and embedding TE-nanostructures inside a tetragonal ZrO2 matrix: the concept and experimental demonstration in graphene oxide-3YSZ system

NASA Astrophysics Data System (ADS)

Estili, Mehdi; Wu, Wen-Wen; Khazaei, Mohammad; Sakka, Yoshio

2014-02-01

Novel low-dimensional thermoelectric (TE) materials suffer from poor mechanical reliability, which limits their applications, especially in mechanically harsh environments. Here, we propose a new concept, in which the novel, abundant, thermally stable TE-nanostructures are dispersed and then intimately embedded inside a protective, mechanically reliable tetragonal ZrO2 (TZP) ceramic matrix with a low thermal conductivity. We also demonstrate an experimental proof-of-principle verification of our concept in reduced-graphene oxide (GO)-3 mol% Y2O3-ZrO2 (3YSZ or 3Y-TZP) nanocomposite system. TE characterizations suggest that our protective TZP matrix does not degrade the intrinsic TE property of the reduced GO network. These preliminary results are promising and encouraging to start research on similar TZP-matrix TE-nanocomposites, which contain more effective TE-nanostructures with larger intrinsic power factors. In this regard, we propose a scalable approach for fabrication of similar dense TE-nanocomposites composed of other one-dimensional and/or two-dimensional TE-nanostructures, which involves an aqueous colloidal approach and a subsequent spark plasma sintering. These new TZP-matrix TE-nanocomposites could be used for sustainable clean power generation, especially in mechanically harsh environments with thermal/mechanical shocks and vibrations, where energy availability, reliability and durability are more important than the energy efficiency. Considering the excellent biocompatibility of TZP matrix, they could even be used inside the body to power implanted medical devices.

Study the structural and optical behaviour of polyaniline/ZrO2 nanocomposites

NASA Astrophysics Data System (ADS)

Sidhu, Gaganpreet Kaur; Kumar, Naresh; Kumar, Rajesh

2018-05-01

In nanoscience, hybrid material based on polymer and nanoparticles are of great interest because of much improved properties of components. Polymers are of enormous interest because of their various properties like flexibility, low weight and easy processing. Here, we studied the influence of ZrO2 nanoparticles on the structural and optical properties of Polyaniline (PANI). ZrO2 mixed with PANI, improve its structural and optical properties. XRD studies reveal that ZrO2 nanoparticles exist in the tetragonal phase in ZrO2/PANI nanocomposites. UV-Vis spectroscopic studies have been carried out to understand the presence of various energy levels and their involvement in absorbance of light. In PANI nanocomposites, aniline monomer attach with ZrO2 nanoparticles through p-p stacking interaction, Vander waal force and hydrogen bonding interaction.

Effect of milling methods on performance of Ni-Y 2O 3-stabilized ZrO 2 anode for solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Cho, Hyoup Je; Choi, Gyeong Man

A Ni-YSZ (Y 2O 3-stabilized ZrO 2) composite is commonly used as a solid oxide fuel cell anode. The composite powders are usually synthesized by mixing NiO and YSZ powders. The particle size and distribution of the two phases generally determine the performance of the anode. Two different milling methods are used to prepare the composite anode powders, namely, high-energy milling and ball-milling that reduce the particle size. The particle size and the Ni distribution of the two composite powders are examined. The effects of milling on the performance are evaluated by using both an electrolyte-supported, symmetric Ni-YSZ/YSZ/Ni-YSZ cell and an anode-supported, asymmetric cell. The performance is examined at 800 °C by impedance analysis and current-voltage measurements. Pellets made by using high-energy milled NiO-YSZ powders have much smaller particle sizes and a more uniform distribution of Ni particles than pellets made from ball-milled powder, and thus the polarization resistance of the electrode is also smaller. The maximum power density of the anode-supported cell prepared by using the high-energy milled powder is ∼850 mW cm -2 at 800 °C compared with ∼500 mW cm -2 for the cell with ball-milled powder. Thus, high-energy milling is found to be more effective in reducing particle size and obtaining a uniform distribution of Ni particles.

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

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

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

DOE PAGES

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.; ...

2017-08-28

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

Conversion of CH4/CO2 to syngas over Ni-Co/Al2O3-ZrO2 nanocatalyst synthesized via plasma assisted co-impregnation method: Surface properties and catalytic performance

NASA Astrophysics Data System (ADS)

Rahemi, Nader; Haghighi, Mohammad; Akbar Babaluo, Ali; Fallah Jafari, Mahdi; Khorram, Sirous

2013-09-01

Ni/Al2O3 catalyst promoted by Co and ZrO2 was prepared by co-impregnation method and treated with glow discharge plasma. The catalytic activity of the synthesized nanocatalysts has been tested toward conversion of CH4/CO2 to syngas. The physicochemical characterizations like XRD, EDX, FESEM, TEM, BET, FTIR, and XPS show that plasma treatment results in smaller particle size, more surface concentration, and uniform morphology. The dispersion of nickel in plasma-treated nanocatalyst was also significantly improved, which was helpful for controlling the ensemble size of active phase atoms on the support surface. Improved physicochemical properties caused 20%-30% enhancement in activity of plasma-treated nanocatalyst that means to achieve the same H2 or CO yield, the plasma-treated nanocatalyst needed about 100 °C lower reaction temperature. The H2/CO ratio got closer to 1 at higher temperatures and finally at 850 °C H2/CO = 1 is attained for plasma-treated nanocatalyst. Plasma-treated nanocatalyst due to smaller Ni particles and strong interaction between active phase and support has lower tendency to keep carbon species on its structure and hence excellent stability can be observed for this catalyst.

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 ZrO(2) additions on the crystallization, mechanical and biological properties of MgO-CaO-SiO(2)-P(2)O(5)-CaF(2) bioactive glass-ceramics.

PubMed

Li, H C; Wang, D G; Meng, X G; Chen, C Z

2014-06-01

A series of ZrO(2) doped MgO-CaO-SiO(2)-P(2)O(5)-CaF(2) bioactive glass-ceramics were obtained by sintering method. The crystallization behavior, phase composition, morphology and structure of glass-ceramics were characterized. The bending strength, elastic modulus, fracture toughness, micro-hardness and thermal expansion coefficient (TEC) of glass-ceramics were investigated. The in vitro bioactivity and cytotoxicity tests were used to evaluate the bioactivity and biocompatibility of glass-ceramics. The sedimentation mechanism and growth process of apatites on sample surface were discussed. The results showed that the mainly crystalline phases of glass-ceramics were Ca(5)(PO4)3F (fluorapatite) and β-CaSiO(3). (β-wollastonite). m-ZrO(2) (monoclinic zirconia) declined the crystallization temperatures of glasses. t-ZrO(2) (tetragonal zirconia) increased the crystallization temperature of Ca(5)(PO4)(3)F and declined the crystallization temperature of β-CaSiO(3). t-ZrO(2) greatly increased the fracture toughness, bending strength and micro-hardness of glass-ceramics. The nanometer apatites were induced on the surface of glass-ceramic after soaking 28 days in SBF (simulated body fluid), indicating the glass-ceramic has good bioactivity. The in vitro cytotoxicity test demonstrated the glass-ceramic has no toxicity to cell. Copyright © 2014 Elsevier B.V. All rights reserved.

Ionic Conductivity Increased by Two Orders of Magnitude in Micrometer-Thick Vertical Yttria-Stabilized ZrO 2 Nanocomposite Films

DOE PAGES

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; ...

2015-09-03

We design and create a unique cell geometry of templated micrometer-thick epitaxial nanocomposite films which contain ~20 nm diameter yttria-stabilized ZrO 2 (YSZ) nanocolumns, strain coupled to a SrTiO 3 matrix. We also enhanced the ionic conductivity of these nanocolumnsby over 2 orders of magnitude compared to plain YSZ films. Concomitant with the higher ionic conduction is the finding that the YSZ nanocolumns in the films have much higher crystallinity and orientation, compared to plain YSZ films. Hence, “oxygen migration highways” are formed in the desired out-of-plane direction. This improved structure is shown to originate from the epitaxial coupling ofmore » the YSZ nanocolumns to the SrTiO 3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO 2 nanocolumns within the SrTiO 3 matrix. Furthermore, this intermediate layer reduces the lattice mismatch between the YSZ nanocolumns and the substrate. Vertical ionic conduction values as high as 10 –2 Ω –1 cm –1 were demonstrated at 360 °C (300 °C lower than plain YSZ films), showing the strong practical potential of these nanostructured films for use in much lower operation temperature ionic devices.« less

Synthesis of Copper-Based Nanostructured Catalysts on SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 Supports for NO Reduction.

PubMed

Namkhang, Pornpan; Kongkachuichay, Paisan

2015-07-01

The selective catalytic reduction of NO over a series of Cu-based catalysts supported on modified silica including SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 prepared via a sol-gel process and a flame spray pyrolysis (FSP) was studied. The prepared catalysts were characterized by means of TEM, XRD, XRF, TPR, and nitrogen physisorption measurement techniques, to determine particle diameter, morphology, crystallinity, phase composition, copper reducibility, surface area, and pore size of catalysts. The particles obtained from sol-gel method were almost spherical while the particles obtained from the FSP were clearly spherical and non-porous nanosized particles. The effects of Si:Al, Si:Ti, and Si:Zr molar ratio of precursor were identified as the domain for different crystalline phase of materials. It was clearly seen that a high SiO2 content inhibited the crystallization of materials. The BET surface area of catalysts obtained from sol-gel method was higher than that from the FSP and it shows that surface area increased with increasing SiO2 molar ratio due to high surface area from SiO2. The catalyst performances were tested for the selective catalytic reduction of NO with H2. It was found that the catalyst prepared over 7 wt% Cu on Si02-Al2O3 support was the most active compared with the others which converted NO as more than 70%. Moreover, the excess copper decreased the performance of NO reduction, due to the formation of CuO agglomeration covered on the porous silica as well as the alumina surface, preventing the direct contact of CO2 and AL2O3.

CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: Influence of Ytterbia Content on Residual Stress and Microstructure of Y2O3-ZrO2 Thin Films Prepared by EB-PVD*

NASA Astrophysics Data System (ADS)

Xiao, Qi-Ling; Shao, Sriu-Ying; He, Hong-Bo; Shao, Jian-Da; Fan, Zheng-Xiu

2008-09-01

Y2O3 stabilized ZrO2 (YSZ) thin films with different Y2O3 molar contents (0, 3, 7, and 12mol%) are deposited on BK7 substrates by electron-beam evaporation technique. The effects of different Y2O3 contents on residual stresses and structures of YSZ thin films are studied. Residual stresses are investigated by means of two different techniques: the curvature measurement and x-ray diffraction method. It is found that the evolution of residual stresses of YSZ thin films by the two different methods is consistent. Residual stresses of films transform from compressive stress into tensile stress and the tensile stress incre ases monotonically with the increase of Y2O3 content. At the same time, the structures of these films change from the mixture of amorphous and monoclinic phases into high temperature cubic phase. The variations of residual stress correspond to the evolution of structures induced by adding of Y2O3 content.

Studies on corrosion resistance and bio-activity of plasma spray deposited hydroxylapatite (HA) based TiO2 and ZrO2 dispersed composite coatings on titanium alloy (Ti-6Al-4V) and the same after post spray heat treatment

NASA Astrophysics Data System (ADS)

Kumari, Renu; Majumdar, Jyotsna Dutta

2017-10-01

In the present study, the effect of plasma spray deposited hydroxylapatite (HA) based TiO2 dispersed (HA + 50 wt.% TiO2), coating and post spray heat treatment to be referred as HA-TiO2 (heat treated at 650 °C for 2 h) and ZrO2 dispersed (HA + 10 wt.% ZrO2), to be referred as HA-ZrO2 coating (heat treated at 750 °C for 2 h) on corrosion resistance and bioactivity of Ti-6Al-4V substrate has been undertaken. There is partial decomposition of HA to tri-calcium-phosphate (Ca3(PO4)2) and formation of CaTiO3 phase in HA-TiO2 coating and CaZrO3 phase in the HA-ZrO2 coating. Corrosion study in Hank's solution shows that there is shifting of corrosion potential (Ecorr) towards active potential (-1.1 V(SCE) for as-sprayed and post spray heat treated HA-TiO2 coating, -1.1 V(SCE) for as-sprayed HA-ZrO2 coating and -1 V(SCE) for HA-ZO2 coating after post spray heat treatment), and deterioration in pitting corrosion (Epit) resistance in as-sprayed coatings and the same after heat treatment (-0.7 V(SCE) for both HA-TiO2 and HA-ZrO2 coating as compared to as received substrate (-0.3 V(SCE)). The corrosion rate was increased for both the coatings with a maximum increase in HA-ZrO2 coating. Bioactivity test shows a higher degree of apatite deposition in as-sprayed coating and the same after heat treatment as compared to as received Ti-6Al-4V though the as-sprayed one showed a superior behavior.

High resistance ratio of bipolar resistive switching in a multiferroic/high-K Bi(Fe0.95Cr0.05)O3/ZrO2/Pt heterostructure

NASA Astrophysics Data System (ADS)

Dong, B. W.; Miao, Jun; Han, J. Z.; Shao, F.; Yuan, J.; Meng, K. K.; Wu, Y.; Xu, X. G.; Jiang, Y.

2018-03-01

An novel heterostructure composed of multiferroic Bi(Fe0.95Cr0.05)O3 (BFCO) and high-K ZrO2 (ZO) layers is investigated. Ferroelectric and electrical properties of the BFZO/ZO heterostructure have been investigated. A pronounced bipolar ferroelectric resistive switching characteristic was achieved in the heterostructure at room temperature. Interestingly, the BFCO/ZO structures exhibit a reproducible resistive switching with a high On/Off resistance ratio ∼2×103 and long retention time. The relationship between polarization and band structure at the interface of BFCO/ZO bilayer under the positive and negative sweepings has been discussed. As a result, the BFCO/ZO multiferroic/high-K heterostructure with high On/Off resistance ratio and long retention characterizes, exhibits a potential in future nonvolatile memory application.

First principles calculations of interactions of ZrCl4 precursors with the bare and hydroxylated ZrO2 surfaces

NASA Astrophysics Data System (ADS)

Iskandarova, I. M.; Knizhnik, A. A.; Bagatur'yants, A. A.; Potapkin, B. V.; Korkin, A. A.

2004-05-01

First-principles calculations have been performed to determine the structures and relative energies of different zirconium chloride groups chemisorbed on the tetragonal ZrO2(001) surface and to study the effects of the surface coverage with metal chloride groups and the degree of hydroxylation on the adsorption energies of metal precursors. It is shown that the molecular and dissociative adsorption energies of the ZrCl4 precursor on the bare t-ZrO2(001) surface are too small to hold ZrCl4 molecules on the surface during an atomic layer deposition (ALD) cycle at temperatures higher than 300°C. On the contrary, it has been found that molecular adsorption on the fully hydroxylated zirconia surface leads to the formation of a stable adsorbed complex. This strong adsorption of ZrCl4 molecules can lead to a decrease in the film growth rate of the ALD process at lower temperatures (<200°C). The energies of interaction between adsorbed ZrCl4 groups at a 50% surface coverage has been found to be relatively small, which explains the maximum film growth rate observed in the ZrCl4:H2O ALD process. Moreover, we found that the adsorbed ZrCl4 precursors after hydrolysis give rise to very stable hydroxyl groups, which can be responsible for film growth at high temperatures (up to 900°C).

The roles of phosphate and tungstate species in surface acidities of TiO2-ZrO2 binary oxides - A comparison study

NASA Astrophysics Data System (ADS)

Chaudhary, Manchal; Shen, Po-fan; Chang, Sue-min

2018-05-01

Porous tungstated and phosphated TiO2-ZrO2 (TZ) binary oxides with high and strong acidity were successfully prepared by means of sol-gel or impregnation approaches. In addition, the influences of the two types of modifiers on the microstructures and acidity were systematically examined, compared, and clarified. The TZ oxide derived from a surfactant-templating method exhibited a high surface area of 195 m2/g with a pore size of 6.3 nm. Moreover, it had a high acidity of 859 μmol/g with a density of 4.4 μmol/nm2 because of defective surface. Phosphation significantly increased the acidity to 1547 μmol/g and showed the highest acid density of 6.7 μmol/nm2 at a surface P density of 22.7P/nm2. On the other hand, tungstated compounds just showed the highest acidity of 972 μmol/g and the highest acid density of 4.8 μmol/nm2 at 4.7 W/nm2. Compared to tungstate species, phosphate anions are more capable of promoting the acidity because they are able to distort the host network and inhibit elemental rearrangement. While Lewis acidity prevailed in the tungstated compounds, Brønsted acidity was dominant in the phosphated oxides. The Wdbnd O and Psbnd OH groups were responsible for strong acidity in the modified compounds. Phosphated compounds formed strong Brønsted acid sites on the Psbnd OH groups with a particular strength, and tungstation produced Lewis acid sites with a continuous strength on the metal ions adjacent to the tungstate moieties. Cyclic NH3 adsorption-desorption processes revealed that the active sites for NH3 adsorption were stable in both the tungstate and phosphate modified compounds, revealing that these solid acids are promising as the adsorbents for removal of base gases.

A theoretical study of the stability of anionic defects in cubic ZrO 2 at extreme conditions

DOE PAGES

Samanta, Amit

2016-02-19

Using first principles density functional theory calculations, we present a study of the structure, mobility, and the thermodynamic stability of anionic defects in the high-temperature cubic phase of ZrO 2. Our results suggest that the local structure of an oxygen interstitial depends on the charge state and the cubic symmetry of the anionic sublattice is unstable at 0 K. In addition, the oxygen interstitials and the vacancies exhibit symmetry breaking transitions to low-energy structures with tetragonal distortion of the oxygen sublattice at 0 K. However, the vibrational entropy stabilizes the defect structures with cubic symmetry at 2600–2980 K. The formationmore » free energies of the anionic defects and Gibbs free energy changes associated with different defect reactions are calculated by including the vibrational free energy contributions and the effect of pressure on these defect structures. By analyzing the defect chemistry, we obtain the defect concentrations at finite temperature and pressure conditions using the zero temperature ab initio results as input and find that at low oxygen partial pressures, neutral oxygen vacancies are most dominant and at high oxygen partial pressures, doubly charged anionic defects are dominant. As a result, the relevance of the results to the thermal protective coating capabilities of zirconium-based ceramic composites is elucidated.« less

Electrochemical reduction of UO2 in LiCl-Li2O molten salt using porous and nonporous anode shrouds

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Won, Chan Yeon; Cha, Ju-Sun; Park, Wooshin; Im, Hun Suk; Hong, Sun-Seok; Hur, Jin-Mok

2014-01-01

Electrochemical reductions of uranium oxide in a molten LiCl-Li2O electrolyte were carried out using porous and nonporous anode shrouds. The study focused on the effect of the type of anode shroud on the current density by running experiments with six anode shrouds. Dense ceramics, MgO, and MgO (3 wt%) stabilized ZrO2 (ZrO2-MgO) were used as nonporous shrouds. STS 20, 100, and 300 meshes and ZrO2-MgO coated STS 40 mesh were used as porous shrouds. The current densities (0.34-0.40 A cm-2) of the electrolysis runs using the nonporous anode shrouds were much lower than those (0.76-0.79 A cm-2) of the runs using the porous shrouds. The ZrO2-MgO shroud (600-700 MPa at 25 °C) showed better bending strength than that of MgO (170 MPa at 25 °C). The high current densities achieved in the electrolysis runs using the porous anode shrouds were attributed to the transport of O2- ions through the pores in meshes of the shroud wall. ZrO2-MgO coating on STS mesh was chemically unstable in a molten LiCl-Li2O electrolyte containing Li metal. The electrochemical reduction runs using STS 20, 100, and 300 meshes showed similar current densities in spite of their different opening sizes. The STS mesh shrouds which were immersed in a LiCl-Li2O electrolyte were stable without any damage or corrosion.

Mechanochemical stabilization and sintering of nanocrystalline the (ZrO2)0.97 (Y2O3)0.03 solid solution from pure oxides

NASA Astrophysics Data System (ADS)

Rendtorff, N. M.; Suárez, G.; Sakka, Y.; Aglietti, E. F.

2011-10-01

The mechanochemical activation processing has proved to be an effective technique to enhance a solid-state reaction at relatively low temperatures. In such a process, the mechanical effects of milling, such as reduction of particle size and mixture homogenization, are accompanied by chemical effects, such as partial decomposition of salts or hydroxides resulting in very active reactants. The objective of the present work is to obtain (ZrO2)0.97(Y2O3)0.03 nanocrystalline tetragonal solid solution powders directly using a high energy milling on a mixture of the pure oxides. A second objective is to evaluate the efficiency of the processing proposed and to characterize both textural and structural evolution of the mixtures during the milling processes and throughout posterior low temperature treatments. The Textural and structural evolution were studied by XRD analysis, specific area measurements (BET) and SEM. Firstly a decrease of the crystallinity of the reactants was observed, followed by the disappearance of Y2O3 diffraction peaks and the partial appearance of the tetragonal phase at room temperature. The solid solution proportion was increased with the high energy milling time, obtaining complete stabilization of the tetragonal solid solution with long milling treatments (60 min).The obtained powders were uniaxially pressed and sintered at different temperatures (600-1400°C) the influence of the milling time was correlated with the sinterization degree and final crystalline composition of the materials. Finally, fully stabilized nanocrystalline zirconia materials were obtained satisfactorily by the proposed method.

Determination and analysis of non-linear index profiles in electron-beam-deposited MgOAl2O3ZrO2 ternary composite thin-film optical coatings

NASA Astrophysics Data System (ADS)

Sahoo, N. K.; Thakur, S.; Senthilkumar, M.; Das, N. C.

2005-02-01

Thickness-dependent index non-linearity in thin films has been a thought provoking as well as intriguing topic in the field of optical coatings. The characterization and analysis of such inhomogeneous index profiles pose several degrees of challenges to thin-film researchers depending upon the availability of relevant experimental and process-monitoring-related information. In the present work, a variety of novel experimental non-linear index profiles have been observed in thin films of MgOAl2O3ZrO2 ternary composites in solid solution under various electron-beam deposition parameters. Analysis and derivation of these non-linear spectral index profiles have been carried out by an inverse-synthesis approach using a real-time optical monitoring signal and post-deposition transmittance and reflection spectra. Most of the non-linear index functions are observed to fit polynomial equations of order seven or eight very well. In this paper, the application of such a non-linear index function has also been demonstrated in designing electric-field-optimized high-damage-threshold multilayer coatings such as normal- and oblique-incidence edge filters and a broadband beam splitter for p-polarized light. Such designs can also advantageously maintain the microstructural stability of the multilayer structure due to the low stress factor of the non-linear ternary composite layers.

Chemicals from ethanol: the acetone synthesis from ethanol employing Ce0.75Zr0.25O2, ZrO2 and Cu/ZnO/Al2O3.

PubMed

Rodrigues, Clarissa Perdomo; Zonetti, Priscila da Costa; Appel, Lucia Gorenstin

2017-04-04

Acetone is an important solvent and widely used in the synthesis of drugs and polymers. Currently, acetone is mainly generated by the Cumene Process, which employs benzene and propylene as fossil raw materials. Phenol is a co-product of this synthesis. However, this ketone can be generated from ethanol (a renewable feedstock) in one-step. The aim of this work is to describe the influence of physical-chemical properties of three different catalysts on each step of this reaction. Furthermore, contribute to improve the description of the mechanism of this synthesis. The acetone synthesis from ethanol was studied employing Cu/ZnO/Al 2 O 3 , Ce 0.75 Zr 0.25 O 2 and ZrO 2 . It was verified that the acidity of the catalysts needs fine-tuning in order to promote the oxygenate species adsorption and avoid the dehydration of ethanol. The higher the reducibility and the H 2 O dissociation activity of the catalysts are, the higher the selectivity to acetone is. In relation to the oxides, these properties are associated with the presence of O vacancies. The H 2 generation, which occurs during the TPSR, indicates the redox character of this synthesis. The main steps of the acetone synthesis from ethanol are the generation of acetaldehyde, the oxidation of this aldehyde to acetate species (which reduces the catalyst), the H 2 O dissociation, the oxidation of the catalyst producing H 2 , and, finally, the ketonization reaction. These pieces of information will support the development of active catalysts for not only the acetone synthesis from ethanol, but also the isobutene and propylene syntheses in which this ketone is an intermediate. Graphical abstract Acetone from ethanol.

Hydrous ZrO2 decorated polyaniline nanofibres: Synthesis, characterization and application as an efficient adsorbent for water defluoridation.

PubMed

Parashar, Kamya; Ballav, Niladri; Debnath, Sushanta; Pillay, Kriveshini; Maity, Arjun

2017-12-15

A new hybrid material comprising hydrous zirconium oxide (HZrO 2 ) supported onto polyaniline (PANI) nanofibres (HZrO 2 @PANI NFs) was prepared via the precipitation of HZrO 2 onto as-synthesized PANI NFs and tested for its defluoridation capabilities. The developed adsorbent (HZrO 2 @PANI NFs) was fully characterized by FTIR, BET, XRD, SEM-EDX, TEM-(S)TEM, XPS, and zeta potential measurements. HZrO 2 @PANI NFs achieved 2-fold BET surface area ∼86.64 m 2 /gas compared to PANI NFs ∼44.72 m 2 /g, implying that the incorporation of HZrO 2 onto the PANI nanofibres enhanced the available surface area for effective fluoride adsorption. Moreover, HZrO 2 @PANI NFs was found to be effective over a wide pH range (3-9) as designated by its high pH pzc ∼9.8. The adsorption kinetics obeyed the pseudo-second-order model well with equilibrium attainment in 30min. Adsorption isotherm was best described by the Langmuir model and the maximum adsorption capacities obtained were 83.23 and 28.77mg/g at pH 3 and 6.5, respectively, which is superior to most ZrO 2 based adsorbents reported in the literature and better than that of native PANI. Furthermore, the developed adsorbent manifested quite a selective fluoride uptake at pH 3 as compared to pH 6.5±0.1 wherein significant chemical affinity competition was presented by phosphate ions followed by bicarbonate and sulfate. The recyclability of HZrO 2 @PANI NFs for four cycles and its applicability to fluoride spiked ground water has also been demonstrated. The adsorption mechanism was interpreted with the help of FTIR, XPS and Zeta potential analysis and the results revealed the involvement of both anion exchange and electrostatic attraction in the adsorption of F - ions. Thus, a new efficient adsorbent with reasonably high adsorption capacity and superior pH tolerance has been developed for fluoride removal. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

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.