Electrodeposition of thin yttria-stabilized zirconia layers using glow-discharge plasma

NASA Astrophysics Data System (ADS)

Ogumi, Zempachi; Uchimoto, Yoshiharu; Tsuji, Yoichiro; Takehara, Zen-ichiro

1992-08-01

A novel process for preparation of thin yttria-stabilized zirconia (YSZ) layers was developed. This process differs from other vapor-phase deposition methods in that a dc bias circuit, separate from the plasma-generation circuit, is used for the electrodeposition process. The YSZ layer was electrodeposited from ZrCl4 and YCl3 on a nonporous calcia-stabilized zirconia substrate. Scanning electron microscopy, electron probe microanalysis, electron spectroscopy for chemical analysis, and x-ray-diffraction measurements confirmed the electrodeposition of a smooth, pinhole-free yttria-stabilized zirconia film of about 3 μm thickness.

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.

Fracture toughness improvements of dental ceramic through use of yttria-stabilized zirconia (YSZ) thin-film coatings.

PubMed

Chan, Ryan N; Stoner, Brian R; Thompson, Jeffrey Y; Scattergood, Ronald O; Piascik, Jeffrey R

2013-08-01

The aim of this study was to evaluate strengthening mechanisms of yttria-stabilized zirconia (YSZ) thin film coatings as a viable method for improving fracture toughness of all-ceramic dental restorations. Bars (2mm×2mm×15mm, n=12) were cut from porcelain (ProCAD, Ivoclar-Vivadent) blocks and wet-polished through 1200-grit using SiC abrasive. A Vickers indenter was used to induce flaws with controlled size and geometry. Depositions were performed via radio frequency magnetron sputtering (5mT, 25°C, 30:1 Ar/O2 gas ratio) with varying powers of substrate bias. Film and flaw properties were characterized by optical microscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Flexural strength was determined by three-point bending. Fracture toughness values were calculated from flaw size and fracture strength. Data show improvements in fracture strength of up to 57% over unmodified specimens. XRD analysis shows that films deposited with higher substrate bias displayed a high %monoclinic volume fraction (19%) compared to non-biased deposited films (87%), and resulted in increased film stresses and modified YSZ microstructures. SEM analysis shows critical flaw sizes of 67±1μm leading to fracture toughness improvements of 55% over unmodified specimens. Data support surface modification of dental ceramics with YSZ thin film coatings to improve fracture toughness. Increase in construct strength was attributed to increase in compressive film stresses and modified YSZ thin film microstructures. It is believed that this surface modification may lead to significant improvements and overall reliability of all-ceramic dental restorations. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Derivative effect of laser cladding on interface stability of YSZ@Ni coating on GH4169 alloy: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Zheng, Haizhong; Li, Bingtian; Tan, Yong; Li, Guifa; Shu, Xiaoyong; Peng, Ping

2018-01-01

Yttria-stabilized zirconia YSZ@Ni core-shell nanoparticles were used to prepare a thermal barrier coating (TBC) on a GH4169 alloy by laser cladding. Microstructural analysis showed that the TBC was composed of two parts: a ceramic and a bonding layer. In places where the ZrO2/Al2O3 eutectic structure was present in the ceramic layer, the Ni atoms diffused into the bonding layer, as confirmed by energy-dispersive X-ray spectroscopy (EDS). The derivative effect of laser cladding results in the original YSZ@Ni core-shell nanoparticles being translated into the Al2O3 crystal, activating the YSZ. The mechanism of ceramic/metal interface cohesion was studied in depth via first-principles and molecular dynamics simulation. The results show that the trend in the diffusion coefficients of Ni, Fe, Al, and Ti is DNi > DFe > DTi > DAl in the melting or solidification process of the material. The enthalpy of formation for Al2O3 is less than that of TiO2, resulting in a thermally grown oxide (TGO) Al2O3 phase transformation. With regard to the electronic structure, the trend in Mulliken population is QO-Ni > QZr-O > QO-Al. Although the bonding is slightly weakened between ZrO2/Al2O3 (QZr-O = 0.158 < QO-Ni = 0.220) compared to that in ZrO2/Ni, TGO Al2O3 can improve the oxidation resistance of the metal matrix. Thus, by comparing the connective and diffusive processes, our findings lay the groundwork for detailed and comprehensive studies of the laser cladding process for the production of composite materials.

Investigation on the thermo-chemical reaction mechanism between yttria-stabilized zirconia (YSZ) and calcium-magnesium-alumino-silicate (CMAS)

NASA Astrophysics Data System (ADS)

Zhang, Dong-Bo; Wang, Bin-Yi; Cao, Jian; Song, Guan-Yu; Liu, Juan-Bo

2015-03-01

Thermal barrier coatings (TBCs) with Y2O3-stabilized ZrO2 (YSZ) top coat play a very important role in advanced turbine blades by considerably increasing the engine efficiency and improving the performance of highly loaded blades. However, at high temperatures, environment factors result in the failure of TBCs. The influence of calcium-magnesium-alumino-silicate (CMAS) is one of environment factors. Although thermo-physical effect is being paid attention to, the thermo-chemical reaction becomes the hot-spot in the research area of TBCs affected by CMAS. In this paper, traditional twolayered structured TBCs were prepared by electron beam physical vapor deposition (EBPVD) as the object of study. TBCs coated with CMAS were heated at 1240°C for 3 h. Additionally, 15 wt.% simulated molten CMAS powder and YSZ powder were mixed and heated at 1240°C or 1350°C for 48 h. SEM and EDS were adopted to detect morphology and elements distribution. According to XRD and TEM results, it was revealed that CMAS react with YSZ at high temperature and form ZrSiO4, Ca0.2Zr0.8O1.8 and Ca0.15Zr0.85O1.85 after reaction, as a result, leading to the failure of TBCs and decreasing the TBC lifetime.

Corrosion Behavior of Yttria-Stabilized Zirconia-Coated 9Cr-1Mo Steel in Molten UCl3-LiCl-KCl Salt

NASA Astrophysics Data System (ADS)

Jagadeeswara Rao, Ch.; Venkatesh, P.; Prabhakara Reddy, B.; Ningshen, S.; Mallika, C.; Kamachi Mudali, U.

2017-02-01

For the electrorefining step in the pyrochemical reprocessing of spent metallic fuels of future sodium cooled fast breeder reactors, 9Cr-1Mo steel has been proposed as the container material. The electrorefining process is carried out using 5-6 wt.% UCl3 in LiCl-KCl molten salt as the electrolyte at 500 °C under argon atmosphere. In the present study, to protect the container vessel from hot corrosion by the molten salt, 8-9% yttria-stabilized zirconia (YSZ) ceramic coating was deposited on 9Cr-1Mo steel by atmospheric plasma spray process. The hot corrosion behavior of YSZ-coated 9Cr-1Mo steel specimen was investigated in molten UCl3-LiCl-KCl salt at 600 °C for 100-, 500-, 1000- and 2000-h duration. The results revealed that the weight change in the YSZ-coated specimen was insignificant even after exposure to molten salt for 2000 h, and delamination of coating did not occur. SEM examination showed the lamellar morphology of the YSZ coating after the corrosion test with occluded molten salt. The XRD analysis confirmed the presence of tetragonal and cubic phases of ZrO2, without any phase change. Formation of UO2 in some regions of the samples was evident from XRD results.

Atomistic modeling of La 3+ doping segregation effect on nanocrystalline yttria-stabilized zirconia

DOE PAGES

Zhang, Shenli; Sha, Haoyan; Castro, Ricardo H. R.; ...

2018-01-01

The effect of La 3+ doping on the structure and ionic conductivity change in nanocrystalline yttria-stabilized zirconia (YSZ) was studied using a combination of Monte Carlo and molecular dynamics simulations.

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.

Structural evolution of plasma-sprayed nanoscale 3 mol% and 5 mol% yttria-stabilized zirconia coatings during sintering

NASA Astrophysics Data System (ADS)

Zhao, Yan; Gao, Yang

2017-12-01

The microstructure of plasma-sprayed nanostructured yttria-stabilized zirconia (YSZ) coatings may change during high-temperature exposure, which would influence the coating performance and service lifetime. In this study, the phase structure and the microstructural evolution of 3YSZ (zirconia-3 mol% yttria) and 5YSZ (zirconia-5 mol% yttria) nanostructured coatings were investigated by means of sintering at 1400 °C for 50-100 h. The microhardness, elastic moduli, and thermal shock cycles of the 3YSZ and 5YSZ nanostructured coatings were also investigated. The results showed that the redistribution of yttrium ions at 1400 °C caused the continuous increase of monoclinic-phase zirconia, but no obvious inter-splat cracking formed at the cross-sections, even after 100 h. Large voids appeared around the nanoporous zone because of the sintering of nanoscale granules upon high-temperature exposure. The microhardness and elastic moduli of the nanostructured coatings first increased and then decreased with increasing sintering times. The growth rate of the nanograins in the 3YSZ coating was lower than that in 5YSZ, which slowed the changes in 3YSZ coating porosity during sintering. Although the 3YSZ coating was prone to monoclinic phase transition, the experimental results showed that the thermal shock resistance of the 3YSZ coating was better than that of the 5YSZ coating.

Yttria stabilized zirconia transparent films prepared by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Yamane, Hisanori; Hirai, Toshio

1989-04-01

Yttria stabilized zirconia (YSZ) transparent films were prepared on quartz glass substrates at the temperature of 1375 K under atmospheric pressure using ZrCl 4, YCl 3 and O 2 gases as source materials. The growth rate of the film thickness was 1.5 to 2.0 μm/h. Cubic YSZ films were obtained at the value of x between 20 to 60, where x is defined by x( wt%) = YCl3×100/( YCl3+ ZrCl4). The lattice parameter of the cubic YSZ increased from 5.14 to 5.19 Å with the increase of x. Transparent films were obtained at the interval where the x value was between 20 to 45. The (100) plane of YSZ is oriented parallel to the surface of the substrate. For transparent film obtained at x = 29 (1.5 μm in thickness) the optical transmittance was 50-70% in the wavelength range of 250-800 nm.

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

NASA Technical Reports Server (NTRS)

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

1997-01-01

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

Brazing of Stainless Steels to Yttria Stabilized Zirconia (YSZ) for Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Shpargel, Tarah P.; Needham, Robert J.; Singh, M.; Kung, Steven C.

2005-01-01

Recently, there has been a great deal of interest in research, development, and commercialization of solid oxide fuel cells. Joining and sealing are critical issues that will need to be addressed before SOFC's can truly perform as expected. Ceramics and metals can be difficult to join together, especially when the joint must withstand up to 900 C operating temperature of the SOFC's. The goal of the present study is to find the most suitable braze material for joining of yttria stabilized zirconia (YSZ) to stainless steels. A number of commercially available braze materials TiCuSil, TiCuNi, Copper-ABA, Gold-ABA, and Gold-ABA-V have been evaluated. The oxidation behavior of the braze materials and steel substrates in air was also examined through thermogravimetric analysis. The microstructure and composition of the brazed regions have been examined by optical and scanning electron microscopy and EDS analysis. Effect of braze composition and processing conditions on the interfacial microstructure and composition of the joint regions will be presented.

Dominant pinning mechanisms in YBa2Cu3O7-x films on single and polycrystalline yttria stabilized zirconia substrates

NASA Astrophysics Data System (ADS)

Harshavardhan, K. S.; Rajeswari, M.; Hwang, D. M.; Chen, C. Y.; Sands, T.; Venkatesan, T.; Tkaczyk, J. E.; Lay, K. W.; Safari, A.

1992-04-01

Critical-current densities have been measured in YBa2Cu3O7-x films deposited on (100) yttria stabilized zirconia (YSZ) and polycrystalline YSZ substrates as a function of temperature (4.5-88 K), magnetic field (0-1 T) and orientation relative to the applied field. The results indicate that in films on polycrystalline substrates, surface and interface pinning play a dominant role at high temperatures. In films on (100) YSZ, pinning is mainly due to intrinsic layer pinning as well as extrinsic pinning associated with the interaction of the fluxoids with point defects and low energy planar (2D) boundaries. The differences are attributed to the intrinsic rigidity of single fluxoids which is reduced in films on polycrystalline substrates thereby weakening the intrinsic layer pinning.

Reaction mechanism of electrochemical-vapor deposition of yttria-stabilized zirconia film

NASA Astrophysics Data System (ADS)

Sasaki, Hirokazu; Yakawa, Chiori; Otoshi, Shoji; Suzuki, Minoru; Ippommatsu, Masamichi

1993-10-01

The reaction mechanism for electrochemical-vapor deposition of yttria-stabilized zirconia was studied. Yttria-stabilized zirconia films were deposited on porous La(Sr)MnOx using the electrochemical-vapor-deposition process. The distribution of yttria concentration through the film was investigated by means of secondary-ion-mass spectroscopy and x-ray microanalysis and found to be nearly constant. The deposition rate was approximately proportional to the minus two-thirds power of the film thickness, the one-third power of the partial pressure of ZrCl4/YCl3 mixed gas, and the two-thirds power of the product of the reaction temperature and the electronic conductivity of yttria-stabilized zirconia film. These experimental results were explained by a model for electron transport through the YSZ film and reaction between the surface oxygen and the metal chloride on the chloride side of the film, both of which affect the deposition rate. If the film thickness is very small, the deposition rate is thought to be controlled by the surface reaction step. On the other hand, if large, the electron transport step is rate controlling.

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

PubMed

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

2014-11-01

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

Energetics of zirconia stabilized by cation and nitrogen substitution

NASA Astrophysics Data System (ADS)

Molodetsky, Irina

Tetragonal and cubic zirconia are used in advanced structural ceramics, fuel cells, oxygen sensors, nuclear waste ceramics and many other applications. These zirconia phases are stabilized at room temperature (relative to monoclinic phase for pure zirconia) by cation and nitrogen substitution. This work is aimed at a better understanding of the mechanisms of stabilization of the high-temperature zirconia. phases. Experimental data are produced on the energetics of zirconia stabilized by yttria and calcia, energetics of nitrogen-oxygen substitution in zirconia and cation doped zirconia, and energetics of x-ray amorphous zirconia. obtained by low-temperature synthesis. High-temperature oxide melt solution enables direct measurement of enthalpies of formation of these refractory oxides. The enthalpy of the monoclinic to cubic phase transition of zirconia is DeltaHm-c = 12.2 +/- 1.2 kJ/mol. For cubic phases of YSZ at low yttria contents, a straight line DeltaH f,YSZ = -(52.4 +/- 3.6)x + (12.2 +/- 1.2) approximates the enthalpy of formation as a function of the yttria content, x (0. 1 < x < 0.3). Use of the quadratic fit DeltaHf,YSZ = 126.36 x 2 - 81.29 x + 12.37 (0.1 ≲ x ≲ 0.53) indicates that yttria stabilizes the cubic phase in enthalpy at low dopant content and destabilizes the cubic phase as yttria content increases. Positive entropy of mixing in YSZ and small enthalpy of long range ordering in 0.47ZrO2-0.53YO1.5, DeltaHord = -2.4 +/- 3.0 kJ/mol, indicate presence of short range ordering in YSZ. The enthalpy of formation of calcia stabilized zirconia as a function of calcia content x, is approximated as DeltaHf,c = (-91.4 +/- 3.8) x + (13.5 +/- 1.7) kJ/mol. The enthalpy of oxygen-nitrogen substitution, DeltaHO-N, in zirconium oxynitrides is a linear function of nitrogen content. DeltaH O-N ˜ -500 kJ/mol N is for Ca (Y)-Zr-N-O and Zr-N-O oxynitrides and DeltaHO-N ˜ -950 kJ/mol N is for Mg-Zr-N-O oxynitrides. X-ray amorphous zirconia is 58.6 +/- 3.3 kJ/mol less

Chemical vapor deposition of yttria-stabilized zirconia as a thermal barrier coating for gas turbine engines

NASA Astrophysics Data System (ADS)

Varanasi, Venu Gopal

The gas turbine engine uses an yttria-stabilized zirconia (YSZ) coating to provide thermal insulation for its turbine blades. This YSZ coating must be tetragonal in crystal structure, columnar in microstructure, and be 100--250 mum thick to provide for adequate protection for the turbine blades in the severe engine environment. Currently, YSZ coatings are fabricated by electron-beam physical vapor deposition (EB-PVD), but this fabrication method is cost intensive. Chemical vapor deposition (CVD) is a more commercially viable processing method and a possible alternative to EB-PVD. The deposition of tetragonal YSZ from gaseous metal and oxidation sources were studied. A chemical equilibrium analysis modeled the feasibility of depositing tetragonal YSZ for both chloride CVD (Zr-Y-C-O-Cl-H-Inert system) and metal-organic CVD (MOCVD) (Zr-Y-C-O-H system). Pure thermochemical properties and the assessed YSZ phase diagram were used in this analysis. Using the molar input of metals ((nY + nZr) and ( nY/(nY + nZr ) = 0.08)) as bases, equilibrium calculations showed that tetragonal YSZ formation was feasible. Tetragonal YSZ formation was feasible with high oxygen content (nO/(nY + nZr) > 8) and high temperature (T > 100°C) in the case of chloride CVD (Zr-Y-C-O-Cl-H-Inert). Tetragonal YSZ formation was feasible with high oxygen content (nO/( nY + nZr) > 5) and high temperature (T > 950°C) in the case of MOCVD (Zr-Y-C-O-H). Although solid carbon formation did not appear in chloride CVD, additional oxygen (nO/( nY + nZr) > 32) and low hydrogen content relative to carbon (nH/nC < 2) were required to avoid solid carbon formation in MOCVD. Coatings were deposited using a set of base conditions derived from the chemical equilibrium analysis. In chloride CVD, YCl3 was not included because of its low vapor pressure, thus, ZrCl4 was oxidized with the H2-CO2 gas mixture. Monoclinic ZrO2 coatings were deposited at the thermochemically optimized conditions (n O/(nY + nZr) > 8, T > 1004�

Heteroepitaxial growth of tin-doped indium oxide films on single crystalline yttria stabilized zirconia substrates

NASA Astrophysics Data System (ADS)

Kamei, Masayuki; Yagami, Teruyuki; Takaki, Satoru; Shigesato, Yuzo

1994-05-01

Heteroepitaxial growth of tin-doped indium oxide (ITO) film was achieved for the first time by using single crystalline yttria stabilized zirconia (YSZ) as substrates. The epitaxial relationship between ITO film and YSZ substrate was ITO[100]∥YSZ[100]. By comparing the electrical properties of this epitaxial ITO film with that of a randomly oriented polycrystalline ITO film grown on a glass substrate, neither the large angle grain boundaries nor the crystalline orientation were revealed to be dominant in determining the carrier mobility in ITO films.

Synthesis of multi-hierarchical structured yttria-stabilized zirconia powders and their enhanced thermophysical properties

NASA Astrophysics Data System (ADS)

Cao, Fengmei; Gao, Yanfeng; Chen, Hongfei; Liu, Xinling; Tang, Xiaoping; Luo, Hongjie

2013-06-01

Multi-hierarchical structured yttria-stabilized zirconia (YSZ) powders were successfully synthesized by a hydrothermal-calcination process. The morphology, crystallinity, and microstructure of the products were characterized by SEM, XRD, TEM, and BET. A possible formation mechanism of the unique structure formed during hydrothermal processing was also investigated. The measured thermophysical results indicated that the prepared YSZ powders had a low thermal conductivity (0.63-1.27 W m-1 K-1), good short-term high-temperature stability up to 1300 °C. The influence of the morphology and microstructure on their thermophysical properties was briefly discussed. The unique multi-hierarchical structure makes the prepared YSZ powders candidates for use in enhanced applications involving thermal barrier coatings.

High-quality crystalline yttria-stabilized-zirconia thin layer for photonic applications

NASA Astrophysics Data System (ADS)

Marcaud, Guillaume; Matzen, Sylvia; Alonso-Ramos, Carlos; Le Roux, Xavier; Berciano, Mathias; Maroutian, Thomas; Agnus, Guillaume; Aubert, Pascal; Largeau, Ludovic; Pillard, Valérie; Serna, Samuel; Benedikovic, Daniel; Pendenque, Christopher; Cassan, Eric; Marris-Morini, Delphine; Lecoeur, Philippe; Vivien, Laurent

2018-03-01

Functional oxides are considered as promising materials for photonic applications due to their extraordinary and various optical properties. Especially, yttria-stabilized zirconia (YSZ) has a high refractive index (˜2.15), leading to a good confinement of the optical mode in waveguides. Furthermore, YSZ can also be used as a buffer layer to expand toward a large family of oxides-based thin-films heterostructures. In this paper, we report a complete study of the structural properties of YSZ for the development of integrated optical devices on sapphire in telecom wavelength range. The substrate preparation and the epitaxial growth using pulsed-laser deposition technique have been studied and optimized. High-quality YSZ thin films with remarkably sharp x-ray diffraction rocking curve peaks in 10-3∘ range have then been grown on sapphire (0001). It was demonstrated that a thermal annealing of sapphire substrate before the YSZ growth allowed controlling the out-of-plane orientation of the YSZ thin film. Single-mode waveguides were finally designed, fabricated, and characterized for two different main orientations of high-quality YSZ (001) and (111). Propagation loss as low as 2 dB/cm at a wavelength of 1380 nm has been demonstrated for both orientations. These results pave the way for the development of a functional oxides-based photonics platform for numerous applications including on-chip optical communications and sensing.

Polypropylene Oil as a Fuel for Ni-YSZ | YSZ | LSCF Solid Oxide Fuel Cell

NASA Astrophysics Data System (ADS)

Pratiwi, Andini W.; Rahmawati, Fitria; Rochman, Refada A.; Syahputra, Rahmat J. E.; Prameswari, Arum P.

2018-01-01

This research aims to convert polypropylene plastic to polypropylene oil through pyrolysis method and use the polypropylene oil as fuel for Solid Oxide Fuel Cell, SOFC, to produce electricity. The material for SOFC single cell are Ni-YSZ, YSZ, and LSCF as anode, electrolyte and cathode, respectively. YSZ is yttria-stabilized-zirconia. Meanwhile, LSCF is a commercial La0.6Sr0.4Co0.2Fe0.8O3. The Ni-YSZ is a composite of YSZ with nickel powder. LSCF and Ni-YSZ slurry coated both side of YSZ electrolyte pellet through screen printing method. The result shows that, the produced polypropylene oil consist of C8 to C27 hydrocarbon chain. Meanwhile, a single cell performance test at 673 K, 773 K and 873 K with polypropylene oil as fuel, found that the maximum power density is 1.729 μW. cm-2 at 673 K with open circuit voltage value of 9.378 mV.

Non-contact temperature Raman measurement in YSZ and alumina ceramics

NASA Astrophysics Data System (ADS)

Thapa, Juddha; Chorpening, Benjamin T.; Buric, Michael P.

2018-02-01

Yttria-stabilized zirconia (YSZ: ZrO2 + Y2O3) and alumina (Al2O3) are widely used in high-temperature applications due to their high-temperature stability, low thermal conductivity, and chemical inertness. Alumina is used extensively in engineered ceramic applications such as furnace tubes and thermocouple protection tubes, while YSZ is commonly used in thermal barrier coatings on turbine blades. Because they are already often found in high temperature and combustion applications, these two substances have been compared as candidates for Raman thermometry in high-temperature energy-related applications. Both ceramics were used with as-received rough surfaces, i.e., without polishing or modification. This closely approximates surface conditions in practical high-temperature situations. A single-line argon ion laser at 488nm was used to excite the materials inside a cylindrical furnace while measuring Raman spectra with a fixed-grating spectrometer. The shift in the peak positions of the most intense A1g peak at 418cm-1 (room temperature position) of alumina ceramic and relatively more symmetric Eg peak at 470cm-1 (room temperature position) of YSZ were measured and reported along with a thermocouple-derived reference temperature up to about 1000°C. This study showed that alumina and YSZ ceramics can be used in high-temperature Raman thermometry with an accuracy of 4.54°C and 10.5°C average standard deviations respectively over the range of about 1000°C. We hope that this result will guide future researchers in selecting materials and utilizing Raman non-contact temperature measurements in harsh environments.

Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

NASA Technical Reports Server (NTRS)

Good, Brian

2011-01-01

Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

Surface modification of yttria stabilized zirconia via polydopamine inspired coating for hydroxyapatite biomineralization

NASA Astrophysics Data System (ADS)

Zain, Norhidayu Muhamad; Hussain, Rafaqat; Kadir, Mohammed Rafiq Abdul

2014-12-01

Yttria stabilized zirconia (YSZ) has been widely used as biomedical implant due to its high strength and enhanced toughening characteristics. However, YSZ is a bioinert material which constrains the formation of chemical bonds with bone tissue following implantation. Inspired by the property of mussels, the surface of YSZ ceramics was functionalized by quinone-rich polydopamine to facilitate the biomineralization of hydroxyapatite. YSZ discs were first immersed in 2 mg/mL of stirred or unstirred dopamine solution at either 25 or 37 °C. The samples were then incubated in 1.5 simulated body fluid (SBF) for 7d. The effect of coating temperature for stirred and unstirred dopamine solutions during substrate grafting was investigated on the basis of chemical compositions, wettability and biomineralization of hydroxyapatite on the YSZ functionalized surface. The results revealed that the YSZ substrate grafted at 37 °C in stirred solution of dopamine possessed significantly improved hydrophilicity (water contact angle of 44.0 ± 2.3) and apatite-mineralization ability (apatite ratio of 1.78). In summary, the coating temperature and stirring condition during grafting procedure affected the chemical compositions of the films and thus influenced the formation of apatite layer on the substrate during the biomineralization process.

Fabrication of biaxially oriented YBCO on (001) biaxially oriented yttria-stabilized-zirconia on polycrystalline substrates

NASA Astrophysics Data System (ADS)

Arendt, P.; Foltyn, S.; Wu, Xin Di; Townsend, J.; Adams, C.; Hawley, M.; Tiwari, P.; Maley, M.; Willis, J.; Moseley, D.

Ion-assisted, ion-beam sputter deposition is used to obtain (001) biaxially oriented films of cubic yttria stabilized zirconia (YSZ) on polycrystalline metal substrates. Yttrium barium copper oxide (YBCO) is then heteroepitaxially pulse laser deposited onto the YSZ. Phi scans of the films show the full-width-half maxima of the YSZ (202) and the YBCO (103) reflections to be 14 deg and 10 deg, respectively. Our best dc transport critical current density measurement for the YBCO is 800,000 A/sq cm at 75 K and 0 T. At 75 K, the total dc transport current in a 1 cm wide YBCO film is 23 A.

Effect of Porosity on Synthetic Sand Infiltration within Yttria-Stabilized Zirconia Pellets

DTIC Science & Technology

Sand infiltration was investigated for several yttria-stabilized zirconia (YSZ) pellets of varying porosity. The pellets were synthesized through...each. Several characterization techniques were used to correlate the sand infiltration to porosity. It was found that there was no significant...difference in the results of low and high porosity samples. Interestingly, sand had infiltrated all samples to some degree although the magnitude of the

Determination of oxygen vacancy limit in Mn substituted yttria stabilized zirconia

NASA Astrophysics Data System (ADS)

Stepień, Joanna; Sikora, Marcin; Kapusta, Czesław; Pomykalska, Daria; Bućko, Mirosław M.

2018-05-01

A series of Mnx(Y0.148Zr0.852)1-xO2-δ ceramics was systematically studied by means of X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) and DC magnetic susceptibility. The XAS and XES results show the changes in manganese oxidation state and a gradual evolution of the local atomic environment around Mn ions upon increasing dopant contents, which is due to structural relaxation caused by the growing amount of oxygen vacancies. Magnetic susceptibility measurements reveal that Mn3O4 precipitates are formed for x ≥ 0.1 and enable independent determination of the actual quantity of Mn ions dissolved in Yttria Stabilized Zirconia (YSZ) solid solution. We show that the amount of oxygen vacancies generated by manganese doping into YSZ is limited to ˜0.17 per formula unit.

Infrared Radiative Properties of Yttria-Stabilized Zirconia Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Eldridge, Jeff I.; Spuckler, Charles M.; Street, Ken W.; Markham, Jim R.; Gray, Hugh R. (Technical Monitor)

2002-01-01

The infrared (IR) transmittance and reflectance of translucent thermal barrier coatings (TBCs) have important implications for both the performance of these coatings as radiation barriers and emitters as well as affecting measurements of TBC thermal conductivity, especially as TBCs are being pushed to higher temperatures. In this paper, the infrared spectral directional-hemispherical transmittance and reflectance of plasma-sprayed 8wt% yttria-stabilized zirconia (8YSZ) TBCs are reported. These measurements are compared to those for single crystal YSZ specimens to show the effects of the plasma-sprayed coating microstructure. It is shown that the coatings exhibit negligible absorption at wavelengths up to about 5 micrometers, and that internal scattering rather than surface reflections dominates the hemispherical reflectance. The translucent nature of the 8YSZ TBCs results in the absorptance/emittance and reflectance of TBC-coated substrates depending on the TBC thickness, microstructure, as well as the radiative properties of the underlying substrate. The effects of these properties on TBC measurements and performance are discussed.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

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.

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.

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

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

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

2011-02-15

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

Brazing of Stainless Steel to Yttria-Stabilized Zirconia Using Gold-Based Brazes for Solid Oxide Fuel Cell Applications

NASA Technical Reports Server (NTRS)

Singh, M.; Shpargel, T. P.; Asthana, R.

2007-01-01

Two gold-base active metal brazes (gold-ABA and gold-ABA-V) were evaluated for oxidation resistance to 850 C, and used to join yttria-stabilized zirconia (YSZ) to a corrosion-resistant ferritic stainless steel for possible use in solid oxide fuel cells. Thermogravimetric analysis and optical microscopy and scanning electron microscopy coupled with energy-dispersive spectroscopy were used to evaluate the braze oxidation behavior, and microstructure and composition of the YSZ/braze/steel joints. Both gold-ABA and gold-ABA-V exhibited nearly linear oxidation kinetics at 850 C, with gold-ABA-V showing faster oxidation than gold-ABA. Both brazes produced metallurgically sound YSZ/steel joints due to chemical interactions of Ti and V with the YSZ and steel substrates.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Micro-tubular solid oxide fuel cell based on a porous yttria-stabilized zirconia support

NASA Astrophysics Data System (ADS)

Panthi, Dhruba; Tsutsumi, Atsushi

2014-08-01

Solid oxide fuel cells (SOFCs) are promising electrochemical energy conversion devices owing to their high power generation efficiency and environmentally benign operation. Micro-tubular SOFCs, which have diameters ranging from a few millimeters to the sub-millimeter scale, offer several advantages over competing SOFCs such as high volumetric power density, good endurance against thermal cycling, and flexible sealing between fuel and oxidant streams. Herein, we successfully realized a novel micro-tubular SOFC design based on a porous yttria-stabilized zirconia (YSZ) support using multi-step dip coating and co-sintering methods. The micro-tubular SOFC consisted of Ni-YSZ, YSZ, and strontium-doped lanthanum manganite (LSM)-YSZ as the anode, electrolyte, and cathode, respectively. In addition, to facilitate current collection from the anode and cathode, Ni and LSM were applied as an anode current collector and cathode current collector, respectively. Micro-crystalline cellulose was selected as a pore former to achieve better shrinkage behavior of the YSZ support so that the electrolyte layer could be densified at a co-sintering temperature of 1300°C. The developed micro-tubular design showed a promising electrochemical performance with maximum power densities of 525, 442, and 354 mW cm-2 at 850, 800, and 750°C, respectively.

Structural and optical properties of electron beam evaporated yttria stabilized zirconia thin films

NASA Astrophysics Data System (ADS)

Kirubaharan, A. Kamalan; Kuppusami, P.; Singh, Akash; Dharini, T.; Ramachandran, D.; Mohandas, E.

2015-06-01

Yttria stabilized zirconia (10 mole % Y2O3) thin films were deposited on quartz substrates using electron beam physical vapor deposition at the substrate temperatures in the range 300 - 973 K. XRD analysis showed cubic crystalline phase of YSZ films with preferred orientation along (111). The surface roughness was found to increase with the increase of deposition temperatures. The optical band gap of ˜5.7 eV was calculated from transmittance curves. The variation in the optical properties is correlated with the changes in the microstructural features of the films prepared as a function of substrate temperature.

Mechanical properties, electrochemical corrosion and in-vitro bioactivity of yttria stabilized zirconia reinforced hydroxyapatite coatings prepared by gas tunnel type plasma spraying.

PubMed

Yugeswaran, S; Yoganand, C P; Kobayashi, A; Paraskevopoulos, K M; Subramanian, B

2012-05-01

Yttria stabilized zirconia reinforced hydroxyapatite coatings were deposited by a gas tunnel type plasma spray torch under optimum spraying conditions. For this purpose, 10, 20 and 30 wt% of yttria stabilized zirconia (YSZ) powders were premixed individually with hydroxyapatite (HA) powder and were used as the feedstocks for the coatings. The effect of YSZ reinforcement on the phase formation and mechanical properties of the coatings such as hardness, adhesive strength and sliding wear rates was examined. The results showed that the reinforcement of YSZ in HA could significantly enhance the hardness and adhesive strength of the coatings. The potentiodynamic polarization and impedance measurements showed that the reinforced coatings exhibited superior corrosion resistance compared to the HA coating in SBF solution. Further the results of the bioactivity test conducted by immersion of coatings in SBF showed that after 10 days of immersion of the obtained coatings with all the above compositions commonly exhibited the onset of bioactive apatite formation except for HA+10%YSZ coating. The cytocompatibility was investigated by culturing the green fluorescent protein (GFP)-labeled marrow stromal cells (MSCs) on the coating surface. The cell culture results revealed that the reinforced coatings have superior cell growth than the pure HA coatings. Copyright © 2012. Published by Elsevier Ltd.

Stabilizing Ir(001) Epitaxy on Yttria-Stabilized Zirconia Using a Thin Ir Seed Layer Grown by Pulsed Laser Deposition

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

Fan, Lisha; Jacobs, Christopher B.; Rouleau, Christopher M.

In this paper, we demonstrate the reproducible epitaxial growth of 100 nm thick Ir(001) films on a heteroepitaxial stack consisting of 5 nm Ir and 100 nm yttria-stabilized zirconia (YSZ) grown on Si(001) substrates. It is shown that a 5 nm thick Ir layer grown by pulsed laser deposition in the same chamber as the YSZ film without breaking the vacuum is the key to stabilizing Ir(001) epitaxial growth. Growth of the Ir seed layer with pure (001) orientation occurs only in a narrow growth temperature window from 550 to 750 °C, and the fraction of Ir(111) increases at substratemore » temperatures outside of this window. The Ir seed layer prevents exposure of the YSZ film to air during sample transfer and enables highly reproducible Ir(001) heteroepitaxy on YSZ buffered Si(001). In contrast, if Ir is grown directly on a bare YSZ layer that was exposed to ambient conditions, the films are prone to change orientation to (111). These results reveal that preserving the chemical and structural purity of the YSZ surface is imperative for achieving Ir(001) epitaxy. The narrow range of the mosaic spread values from eight experiments demonstrates the high yield and high reproducibility of Ir(001) heteroepitaxy by this approach. Lastly, the improved Ir(001) epitaxial growth method is of great significance for integrating a variety of technologically important materials such as diamond, graphene, and functional oxides on a Si platform.« less

Stabilizing Ir(001) Epitaxy on Yttria-Stabilized Zirconia Using a Thin Ir Seed Layer Grown by Pulsed Laser Deposition

DOE PAGES

Fan, Lisha; Jacobs, Christopher B.; Rouleau, Christopher M.; ...

2016-11-18

In this paper, we demonstrate the reproducible epitaxial growth of 100 nm thick Ir(001) films on a heteroepitaxial stack consisting of 5 nm Ir and 100 nm yttria-stabilized zirconia (YSZ) grown on Si(001) substrates. It is shown that a 5 nm thick Ir layer grown by pulsed laser deposition in the same chamber as the YSZ film without breaking the vacuum is the key to stabilizing Ir(001) epitaxial growth. Growth of the Ir seed layer with pure (001) orientation occurs only in a narrow growth temperature window from 550 to 750 °C, and the fraction of Ir(111) increases at substratemore » temperatures outside of this window. The Ir seed layer prevents exposure of the YSZ film to air during sample transfer and enables highly reproducible Ir(001) heteroepitaxy on YSZ buffered Si(001). In contrast, if Ir is grown directly on a bare YSZ layer that was exposed to ambient conditions, the films are prone to change orientation to (111). These results reveal that preserving the chemical and structural purity of the YSZ surface is imperative for achieving Ir(001) epitaxy. The narrow range of the mosaic spread values from eight experiments demonstrates the high yield and high reproducibility of Ir(001) heteroepitaxy by this approach. Lastly, the improved Ir(001) epitaxial growth method is of great significance for integrating a variety of technologically important materials such as diamond, graphene, and functional oxides on a Si platform.« less

Atomic structure and composition of the yttria-stabilized zirconia (111) surface.

PubMed

Vonk, Vedran; Khorshidi, Navid; Stierle, Andreas; Dosch, Helmut

2013-06-01

Anomalous and nonanomalous surface X-ray diffraction is used to investigate the atomic structure and composition of the yttria-stabilized zirconia (YSZ)(111) surface. By simulation it is shown that the method is sensitive to Y surface segregation, but that the data must contain high enough Fourier components in order to distinguish between different models describing Y/Zr disorder. Data were collected at room temperature after two different annealing procedures. First by applying oxidative conditions at 10 - 5  mbar O 2 and 700 K to the as-received samples, where we find that about 30% of the surface is covered by oxide islands, which are depleted in Y as compared with the bulk. After annealing in ultrahigh vacuum at 1270 K the island morphology of the surface remains unchanged but the islands and the first near surface layer get significantly enriched in Y. Furthermore, the observation of Zr and oxygen vacancies implies the formation of a porous surface region. Our findings have important implications for the use of YSZ as solid oxide fuel cell electrode material where yttrium atoms and zirconium vacancies can act as reactive centers, as well as for the use of YSZ as substrate material for thin film and nanoparticle growth where defects control the nucleation process.

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

DOE PAGES

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

2016-02-15

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

Oxygen diffusion in nanocrystalline yttria-stabilized zirconia: the effect of grain boundaries.

PubMed

De Souza, Roger A; Pietrowski, Martha J; Anselmi-Tamburini, Umberto; Kim, Sangtae; Munir, Zuhair A; Martin, Manfred

2008-04-21

The transport of oxygen in dense samples of yttria-stabilized zirconia (YSZ), of average grain size d approximately 50 nm, has been studied by means of 18O/16O exchange annealing and secondary ion mass spectrometry (SIMS). Oxygen diffusion coefficients (D*) and oxygen surface exchange coefficients (k*) were measured for temperatures 673

Dense zig-zag microstructures in YSZ thin films by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Stender, Dieter; Schäuble, Nina; Weidenkaff, Anke; Montagne, Alex; Ghisleni, Rudy; Michler, Johann; Schneider, Christof W.; Wokaun, Alexander; Lippert, Thomas

2015-01-01

The very brittle oxygen ion conductor yttria stabilized zirconia (YSZ) is a typical solid electrolyte for miniaturized thin film fuel cells. In order to decrease the fuel cell operating temperature, the thickness of yttria stabilized zirconia thin films is reduced. Often, these thin membranes suffer from mechanical failure and gas permeability. To improve these mechanical issues, a glancing angle deposition approach is used to grow yttria stabilized zirconia thin films with tilted columnar structures. Changes of the material flux direction during the deposition result in a dense, zigzag-like structure with columnar crystallites. This structure reduces the elastic modulus of these membranes as compared to columnar yttria stabilized zirconia thin films as monitored by nano-indentation which makes them more adaptable to applied stress.

Insight into the grain boundary effect on the ionic transport of yttria-stabilized zirconia at elevated temperatures from a molecular modeling perspective

NASA Astrophysics Data System (ADS)

Chang, Kai-Shiun; Lin, Yi-Feng; Tung, Kuo-Lun

A molecular dynamics (MD) simulation is used to reveal the grain boundary effect on the ionic transport of yttria-stabilized zirconia (YSZ). The oxygen ion displacements and diffusivities of the ideal and grain boundary-inserted YSZ models are analyzed at elevated temperatures. An optimized Y 2O 3 concentration within YSZ for the best ionic conductivity is achieved by balancing the trade-off between the increased vacancies and the decreased accessible free space. The mass transfer resistance of the grain boundary in YSZ can be more easily found at higher temperatures by observing the oxygen ion diffusivities or traveling trajectories. At lower temperatures, the grain interior and the grain boundary control the ionic transport. In contrast, the grain boundary effect on the diffusion barrier is gradually eliminated at elevated temperatures. The modeled results in this work agree well with previous experimental data.

Novel Cranial Implants of Yttria-Stabilized Zirconia as Acoustic Windows for Ultrasonic Brain Therapy.

PubMed

Gutierrez, Mario I; Penilla, Elias H; Leija, Lorenzo; Vera, Arturo; Garay, Javier E; Aguilar, Guillermo

2017-11-01

Therapeutic ultrasound can induce changes in tissues by means of thermal and nonthermal effects. It is proposed for treatment of some brain pathologies such as Alzheimer's, Parkinson's, Huntington's diseases, and cancer. However, cranium highly absorbs ultrasound reducing transmission efficiency. There are clinical applications of transcranial focused ultrasound and implantable ultrasound transducers proposed to address this problem. In this paper, biocompatible materials are proposed for replacing part of the cranium (cranial implants) based on low porosity polycrystalline 8 mol% yttria-stabilized-zirconia (8YSZ) ceramics as acoustic windows for brain therapy. In order to assess the viability of 8YSZ implants to effectively transmit ultrasound, various 8YSZ ceramics with different porosity are tested; their acoustic properties are measured; and the results are validated using finite element models simulating wave propagation to brain tissue through 8YSZ windows. The ultrasound attenuation is found to be linearly dependent on ceramics' porosity. Results for the nearly pore-free case indicate that 8YSZ is highly effective in transmitting ultrasound, with overall maximum transmission efficiency of ≈81%, compared to near total absorption of cranial bone. These results suggest that 8YSZ polycrystals could be suitable acoustic windows for ultrasound brain therapy at 1 MHz. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Y-Ba-Cu-O thin films and yttria-stabilized zirconia intermediate layers on metal alloys grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Reade, R. P.; Mao, X. L.; Russo, R. E.

1991-08-01

The use of an intermediate layer is necessary for the growth of YBaCuO thin films on polycrystalline metallic alloys for tape conductor applications. A pulsed laser deposition process to grow controlled-orientation yttria-stabilized zirconia (YSZ) films as intermediate layers on Haynes Alloy No. 230 was developed and characterized. YBaCuO films deposited on these YSZ-coated substrates are primarily c-axis oriented and superconducting as deposited. The best YBaCuO films grow on (001)-oriented YSZ intermediate layers and have Tc (R = 0) = 86.0 K and Jc about 3000 A/sq cm at 77 K.

Effects of Laser Remelting and Oxidation on NiCrAlY/8Y2O3-ZrO2 Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Xu, S. Q.; Zhu, C.; Zhang, Y.

2018-02-01

In this study, three groups of thermal barrier coatings (TBCs) samples were remelted by CO2 laser with different laser energy densities (1, 5 and 10 J/mm2) to seal the surface of yttria-stabilized zirconia (YSZ) coatings. Microscopic observations showed that the cracks size and the remelted depth in YSZ coatings increased. A 50-μm-thick dense layer was formed on the surface of YSZ coating in samples with 1 J/mm2 energy density. Microindentation tests showed that the Vickers hardness of YSZ coatings increases with the increase in laser energy density. After isothermal oxidation at 1200 °C for 200 h, thinner thermally growth oxides were found in laser remelted YSZ samples under energy density of 1 J/mm2 (6.32 ± 0.28 μm). Cyclic oxidation results showed that the weight gain per unit area of low energy density laser remelted TBCs was smaller than that of the high energy density laser remelted and as-sprayed TBCs.

Ionic conductivity and thermal stability of magnetron-sputtered nanocrystalline yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Sillassen, M.; Eklund, P.; Sridharan, M.; Pryds, N.; Bonanos, N.; Bøttiger, J.

2009-05-01

Thermally stable, stoichiometric, cubic yttria-stabilized zirconia (YSZ) thin-film electrolytes have been synthesized by reactive pulsed dc magnetron sputtering from a Zr-Y (80/20 at. %) alloy target. Films deposited at floating potential had a ⟨111⟩ texture. Single-line profile analysis of the 111 x-ray diffraction peak yielded a grain size of ˜20 nm and a microstrain of ˜2% regardless of deposition temperature. Films deposited at 400 °C and selected bias voltages in the range from -70 to -200 V showed a reduced grain size for higher bias voltages, yielding a grain size of ˜6 nm and a microstrain of ˜2.5% at bias voltages of -175 and -200 V with additional incorporation of argon. The films were thermally stable; very limited grain coarsening was observed up to an annealing temperature of 800 °C. Temperature-dependent impedance spectroscopy analysis of the YSZ films with Ag electrodes showed that the in-plane ionic conductivity was within one order of magnitude higher in films deposited with substrate bias corresponding to a decrease in grain size compared to films deposited at floating potential. This suggests that there is a significant contribution to the ionic conductivity from grain boundaries. The activation energy for oxygen ion migration was determined to be between 1.14 and 1.30 eV.

Environmental Barrier Coatings Having a YSZ Top Coat

NASA Technical Reports Server (NTRS)

Lee, Kang N.; Gray, Hugh (Technical Monitor)

2002-01-01

Environmental barrier coatings (EBCs) with a Si bond coat, a yttria-stabilized zirconia (YSZ) top coat, and various intermediate coats were investigated. EBCs were processed by atmospheric pressure plasma spraying. The EBC durability was determined by thermal cycling tests in water vapor at 1300 C and 1400 C, and in air at 1400 C and 1500 C. EBCs with a mullite (3Al2O3 (dot) 2SiO2) + BSAS (1 - xBaO (dot) xSrO (dot) Al2O3 (dot) 2SiO2) intermediate coat were more durable than EBCs with a mullite intermediate coat, while EBCs with a mullite/BSAS duplex intermediate coat resulted in inferior durability. The improvement with a mullite + BSAS intermediate coat was attributed to enhanced compliance of the intermediate coat due to the addition of a low modulus BSAS second phase. Mullite + BSAS/YSZ and BSAS/YSZ interfaces produced a low melting (less than 1400 C) reaction product, which is expected to degrade the EBC performance by increasing the thermal conductivity. EBCs with a mullite + BSAS / graded mullite + YSZ intermediate coat showed the best durability among the EBCs investigated in this study. This improvement was attributed to diffused CTE (Coefficient of Thermal Expansion) mismatch stress and improved chemical stability due to the compositionally graded mullite+YSZ layer.

Synthesis and thermal stability of zirconia and yttria-stabilized zirconia microspheres.

PubMed

Leib, Elisabeth W; Vainio, Ulla; Pasquarelli, Robert M; Kus, Jonas; Czaschke, Christian; Walter, Nils; Janssen, Rolf; Müller, Martin; Schreyer, Andreas; Weller, Horst; Vossmeyer, Tobias

2015-06-15

Zirconia microparticles produced by sol-gel synthesis have great potential for photonic applications. To this end, identifying synthetic methods that yield reproducible control over size uniformity is important. Phase transformations during thermal cycling can disintegrate the particles. Therefore, understanding the parameters driving these transformations is essential for enabling high-temperature applications. Particle morphology is expected to influence particle processability and stability. Yttria-doping should improve the thermal stability of the particles, as it does in bulk zirconia. Zirconia and YSZ particles were synthesized by improved sol-gel approaches using fatty acid stabilizers. The particles were heated to 1500 °C, and structural and morphological changes were monitored by SEM, ex situ XRD and high-energy in situ XRD. Zirconia particles (0.4-4.3 μm in diameter, 5-10% standard deviation) synthesized according to the modified sol-gel approaches yielded significantly improved monodispersities. As-synthesized amorphous particles transformed to the tetragonal phase at ∼450 °C with a volume decrease of up to ∼75% and then to monoclinic after heating from ∼650 to 850 °C. Submicron particles disintegrated at ∼850 °C and microparticles at ∼1200 °C due to grain growth. In situ XRD revealed that the transition from the amorphous to tetragonal phase was accompanied by relief in microstrain and the transition from tetragonal to monoclinic was correlated with the tetragonal grain size. Early crystallization and smaller initial grain sizes, which depend on the precursors used for particle synthesis, coincided with higher stability. Yttria-doping reduced grain growth, stabilized the tetragonal phase, and significantly improved the thermal stability of the particles. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Degradation of yttria-stabilized zirconia thermal barrier coatings by vanadium pentoxide, phosphorous pentoxide, and sodium sulfate

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

Mohan, P.; Yuan, B.; Patterson, T.

2007-11-15

The presence of vanadium, phosphorus, and sodium impurities in petcoke and coal/petcoke blends used in integrated gasification combined cycle (IGCC) plants warrants a clear understanding of high-temperature material degradation for the development of fuel-flexible gas turbines. In this study, degradation reactions of free-standing air plasma-sprayed (APS) yttria-stabilized zirconia (YSZ) in contact with V{sub 2}O{sub 5}, P{sub 2}O{sub 5}, and Na{sub 2}SO{sub 4} were investigated at temperatures up to 1200{sup o}C. Phase transformations and microstructural development were examined using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Molten V{sub 2}O{sub 5} reacted with solid YSZ to form ZrV{sub 2}O{sub 7}more » at temperatures below 747{sup o}C. However, at temperatures above 747{sup o}C, molten V{sub 2}O{sub 5} reacted with YSZ to form yttrium vanadate (YVO{sub 4}). The formation of YVO{sub 4} led to the depletion of the Y2O{sub 3} stabilizer and deleterious transformation to the monoclinic ZrO{sub 2} phase. In addition, studies on YSZ degradation by Na{sub 2}SO{sub 4} and a Na{sub 2}SO{sub 4}+V{sub 2}O{sub 5} mixture (50-50 mol%) showed that Na{sub 2}SO{sub 4} itself had no effect on the degradation of YSZ. However, in the presence of V{sub 2}O{sub 5} at high temperatures, Na{sub 2}SO{sub 4} forms vanadate compounds having a lower melting point such as sodium metavanadate (610{sup o}C), which was found to degrade YSZ by the formation of YVO{sub 4} at a relatively lower temperature of 700{sup o}C. P{sub 2}O{sub 5} was found to react with APS YSZ by the formation of ZrP{sub 2}O{sub 7} at all the temperatures studied. At temperatures as low as 200{sup o}C and as high as 1200{sup o}C, molten P{sub 2}O{sub 5} was observed to react with solid YSZ to yield ZrP{sub 2}O{sub 7}, which led to the depletion of ZrO{sub 2} in YSZ that promoted the formation of the fluorite-cubic ZrO{sub 2} phase.« less

Spectroscopic investigation of the electronic structure of yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Götsch, Thomas; Bertel, Erminald; Menzel, Alexander; Stöger-Pollach, Michael; Penner, Simon

2018-03-01

The electronic structure and optical properties of yttria-stabilized zirconia are investigated as a function of the yttria content using multiple experimental and theoretical methods, including electron energy-loss spectroscopy, Kramers-Kronig analysis to obtain the optical parameters, photoelectron spectroscopy, and density functional theory. It is shown that many properties, including the band gaps, the crystal field splitting, the so-called defect gap between acceptor (YZr') and donor (VO••) states, as well as the index of refraction in the visible range exhibit the same "zig-zag-like" trend as the unit cell height does, showing the influence of an increased yttria content as well as of the tetragonal-cubic phase transition between 8 mol % and 20 mol %Y2O3 . Also, with Čerenkov spectroscopy (CS), a new technique is presented, providing information complementary to electron energy-loss spectroscopy. In CS, the Čerenkov radiation emitted inside the TEM is used to measure the onset of optical absorption. The apparent absorption edges in the Čerenkov spectra correspond to the energetic difference between the disorder states close to the valence band and the oxygen-vacancy-related electronic states within the band gap. Theoretical computations corroborate this assignment: they find both, the acceptor states and the donor states, at the expected energies in the band structures for diverse yttria concentrations. In the end, a schematic electronic structure diagram of the area around the band gap is constructed, including the chemical potential of the electrons obtained from photoelectron spectroscopy. The latter reveal that tetragonal YSZ corresponds to a p -type semiconductor, whereas the cubic samples exhibit n -type semiconductor properties.

The crystal structure and morphology of NiO-YSZ composite that prepared from local zircon concentrate of Bangka Island

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

Rahmawati, F., E-mail: fitria@mipa.uns.ac.id; Apriyani, K.; Heraldy, E.

2016-03-29

In order to increase the economic value of local zircon concentrate from Bangka Island, NiO-YSZ was synthesized from Zirconia, ZrO{sub 2} that was prepared from local zircon concentrate. The NiO-YSZ composite was synthesized by solid state reaction method. XRD analysis equipped with Le Bail refinement was carried out to analyze the crystal structure and cell parameters of the prepared materials. The result showed that zirconia was crystallized in tetragonal structure with a space group of P42/NMC. Yttria-Stabilized-Zirconia (YSZ) was prepared by doping 8% mol yttrium oxide into zirconia and then sintered at 1250°C for 3 hours. Doping of 8% molmore » Yttria allowed phase transformation of zirconia from tetragonal into the cubic structure. Meanwhile, the composite of NiO-YSZ consists of two crystalline phases, i.e. the NiO with cubic structure and the YSZ with cubic structure. SEM analysis of the prepared materials shows that the addition of NiO into YSZ allows the morphology to become more roughness with larger grain size.« less

Microstructure and mechanical properties of plasma sprayed HA/YSZ/Ti-6Al-4V composite coatings.

PubMed

Khor, K A; Gu, Y W; Pan, D; Cheang, P

2004-08-01

Plasma sprayed hydroxyapatite (HA) coatings on titanium alloy substrate have been used extensively due to their excellent biocompatibility and osteoconductivity. However, the erratic bond strength between HA and Ti alloy has raised concern over the long-term reliability of the implant. In this paper, HA/yttria stabilized zirconia (YSZ)/Ti-6Al-4V composite coatings that possess superior mechanical properties to conventional plasma sprayed HA coatings were developed. Ti-6Al-4V powders coated with fine YSZ and HA particles were prepared through a unique ceramic slurry mixing method. The so-formed composite powder was employed as feedstock for plasma spraying of the HA/YSZ/Ti-6Al-4V coatings. The influence of net plasma energy, plasma spray standoff distance, and post-spray heat treatment on microstructure, phase composition and mechanical properties were investigated. Results showed that coatings prepared with the optimum plasma sprayed condition showed a well-defined splat structure. HA/YSZ/Ti-6Al-4V solid solution was formed during plasma spraying which was beneficial for the improvement of mechanical properties. There was no evidence of Ti oxidation from the successful processing of YSZ and HA coated Ti-6Al-4V composite powders. Small amount of CaO apart from HA, ZrO(2) and Ti was present in the composite coatings. The microhardness, Young's modulus, fracture toughness, and bond strength increased significantly with the addition of YSZ. Post-spray heat treatment at 600 degrees C and 700 degrees C for up to 12h was found to further improve the mechanical properties of coatings. After the post-spray heat treatment, 17.6% increment in Young's modulus (E) and 16.3% increment in Vicker's hardness were achieved. The strengthening mechanisms of HA/YSZ/Ti-6Al-4V composite coatings were related to the dispersion strengthening by homogeneous distribution of YSZ particles in the matrix, the good mechanical properties of Ti-6Al-4V and the formation of solid solution among HA

High-power hybrid plasma spraying of large yttria-stabilized zirconia powder

NASA Astrophysics Data System (ADS)

Huang, Heji; Eguchi, Keisuke; Yoshida, Toyonobu

2006-03-01

To testify to the advantage of large ceramic powder spraying, numerical simulations and experimental studies on the behavior of large yttria-stabilized zirconia (YSZ) powder in a high-power hybrid plasma spraying process have been carried out. Numeric predictions and experimental results showed that, with the high radio frequency (RF) input power of 100 kW, the most refractory YSZ powder with particle sizes as large as 88 μm could be fully melted and well-flattened splats could be formed. A large degree of flattening (ξ) of 4.7 has been achieved. The improved adhesive strength between the large splat and the substrate was confirmed based on the measurement of the crack density inside of the splats. A thick YSZ coating >300 μm was successfully deposited on a large CoNiCrAlY-coated Inconel substrate (50×50×4 mm in size). The ultradense microstructure without clear boundaries between the splats and the clean and crack-free interface between the top-coat and the bond-coat also indicate the good adhesion. These results showed that highpower hybrid plasma spraying of large ceramic powder is a very promising process for deposition of highquality coatings, especially in the application of thermal barrier coatings (TBCs).

Influence of miscut Y2O3-stabilized ZrO2 substrates on the azimuthal domain structure and ferroelectric properties of epitaxial La-substituted Bi4Ti3O12 films

NASA Astrophysics Data System (ADS)

Lee, Sung Kyun; Hesse, Dietrich; Gösele, Ulrich; Lee, Ho Nyung

2006-09-01

We have investigated the influence of both miscut angle and miscut direction of Y2O3-stabilized ZrO2 (YSZ) (100) single crystal substrates on the azimuthal domain structure of SrRuO3 electrode layers as well as of La-substituted Bi4Ti3O12 (BLT) ferroelectric thin films, both grown on these substrates by pulsed laser deposition. X-ray diffraction ϕ scan and pole figure characterizations revealed that the YSZ[011] miscut direction is more effective to uniformly reduce the number of azimuthal domain variants in the films than the YSZ[001] miscut direction. The BLT films on YSZ(100) substrates with miscut angle of 5° and [011] miscut direction involve only half the number of azimuthal domains, compared to the BLT films on exactly cut YSZ(100) substrates. Atomic force microscopy and plan-view transmission electron microscopy also confirmed that almost all BLT grains on these miscut YSZ(100) substrates are arranged along only two (out of four) specific azimuthal directions. The BLT films on YSZ(100) substrates with 5° miscut towards YSZ[011] showed an about 1.3 times higher remanent polarization (Pr=12.5μC /cm2) than the BLT films on exactly cut YSZ(100) substrates (Pr=9.5μC/cm2), due most probably to a lower areal density of azimuthal domain boundaries. It thus appears that reducing the structural domains can be an effective way to further enhance the ferroelectric properties of multiply twinned, epitaxial ferroelectric films.

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Thermodynamic Assessment of the Y2o3-yb2o3-zro2 System

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Design and Fabrication of Porous Yttria-Stabilized Zirconia Ceramics for Hot Gas Filtration Applications

NASA Astrophysics Data System (ADS)

Shahini, Shayan

Hot gas filtration has received growing attention in a variety of applications over the past few years. Yttria-stabilized zirconia (YSZ) is a promising candidate for such an application. In this study, we fabricated disk-type porous YSZ filters using the pore forming procedure, in which poly methyl methacrylate (PMMA) was used as the pore-forming agent. After fabricating the pellets, we characterized them to determine their potential for application as gas filters. We investigated the effect of sintering temperature, polymer particle size, and polymer-to-ceramic ratio on the porosity, pore size, gas permeability, and Vickers hardness of the sintered pellets. Furthermore, we designed two sets of experiments to investigate the robustness of the fabricated pellets--i.e., cyclic heating/cooling and high temperature exposure. This study ushers in a robust technique to fabricate such porous ceramics, which have the potential to be utilized in hot gas filtration.

Slurry spin coating of thin film yttria stabilized zirconia/gadolinia doped ceria bi-layer electrolytes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Kim, Hyun Joong; Kim, Manjin; Neoh, Ke Chean; Han, Gwon Deok; Bae, Kiho; Shin, Jong Mok; Kim, Gyu-Tae; Shim, Joon Hyung

2016-09-01

Thin ceramic bi-layered membrane comprising yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is fabricated by the cost-effective slurry spin coating technique, and it is evaluated as an electrolyte of solid oxide fuel cells (SOFCs). It is demonstrated that the slurry spin coating method is capable of fabricating porous ceramic films by adjusting the content of ethyl-cellulose binders in the source slurry. The porous GDC layer deposited by spin coating under an optimal condition functions satisfactorily as a cathode-electrolyte interlayer in the test SOFC stack. A 2-μm-thick electrolyte membrane of the spin-coated YSZ/GDC bi-layer is successfully deposited as a dense and stable film directly on a porous NiO-YSZ anode support without any interlayers, and the SOFC produces power output over 200 mW cm-2 at 600 °C, with an open circuit voltage close to 1 V. Electrochemical impedance spectra analysis is conducted to evaluate the performance of the fuel cell components in relation with the microstructure of the spin-coated layers.

Initial Bacterial Adhesion on Different Yttria-Stabilized Tetragonal Zirconia Implant Surfaces in Vitro

PubMed Central

Karygianni, Lamprini; Jähnig, Andrea; Schienle, Stefanie; Bernsmann, Falk; Adolfsson, Erik; Kohal, Ralf J.; Chevalier, Jérôme; Hellwig, Elmar; Al-Ahmad, Ali

2013-01-01

Bacterial adhesion to implant biomaterials constitutes a virulence factor leading to biofilm formation, infection and treatment failure. The aim of this study was to examine the initial bacterial adhesion on different implant materials in vitro. Four implant biomaterials were incubated with Enterococcus faecalis, Staphylococcus aureus and Candida albicans for 2 h: 3 mol % yttria-stabilized tetragonal zirconia polycrystal surface (B1a), B1a with zirconium oxide (ZrO2) coating (B2a), B1a with zirconia-based composite coating (B1b) and B1a with zirconia-based composite and ZrO2 coatings (B2b). Bovine enamel slabs (BES) served as control. The adherent microorganisms were quantified and visualized using scanning electron microscopy (SEM); DAPI and live/dead staining. The lowest bacterial count of E. faecalis was detected on BES and the highest on B1a. The fewest vital C. albicans strains (42.22%) were detected on B2a surfaces, while most E. faecalis and S. aureus strains (approximately 80%) were vital overall. Compared to BES; coated and uncoated zirconia substrata exhibited no anti-adhesive properties. Further improvement of the material surface characteristics is essential. PMID:28788415

Double-Layer Gadolinium Zirconate/Yttria-Stabilized Zirconia Thermal Barrier Coatings Deposited by the Solution Precursor Plasma Spray Process

NASA Astrophysics Data System (ADS)

Jiang, Chen; Jordan, Eric H.; Harris, Alan B.; Gell, Maurice; Roth, Jeffrey

2015-08-01

Advanced thermal barrier coatings (TBCs) with lower thermal conductivity, increased resistance to calcium-magnesium-aluminosilicate (CMAS), and improved high-temperature capability, compared to traditional yttria-stabilized zirconia (YSZ) TBCs, are essential to higher efficiency in next generation gas turbine engines. Double-layer rare-earth zirconate/YSZ TBCs are a promising solution. From a processing perspective, solution precursor plasma spray (SPPS) process with its unique and beneficial microstructural features can be an effective approach to obtaining the double-layer microstructure. Previously durable low-thermal-conductivity YSZ TBCs with optimized layered porosity, called the inter-pass boundaries (IPBs) were produced using the SPPS process. In this study, an SPPS gadolinium zirconate (GZO) protective surface layer was successfully added. These SPPS double-layer TBCs not only retained good cyclic durability and low thermal conductivity, but also demonstrated favorable phase stability and increased surface temperature capabilities. The CMAS resistance was evaluated with both accumulative and single applications of simulated CMAS in isothermal furnaces. The double-layer YSZ/GZO exhibited dramatic improvement in the single application, but not in the continuous one. In addition, to explore their potential application in integrated gasification combined cycle environments, double-layer TBCs were tested under high-temperature humidity and encouraging performance was recorded.

Controlling Microstructure of Yttria-Stabilized Zirconia Prepared from Suspensions and Solutions by Plasma Spraying with High Feed Rates

NASA Astrophysics Data System (ADS)

Musalek, Radek; Medricky, Jan; Tesar, Tomas; Kotlan, Jiri; Pala, Zdenek; Lukac, Frantisek; Illkova, Ksenia; Hlina, Michal; Chraska, Tomas; Sokolowski, Pawel; Curry, Nicholas

2017-12-01

Introduction of suspension and solution plasma spraying led to a breakthrough in the deposition of yttria-stabilized zirconia (YSZ) coatings and enabled preparation of new types of layers. However, their deposition with high feed rates needed, for example, for the deposition of thermal barrier coatings (TBCs) on large-scale components, is still challenging. In this study, possibility of high-throughput plasma spraying of YSZ coatings is demonstrated for the latest generation of high-enthalpy hybrid water-stabilized plasma (WSP-H) torch technology. The results show that microstructure of the coatings prepared by WSP-H may be tailored for specific applications by the choice of deposition conditions, in particular formulation of the liquid feedstock. Porous and columnar coatings with low thermal conductivity (0.5-0.6 W/mK) were prepared from commercial ethanol-based suspension. Dense vertically cracked coatings with higher thermal conductivity but also higher internal cohesion were deposited from suspension containing ethanol/water mixture and coarser YSZ particles. Spraying of solution formulated from diluted zirconium acetate and yttrium nitrate hexahydrate led also to the successful deposition of YSZ coating combining regions of porous and denser microstructure and providing both low thermal conductivity and improved cohesion of the coating. Enthalpy content, liquid-plasma interaction and coating buildup mechanisms are also discussed.

Wear behavior of carbide tool coated with Yttria-stabilized zirconia nano particles.

NASA Astrophysics Data System (ADS)

Jadhav, Pavandatta M.; Reddy, Narala Suresh Kumar

2018-04-01

Wear mechanism takes predominant role in reducing the tool life during machining of Titanium alloy. Challenges of wear mechanisms such as variation in chip, high pressure loads and spring back are responsible for tool wear. In addition, many tool materials are inapt for machining due to low thermal conductivity and volume specific heat of these materials results in high cutting temperature during machining. To confront this issue Electrostatic Spray Coating (ESC) coating technique is utilized to enhance the tool life to an acceptable level. The Yttria Stabilized Zirconia (YSZ) acts as a thermal barrier coating having high thermal expansion coefficient and thermal shock resistance. This investigation focuses on the influence of YSZ nanocoating on the tungsten carbide tool material and improve the machinability of Ti-6Al-4V alloy. YSZ nano powder was coated on the tungsten carbide pin by using ESC technique. The coatings have been tested for wear and friction behavior by using a pin-on-disc tribological tester. The dry sliding wear test was performed on Titanium alloy (Ti-6Al-4V) disc and YSZ coated tungsten carbide (pin) at ambient atmosphere. The performance parameters like wear rate and temperature rise were considered upon performing the dry sliding test on Ti-6Al-4V alloy disc. The performance parameters were calculated by using coefficient of friction and frictional force values which were obtained from the pin on disc test. Substantial resistance to wear was achieved by the coating.

Scandia-and-Yttria-Stabilized Zirconia for Thermal Barriers

NASA Technical Reports Server (NTRS)

Mess, Derek

2003-01-01

yttria in suitable proportions has shown promise of being a superior thermal- barrier coating (TBC) material, relative to zirconia stabilized with yttria only. More specifically, a range of compositions in the zirconia/scandia/yttria material system has been found to afford increased resistance to deleterious phase transformations at temperatures high enough to cause deterioration of yttria-stabilized zirconia. Yttria-stabilized zirconia TBCs have been applied to metallic substrates in gas turbine and jet engines to protect the substrates against high operating temperatures. These coatings have porous and microcracked structures, which can accommodate strains induced by thermal-expansion mismatch and thermal shock. The longevity of such a coating depends upon yttria as a stabilizing additive that helps to maintain the zirconia in an yttria-rich, socalled non-transformable tetragonal crystallographic phase, thus preventing transformation to the monoclinic phase with an associated deleterious volume change. However, at a temperature greater than about 1,200 C, there is sufficient atomic mobility that the equilibrium, transformable zirconia phase is formed. Upon subsequent cooling, this phase transforms to the monoclinic phase, with an associated volume change that adversely affects the integrity of the coating. Recently, scandia was identified as a stabilizer that could be used instead of, or in addition to, yttria. Of particular interest are scandia-and-yttria-stabilized zirconia (SYSZ) compositions of about 6 mole percent scandia and 1 mole percent yttria, which have been found to exhibit remarkable phase stability at a temperature of 1,400 C in simple aging tests. Unfortunately, scandia is expensive, so that the problem becomes one of determining whether there are compositions with smaller proportions of scandia that afford the required high-temperature stability. In an attempt to solve this problem, experiments were performed on specimens made with reduced

Phase analysis of plasma-sprayed zirconia-yttria coatings

NASA Technical Reports Server (NTRS)

Shankar, N. R.; Berndt, C. C.; Herman, H.

1983-01-01

Phase analysis of plasma-sprayed 8 wt pct-yttria-stabilized zirconia (YSZ) thermal barrier coatings and powders was carried out by X-ray diffraction. Step scanning was used for increased peak resolution. Plasma spraying of the YSZ powder into water or onto a steel substrate to form a coating reduced the cubic and monoclinic phases with a simultaneous increase in the tetragonal phase. Heat treatment of the coating at 1150 C for 10 h in an Ar atmosphere increased the amount of cubic and monoclinic phases. The implications of these transformations on coating performance and integrity are discussed.

Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles.

PubMed

Pan, Yonghe; Gao, Yan; Kong, Dandan; Wang, Guodong; Hou, Jianbo; Hu, Shanwei; Pan, Haibin; Zhu, Junfa

2012-04-10

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures. © 2012 American Chemical Society

Microscopic observation of laser glazed yttria-stabilized zirconia coatings

NASA Astrophysics Data System (ADS)

Morks, M. F.; Berndt, C. C.; Durandet, Y.; Brandt, M.; Wang, J.

2010-08-01

Thermal barrier coatings (TBCs) are frequently used as insulation system for hot components in gas-turbine, combustors and power plant industries. The corrosive gases which come from combustion of low grade fuels can penetrate into the TBCs and reach the metallic components and bond coat and cause hot corrosion and erosion damage. Glazing the top coat by laser beam is advanced approach to seal TBCs surface. The laser beam has the advantage of forming a dense thin layer composed of micrograins. Plasma-sprayed yttria-stabilized zirconia (YSZ) coating was glazed with Nd-YAG laser at different operating conditions. The surface morphologies, before and after laser treatment, were investigated by scanning electron microscopy. Laser beam assisted the densification of the surface by remelting a thin layer of the exposed surface. The laser glazing converted the rough surface of TBCs into smooth micron-size grains with size of 2-9 μm and narrow grain boundaries. The glazed surfaces showed higher Vickers hardness compared to as-sprayed coatings. The results revealed that the hardness increases as the grain size decreases.

Atomistic modeling of La3+ doping segregation effect on nanocrystalline yttria-stabilized zirconia.

PubMed

Zhang, Shenli; Sha, Haoyan; Castro, Ricardo H R; Faller, Roland

2018-05-16

The effect of La3+ doping on the structure and ionic conductivity change in nanocrystalline yttria-stabilized zirconia (YSZ) was studied using a combination of Monte Carlo and molecular dynamics simulations. The simulation revealed the segregation of La3+ at eight tilt grain boundary (GB) structures and predicted an average grain boundary (GB) energy decrease of 0.25 J m-2, which is close to the experimental values reported in the literature. Cation stabilization was found to be the main reason for the GB energy decrease, and energy fluctuations near the grain boundary are smoothed out with La3+ segregation. Both dynamic and energetic analysis on the Σ13(510)/[001] GB structure revealed La3+ doping hinders O2- diffusion in the GB region, where the diffusion coefficient monotonically decreases with increasing La3+ doping concentration. The effect was attributed to the increase in the site-dependent migration barriers for O2- hopping caused by segregated La3+, which also leads to anisotropic diffusion at the GB.

Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

NASA Astrophysics Data System (ADS)

Francillon, Wesley

This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is

18O-tracer diffusion along nanoscaled Sc2O3/yttria stabilized zirconia (YSZ) multilayers: on the influence of strain.

PubMed

Aydin, Halit; Korte, Carsten; Janek, Jürgen

2013-06-01

The oxygen tracer diffusion coefficient describing transport along nano-/microscaled YSZ/Sc 2 O 3 multilayers as a function of the thick-ness of the ion-conducting YSZ layers has been measured by isotope exchange depth profiling (IEDP), using secondary ion mass spec-trometry (SIMS). The multilayer samples were prepared by pulsed laser deposition (PLD) on (0001) Al 2 O 3 single crystalline substrates. The values for the oxygen tracer diffusion coefficient were analyzed as a combination of contributions from bulk and interface contributions and compared with results from YSZ/Y 2 O 3 -multilayers with similar microstructure. Using the Nernst-Einstein equation as the relation between diffusivity and electrical conductivity we find very good agreement between conductivity and diffusion data, and we exclude substantial electronic conductivity in the multilayers. The effect of hetero-interface transport can be well explained by a simple interface strain model. As the multilayer samples consist of columnar film crystallites with a defined inter-face structure and texture, we also discuss the influence of this particular microstructure on the interfacial strain.

18O-tracer diffusion along nanoscaled Sc2O3/yttria stabilized zirconia (YSZ) multilayers: on the influence of strain

PubMed Central

Aydin, Halit; Korte, Carsten; Janek, Jürgen

2013-01-01

The oxygen tracer diffusion coefficient describing transport along nano-/microscaled YSZ/Sc2O3 multilayers as a function of the thick­ness of the ion-conducting YSZ layers has been measured by isotope exchange depth profiling (IEDP), using secondary ion mass spec­trometry (SIMS). The multilayer samples were prepared by pulsed laser deposition (PLD) on (0001) Al2O3 single crystalline substrates. The values for the oxygen tracer diffusion coefficient were analyzed as a combination of contributions from bulk and interface contributions and compared with results from YSZ/Y2O3-multilayers with similar microstructure. Using the Nernst–Einstein equation as the relation between diffusivity and electrical conductivity we find very good agreement between conductivity and diffusion data, and we exclude substantial electronic conductivity in the multilayers. The effect of hetero-interface transport can be well explained by a simple interface strain model. As the multilayer samples consist of columnar film crystallites with a defined inter­face structure and texture, we also discuss the influence of this particular microstructure on the interfacial strain. PMID:27877580

Radiation tolerance of nanocrystalline ceramics: insights from Yttria Stabilized Zirconia.

PubMed

Dey, Sanchita; Drazin, John W; Wang, Yongqiang; Valdez, James A; Holesinger, Terry G; Uberuaga, Blas P; Castro, Ricardo H R

2015-01-13

Materials for applications in hostile environments, such as nuclear reactors or radioactive waste immobilization, require extremely high resistance to radiation damage, such as resistance to amorphization or volume swelling. Nanocrystalline materials have been reported to present exceptionally high radiation-tolerance to amorphization. In principle, grain boundaries that are prevalent in nanomaterials could act as sinks for point-defects, enhancing defect recombination. In this paper we present evidence for this mechanism in nanograined Yttria Stabilized Zirconia (YSZ), associated with the observation that the concentration of defects after irradiation using heavy ions (Kr(+), 400 keV) is inversely proportional to the grain size. HAADF images suggest the short migration distances in nanograined YSZ allow radiation induced interstitials to reach the grain boundaries on the irradiation time scale, leaving behind only vacancy clusters distributed within the grain. Because of the relatively low temperature of the irradiations and the fact that interstitials diffuse thermally more slowly than vacancies, this result indicates that the interstitials must reach the boundaries directly in the collision cascade, consistent with previous simulation results. Concomitant radiation-induced grain growth was observed which, as a consequence of the non-uniform implantation, caused cracking of the nano-samples induced by local stresses at the irradiated/non-irradiated interfaces.

Radiation Tolerance of Nanocrystalline Ceramics: Insights from Yttria Stabilized Zirconia

PubMed Central

Dey, Sanchita; Drazin, John W.; Wang, Yongqiang; Valdez, James A.; Holesinger, Terry G.; Uberuaga, Blas P.; Castro, Ricardo H. R.

2015-01-01

Materials for applications in hostile environments, such as nuclear reactors or radioactive waste immobilization, require extremely high resistance to radiation damage, such as resistance to amorphization or volume swelling. Nanocrystalline materials have been reported to present exceptionally high radiation-tolerance to amorphization. In principle, grain boundaries that are prevalent in nanomaterials could act as sinks for point-defects, enhancing defect recombination. In this paper we present evidence for this mechanism in nanograined Yttria Stabilized Zirconia (YSZ), associated with the observation that the concentration of defects after irradiation using heavy ions (Kr+, 400 keV) is inversely proportional to the grain size. HAADF images suggest the short migration distances in nanograined YSZ allow radiation induced interstitials to reach the grain boundaries on the irradiation time scale, leaving behind only vacancy clusters distributed within the grain. Because of the relatively low temperature of the irradiations and the fact that interstitials diffuse thermally more slowly than vacancies, this result indicates that the interstitials must reach the boundaries directly in the collision cascade, consistent with previous simulation results. Concomitant radiation-induced grain growth was observed which, as a consequence of the non-uniform implantation, caused cracking of the nano-samples induced by local stresses at the irradiated/non-irradiated interfaces. PMID:25582769

Radiation tolerance of nanocrystalline ceramics: Insights from yttria stabilized zirconia

DOE PAGES

Dey, Sanchita; Drazin, John W.; Wang, Yongqiang; ...

2015-01-13

Materials for applications in hostile environments, such as nuclear reactors or radioactive waste immobilization, require extremely high resistance to radiation damage, such as resistance to amorphization or volume swelling. Nanocrystalline materials have been reported to present exceptionally high radiation-tolerance to amorphization. In principle, grain boundaries that are prevalent in nanomaterials could act as sinks for point-defects, enhancing defect recombination. In this paper we present evidence for this mechanism in nanograined Yttria Stabilized Zirconia (YSZ), associated with the observation that the concentration of defects after irradiation using heavy ions (Kr⁺, 400 keV) is inversely proportional to the grain size. HAADF imagesmore » suggest the short migration distances in nanograined YSZ allow radiation induced interstitials to reach the grain boundaries on the irradiation time scale, leaving behind only vacancy clusters distributed within the grain. Because of the relatively low temperature of the irradiations and the fact that interstitials diffuse thermally more slowly than vacancies, this result indicates that the interstitials must reach the boundaries directly in the collision cascade, consistent with previous simulation results. Concomitant radiation-induced grain growth was observed which, as a consequence of the non-uniform implantation, caused cracking of the nano-samples induced by local stresses at the irradiated/non-irradiated interfaces.« less

Physical vapor deposition and metalorganic chemical vapor deposition of yttria-stabilized zirconia thin films

NASA Astrophysics Data System (ADS)

Kaufman, David Y.

Two vapor deposition techniques, dual magnetron oblique sputtering (DMOS) and metalorganic chemical vapor deposition (MOCVD), have been developed to produce yttria-stabilized zirconia (YSZ) films with unique microstructures. In particular, biaxially textured thin films on amorphous substrates and dense thin films on porous substrates have been fabricated by DMOS and MOCVD, respectively. DMOS YSZ thin films were deposited by reactive sputtering onto Si (native oxide surface) substrates positioned equidistant between two magnetron sources such that the fluxes arrived at oblique angles with respect to the substrate normal. Incident fluxes from two complimentary oblique directions were necessary for the development of biaxial texture. The films displayed a strong [001] out-of-plane orientation with the <110> direction in the film aligned with the incident flux. Biaxial texture improved with increasing oblique angle and film thickness, and was stronger for films deposited with Ne than with Ar. The films displayed a columnar microstructure with grain bundling perpendicular to the projected flux direction, the degree of which increased with oblique angle and thickness. The texture decreased by sputtering at pressures at which the flux of sputtered atoms was thermalized. These results suggested that grain alignment is due to directed impingement of both sputtered atoms and reflected energetic neutrals. The best texture, a {111} phi FWHM of 23°, was obtained in a 4.8 mum thick film deposited at an oblique angle of 56°. MOCVD YSZ thin films were deposited in a vertical cold-wall reactor using Zr(tmhd)4 and Y(tmhd)3 precursors. Fully stabilized YSZ films with 9 mol% could be deposited by controlling the bubbler temperatures. YSZ films on Si substrates displayed a transition at 525°C from surface kinetic limited growth, with an activation energy of 5.5 kJ/mole, to mass transport limited growth. Modifying the reactor by lowering the inlet height and introducing an Ar baffle

Effect of far-field stresses and residual stresses incorporation in predicting fracture toughness of carbon nanotube reinforced yttria stabilized zirconia

NASA Astrophysics Data System (ADS)

Mahato, Neelima; Nisar, Ambreen; Mohapatra, Pratyasha; Rawat, Siddharth; Ariharan, S.; Balani, Kantesh

2017-10-01

Yttria-stabilized zirconia (YSZ) is a potential thermal insulating ceramic for high temperature applications (>1000 °C). YSZ reinforced with multi-walled carbon nanotubes (MWNTs) was processed via spark plasma sintering to produce dense, crack-free homogeneous sample and avoid any degradation of MWNTs when sintered using conventional routes. Despite porosity, the addition of MWNT has a profound effect in improving the damage tolerance of YSZ by allowing the retention of tetragonal phase. However, at some instances, the crack lengths in the MWNT reinforced YSZ matrices have been found to be longer than the standalone counterparts. Therefore, it becomes inappropriate to apply Anstis equation to calculate fracture toughness values. In this regard, a combined analytical cum numerical method is used to estimate the theoretical fracture toughness and quantitatively analyze the mechanics of matrix cracking in the reinforced composite matrices incorporating the effects of various factors (such as far-field stresses, volume fraction of MWNTs, change in the modulus and Poisson's ratio values along with the increase in porosity, and bridging and phase transformation mechanism) affecting the fracture toughness of YSZ-MWNT composites. The results suggest that the incorporation of far-field stresses cannot be ignored in estimating the theoretical fracture toughness of YSZ-MWNT composites.

Effects of sputtering mode on the microstructure and ionic conductivity of yttria-stabilized zirconia films

NASA Astrophysics Data System (ADS)

Yeh, Tsung-Her; Lin, Ruei-De; Cherng, Bo-Ruei; Cherng, Jyh-Shiarn

2018-05-01

The microstructure and ionic conductivity of reactively sputtered yttria-stabilized zirconia (YSZ) films are systematically studied. Those films were reactively sputtered in various sputtering modes using a closed-loop controlled system with plasma emission monitoring. A transition-mode sputtering corresponding to 45% of target poisoning produces a microstructure with ultrafine crystallites embedded in an amorphous matrix, which undergoes an abnormal grain growth upon annealing at 800 °C. At 500 °C, the measured ionic conductivity of this annealed film is higher, by about a half order of magnitude, than those of its poisoned-mode counterparts, which are in turn significantly higher than that of the YSZ bulk by about two orders of magnitude. The abnormally-grown ultra-large grain size of the film deposited in the transition mode and then annealed is believed to be responsible for the former comparison due to the suppression of the grain boundary blocking effect, while the latter comparison can be attributed to the interface effect.

Manufacturing of Composite Coatings by Atmospheric Plasma Spraying Using Different Feed-Stock Materials as YSZ and MoSi2

NASA Astrophysics Data System (ADS)

Koch, D.; Mauer, G.; Vaßen, R.

2017-04-01

Yttria-stabilized zirconia (YSZ) is the state-of-the-art material for the top coat of thermal barrier coatings. To increase the efficiency and lifetime of gas turbines, the integration of MoSi2 as a healing material was proposed. A new method of manufacture was explored in order to enable the spraying of a homogeneous mixed layer of YSZ and MoSi2. As the chemical and physical properties of these powders are very different, they require contrasting process conditions. Due to the evaporation of Si from MoSi2 at spraying conditions suitable for YSZ, more moderate conditions and a shorter time of flight are required for depositing MoSi2. At the same time, the spraying conditions still need to be sufficient for melting the YSZ particles in order to produce a coating. To obtain a homogeneous mixture, both conditions can be matched using an injection system that allows powder injection at two different locations of the plasma jet. Two-color pyrometry during flight (DPV-2000, Tecnar) was used to monitor the actual particle temperature. By optimizing the injection point for the MoSi2, a mixed coating was obtained without decomposition of the MoSi2, which has been analyzed by means of XRD and SEM.

Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

NASA Astrophysics Data System (ADS)

Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

2018-03-01

Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

3D Microstructure Effects in Ni-YSZ Anodes: Prediction of Effective Transport Properties and Optimization of Redox Stability

PubMed Central

Pecho, Omar M.; Stenzel, Ole; Iwanschitz, Boris; Gasser, Philippe; Neumann, Matthias; Schmidt, Volker; Prestat, Michel; Hocker, Thomas; Flatt, Robert J.; Holzer, Lorenz

2015-01-01

This study investigates the influence of microstructure on the effective ionic and electrical conductivities of Ni-YSZ (yttria-stabilized zirconia) anodes. Fine, medium, and coarse microstructures are exposed to redox cycling at 950 °C. FIB (focused ion beam)-tomography and image analysis are used to quantify the effective (connected) volume fraction (Φeff), constriction factor (β), and tortuosity (τ). The effective conductivity (σeff) is described as the product of intrinsic conductivity (σ0) and the so-called microstructure-factor (M): σeff = σ0 × M. Two different methods are used to evaluate the M-factor: (1) by prediction using a recently established relationship, Mpred = εβ0.36/τ5.17, and (2) by numerical simulation that provides conductivity, from which the simulated M-factor can be deduced (Msim). Both methods give complementary and consistent information about the effective transport properties and the redox degradation mechanism. The initial microstructure has a strong influence on effective conductivities and their degradation. Finer anodes have higher initial conductivities but undergo more intensive Ni coarsening. Coarser anodes have a more stable Ni phase but exhibit lower YSZ stability due to lower sintering activity. Consequently, in order to improve redox stability, it is proposed to use mixtures of fine and coarse powders in different proportions for functional anode and current collector layers. PMID:28793523

Evidence of yttrium silicate inclusions in YSZ-porcelain veneers.

PubMed

Stoner, Brian R; Griggs, Jason A; Neidigh, John; Piascik, Jeffrey R

2014-04-01

This report introduces the discovery of crystalline defects that can form in the porcelain veneering layer when in contact with yttria-stabilized zirconia (YSZ). The focus was on dental prostheses and understanding the defects that form in the YSZ/porcelain system; however the data reported herein may have broader implications toward the use and stability of YSZ-based ceramics in general. Specimens were cut from fully sintered YSZ plates and veneering porcelain was applied (<1 mm thick) to one surface and fired under manufacturer's recommended protocol. Scanning electron microscopy (SEM) with integrated electron dispersive X-ray (EDAX) was used for microstructural and elemental analysis. EDAX, for chemical analysis and transmission electron diffraction (TED) for structural analysis were both performed in the transmission electron microscope (TEM). Additionally, in order to spatially resolve Y-rich precipitates, micro-CT scans were conducted at varying depths within the porcelain veneer. Local EDAX (SEM) was performed in the regions of visible inclusions and showed significant increases in yttrium concentration. TEM specimens also showed apparent inclusions in the porcelain and selected area electron diffraction was performed on these regions and found the inclusions to be crystalline and identified as either yttrium-silicate (Y2 SiO5 ) or yttrium-disilicate (Y2 Si2 O7 ). Micro-CT data showed that yttrium-silicate precipitates were distributed throughout the thickness of the porcelain veneer. Future studies are needed to determine whether many of the premature failures associated with this materials system may be the result of crystalline flaws that form as a result of high temperature yttrium diffusion near the surfaces of YSZ. © 2013 Wiley Periodicals, Inc.

Impact of yttria stabilized zirconia nanoinclusions on the thermal conductivity of n-type Si80Ge20 alloys prepared by spark plasma sintering

NASA Astrophysics Data System (ADS)

Lahwal, Ali; Bhattacharya, S.; He, Jian; Wu, Di; Peterson, A.; Poon, S. J.; Williams, L.; Dehkordi, A. Mehdizadeh; Tritt, T. M.

2015-04-01

Nanocomposites have become a new paradigm for thermoelectric research in recent years and have resulted in the reduction of thermal conductivity via the nano-inclusion and grain boundary scattering. In this work, we report the preparation and thermoelectric study of SiGe-yttria stabilized zirconia (YSZ) nanocomposites prepared by Spark Plasma Sintering (SPS). We experimentally investigated the reduction of lattice thermal conductivity (κL) in the temperature range (30-800 K) of n-type Si80Ge20P2 alloys with the incorporation of YSZ nanoparticles (20-40 nm diameter) into the Si-Ge matrix. These samples synthesized by using the SPS technique were found to have densities > 95% of the theoretical density. The thermal conductivity, at both low and high temperatures, was measured by steady state and laser flash techniques, respectively. At room temperature, we observed approximately a 50% reduction in the lattice thermal conductivity as result of adding 10% YSZ by volume to the Si80Ge20P2 host matrix. A phenomenological model developed by Callaway was used to corroborate both the temperature dependence and reduction of κ L over the measured temperature range (30-800 K) of both Si80Ge20P2 and Si80Ge20P2 + YSZ samples. The observed κL is discussed and interpreted in terms of various phonon scattering mechanisms such as alloy disorder, the Umklapp phonon scattering, and boundary scattering. In addition, a contribution from the phonon scattering by YSZ nanoparticles was further included to account for the κL of Si80Ge20P2 + YSZ sample. The theoretical calculations are in reasonably good agreement with the experimental results for both the Si80Ge20P2 and Si80Ge20P2 + YSZ alloys.

Internal Nano Voids in Yttria-Stabilised Zirconia (YSZ) Powder

PubMed Central

Barad, Chen; Shekel, Gal; Shandalov, Michael; Hayun, Hagay; Kimmel, Giora; Shamir, Dror; Gelbstein, Yaniv

2017-01-01

Porous yttria-stabilised zirconia ceramics have been gaining popularity throughout the years in various fields, such as energy, environment, medicine, etc. Although yttria-stabilised zirconia is a well-studied material, voided yttria-stabilised zirconia powder particles have not been demonstrated yet, and might play an important role in future technology developments. A sol-gel synthesis accompanied by a freeze-drying process is currently being proposed as a method of obtaining sponge-like nano morphology of embedded faceted voids inside yttria-stabilised zirconia particles. The results rely on a freeze-drying stage as an effective and simple method for generating nano-voided yttria-stabilised zirconia particles without the use of template-assisted additives. PMID:29258227

Internal Nano Voids in Yttria-Stabilised Zirconia (YSZ) Powder.

PubMed

Barad, Chen; Shekel, Gal; Shandalov, Michael; Hayun, Hagay; Kimmel, Giora; Shamir, Dror; Gelbstein, Yaniv

2017-12-18

Porous yttria-stabilised zirconia ceramics have been gaining popularity throughout the years in various fields, such as energy, environment, medicine, etc. Although yttria-stabilised zirconia is a well-studied material, voided yttria-stabilised zirconia powder particles have not been demonstrated yet, and might play an important role in future technology developments. A sol-gel synthesis accompanied by a freeze-drying process is currently being proposed as a method of obtaining sponge-like nano morphology of embedded faceted voids inside yttria-stabilised zirconia particles. The results rely on a freeze-drying stage as an effective and simple method for generating nano-voided yttria-stabilised zirconia particles without the use of template-assisted additives.

Ageing and thermal recovery of paramagnetic centers induced by electron irradiation in yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Costantini, J. M.; Beuneu, F.

We have used electron spin resonance spectroscopy to study the defects induced in yttria-stabilized zirconia (YSZ) single crystals by 2.5-MeV electron irradiations. Two paramagnetic centers are produced: the first one with an axial <111> symmetry is similar to the trigonal Zr3+ electron center (T center) found after X-ray irradiation or thermo-chemical reduction, whereas the second one is a new oxygen hole center with an axial <100> symmetry different from the orthorhombic O- center induced by X-ray irradiation. At a fluence around 10(18) e/cm(2) , both centers are bleached out near 600 K, like the corresponding X-ray induced defects. At a fluence around 10(19) e/cm(2) , defects are much more stable, since complete thermal bleaching occurs near 1000 K. Accordingly, ageing of as-irradiated samples shows that high-dose defects at more stable than the low-dose ones.

Synthesis of nanocrystalline Ni/Ce-YSZ powder via a polymerization route

NASA Astrophysics Data System (ADS)

Abolghasemi, Z.; Tamizifar, M.; Arzani, K.; Nemati, A.; Khanfekr, A.; Bolandi, M.

2013-08-01

Pechini process was used for preparation of three kinds of nanocrystalline powders of yttria-stabilized zirconia (YSZ): doped with 1.5 mol% nickel oxide, doped with 15 mol% ceria, and doped with 1.5 mol% nickel oxide plus 15 mol% ceria. Zirconium chloride, yttrium nitrate, cerium nitrate, nickel nitrate, citric acid and ethylene glycol were polymerized at 80 °C to produce a gel. XRD, SEM and TEM analyses were used to investigate the crystalline phases and microstructures of obtained compounds. The results of XRD revealed the formation of nanocrystalline powder at 900 °C. Morphology of the powder calcined at 900 °C, examined with a scanning electron microscope, showed that the presence of nickel and cerium inhibited the grain growth in the system. The average crystallite size of the material doped with nickel oxide (9.33 nm) was bigger than the one doped with cerium oxide (9.29 nm), while the YSZ doping with the two oxides simultaneously promoted the grain growth with crystallite size of 11.37 nm. Yttria-stabilized zirconia powder with a mean crystallite size of 9.997 nm was prepared successfully by this method.

Determination of Scattering and Absorption Coefficients for Plasma-Sprayed Yttria-Stabilized Zirconia Thermal Barrier Coatings at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Eldridge, Jeffrey I.; Spuckler, Charles M.; Markham, James R.

2009-01-01

The temperature dependence of the scattering and absorption coefficients for a set of freestanding plasma-sprayed 8 wt% yttria-stabilized zirconia (8YSZ) thermal barrier coatings (TBCs) was determined at temperatures up to 1360 C in a wavelength range from 1.2 micrometers up to the 8YSZ absorption edge. The scattering and absorption coefficients were determined by fitting the directional-hemispherical reflectance and transmittance values calculated by a four-flux Kubelka Munk method to the experimentally measured hemispherical-directional reflectance and transmittance values obtained for five 8YSZ thicknesses. The scattering coefficient exhibited a continuous decrease with increasing wavelength and showed no significant temperature dependence. The scattering is primarily attributed to the relatively temperature-insensitive refractive index mismatch between the 8YSZ and its internal voids. The absorption coefficient was very low (less than 1 per centimeter) at wavelengths between 2 micrometers and the absorption edge and showed a definite temperature dependence that consisted of a shift of the absorption edge to shorter wavelengths and an increase in the weak absorption below the absorption edge with increasing temperature. The shift in the absorption edge with temperature is attributed to strongly temperature-dependent multiphonon absorption. While TBC hemispherical transmittance beyond the absorption edge can be predicted by a simple exponential decrease with thickness, below the absorption edge, typical TBC thicknesses are well below the thickness range where a simple exponential decrease in hemispherical transmittance with TBC thickness is expected. [Correction added after online publication August 11, 2009: "edge to a shorter wavelengths" has been updated as edge to shorter wavelengths."

Development and evaluation of suspension plasma sprayed yttria stabilized zirconia coatings as thermal barriers

NASA Astrophysics Data System (ADS)

van Every, Kent J.

The insulating effects from thermal barrier coatings (TBCs) in gas turbine engines allow for increased operational efficiencies and longer service lifetimes. Consequently, improving TBCs can lead to enhanced gas turbine engine performance. This study was conducted to investigate if yttria-stabilized zirconia (YSZ) coatings, the standard industrial choice for TBCs, produced from nano-sized powder could provide better thermal insulation than current commericial YSZ coatings generated using micron-sized powders. The coatings for this research were made via the recently developed suspension plasma spraying (SPS) process. With SPS, powders are suspended in a solvent containing dispersing agents; the suspension is then injected directly into a plasma flow that evaporates the solvent and melts the powder while transporting it to the substrate. Although related to the industrial TBC production method of air plasma spraying (APS), SPS has two important differences---the ability to spray sub-micron diameter ceramic particles, and the ability to alloy the particles with chemicals dissolved in the solvent. These aspects of SPS were employed to generate a series of coatings from suspensions containing ˜100 nm diameter YSZ powder particles, some of which were alloyed with neodymium and ytterbium ions from the solvent. The SPS coatings contained columnar structures not observed in APS TBCs; thus, a theory was developed to explain the formation of these features. The thermal conductivity of the coatings was tested to evaluate the effects of these unique microstructures and the effects of the alloying process. The results for samples in the as-sprayed and heat-treated conditions were compared to conventional YSZ TBCs. This comparison showed that, relative to APS YSZ coatings, the unalloyed SPS samples typically exhibited higher as-sprayed and lower heat-treated thermal conductivities. All thermal conductivity values for the alloyed samples were lower than conventional YSZ TBCs

Effect of Ni content on the morphological evolution of Ni-YSZ solid oxide fuel cell electrodes

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

Chen-Wiegart, Yu-chen Karen; Kennouche, David; Scott Cronin, J.

2016-02-22

The coarsening of Ni in Ni–yttria-stabilized zirconia (YSZ) anodes is a potential cause of long term solid oxide fuel cells (SOFC) performance degradation. The specifics of the Ni-YSZ structure—including Ni/YSZ ratio, porosity, and particle size distributions—are normally selected to minimize anode polarization resistance, but they also impact long-term stability. A better understanding of how these factors influence long-term stability is important for designing more durable anodes. The effect of structural details, e.g., Ni-YSZ ratio, on Ni coarsening has not been quantified. Furthermore, prior measurements have been done by comparing evolved structures with control samples, such that sample-to-sample variations introduce errors.more » Here, we report a four dimensional (three spatial dimensions and time) study of Ni coarsening in Ni-YSZ anode functional layers with different Ni/YSZ ratios, using synchrotron x-ray nano-tomography. The continuous structural evolution was observed and analyzed at sub-100 nm resolution. It is shown quantitatively that increasing the Ni/YSZ ratio increases the Ni coarsening rate. This is due to both increased pore volume and a decrease in the YSZ volume fraction, such that there is more free volume and a less obtrusive YSZ network, both of which allow greater Ni coarsening. The results are shown to be in good agreement with a power-law coarsening model. The finding is critical for informing the design of SOFC electrode microstructures that limit coarsening and performance degradation.« less

Effect of Ni content on the morphological evolution of Ni-YSZ solid oxide fuel cell electrodes

NASA Astrophysics Data System (ADS)

Chen-Wiegart, Yu-chen Karen; Kennouche, David; Scott Cronin, J.; Barnett, Scott A.; Wang, Jun

2016-02-01

The coarsening of Ni in Ni-yttria-stabilized zirconia (YSZ) anodes is a potential cause of long term solid oxide fuel cells (SOFC) performance degradation. The specifics of the Ni-YSZ structure—including Ni/YSZ ratio, porosity, and particle size distributions—are normally selected to minimize anode polarization resistance, but they also impact long-term stability. A better understanding of how these factors influence long-term stability is important for designing more durable anodes. The effect of structural details, e.g., Ni-YSZ ratio, on Ni coarsening has not been quantified. Furthermore, prior measurements have been done by comparing evolved structures with control samples, such that sample-to-sample variations introduce errors. Here, we report a four dimensional (three spatial dimensions and time) study of Ni coarsening in Ni-YSZ anode functional layers with different Ni/YSZ ratios, using synchrotron x-ray nano-tomography. The continuous structural evolution was observed and analyzed at sub-100 nm resolution. It is shown quantitatively that increasing the Ni/YSZ ratio increases the Ni coarsening rate. This is due to both increased pore volume and a decrease in the YSZ volume fraction, such that there is more free volume and a less obtrusive YSZ network, both of which allow greater Ni coarsening. The results are shown to be in good agreement with a power-law coarsening model. The finding is critical for informing the design of SOFC electrode microstructures that limit coarsening and performance degradation.

Study of Laser Drilled Hole Quality of Yttria Stabilized Zirconia

NASA Astrophysics Data System (ADS)

Saini, Surendra K.; Dubey, Avanish K.; Pant, Piyush; Upadhyay, B. N.; Choubey, A.

2017-09-01

The Yttria Stabilized Zirconia ceramic is extensively used in aerospace, automotives, medical and microelectronics industries. These applications demand manufacturing of different macro and micro features with close tolerances in this material. To make miniature holes with accurate dimensions in advanced ceramics such as Yttria Stabilized Zirconia is very difficult due to its tailored attributes such as high toughness, hardness, strength, resistance to wear, corrosion and temperature. Due to inherent characteristics of laser drilling, researchers are working to fulfill the requirement of creation of micro holes in advanced ceramics. The present research investigates the laser drilling of 2 mm thick Yttria Stabilized Zirconia with the aim to achieve good micro holes with reduced geometrical inaccuracies and improved hole quality. The results show that multiple quality response comprising hole circularity, hole taper and recast layer thickness has been improved at optimally selected process parameters.

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

DOE PAGES

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

2015-07-28

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

High performance novel gadolinium doped ceria/yttria stabilized zirconia/nickel layered and hybrid thin film anodes for application in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Garcia-Garcia, F. J.; Beltrán, A. M.; Yubero, F.; González-Elipe, A. R.; Lambert, R. M.

2017-09-01

Magnetron sputtering under oblique angle deposition was used to produce Ni-containing ultra thin film anodes comprising alternating layers of gadolinium doped ceria (GDC) and yttria stabilized zirconia (YSZ) of either 200 nm or 1000 nm thickness. The evolution of film structure from initial deposition, through calcination and final reduction was examined by XRD, SEM, TEM and TOF-SIMS. After subsequent fuel cell usage, the porous columnar architecture of the two-component layered thin film anodes was maintained and their resistance to delamination from the underlying YSZ electrolyte was superior to that of corresponding single component Ni-YSZ and Ni-GDC thin films. Moreover, the fuel cell performance of the 200 nm layered anodes compared favorably with conventional commercially available thick anodes. The observed dependence of fuel cell performance on individual layer thicknesses prompted study of equivalent but more easily fabricated hybrid anodes consisting of simultaneously deposited Ni-GDC and Ni-YSZ, which procedure resulted in exceptionally intimate mixing and interaction of the components. The hybrids exhibited very unusual and favorable Isbnd V characteristics, along with exceptionally high power densities at high currents. Their discovery is the principal contribution of the present work.

Development of graded Ni-YSZ composite coating on Alloy 690 by Pulsed Laser Deposition technique to reduce hazardous metallic nuclear waste inventory.

PubMed

Sengupta, Pranesh; Rogalla, Detlef; Becker, Hans Werner; Dey, Gautam Kumar; Chakraborty, Sumit

2011-08-15

Alloy 690 based 'nuclear waste vitrification furnace' components degrade prematurely due to molten glass-alloy interactions at high temperatures and thereby increase the volume of metallic nuclear waste. In order to reduce the waste inventory, compositionally graded Ni-YSZ (Y(2)O(3) stabilized ZrO(2)) composite coating has been developed on Alloy 690 using Pulsed Laser Deposition technique. Five different thin-films starting with Ni80YSZ20 (Ni 80 wt%+YSZ 20 wt%), through Ni60YSZ40 (Ni 60 wt%+YSZ 40 wt%), Ni40YSZ60 (Ni 40 wt%+YSZ 60 wt%), Ni20YSZ80 (Ni 20 wt%+YSZ 80 wt%) and Ni0YSZ100 (Ni 0 wt%+YSZ 100 wt%), were deposited successively on Alloy 690 coupons. Detailed analyses of the thin-films identify them as homogeneous, uniform, pore free and crystalline in nature. A comparative study of coated and uncoated Alloy 690 coupons, exposed to sodium borosilicate melt at 1000°C for 1-6h suggests that the graded composite coating could substantially reduced the chemical interactions between Alloy 690 and borosilicate melt. Copyright © 2011 Elsevier B.V. All rights reserved.

Examination of charge transfer in Au/YSZ for high-temperature optical gas sensing

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

Baltrus, John P.; Ohodnicki, Paul R.

2014-01-01

Au-nanoparticle incorporated oxide thin film materials demonstrate significant promise as functionalsensor materials for high temperature optical gas sensing in severe environments relevant for fossil andnuclear based power generation. The Au/yttria-stabilized zirconia (YSZ) system has been extensivelystudied in the literature and serves as a model system for fundamental investigations that seek to betterunderstand the mechanistic origin of the plasmonic gas sensing response. In this work, X-ray photoelec-tron spectroscopy techniques are applied to Au/YSZ films in an attempt to provide further experimentalevidence for a proposed sensing mechanism involving a change in free carrier density of Au nanoparticles due to charge transfer.

Effect of Ni content on the morphological evolution of Ni-YSZ solid oxide fuel cell electrodes

DOE PAGES

Chen-Wiegart, Yu-chen Karen; Kennouche, David; Scott Cronin, J.; ...

2016-02-25

The coarsening of Ni in Ni–yttria-stabilized zirconia (YSZ) anodes is a potential cause of long term solid oxide fuel cells (SOFC) performance degradation. The specifics of the Ni-YSZ structure—including Ni/YSZ ratio, porosity, and particle size distributions—are normally selected to minimize anode polarization resistance, but they also impact long-term stability. A better understanding of how these factors influence long-term stability is important for designing more durable anodes. The effect of structural details, e.g., Ni-YSZ ratio, on Ni coarsening has not been quantified. Furthermore, prior measurements have been done by comparing evolved structures with control samples, such that sample-to-sample variations introduce errors.more » Here in this paper, we report a four dimensional (three spatial dimensions and time) study of Ni coarsening in Ni-YSZ anode functional layers with different Ni/YSZ ratios, using synchrotron x-ray nano-tomography. The continuous structural evolution was observed and analyzed at sub-100 nm resolution. It is shown quantitatively that increasing the Ni/YSZ ratio increases the Ni coarsening rate. This is due to both increased pore volume and a decrease in the YSZ volume fraction, such that there is more free volume and a less obtrusive YSZ network, both of which allow greater Ni coarsening. The results are shown to be in good agreement with a power-law coarsening model. In conclusion, the finding is critical for informing the design of SOFC electrode microstructures that limit coarsening and performance degradation.« less

Effect of Ni content on the morphological evolution of Ni-YSZ solid oxide fuel cell electrodes

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

Chen-Wiegart, Yu-chen Karen; Kennouche, David; Scott Cronin, J.

The coarsening of Ni in Ni–yttria-stabilized zirconia (YSZ) anodes is a potential cause of long term solid oxide fuel cells (SOFC) performance degradation. The specifics of the Ni-YSZ structure—including Ni/YSZ ratio, porosity, and particle size distributions—are normally selected to minimize anode polarization resistance, but they also impact long-term stability. A better understanding of how these factors influence long-term stability is important for designing more durable anodes. The effect of structural details, e.g., Ni-YSZ ratio, on Ni coarsening has not been quantified. Furthermore, prior measurements have been done by comparing evolved structures with control samples, such that sample-to-sample variations introduce errors.more » Here in this paper, we report a four dimensional (three spatial dimensions and time) study of Ni coarsening in Ni-YSZ anode functional layers with different Ni/YSZ ratios, using synchrotron x-ray nano-tomography. The continuous structural evolution was observed and analyzed at sub-100 nm resolution. It is shown quantitatively that increasing the Ni/YSZ ratio increases the Ni coarsening rate. This is due to both increased pore volume and a decrease in the YSZ volume fraction, such that there is more free volume and a less obtrusive YSZ network, both of which allow greater Ni coarsening. The results are shown to be in good agreement with a power-law coarsening model. In conclusion, the finding is critical for informing the design of SOFC electrode microstructures that limit coarsening and performance degradation.« less

An Investigation of LSF-YSZ Conductive Scaffolds for Infiltrated SOFC Cathodes

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

Cheng, Yuan; Oh, Tae-Sik; Wilson, Rachel

Porous composites of Sr-doped LaFeO 3 (LSF) and yttria-stabilized zirconia (YSZ) were investigated as conductive scaffolds for infiltrated SOFC cathodes with the goal of producing scaffolds for which only a few perovskite infiltration steps are required to achieve sufficient conductivity. While no new phases form when LSF-YSZ composites are calcined to 1623 K, shifts in the lattice parameters indicate Zr can enter the perovskite phase. Measurements on dense, LSF-YSZ composites show that the level of Zr doping depends on the Sr:La ratio. Because conductivity of undoped LSF increases with Sr content while both the ionic and electronic conductivities of Zr-dopedmore » LSF decrease with the level of Zr in the perovskite phase, there is an optimum initial Sr content corresponding to La 0.9Sr 0.1FeO 3 (LSF91). Although scaffolds made with 100% LSF had a higher conductivity than scaffolds made with 50:50 LSF-YSZ mixtures, the 50:50 mixture provides the optimal interfacial structure with the electrolyte and sufficient conductivity, providing the best cathode performance upon infiltration of La 0.6Sr 0.4Co 0.2Fe 0.8O 3 (LSCF).« less

An Investigation of LSF-YSZ Conductive Scaffolds for Infiltrated SOFC Cathodes

DOE PAGES

Cheng, Yuan; Oh, Tae-Sik; Wilson, Rachel; ...

2017-03-24

Porous composites of Sr-doped LaFeO 3 (LSF) and yttria-stabilized zirconia (YSZ) were investigated as conductive scaffolds for infiltrated SOFC cathodes with the goal of producing scaffolds for which only a few perovskite infiltration steps are required to achieve sufficient conductivity. While no new phases form when LSF-YSZ composites are calcined to 1623 K, shifts in the lattice parameters indicate Zr can enter the perovskite phase. Measurements on dense, LSF-YSZ composites show that the level of Zr doping depends on the Sr:La ratio. Because conductivity of undoped LSF increases with Sr content while both the ionic and electronic conductivities of Zr-dopedmore » LSF decrease with the level of Zr in the perovskite phase, there is an optimum initial Sr content corresponding to La 0.9Sr 0.1FeO 3 (LSF91). Although scaffolds made with 100% LSF had a higher conductivity than scaffolds made with 50:50 LSF-YSZ mixtures, the 50:50 mixture provides the optimal interfacial structure with the electrolyte and sufficient conductivity, providing the best cathode performance upon infiltration of La 0.6Sr 0.4Co 0.2Fe 0.8O 3 (LSCF).« less

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.

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.

Thickness determination of large-area films of yttria-stabilized zirconia produced by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Pryds, N.; Toftmann, B.; Bilde-Sørensen, J. B.; Schou, J.; Linderoth, S.

2006-04-01

Films of yttria-stabilized zirconia (YSZ) on a polished silicon substrate of diameter up to 125 mm have been produced in a large-area pulsed laser deposition (PLD) setup under typical PLD conditions. The film thickness over the full film area has been determined by energy-dispersive X-ray spectrometry in a scanning electron microscope (SEM) with use of a method similar to one described by Bishop and Poole. The attenuation of the electron-induced X-rays from the Si wafer by the film was monitored at a number of points along a diameter and the thickness was determined by Monte Carlo simulations of the attenuation for various values of film thickness with the program CASINO. These results have been compared with direct measurements in the SEM of the film thickness on a cross-section on one of the wafers. The results of these measurements demonstrate the ability of this technique to accurately determine the thickness of a large film, i.e. up to diameters of 125 mm, in a relatively short time, without destroying the substrate, without the need of a standard sample and without the need of a flat substrate. We have also demonstrated that by controlling the deposition parameters large-area YSZ films with uniform thickness can be produced.

Preparation and Characterization of Anode-Supported YSZ Thin Film Electrolyte by Co-Tape Casting and Co-Sintering Process

NASA Astrophysics Data System (ADS)

Liu, Q. L.; Fu, C. J.; Chan, S. H.; Pasciak, G.

2011-06-01

In this study, a co-tape casting and co-sintering process has been developed to prepare yttria-stabilized zirconia (YSZ) electrolyte films supported on Ni-YSZ anode substrates in order to substantially reduce the fabrication cost of solid oxide fuel cells (SOFC). Through proper control of the process, the anode/electrolyte bilayer structures with a size of 7.8cm × 7.8cm were achieved with good flatness. Scanning electron microscopy (SEM) observation indicated that the YSZ electrolyte film was about 16 μm in thickness, highly dense, crack free and well-bonded to the anode support. The electrochemical properties of the prepared anode-supported electrolyte film was evaluated in a button cell mode incorporating a (LaSr)MnO3-YSZ composite cathode. With humidified hydrogen as the fuel and stationary air as the oxidant, the cell demonstrated an open-circuit voltage of 1.081 V and a maximum power density of 1.01 W/cm2 at 800°C. The obtained results represent the important progress in the development of anode-supported intermediate temperature SOFC with reduced fabrication cost.

Effect of Nano-Si3N4 Additives and Plasma Treatment on the Dry Sliding Wear Behavior of Plasma Sprayed Al2O3-8YSZ Ceramic Coatings

NASA Astrophysics Data System (ADS)

Gou, Junfeng; Zhang, Jian; Zhang, Qiwen; Wang, You; Wang, Chaohui

2017-04-01

In this paper, the effect of nano-Si3N4 additives and plasma treatment on the wear behavior of Al2O3-8YSZ ceramic coatings was studied. Nano-Al2O3, nano-8YSZ (8 wt.% Y2O3-stabilized ZrO2) and nano-Si3N4 powders were used as raw materials to fabricate four types of sprayable feedstocks. Plasma treatment was used to improve the properties of the feedstocks. The surface morphologies of the ceramic coatings were observed. The mechanical properties of the ceramic coatings were measured. The dry sliding wear behavior of the Al2O3-8YSZ coatings with and without Si3N4 additives was studied. Nano-Si3N4 additives and plasma treatment can improve the morphologies of the coatings by prohibiting the initiation of micro-cracks and reducing the unmelted particles. The hardness and bonding strength of AZSP (Al2O3-18 wt.% 8YSZ-10 wt.% Si3N4-plasma treatment) coating increased by 79.2 and 44% compared to those of AZ (Al2O3-20 wt.% 8YSZ) coating. The porosity of AZSP coating decreased by 85.4% compared to that of AZ coating. The wear test results showed that the addition of nano-Si3N4 and plasma treatment could improve the wear resistance of Al2O3-8YSZ coatings.

Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

PubMed

Ai, Na; Li, Na; Rickard, William D A; Cheng, Yi; Chen, Kongfa; Jiang, San Ping

2017-03-09

Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y 2 O 3 -ZrO 2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO 3-δ (LC) and Sm 0.95 CoO 3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm -2 and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm 0.95 Co 0.95 Pd 0.05 O 3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm -2 at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel erbia-yttria co-doped zirconia fluorescent thermal history sensor

NASA Astrophysics Data System (ADS)

Copin, E. B.; Massol, X.; Amiel, S.; Sentenac, T.; Le Maoult, Y.; Lours, P.

2017-01-01

Thermochromic pigments are commonly used for off-line temperature mapping on components from systems operating at a temperature higher than 1073 K. However, their temperature resolution is often limited by the discrete number of color transitions they offer. This paper investigates the potential of erbia-yttria co-doped zirconia as a florescent thermal history sensor alternative to thermochromic pigments. Samples of yttria-stabilized zirconia powder (YSZ, 8.3 mol% YO1.5) doped with 1.5 mol% ErO1.5 and synthesized by a sol-gel route are calcined for 15 minutes under isothermal conditions between 1173 and 1423 K. The effects of temperature on their crystal structure and room temperature fluorescence properties are then studied. Results show a steady increase of the crystallinity of the powders with temperature, causing a significant and permanent increase of the emission intensity and fluorescence lifetime which could be used to determine temperature with a calculated theoretical resolution lower than 1 K for intensity. The intensity ratio obtained using a temperature insensitive YSZ:Eu3+ reference phosphor is proposed as a more robust parameter regarding experimental conditions for determining thermal history. Finally, the possibilities for integrating this fluorescent marker into sol-gel deposited coatings for future practical thermal history sensing applications is also discussed.

Doped ZrO2 for future lead free piezoelectric devices

NASA Astrophysics Data System (ADS)

Starschich, S.; Böttger, U.

2018-01-01

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

Thickness effects of yttria-doped ceria interlayers on solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Fan, Zeng; An, Jihwan; Iancu, Andrei; Prinz, Fritz B.

2012-11-01

Determining the optimal thickness range of the interlayed yttria-doped ceria (YDC) films promises to further enhance the performance of solid oxide fuel cells (SOFCs) at low operating temperatures. The YDC interlayers are fabricated by the atomic layer deposition (ALD) method with one super cycle of the YDC deposition consisting of 6 ceria deposition cycles and one yttria deposition cycle. YDC films of various numbers of ALD super cycles, ranging from 2 to 35, are interlayered into bulk fuel cells with a 200 um thick yttria-stabilized zirconia (YSZ) electrolyte. Measurements and analysis of the linear sweep voltammetry of these fuel cells reveal that the performance of the given cells is maximized at 10 super cycles. Auger elemental mapping and X-ray photoelectron spectroscopy (XPS) techniques are employed to determine the film completeness, and they verify 10 super cycles of YDC to be the critical thickness point. This optimal YDC interlayer condition (6Ce1Y × 10 super cycles) is applied to the case of micro fuel cells as well, and the average performance enhancement factor is 1.4 at operating temperatures of 400 and 450 °C. A power density of 1.04 W cm-2 at 500 °C is also achieved with the optimal YDC recipe.

Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

PubMed Central

Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

2011-01-01

The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550–700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300–400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum – most likely along Pt grain boundaries – as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum. PMID:22210951

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.

YBa2Cu307 superconducting microbolometer linear arrays

NASA Astrophysics Data System (ADS)

Johnson, Burgess R.; Ohnstein, Thomas R.; Marsh, Holly A.; Dunham, Scott B.; Kruse, Paul W.

1992-09-01

Single pixels and linear arrays of microbolometers employing the high-T(subscript c) superconductor YBa(subscript 2)Cu(subscript 3)O(subscript 7) have been fabricated by silicon micromachining techniques. The substrates are 3 in. diameter silicon wafers upon which buffer layers of Si(subscript 3)N(subscript 4) and yttria-stabilized zirconia (YSZ) have been deposited. The YBa(subscript 2)Cu(subscript 3)O(subscript 7) was deposited by ion beam sputtering upon the yttria-stabilized zirconia (YSZ), then photolithographically patterned into serpentines 4 micrometers wide. Anisotropic etching in KOH removed the silicon underlying each pixel, thereby providing the necessary thermal isolation. When operated at 70 degree(s)K with 1 (mu) A dc bias, the D(superscript *) is 7.5 X 10(superscript 8) cm Hz(superscript 1/2)/Watt with a thermal response time of 24 msec.

Straight-chain halocarbon forming fluids for TRISO fuel kernel production - Tests with yttria-stabilized zirconia microspheres

NASA Astrophysics Data System (ADS)

Baker, M. P.; King, J. C.; Gorman, B. P.; Braley, J. C.

2015-03-01

Current methods of TRISO fuel kernel production in the United States use a sol-gel process with trichloroethylene (TCE) as the forming fluid. After contact with radioactive materials, the spent TCE becomes a mixed hazardous waste, and high costs are associated with its recycling or disposal. Reducing or eliminating this mixed waste stream would not only benefit the environment, but would also enhance the economics of kernel production. Previous research yielded three candidates for testing as alternatives to TCE: 1-bromotetradecane, 1-chlorooctadecane, and 1-iodododecane. This study considers the production of yttria-stabilized zirconia (YSZ) kernels in silicone oil and the three chosen alternative formation fluids, with subsequent characterization of the produced kernels and used forming fluid. Kernels formed in silicone oil and bromotetradecane were comparable to those produced by previous kernel production efforts, while those produced in chlorooctadecane and iodododecane experienced gelation issues leading to poor kernel formation and geometry.

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

DOE PAGES

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou; ...

2017-03-18

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

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

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

Stabilization of orthorhombic phase in single-crystal ZnSnN 2 films

DOE PAGES

Senabulya, Nancy; Feldberg, Nathaniel; Makin, Robert. A.; ...

2016-09-22

Here, we report on the crystal structure of epitaxial ZnSnN 2 films synthesized via plasma-assisted vapor deposition on (111) yttria stabilized zirconia (YSZ) and (001) lithium gallate (LiGaO 2) substrates. X-ray diffraction measurements performed on ZnSnN 2 films deposited on LiGaO 2 substrates show evidence of single-crystal, phase-pure orthorhombic structure in the Pn2 1a symmetry [space group (33)], with lattice parameters in good agreement with theoretically predicted values. This Pn2 1a symmetry is imposed on the ZnSnN 2 films by the LiGaO 2 substrate, which also has orthorhombic symmetry. A structural change from the wurtzite phase to the orthorhombic phasemore » in films grown at high substrate temperatures ~550°C and low values of nitrogen flux ~10 –5 Torr is observed in ZnSnN 2 films deposited on YSZ characterized by lattice contraction in the basal plane and a 5.7% expansion of the out-of-plane lattice parameter.« less

Zirconium nitride precipitation in nominally pure yttria-stabilized zirconia

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

Gomez-Garcia, D.; Martinez-Fernandez, J.; Dominguez-Rodriguez, A.

Nominally pure yttria-stabilized zirconia alloys are shown to contain unexpectedly large amounts of dissolved nitrogen. Its presence in the lattice was detected through the observation of large precipitates in alloys with three different concentrations of yttria deformed in compression in argon in the temperature range 1,600--1,800 C. Electron diffraction, EDS and PEELS analyses, and Moire imaging were used to identify the precipitates as ZrN. The possible origin of the nitrogen, its likely effects on properties, and the role of annealing atmosphere are briefly discussed.

DFT-based ab initio MD simulation of the ionic conduction in doped ZrO₂ systems under epitaxial strain.

PubMed

Oka, M; Kamisaka, H; Fukumura, T; Hasegawa, T

2015-11-21

The oxygen ionic conduction in ZrO2 systems under tensile epitaxial strain was investigated by performing ab initio molecular dynamics (MD) calculations based on density functional theory (DFT) to elucidate the essential factors in the colossal ionic conductivity observed in the yttria stabilized ZrO2 (YSZ)/SrTiO3 heterostructure. Three factors were evaluated: lattice strain, oxygen vacancies, and dopants. Phonon calculations based on density functional perturbation theory (DFPT) were used to obtain the most stable structure for nondoped ZrO2 under 7% tensile strain along the a- and b-axes. This structure has the space group Pbcn, which is entirely different from that of cubic ZrO2, suggesting that previous ab initio MD calculations assuming cubic ZrO2 may have overestimated the ionic conductivity due to relaxation from the initial structure to the stable structure (Pbcn). Our MD calculations revealed that the ionic conductivity is enhanced only when tensile strain and oxygen vacancies are incorporated, although the presently obtained diffusion constant is far below the range for the colossal ionic conduction experimentally observed. The enhanced ionic conductivity is due to the combined effects of oxygen sublattice formation induced by strain and deformation of this sublattice by oxygen vacancies.

Formulation of steam-methane reforming rate in Ni-YSZ porous anode of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Sugihara, Shinichi; Kawamura, Yusuke; Iwai, Hiroshi

2018-02-01

The steam-methane reforming reaction on a Ni-YSZ (yttria-stabilized zirconia) cermet was experimentally investigated under atmospheric pressure and in the temperature range from 650 to 750 °C. We examined the effects of the partial pressures of methane and steam in the supply gas on the reaction rate. The experiments were conducted with a low Ni contained Ni-YSZ cermet sheet of thickness 0.1 mm. Its porous microstructure and accompanied parameters were quantified using the FIB-SEM (focused ion beam scanning electron microscopy) technique. A power-law-type rate equation incorporating the reaction-rate-limiting conditions was obtained on the basis of the unit surface area of the Ni-pore contact surface in the cermet. The kinetics indicated a strong positive dependence on the methane partial pressure and a negative dependence on the steam partial pressure. The obtained rate equation successfully reproduced the experimental results for Ni-YSZ samples having different microstructures in the case of low methane consumption. The equation also reproduced the limiting-reaction behaviours at different temperatures.

Evaluation of laser bacterial anti-fouling of transparent nanocrystalline yttria-stabilized-zirconia cranial implant.

PubMed

Damestani, Yasaman; De Howitt, Natalie; Halaney, David L; Garay, Javier E; Aguilar, Guillermo

2016-10-01

The development and feasibility of a novel nanocrystalline yttria-stabilized-zirconia (nc-YSZ) cranial implant has been recently established. The purpose of what we now call "window to the brain (WttB)" implant (or platform), is to improve patient care by providing a technique for delivery and/or collection of light into/from the brain, on demand, over large areas, and on a chronically recurring basis without the need for repeated craniotomies. WttB holds the transformative potential for enhancing light-based diagnosis and treatment of a wide variety of brain pathologies including cerebral edema, traumatic brain injury, stroke, glioma, and neurodegenerative diseases. However, bacterial adhesion to the cranial implant is the leading factor for biofilm formation (fouling), infection, and treatment failure. Escherichia coli (E. coli), in particular, is the most common isolate in gram-negative bacillary meningitis after cranial surgery or trauma. The transparency of our WttB implant may provide a unique opportunity for non-invasive treatment of bacterial infection under the implant using medical lasers. A drop of a diluted overnight culture of BL21-293 E. coli expressing luciferase was seeded between the nc-YSZ implant and the agar plate. This was followed by immediate irradiation with selected laser. After each laser treatment the nc-YSZ was removed, and cultures were incubated for 24 hours at 37 °C. The study examined continuous wave (CW) and pulsed wave (PW) modes of near-infrared (NIR) 810 nm laser wavelength with a power output ranging from 1 to 3 W. During irradiation, the temperature distribution of nc-YSZ surface was monitored using an infrared thermal camera. Relative luminescence unit (RLU) was used to evaluate the viability of bacteria after the NIR laser treatment. Analysis of RLU suggests that the viability of E. coli biofilm formation was reduced with NIR laser treatment when compared to the control group (P < 0.01) and loss of viability

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.

Revisiting the Birth of 7YSZ Thermal Barrier Coatings: Steve Stecura

NASA Technical Reports Server (NTRS)

Smialek, James L.; Miller, Robert A.

2017-01-01

Thermal barrier coatings are widely used in all turbine engines, typically using a 7 wt% Y2O3-ZrO2 formulation. Extensive research and development over many decades have refined the processing and structure of these coatings for increased durability and reliability. New compositions demonstrate some unique advantages and are gaining in application. However, the "7YSZ" formulation predominates and is still in widespread use. This special composition has been universally found to produce nanoscale precipitates of metastable t' tetragonal phase, giving rise to a unique toughening mechanism via ferro-elastic switching under stress. This note recalls the original study that identified superior properties of 6 to 8 wt% YSZ plasma sprayed thermal barrier coatings, published in 1978. The impact of this discovery, arguably, continues in some form to this day. At one point, 7YSZ thermal barrier coatings were used in every new aircraft and ground power turbine engine produced worldwide. It is a tribute to its inventor, Dr. Stephan J. Stecura, NASA retiree.

Suppressed Sr segregation and performance of directly assembled La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode on Y2O3-ZrO2 electrolyte of solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Ai, Na; He, Shuai; Li, Na; Zhang, Qi; Rickard, William D. A.; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Active and stable oxygen electrode is probably the most important in the development of solid oxide electrolysis cells (SOECs) technologies. Herein, we report the successful development of mixed ionic and electronic conducting (MIEC) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) perovskite oxides directly assembled on barrier-layer-free yttria-stabilized zirconia (YSZ) electrolyte as highly active and stable oxygen electrodes of SOECs. Electrolysis polarization effectively induces the formation of electrode/electrolyte interface, similar to that observed under solid oxide fuel cell (SOFC) operation conditions. However, in contrast to the significant performance decay under SOFC operation conditions, the cell with directly assembled LSCF oxygen electrodes shows excellent stability, tested for 300 h at 0.5 A cm-2 and 750 °C under SOEC operation conditions. Detailed microstructure and phase analysis reveal that Sr segregation is inevitable for LSCF electrode, but anodic polarization substantially suppresses Sr segregation and migration to the electrode/electrolyte interface, leading to the formation of stable and efficient electrode/electrolyte interface for water and CO2 electrolysis under SOECs operation conditions. The present study demonstrates the feasibility of using directly assembled MIEC cobaltite based oxygen electrodes on barrier-layer-free YSZ electrolyte of SOECs.

Mechanical Properties of Layered La2Zr2O7 Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Improving the Thermal Shock Resistance of Thermal Barrier Coatings Through Formation of an In Situ YSZ/Al2O3 Composite via Laser Cladding

NASA Astrophysics Data System (ADS)

Soleimanipour, Zohre; Baghshahi, Saeid; Shoja-razavi, Reza

2017-04-01

In the present study, laser cladding of alumina on the top surface of YSZ thermal barrier coatings (TBC) was conducted via Nd:YAG pulsed laser. The thermal shock behavior of the TBC before and after laser cladding was modified by heating at 1000 °C for 15 min and quenching in cold water. Phase analysis, microstructural evaluation and elemental analysis were performed using x-ray diffractometry, scanning electron microscopy (SEM), and energy-dispersive spectroscopy. The results of thermal shock tests indicated that the failure in the conventional YSZ (not laser clad) and the laser clad coatings happened after 200 and 270 cycles, respectively. The SEM images of the samples showed that delamination and spallation occurred in both coatings as the main mechanism of failure. Formation of TGO was also observed in the fractured cross section of the samples, which is also a main reason for degradation. Thermal shock resistance in the laser clad coatings improved about 35% after cladding. The improvement is due to the presence of continuous network cracks perpendicular to the surface in the clad layer and also the thermal stability and high melting point of alumina in Al2O3/ZrO2 composite.

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

DOE PAGES

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

2016-02-29

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

Effects of Dopant Metal Variation and Material Synthesis Method on the Material Properties of Mixed Metal Ferrites in Yttria Stabilized Zirconia for Solar Thermochemical Fuel Production

DOE PAGES

Leonard, Jeffrey; Reyes, Nichole; Allen, Kyle M.; ...

2015-01-01

Mixed metal ferrites have shown much promise in two-step solar-thermochemical fuel production. Previous work has typically focused on evaluating a particular metal ferrite produced by a particular synthesis process, which makes comparisons between studies performed by independent researchers difficult. A comparative study was undertaken to explore the effects different synthesis methods have on the performance of a particular material during redox cycling using thermogravimetry. This study revealed that materials made via wet chemistry methods and extended periods of high temperature calcination yield better redox performance. Differences in redox performance between materials made via wet chemistry methods were minimal and thesemore » demonstrated much better performance than those synthesized via the solid state method. Subsequently, various metal ferrite samples (NiFe 2 O 4 , MgFe 2 O 4 , CoFe 2 O 4 , and MnFe 2 O 4 ) in yttria stabilized zirconia (8YSZ) were synthesized via coprecipitation and tested to determine the most promising metal ferrite combination. It was determined that 10 wt.% CoFe 2 O 4 in 8YSZ produced the highest and most consistent yields of O 2 and CO. By testing the effects of synthesis methods and dopants in a consistent fashion, those aspects of ferrite preparation which are most significant can be revealed. More importantly, these insights can guide future efforts in developing the next generation of thermochemical fuel production materials.« less

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.

Unctuous ZrO2 nanoparticles with improved functional attributes as lubricant additives

NASA Astrophysics Data System (ADS)

Espina Casado, Jorge; Fernández González, Alfonso; José del Reguero Huerga, Ángel; Rodríguez-Solla, Humberto; Díaz-García, Marta Elena; Badía-Laíño, Rosana

2017-12-01

One of the main drawbacks in the application of metal-oxide nanoparticles as lubricant additives is their poor stability in organic media, despite the good anti-wear, friction-reducing and high-load capacity properties described for these materials. In this work, we present a novel procedure to chemically cap the surface of ZrO2 nanoparticles (ZrO2NPs) with long hydrocarbon chains in order to obtain stable dispersions of ZrO2NPs in non-aqueous media without disrupting their attributes as lubricant additives. C-8, C-10 and C-16 saturated flexible chains were attached to the ZrO2NP surface and their physical and chemical characterization was performed by transmission electron microscopy, thermogravimetric analysis, attenuated total reflectance Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy and solid-state nuclear magnetic resonance. The dispersion stability of the modified ZrO2NPs in non-aqueous media was studied using static multiple light scattering. Tribological tests demonstrated that dispersions of the long-chain capped ZrO2NPs in base lubricating oils exhibited low friction coefficients and improved the anti-wear properties of the base oil when compared with the raw lubricating oil.

Characterization of Ni-YSZ anodes for solid oxide fuel cells fabricated by solution precursor plasma spraying with axial feedstock injection

NASA Astrophysics Data System (ADS)

Metcalfe, Craig; Lay-Grindler, Elisa; Kesler, Olivera

2014-02-01

Nickel and yttria-stabilized zirconia (YSZ) anodes were fabricated by solution precursor plasma spraying (SPPS) and incorporated into metal-supported solid oxide fuel cells (SOFC). A power density of 0.45 W cm-2 at 0.7 V and a peak power density of 0.52 W cm-2 at 750 °C in humidified H2 was obtained, which are the first performance results reported for an SOFC having an anode fabricated by SPPS. The effects of solution composition, plasma gas composition, and stand-off distance on the composition of the deposited Ni-YSZ coatings by SPPS were evaluated. It was found that the addition of citric acid to the aqueous solution delayed re-solidification of NiO particles, improving the deposition efficiency and coating adhesion. The composition of the deposited coatings was found to vary with torch power. Increasing torch power led to coatings with decreasing Ni content, as a result of Ni vaporizing in-flight at stand-off distances less than 60 mm from the torch nozzle exit.

Evolution of the plasma-sprayed microstructure in 7 wt% yttria-stabilized zirconia thermal barrier coatings during uniaxial stress relaxation and the concomitant changes in material properties

NASA Astrophysics Data System (ADS)

Petorak, Christopher

The understanding of failure mechanisms in plasma sprayed 7 wt% yttria stabilized zirconia (YSZ) is a key step toward optimizing thermal barrier coating (TBC) usage, design, and life prediction. The purpose of the present work is to characterize and understand the stress relaxation behavior occurring in plasma-sprayed YSZ coatings, so that the correlating magnitude of unfavorable tensile stress, which coatings experienced upon cooling, may be reduced through microstructural design. The microstructure and properties of as-sprayed coatings changes immensely during service at high temperature, and therefore the effects of long heat-treatment times, and the concomitant change within the microstructure, on the time-dependent mechanical behavior of stand-alone YSZ coatings was studied in parallel with the as-sprayed coating condition. Aside from influencing the mechanical properties, stress relaxation also affects the insulating efficiency of plasma-sprayed 7wt% YSZ coatings. Directionally dependent changes in microstructure due to stress relaxation of a uniaxially applied stress at 1200°C were observed in plasma-sprayed coatings. Small angle neutron scattering (SANS) investigation of coatings after stress relaxation displayed a 46% reduction in the specific surface area connected to the load-orientation dependent closure of void surface area perpendicular to the applied load when compared to coatings sintered in air, i.e. no applied load. These anisotropic microstructural changes were linked to the thermal properties of the coating. For example, a coating stress relaxed from 60 MPa for 5-min at 1200°C exhibited a thermal conductivity of 2.1 W/m-K. A coating that was only heat-treated for 5-min at 1200°C (i.e. no stress applied) exhibited a thermal conductivity of 1.7 W/m·K. In the current study, uniaxial stress relaxation in plasma-sprayed 7wt% YSZ coatings was determined the result of: (1) A more uniform distribution of the applied load with time, (2) A reduction

Thermal Aging Behavior of Axial Suspension Plasma-Sprayed Yttria-Stabilized Zirconia (YSZ) Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Zhao, Yuexing; Wang, Liang; Yang, Jiasheng; Li, Dachuan; Zhong, Xinghua; Zhao, Huayu; Shao, Fang; Tao, Shunyan

2015-02-01

7.5YSZ thermal barrier coatings (TBCs) were deposited onto the stainless steel substrates using axial suspension plasma spraying (ASPS). Free-standing coatings were isothermally aged in air from 1200 to 1600 °C for 24 h and at 1550 °C for 20 to 100 h, respectively. Thermal aging behavior such as phase composition, microstructure evolutions, grain growth, and mechanical properties for thermal-aged coatings were investigated. Results show that the as-sprayed metastable tetragonal (t'-ZrO2) phase decomposes into equilibrium tetragonal (t-ZrO2) and cubic (c-ZrO2) phases during high-temperature exposures. Upon further cooling, the c-ZrO2 may be retained or transform into another metastable tetragonal (t″-ZrO2) phase, and tetragonal → monoclinic phase transformation occurred after 1550 °C/40 h aging treatment. The coating exhibits a unique structure with segmentation cracks and micro/nano-size grains, and the grains grow gradually with increasing aging temperature and time. In addition, the hardness ( H) and Young's modulus ( E) significantly increased as a function of temperature due to healing of pores or cracks and grain growth of the coating. And a nonmonotonic variation is found in the coatings thermal aged at a constant temperature (1550 °C) with prolonged time, this is a synergetic effect of coating sintering and m-ZrO2 phase formation.

Improvement of adhesion and barrier properties of biomedical stainless steel by deposition of YSZ coatings using RF magnetron sputtering

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

Sánchez-Hernández, Z.E.; CICATA—Altamira, IPN. Grupo CIAMS, Km 14.5, Carretera Tampico-Puerto Industrial Altamira, C. P. 89600, Altamira, Tamps, México; Domínguez-Crespo, M.A., E-mail: mdominguezc@ipn.mx

The AISI 316L stainless steel (SS) has been widely used in both artificial knee and hip joints in biomedical applications. In the present study, yttria stabilized zirconia (YSZ, ZrO{sub 2} + 8% Y{sub 2}O{sub 3}) films were deposited on AISI 316L SS by radio-frequency magnetron sputtering using different power densities (50–250 W) and deposition times (30–120 min) from a YSZ target. The crystallographic orientation and surface morphology were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effects of the surface modification on the corrosion performance of AISI 316L SS were evaluated in phosphatemore » buffered saline (PBS) solution using an electrochemical test on both the virgin and coated samples. The YSZ coatings have a (111) preferred orientation during crystal growth along the c-axis for short deposition times (30–60 min), whereas a polycrystalline structure forms during deposition times from 90 to 120 min. The corrosion protective character of the YSZ coatings depends on the crystal size and film thickness. A significant increase in adhesion and corrosion resistance by at least a factor of 46 and a higher breakdown potential were obtained for the deposited coatings at 200 W (120 min). - Highlights: • Well-formed and protective YSZ coatings were achieved on AISI 316L SS substrates. • Films grown at high power and long deposition time have polycrystalline structures. • The crystal size varies from ∼ 5 to 30 nm as both power and deposition time increased. • The differences of corrosion resistance are attributed to internal film structure.« less

Plasma sprayed metal supported YSZ/Ni-LSGM-LSCF ITSOFC with nanostructured anode

NASA Astrophysics Data System (ADS)

Hwang, Changsing; Tsai, Chun-Huang; Lo, Chih-Hung; Sun, Cha-Hong

Intermediate temperature solid oxide fuel cells (ITSOFCs) supported by a porous Ni-substrate and based on Sr and Mg doped lanthanum gallate (LSGM) electrolyte, lanthanum strontium cobalt ferrite (LSCF) cathode and nanostructured yttria stabilized zirconia-nickel (YSZ/Ni) cermet anode have been fabricated successfully by atmospheric plasma spraying (APS). From ac impedance analysis, the sprayed YSZ/Ni cermet anode with a novel nanostructure and advantageous triple phase boundaries after hydrogen reduction has a low resistance. It shows a good electrocatalytic activity for hydrogen oxidation reactions. The sprayed LSGM electrolyte with ∼60 μm in thickness and ∼0.054 S cm -1 conductivity at 800 °C shows a good gas tightness and gives an open circuit voltage (OCV) larger than 1 V. The sprayed LSCF cathode with ∼30 μm in thickness and ∼30% porosity has a minimum resistance after being heated at 1000 °C for 2 h. This cathode keeps right phase structure and good porous network microstructure for conducting electrons and negative oxygen ions. The APS sprayed cell after being heated at 1000 °C for 2 h has a minimum inherent resistance and achieves output power densities of ∼440 mW cm -2 at 800 °C, ∼275 mW cm -2 at 750 °C and ∼170 mW cm -2 at 700 °C. Results from SEM, XRD, ac impedance analysis and I- V- P measurements are presented here.

Structural characterization of hard materials by transmission electron microscopy (TEM): Diamond-Silicon Carbide composites and Yttria-stabilized Zirconia

NASA Astrophysics Data System (ADS)

Park, Joon Seok

2008-10-01

Diamond-Silicon Carbide (SiC) composites are excellent heat spreaders for high performance microprocessors, owing to the unparalleled thermal conductivity of the former component. Such a combination is obtained by the infiltration of liquid silicon in a synthetic diamond compact, where a rigid SiC matrix forms by the reaction between the raw materials. As well as the outstanding thermal properties, this engineered compound also retains the extreme hardness of the artificial gem. This makes it difficult to perform structural analysis by transmission electron microscopy (TEM), for it is not possible to produce thin foils out of this solid by conventional polishing methods. For the first time, a dual-beam focused ion beam (FIB) instrument successfully allowed site-specific preparation of electron-transparent specimens by the lift-out technique. Subsequent TEM studies revealed that the highest concentration of structural defects occurs in the vicinity of the diamond-SiC interfaces, which are believed to act as the major barriers to the transport of thermal energy. Diffraction contrast analyses showed that the majority of the defects in diamond are isolated perfect screw or 60° dislocations. On the other hand, SiC grains contain partial dislocations and a variety of imperfections such as microtwins, stacking faults and planar defects that are conjectured to consist of antiphase (or inversion) boundaries. Clusters of nanocrystalline SiC were also observed at the diamond-SiC boundaries, and a specific heteroepitaxial orientation relationship was discovered for all cubic SiC that grows on diamond {111} facets. Yttria-stabilized Zirconia (YSZ) is the most common electrolyte material for solid oxide fuel cell (SOFC) applications. It is an ionic conductor in which charge transfer is achieved by the transport of oxygen ions (O 2-). Like the diamond composite above, it is hard and brittle, and difficult to make into electron transparent TEM samples. Provided an effective

Anomalous Epitaxial Growth in Thermally Sprayed YSZ and LZ Splats

NASA Astrophysics Data System (ADS)

Chen, Lin; Yang, Guan-Jun

2017-08-01

Thermally sprayed coatings are essentially layered materials, and lamellar interfaces are of great importance to coatings' performances. In the present study, to investigate the microstructures and defect features at thermally sprayed coating interfaces, homoepitaxial 8 mol.% yttria-stabilized zirconia (YSZ) and heteroepitaxial lanthanum zirconia (LZ) films were fabricated. The epitaxial interfaces were examined by high-resolution transmission electron microscope (HR-TEM) in detail. As a result, we report, for the first time, an anomalous incommensurate homoepitaxial growth with mismatch-induced dislocations in thermally sprayed YSZ splats to create a homointerface. We also find the anomalous heteroepitaxial growth in thermally sprayed LZ splats. The mechanism of the anomalous incommensurate growth was analyzed in detail. Essentially, it is a pseudo-heteroepitaxy because of the lattice mismatch between the film and the locally heated substrate, as the locally heated substrate is significantly strained by its cold surroundings. Moreover, the super-high-density dislocations were found in the interfacial region, which resulted from sufficient thermal fluctuations and extremely rapid cooling rates. Both the anomalous lattice mismatch and super-high-density dislocations lead to weak interfaces and violent cracking in thermally sprayed coatings. These were also the essential differences between the conventional and the present epitaxy by thermal spray technique.

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.

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

High-yield sol-gel synthesis of well-dispersed, colorless ZrO(2) nanocrystals.

PubMed

Mizuno, Mikihisa; Sasaki, Yuichi; Lee, Sungkil; Katakura, Hitoshi

2006-08-15

A 93% high-yield synthesis of well-dispersed, colorless zirconium dioxide (ZrO(2)) nanocrystals is reported. In this synthesis, hydrolysis and condensation reactions of zirconium(IV) tert-butoxide in the presence of oleic acid (100 degrees C) formed ZrO(2) precursors. The ZrO(2) precursors were made of -Zr-O-Zr- networks surrounded by oleic acid molecules. Annealing (280 degrees C) the precursors dispersed in dioctyl ether caused crystallization of the -Zr-O-Zr- networks, thereby generating 4 nm ZrO(2) nanocrystals stabilized with oleic acid. The particles were highly crystalline and tetragonal phase. A dense ZrO(2) nanocrystal dispersion in toluene (280 mg/mL) showed a transmittance of about 90% (3 mm optical path length) in the whole visible region.

ZrO2-Nanoparticle-Modified Graphite Felt: Bifunctional Effects on Vanadium Flow Batteries.

PubMed

Zhou, Haipeng; Shen, Yi; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

2016-06-22

To improve the electrochemical performance of graphite felt (GF) electrodes in vanadium flow batteries (VFBs), we synthesize a series of ZrO2-modified GF (ZrO2/GF) electrodes with varying ZrO2 contents via a facile immersion-precipitation approach. It is found that the uniform immobilization of ZrO2 nanoparticles on the GF not only significantly promotes the accessibility of vanadium electrolyte, but also provides more active sites for the redox reactions, thereby resulting in better electrochemical activity and reversibility toward the VO(2+)/VO2(+) and V(2+)/V(3+) redox reactions as compared with those of GF. In particular, The ZrO2/GF composite with 0.3 wt % ZrO2 displays the best electrochemical performance with voltage and energy efficiencies of 71.9% and 67.4%, respectively, which are much higher than those of 57.3% and 53.8% as obtained from the GF electrode at 200 mA cm(-2). The cycle life tests demonstrate that the ZrO2/GF electrodes exhibit outstanding stability. The ZrO2/GF-based VFB battery shows negligible activity decay after 200 cycles.

An X-Ray Diffraction Investigation of alpha-Al2O2 Addition to Yttria Stabilized Zirconia (YSZ) Thermal Barrier Coatings Subject to Destabilizing Vanadium Pentoxide (V2O5) Exposure

DTIC Science & Technology

1993-09-01

which is found in several electrical ceramics. flu I ’I I I’ p Figuve 8. System A1aO3-ZrOa Phase Diagram. 11 S. A240.gOiV20 Phas DtagZM The Al3O- V2O5 ...Raot=Lon of V,05 With Y20, Assuming that V205 and Y203 react on an equimolar basis, the creation of yttria vanadate is: V2O5 + YZO3 - 2YV0 4 (2) As...that with a glass phase formation that some phases were "hidden" from XRD analysis and were under-counted, while other phases were over- counted

Growth and micro structural studies on Yittria Stabilized Zirconia (YSZ) and Strontium Titanate (STO) buffer layers

NASA Technical Reports Server (NTRS)

Srinivas, S.; Pinto, R.; Pai, S. P.; Dsousa, D. P.; Apte, P. R.; Kumar, D.; Purandare, S. C.; Bhatnagar, A. K.

1995-01-01

Microstructure of Yittria Stabilized Zirconia (YSZ) and Strontium Titanate (STO) of radio frequency magnetron sputtered buffer layers was studied at various sputtering conditions on Si (100), Sapphire and LaAlO3 (100) substrates. The effect of substrate temperatures up to 800 C and sputtering gas pressures in the range of 50 mTorr. of growth conditions was studied. The buffer layers of YSZ and STO showed a strong tendency for columnar growth was observed above 15 mTorr sputtering gas pressure and at high substrate temperatures. Post annealing of these films in oxygen atmosphere reduced the oxygen deficiency and strain generated during growth of the films. Strong c-axis oriented superconducting YBa2Cu3O7-x (YBCO) thin films were obtained on these buffer layers using pulsed laser ablation technique. YBCO films deposited on multilayers of YSZ and STO were shown to have better superconducting properties.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

YSZ-based sensor using Cr-Fe-based spinel-oxide electrodes for selective detection of CO.

PubMed

Anggraini, Sri Ayu; Fujio, Yuki; Ikeda, Hiroshi; Miura, Norio

2017-08-22

A selective carbon monoxide (CO) sensor was developed by the use of both of CuCrFeO 4 and CoCrFeO 4 as the sensing electrode (SE) for yttria-stabilized zirconia (YSZ)-based potentiometric sensor. The sensing-characteristic examinations of the YSZ-based sensors using each of spinel oxides as the single-SE sensor showed that CuCrFeO 4 -SE had the ability to detect CO, hydrocarbons and NO x gases, while CoCrFeO 4 -SE was sensitive to hydrocarbons and NO x gases. Thus, when both SEs were paired as a combined-SEs sensor, the resulting sensor could generate a selective response to CO at 450 °C under humid conditions. The sensor was also capable of detecting CO in the concentration range of 20-700 ppm. Its sensing mechanism that was examined via polarization-curve measurements was confirmed to be based on mixed-potential model. The CO response generated by the combined-SEs sensor was unaffected by the change of water vapor concentration in the range of 1.3-11.5 vol% H 2 O. Additionally, the sensing performance was stable during 13 days tested. Copyright © 2017 Elsevier B.V. All rights reserved.

Role of temperature in the radiation stability of yttria stabilized zirconia under swift heavy ion irradiation: A study from the perspective of nuclear reactor applications

NASA Astrophysics Data System (ADS)

Kalita, Parswajit; Ghosh, Santanu; Sattonnay, Gaël; Singh, Udai B.; Grover, Vinita; Shukla, Rakesh; Amirthapandian, S.; Meena, Ramcharan; Tyagi, A. K.; Avasthi, Devesh K.

2017-07-01

The search for materials that can withstand the harsh radiation environments of the nuclear industry has become an urgent challenge in the face of ever-increasing demands for nuclear energy. To this end, polycrystalline yttria stabilized zirconia (YSZ) pellets were irradiated with 80 MeV Ag6+ ions to investigate their radiation tolerance against fission fragments. To better simulate a nuclear reactor environment, the irradiations were carried out at the typical nuclear reactor temperature (850 °C). For comparison, irradiations were also performed at room temperature. Grazing incidence X-ray diffraction and Raman spectroscopy measurements reveal degradation in crystallinity for the room temperature irradiated samples. No bulk structural amorphization was however observed, whereas defect clusters were formed as indicated by transmission electron microscopy and supported by thermal spike simulation results. A significant reduction of the irradiation induced defects/damage, i.e., improvement in the radiation tolerance, was seen under irradiation at 850 °C. This is attributed to the fact that the rapid thermal quenching of the localized hot molten zones (arising from spike in the lattice temperature upon irradiation) is confined to 850 °C (i.e., attributed to the resistance inflicted on the rapid thermal quenching of the localized hot molten zones by the high temperature of the environment) thereby resulting in the reduction of the defects/damage produced. Our results present strong evidence for the applicability of YSZ as an inert matrix fuel in nuclear reactors, where competitive effects of radiation damage and dynamic thermal healing mechanisms may lead to a strong reduction in the damage production and thus sustain its physical integrity.

Phonon anharmonicity of monoclinic zirconia and yttrium-stabilized zirconia

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

Li, Chen W.; Smith, Hillary L.; Lan, Tian

2015-04-13

Inelastic neutron scattering measurements on monoclinic zirconia (ZrO 2) and 8 mol% yttrium-stabilized zirconia were performed at temperatures from 300 to 1373 ωK. We reported temperature-dependent phonon densities of states (DOS) and Raman spectra obtained at elevated temperatures. First-principles lattice dynamics calculations with density functional theory gave total and partial phonon DOS curves and mode Grüneisen parameters. These mode Grüneisen parameters were used to predict the experimental temperature dependence of the phonon DOS with partial success. However, substantial anharmonicity was found at elevated temperatures, especially for phonon modes dominated by the motions of oxygen atoms. Yttrium-stabilized zirconia (YSZ) was somewhatmore » more anharmonic and had a broader phonon spectrum at low temperatures, owing in part to defects in its structure. YSZ also has a larger vibrational entropy than monoclinic zirconia.« less

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

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

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

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

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

DOE PAGES

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

2016-08-26

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

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

PubMed

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

2013-02-27

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

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.

Miscibility of amorphous ZrO2-Al2O3 binary alloy

NASA Astrophysics Data System (ADS)

Zhao, C.; Richard, O.; Bender, H.; Caymax, M.; De Gendt, S.; Heyns, M.; Young, E.; Roebben, G.; Van Der Biest, O.; Haukka, S.

2002-04-01

Miscibility is a key factor for maintaining the homogeneity of the amorphous structure in a ZrO2-Al2O3 binary alloy high-k dielectric layer. In the present work, a ZrO2/Al2O3 laminate thin layer has been prepared by atomic layer chemical vapor deposition on a Si (100) wafer. This layer, with artificially induced inhomogeneity (lamination), enables one to study the change in homogeneity of the amorphous phase in the ZrO2/Al2O3 system during annealing. High temperature grazing incidence x-ray diffraction (HT-XRD) was used to investigate the change in intensity of the constructive interference peak of the x-ray beams which are reflected from the interfaces of ZrO2/Al2O3 laminae. The HT-XRD spectra show that the intensity of the peak decreases with an increase in the anneal temperature, and at 800 °C, the peak disappears. The same samples were annealed by a rapid thermal process (RTP) at temperatures between 700 and 1000 °C for 60 s. Room temperature XRD of the RTP annealed samples shows a similar decrease in peak intensity. Transmission electronic microscope images confirm that the laminate structure is destroyed by RTP anneals and, just below the crystallization onset temperature, a homogeneous amorphous ZrAlxOy phase forms. The results demonstrate that the two artificially separated phases, ZrO2 and Al2O3 laminae, tend to mix into a homogeneous amorphous phase before crystallization. This observation indicates that the thermal stability of ZrO2-Al2O3 amorphous phase is suitable for high-k applications.

Roles of reaction kinetics of CO 2 on a PrBaCo 2O 5.5+δ surfaces

DOE PAGES

Xu, Xing; Mace, Brennan; Enriquez, Erik; ...

2017-08-18

A symmetric PBCO/YSZ/PBCO cell (where PBCO refers to PrBaCo 2O 5.5+δ, and YSZ to yttria stabilized zirconia) was designed and fabricated for the investigation of the catalytic nature and reaction kinetics of CO 2 on PBCO surfaces. The electrochemical impedance spectroscopy was employed to probe the CO 2 reaction behavior on the PBCO electrode. The symmetric equivalent circuit cell characterization reveals that the surface resistance of CO 2 on PBCO is only 30.2 Ω cm 2 and the maximum surface exchange coefficient k chem is 2.0 × 10 -4 cm s -1 at 1147 K, suggesting that PBCO can bemore » an excellent candidate for CO 2 reduction.« less

Fabrication of dense and porous Li2ZrO3 nanofibers with electrospinning method

NASA Astrophysics Data System (ADS)

Yuan, Kangkang; Jin, Xiaotong; Xu, Chonghe; Wang, Xinqiang; Zhang, Guanghui; Zhu, Luyi; Xu, Dong

2018-06-01

Lithium zirconate (Li2ZrO3) has been extensively studied as CO2 capture material, electrolyte material and coating material. Most of the previous studies were focused on the powder structure, while seldom taking a consideration of fiber structure. In the present work, dense and porous Li2ZrO3 nanofibers with surface area of 16 m2 g-1 were prepared by electrospinning method. IR spectral results showed that lithium carbonate was the intermediate for the formation of Li2ZrO3. The phase transformation of Li2ZrO3 underwent the pathway of amorphous precursor fibers, tetragonal zirconia and Li2CO3, tetragonal Li2ZrO3, and monoclinic Li2ZrO3. XRD and XPS results further suggested that Li2O diffusion from the fiber body to surface occurred for Li2ZrO3 nanofibers when heat-treated above 900 °C, and the tetragonal Li2ZrO3 with high surface area could be obtained at 800 °C. Bamboo structure appeared both for the dense and porous nanofibers heat-treated at 1000 °C. The high surface area and high thermal stability of tetragonal phase of Li2ZrO3 make it a promising candidate in CO2 absorption, electrolyte and coating material.

[Interface compatibility between tooth-like yttria-stabilized tetragonal zirconia polycrystal by adding rare-earth oxide and Vita VM9 veneering porcelain].

PubMed

Gao, Yan; Zhang, Fu-qiang; He, Fan

2011-10-01

To evaluate the interface compatibility between tooth-like yttria-stabilized tetragonal zirconia polycrystal(Y-TZP) by adding rare-earth oxide and Vita VM9 veneering porcelain. Six kinds(S1,S2,S3,S4,S5,S6) of tooth-like yttria stabilized tetragonal zirconia polycrystal were made by introducing internal colorating technology to detect the thermal shock resistance and interface bonding strength with Vita VM9 Bsaedentin. Statistical analysis was performed using SAS6.12 software package. There was no gap between the layers via hot shocking test.The shear bonding strength between Y-TZP and VitaVM9 was higher and the value was (36.03±3.82) to (37.98±4.89) MPa. By adding rare-earth oxide to yttria-stabilized tetragonal zirconia polycrystal ,better compatibility between the layer (TZP and Vita VM9) can be formed which is of better interface integrate and available for clinical applications.

Study on the influences of reduction temperature on nickel-yttria-stabilized zirconia solid oxide fuel cell anode using nickel oxide-film electrode

NASA Astrophysics Data System (ADS)

Jiao, Zhenjun; Ueno, Ai; Suzuki, Yuji; Shikazono, Naoki

2016-10-01

In this study, the reduction processes of nickel oxide at different temperatures were investigated using nickel-film anode to study the influences of reduction temperature on the initial performances and stability of nickel-yttria-stabilized zirconia anode. Compared to conventional nickel-yttria-stabilized zirconia composite cermet anode, nickel-film anode has the advantage of direct observation at nickel-yttria-stabilized zirconia interface. The microstructural changes were characterized by scanning electron microscopy. The reduction process of nickel oxide is considered to be determined by the competition between the mechanisms of volume reduction in nickel oxide-nickel reaction and nickel sintering. Electrochemical impedance spectroscopy was applied to analyze the time variation of the nickel-film anode electrochemical characteristics. The anode performances and microstructural changes before and after 100 hours discharging and open circuit operations were analyzed. The degradation of nickel-film anode is considered to be determined by the co-effect between the nickel sintering and the change of nickel-yttria-stabilized zirconia interface bonding condition.

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

Enhanced Sintering of β"-Al2O3/YSZ with the Sintering Aids of TiO2 and MnO2

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

Lu, Xiaochuan; Li, Guosheng; Kim, Jin Yong

2015-07-11

β"-Al2O3 has been the dominated choice for the electrolyte materials of sodium batteries because of its high ionic conductivity, excellent stability with the electrode materials, satisfactory mechanical strength, and low material cost. To achieve adequate electrical and mechanical performance, sintering of β"-Al2O3 is typically carried out at temperatures above 1600oC with deliberate efforts on controlling the phase, composition, and microstructure. Here, we reported a simple method to fabricate β"-Al2O3/YSZ electrolyte at relatively lower temperatures. With the starting material of boehmite, single phase of β"-Al2O3 can be achieved at as low as 1200oC. It was found that TiO2 was extremely effectivemore » as a sintering aid for the densification of β"-Al2O3 and similar behavior was observed with MnO2 for YSZ. With the addition of 2 mol% TiO2 and 5 mol% MnO2, the β"-Al2O3/YSZ composite was able to be densified at as low as 1400oC with a fine microstructure and good electrical/mechanical performance. This study demonstrated a new approach of synthesis and sintering of β"-Al2O3/YSZ composite, which represented a simple and low-cost method for fabrication of high-performance β"-Al2O3/YSZ electrolyte.« less

Improvement of Toluene Selectivity via the Application of an Ethanol Oxidizing Catalytic Cell Upstream of a YSZ-Based Sensor for Air Monitoring Applications

PubMed Central

Sato, Tomoaki; Breedon, Michael; Miura, Norio

2012-01-01

The sensing characteristics of a yttria-stabilized zirconia (YSZ)-based sensor utilizing a NiO sensing-electrode (SE) towards toluene (C7H8) and interfering gases (C3H6, H2, CO, NO2 and C2H5OH) were evaluated with a view to selective C7H8 monitoring in indoor atmospheres. The fabricated YSZ-based sensor showed preferential responses toward 480 ppb C2H5OH, rather than the target 50 ppb C7H8 at an operational temperature of 450 °C under humid conditions (RH ≃ 32%). To overcome this limitation, the catalytic activity of Cr2O3, SnO2, Fe2O3 and NiO powders were evaluated for their selective ethanol oxidation ability. Among these oxides, SnO2 was found to selectively oxidize C2H5OH, thus improving C7H8 selectivity. An inline pre-catalytic cell loaded with SnO2 powder was installed upstream of the YSZ-based sensor utilizing NiO-SE, which enabled the following excellent abilities by selectively catalyzing common interfering gases; sensitive ppb level detection of C7H8 lower than the established Japanese Guideline value; low interferences from 50 ppb C3H6, 500 ppb H2, 100 ppb CO, 40 ppb NO2, as well as 480 ppb C2H5OH. These operational characteristics are all indicative that the developed sensor may be suitable for real-time C7H8 concentration monitoring in indoor environments. PMID:22666053

Nb and Pd co-doped La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ as a stable, high performance electrode for barrier-layer-free Y2O3-ZrO2 electrolyte of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Chen, Kongfa; He, Shuai; Li, Na; Cheng, Yi; Ai, Na; Chen, Minle; Rickard, William D. A.; Zhang, Teng; Jiang, San Ping

2018-02-01

La0.6Sr0.2Co0.2Fe0.8O3-δ (LSCF) is the most intensively investigated high performance cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs), but strontium segregation and migration at the electrode/electrolyte interface is a critical issue limiting the electrocatalytic activity and stability of LSCF based cathodes. Herein, we report a Nb and Pd co-doped LSCF (La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ, LSCFNPd) perovskite as stable and active cathode on a barrier-layer-free anode-supported yttria-stabilized zirconia (YSZ) electrolyte cell using direct assembly method without pre-sintering at high temperatures. The cell exhibits a peak power density of 1.3 W cm-2 at 750 °C and excellent stability with no degradation during polarization at 500 mA cm-2 and 750 °C for 175 h. Microscopic and spectroscopic analysis show that the electrochemical polarization promotes the formation of electrode/electrolyte interface in operando and exsolution of Pd/PdO nanoparticles. The Nb doping in the B-site of LSCF significantly reduces the Sr surface segregation, enhancing the stability of the cathode, while the exsoluted Pd/PdO nanoparticles increases the electrocatalytic activity for the oxygen reduction reaction. The present study opens up a new route for the development of cobaltite-based perovskite cathodes with high activity and stability for barrier-layer-free YSZ electrolyte based IT-SOFCs.

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.

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.

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

PubMed Central

Chen, Yun; Gerdes, Kirk; Song, Xueyan

2016-01-01

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

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.

Improved Tribological Performance of Amorphous Carbon (a-C) Coating by ZrO2 Nanoparticles

PubMed Central

Tang, Jinzhu; Ding, Qi; Zhang, Songwei; Wu, Guizhi; Hu, Litian

2016-01-01

Nanomaterials, such as Graphene, h-BN nanoparticles and MoS2 nanotubes, have shown their ability in improving the tribological performance of amorphous carbon (a-C) coatings. In the current study, the effectiveness of ZrO2 nanoparticles (ZrO2-NPs) in lubricating the self-mated nonhydrogenated a-C contacts was investigated in boundary lubrication regime. The results showed that 13% less friction and 50% less wear compared to the base oil were achieved by employing ZrO2-NPs in the base oil in self-mated a-C contacts. Via analyzing the ZrO2-NPs and the worn a-C surface after tests, it was found that the improved lubrication by ZrO2-NPs was based on “polishing effects”, which is a new phenomenon observed between a-C and nanoparticles. Under the “polishing effect”, micro-plateaus with extremely smooth surface and uniform height were produced on the analyzed a-C surface. The resulting topography of the a-C coating is suitable for ZrO2-NPs to act as nano-bearings between rubbing surfaces. Especially, the ZrO2-NPs exhibited excellent mechanical and chemical stability, even under the severe service condition, suggesting that the combination of nonhydrogenated a-C coating with ZrO2-NPs is an effective, long lasting and environment-friendly lubrication solution. PMID:28773916

Kinetic Monte Carlo Investigation of the Effects of Vacancy Pairing on Oxygen Diffusivity in Yttria-Stabilized Zirconia

NASA Technical Reports Server (NTRS)

Good, Brian S.

2011-01-01

Yttria-stabilized zirconia s high oxygen diffusivity and corresponding high ionic conductivity, and its structural stability over a broad range of temperatures, have made the material of interest for use in a number of applications, for example, as solid electrolytes in fuel cells. At low concentrations, the stabilizing yttria also serves to increase the oxygen diffusivity through the presence of corresponding oxygen vacancies, needed to maintain charge neutrality. At higher yttria concentration, however, diffusivity is impeded by the larger number of relatively high energy migration barriers associated with yttrium cations. In addition, there is evidence that oxygen vacancies preferentially occupy nearest-neighbor sites around either dopant or Zr cations, further affecting vacancy diffusion. We present the results of ab initio calculations that indicate that it is energetically favorable for oxygen vacancies to occupy nearest-neighbor sites adjacent to Y ions, and that the presence of vacancies near either species of cation lowers the migration barriers. Kinetic Monte Carlo results from simulations incorporating this effect are presented and compared with results from simulations in which the effect is not present.

ZrO2/MoS2 heterojunction photocatalysts for efficient photocatalytic degradation of methyl orange

NASA Astrophysics Data System (ADS)

Prabhakar Vattikuti, Surya Veerendra; Byon, Chan; Reddy, Chandragiri Venkata

2016-10-01

We report a simple solution-chemistry approach for the synthesis of ZrO2/MoS2 hybrid photocatalysts, which contain MoS2 as a cocatalyst. The material is usually obtained by a wet chemical method using ZrO(NO3)2 or (NH4)6Mo7O24·4H2O and C8H6S as precursors. The structural features of obtained materials were characterized by X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), thermal analysis (TG-DTA), N2 adsorption-desorption, and photoluminescence (PL). The influence on the photocatalytic activity of the MoS2 cocatalyst concentration with ZrO2 nanoparticles was studied. The MZr-2 hybrid sample had the highest photocatalytic activity for the degradation of methyl orange (MO), which was 8.45 times higher than that of pristine ZrO2 ascribed to high specific surface area and absorbance efficiency. Recycling experiments revealed that the reusability of the MZr-2 hybrid was due to the low photocorrosive effect and good catalytic stability. PL spectra confirmed the electronic interaction between ZrO2 and MoS2. The photoinduced electrons could be easily transferred from CB of ZrO2 to the MoS2 cocatalyst, which facilitate effective charge separation and enhanced the photocatalytic degradation in the UV region. A photocatalytic mechanism is proposed. It is believed that the ZrO2/MoS2 hybrid structure has promise as a photocatalyst with low cost and high efficiency for photoreactions.

Development of a High Temperature Heater using an Yttria Stabilized Zirconia Cored Brick Matrix

NASA Technical Reports Server (NTRS)

Smith, K. W.; Decoursin, D. G.

1971-01-01

The Ames pilot heater is a ceramic regenerative heater that provides high temperature air for aerodynamic and combustion experiments. The development of this heater to provide a heat storage bed with temperature capability of about 4600 R is described. A bed was designed and installed having cored brick elements of yttria-stabilized zirconia. The bed dimensions were 14 inches in diameter by 10 feet high. The thermal stress limitations of the bed were studied and maximum air flow rates based upon these limits were established. A combustion reheat system was designed and installed to provide the necessary control over the bed temperature distribution. The revised heater system was successfully operated at a maximum bed temperature of 4600 R. The successful operation demonstrated that yttria-stabilized zirconia cored brick can satisfy the high temperature-long duration requirement for storage heater applications.

The Evolution of Solid Oxide Fuel Cell Nickel-Yttria Stabilized Zirconia Anodes Studied Using Electrochemical and Three-Dimensional Microstructural Characterizations

NASA Astrophysics Data System (ADS)

Kennouche, David O.

This thesis focuses on Solid Oxide Fuel Cells (SOFCs). The 21st century will see major changes in the way energy is produced, stored, and used around the world. SOFCs, which provide an efficient, scalable, and low-pollution alternative method for electricity generation, are expected to play an important role. SOFCs can also be operated in electrolysis mode for energy storage, important since health and economic reasons are causing a shift towards intermittent renewable energy resources. However, multiple limitations mainly linked to cost and durability have prevented the expansion of this technology to mass markets. This work focuses on the Nickel - Yttria Stabilized Zirconia (Ni-YSZ) anode that is widely used in SOFCs. Coarsening of Ni in the Ni-YSZ anode has been widely cited as a primary cause of long-term SOFC degradation. While there have been numerous studies of Ni coarsening reported, these have typically only tracked the evolution of Ni particle size, not the entire microstructure, and have typically not been correlated directly with electrochemical performance. In this thesis, the advanced tomography techniques Focused Ion Beam - Scanning Electron Microscopy (FIB-SEM) tomography and Trans- mission X-ray Microscopy (TXM) have been utilized to enable insight into the evolution of Ni-YSZ structure and how it relates to performance degradation. Extensive anode aging studies were done for relatively short times using temperatures higher than in normal SOFC operation in order to accelerate microstructural evolution. In addition the microstructure changes were correlated with changes in anode polarization resistance. While most of the measurements were done by comparing different anodes aged under different conditions, the first example of a "pseudo in situ" measurement where the same anode was 3D imaged repeatedly with intervening aging steps, was also demonstrated. A microstructural evolution model that focuses on the active three-phase boundary density was

Sliding Wear Response of Nanostructured YSZ Suspension Plasma-Sprayed Coating

NASA Astrophysics Data System (ADS)

Kossman, S.; Chicot, D.; Decoopman, X.; Iost, A.; van Gorp, A.; Meillot, E.; Puchi-Cabrera, E. S.; Santana, Y. Y.; Staia, M. H.

2014-12-01

Nanostructured yttria-stabilized zirconia coatings for applications in high-temperature environments can be deposited by suspension plasma spraying (SPS) techniques. The present research has been conducted in order to study the sliding wear response of a SPS ZrO2-8% mol. Y2O3 coating (75 μm in thickness) deposited onto a Haynes 230 substrate, using pin-on-disc tests. Some of the coated samples were subsequently heat-treated for 1 h at 300 and 600 °C. Samples characterization prior and after the wear tests was carried out by SEM, EDS, XRD and optical profilometry techniques. Instrumented indentation was employed to determine elastic modulus and hardness. The results have shown that the as-sprayed and heat-treated samples experienced severe wear (10-13 m3/Nm) and the worst wear performance corresponded to the sample heat treated at 600 °C. Such a behavior could be related to both the structural changes that took place during heat treatment and the nature and level of the residual stresses in the coatings. In general, the morphologies of the wear tracks observed by SEM have shown a smoothing of the surface, brittle fracture, smearing and grain pull-out.

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.

Colour centre recovery in yttria-stabilised zirconia: photo-induced versus thermal processes

NASA Astrophysics Data System (ADS)

Costantini, Jean-Marc; Touati, Nadia; Binet, Laurent; Lelong, Gérald; Guillaumet, Maxime; Beuneu, François

2018-05-01

The photo-annealing of colour centres in yttria-stabilised zirconia (YSZ) was studied by electron paramagnetic resonance spectroscopy upon UV-ray or laser light illumination, and compared to thermal annealing. Stable hole centres (HCs) were produced in as-grown YSZ single crystals by UV-ray irradiation at room temperature (RT). The HCs produced by 200-MeV Au ion irradiation, as well as the F+-type centres (? centres involving oxygen vacancies) were left unchanged upon UV illumination. In contrast, a significant photo-annealing of the latter point defects was achieved in 1.4-MeV electron-irradiated YSZ by 553-nm laser light irradiation at RT. Almost complete photo-bleaching was achieved by laser irradiation inside the absorption band of ? centres centred at a wavelength 550 nm. Thermal annealing of these colour centres was also followed by UV-visible absorption spectroscopy showing full bleaching at 523 K. Colour-centre evolutions by photo-induced and thermally activated processes are discussed on the basis of charge exchange processes between point defects.

Multiobjective Optimization of Atmospheric Plasma Spray Process Parameters to Deposit Yttria-Stabilized Zirconia Coatings Using Response Surface Methodology

NASA Astrophysics Data System (ADS)

Ramachandran, C. S.; Balasubramanian, V.; Ananthapadmanabhan, P. V.

2011-03-01

Atmospheric plasma spraying is used extensively to make Thermal Barrier Coatings of 7-8% yttria-stabilized zirconia powders. The main problem faced in the manufacture of yttria-stabilized zirconia coatings by the atmospheric plasma spraying process is the selection of the optimum combination of input variables for achieving the required qualities of coating. This problem can be solved by the development of empirical relationships between the process parameters (input power, primary gas flow rate, stand-off distance, powder feed rate, and carrier gas flow rate) and the coating quality characteristics (deposition efficiency, tensile bond strength, lap shear bond strength, porosity, and hardness) through effective and strategic planning and the execution of experiments by response surface methodology. This article highlights the use of response surface methodology by designing a five-factor five-level central composite rotatable design matrix with full replication for planning, conduction, execution, and development of empirical relationships. Further, response surface methodology was used for the selection of optimum process parameters to achieve desired quality of yttria-stabilized zirconia coating deposits.

The impact of steam and current density on carbon formation from biomass gasification tar on Ni/YSZ, and Ni/CGO solid oxide fuel cell anodes

NASA Astrophysics Data System (ADS)

Mermelstein, Joshua; Millan, Marcos; Brandon, Nigel

The combination of solid oxide fuel cells (SOFCs) and biomass gasification has the potential to become an attractive technology for the production of clean renewable energy. However the impact of tars, formed during biomass gasification, on the performance and durability of SOFC anodes has not been well established experimentally. This paper reports an experimental study on the mitigation of carbon formation arising from the exposure of the commonly used Ni/YSZ (yttria stabilized zirconia) and Ni/CGO (gadolinium-doped ceria) SOFC anodes to biomass gasification tars. Carbon formation and cell degradation was reduced through means of steam reforming of the tar over the nickel anode, and partial oxidation of benzene model tar via the transport of oxygen ions to the anode while operating the fuel cell under load. Thermodynamic calculations suggest that a threshold current density of 365 mA cm -2 was required to suppress carbon formation in dry conditions, which was consistent with the results of experiments conducted in this study. The importance of both anode microstructure and composition towards carbon deposition was seen in the comparison of Ni/YSZ and Ni/CGO anodes exposed to the biomass gasification tar. Under steam concentrations greater than the thermodynamic threshold for carbon deposition, Ni/YSZ anodes still exhibited cell degradation, as shown by increased polarization resistances, and carbon formation was seen using SEM imaging. Ni/CGO anodes were found to be more resilient to carbon formation than Ni/YSZ anodes, and displayed increased performance after each subsequent exposure to tar, likely due to continued reforming of condensed tar on the anode.

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.

Selection by current compliance of negative and positive bipolar resistive switching behaviour in ZrO2-x /ZrO2 bilayer memory

NASA Astrophysics Data System (ADS)

Huang, Ruomeng; Yan, Xingzhao; Morgan, Katrina A.; Charlton, Martin D. B.; (Kees de Groot, C. H.

2017-05-01

We report here a ZrO2-x /ZrO2-based bilayer resistive switching memory with unique properties that enables the selection of the switching mode by applying different electroforming current compliances. Two opposite polarity modes, positive bipolar and negative bipolar, correspond to the switching in the ZrO2 and ZrO2-x layer, respectively. The ZrO2 layer is proved to be responsible for the negative bipolar mode which is also observed in a ZrO2 single layer device. The oxygen deficient ZrO2-x layer plays the dominant role in the positive bipolar mode, which is exclusive to the bilayer memory. A systematic investigation of the ZrO2-x composition in the bilayer memory suggests that ZrO1.8 layer demonstrates optimum switching performance with low switching voltage, narrow switching voltage distribution and good cycling endurance. An excess of oxygen vacancies, beyond this composition, leads to a deterioration of switching properties. The formation and dissolution of the oxygen vacancy filament model has been proposed to explain both polarity switching behaviours and the improved properties in the bilayer positive bipolar mode are attributed to the confined oxygen vacancy filament size within the ZrO2-x layer.

On the bulk degradation of yttria-stabilized nanocrystalline zirconia dental implant abutments: an electron backscatter diffraction study.

PubMed

Ocelík, V; Schepke, U; Rasoul, H Haji; Cune, M S; De Hosson, J Th M

2017-08-01

Degradation of yttria-stabilized zirconia dental implants abutments due to the tetragonal to monoclinic phase transformation was studied in detail by microstructural characterization using Electron Back Scatter Diffraction (EBSD). The amount and distribution of the monoclinic phase, the grain-size distribution and crystallographic orientations between tetragonal and monoclinic crystals in 3 mol.% yttria-stabilized polycrystalline zirconia (3Y-TZP) were determined in two different types of nano-crystalline dental abutments, even for grains smaller than 400 nm. An important and novel conclusion is that no substantial bulk degradation of 3Y-TZP dental implant abutments was detected after 1 year of clinical use.

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.

Thermal analysis of 3-mol%-yttria-stabilized tetragonal zirconia powder doped with copper oxide

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

Seidensticker, J.R.; Mayo, M.J.

Thermal analysis was performed upon 3-mol%-yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) which had been doped with CuO using an aqueous adsorption technique. Cyclic differential thermal analysis (DTA) scans indicated that the CuO present on the powder surfaces first transforms to Cu{sub 2}O and then melts. The molten Cu{sub 2}O then reacts with yttria at the powder surfaces to form a new phase containing Y, Cu, and O. Because Y takes time to diffuse to the particle surfaces, the apparent melting point of this new phase appears at higher temperatures in initial DTA scans than in subsequent scans. Vaporization of the moltenmore » copper-oxide-rich phase at the temperatures studied causes a gradual shift in composition from Y{sub 2}Cu{sub 4}O{sub 5} to the less copper-rich Y{sub 2}Cu{sub 2}O{sub 5} phase. The presence of the Y{sub 2}Cu{sub 2}O{sub 5} phase in CuO-doped 3Y-TZP allows for previous sintering and superplasticity results to be explained.« less

Mechanical and thermal properties of SrO/BaO modified Y2O3-Al2O3-B2O3-SiO2 glasses and their compatibility with solid oxide fuel cell components

NASA Astrophysics Data System (ADS)

Kaur, Navdeep; Kaur, Gurbinder; Kumar, Devender; Singh, K.

2018-07-01

In this study, various compositions of (30-x) SrO-xBaO-10Al2O3-45SiO2-5B2O3-10Y2O3 (mol%) (5 ≤ x ≤ 25) were synthesized using the melt-quench technique. The as-prepared glasses were characterized by X-ray diffraction, micro-hardness testing, dilatometry, and scanning electron microscopy to determine their thermal and mechanical properties. Powders of the glasses were used to make diffusion couples with Crofer 22 APU (interconnect) and yttria stabilized zirconia (YSZ) for the interfacial study. Diffusion couples of the pre-oxidized Crofer 22 APU/glasses and YSZ/glasses were tested for 500 h at 850 °C. The coefficients of thermal expansion obtained for all the glasses were in the required range for applications in solid oxide fuel cells. The highest hardness and fracture toughness were obtained for the glass with x = 10 mol% due to the mixed modifier effect. However, the glass with x = 15 mol% exhibited better adhesion with YSZ and Crofer 22 APU.

Artificial in-plane ordering of textured YBa2Cu3O(7-x) films deposited on polycrystalline yttria-stabilized zirconia substrates

NASA Astrophysics Data System (ADS)

Harshavardhan, K. S.; Rajeswari, M.; Hwang, D. M.; Chen, C. Y.; Sands, T. D.; Venkatesan, T.; Tkaczyk, J. E.; Lay, K. W.; Safari, A.; Johnson, L.

1992-12-01

Anisotropic surface texturing of the polycrystalline yttria-stabilized zirconia substrates, prior to YBa2Cu3O(7-x) film deposition, is shown to promote in-plane (basal plane) ordering of the film growth in addition to the c-axis texturing. The Jc's of the films in the weak-link-dominated low-field regime are enhanced considerably, and this result is attributed to the reduction of weak links resulting from a reduction in the number of in-plane large-angle grain boundaries.

Defect studies of nanocrystalline zirconia powders and sintered ceramics

NASA Astrophysics Data System (ADS)

Čížek, Jakub; Melikhova, Oksana; Procházka, Ivan; Kuriplach, Jan; Kužel, Radomír; Brauer, Gerhard; Anwand, Wolfgang; Konstantinova, Tatyana E.; Danilenko, Igor A.

2010-01-01

The main objective of the present paper is to communicate a study of defects behavior in zirconia-based nanomaterials—pressure-compacted yttria-stabilized zirconia (YSZ) nanopowders with different contents of Y2O3 and ceramics obtained by sintering the YZS nanopowders. In addition, YZS single crystals were also investigated. Positron annihilation techniques including positron lifetime and coincidence Doppler broadening with a conventional positron source and Doppler broadening experiments on a monoenergetic positron beam were involved in this study as the principal tools. These techniques were supplemented with transmission electron microscopy and x-ray diffraction observations. In order to get better support of the experimental data interpretation, the state-of-art theoretical calculations of positron parameters were performed for the perfect ZrO2 lattice and selected defect configurations in the YSZ. Theoretical calculations have indicated that neither the oxygen vacancies nor their neutral complexes with substitutional yttrium atoms are capable of positron trapping. On the other hand, the zirconium vacancies are deep positron traps and obviously are responsible for the saturated positron trapping observed in the YSZ single crystals. In the compacted YSZ nanopowders, a majority of positrons is trapped either in the vacancylike defects situated in the negative space-charge layers along grain boundaries (τ1≈185ps) or in vacancy clusters at intersections of grain boundaries (τ2≈370ps) . The intensity ratio I2/I1 was found to be correlated with the mean grain size d as I2/I1˜d-2 . A small fraction of positrons (≈10%) form positronium in large pores (τ3≈2ns,τ4≈30ns) . A significant grain growth during sintering of the YSZ nanopowders above 1000°C was observed.

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

Suspension chemistry and electrophoretic deposition of zirconia electrolyte on conducting and non-conducting substrates

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

Das, Debasish; Basu, Rajendra N., E-mail: rnbasu@cgcri.res.in

2013-09-01

Graphical abstract: - Highlights: • Stable suspension of yttria stabilized zirconia (YSZ) obtained in isopropanol medium. • Suspension chemistry and process parameters for electrophoretic deposition optimized. • Deposited film quality changed with iodine and water (dispersants) concentration. • Dense YSZ film (∼5 μm) fabricated onto non-conducting porous NiO-YSZ anode substrate. - Abstract: Suspensions of 8 mol% yttria stabilized zirconia (YSZ) particulates in isopropanol medium are prepared using acetylacetone, iodine and water as dispersants. The effect of dispersants concentration on suspension stability, particle size distribution, electrical conductivity and pH of the suspensions are studied in detail to optimize the suspension chemistry.more » Electrophoretic deposition (EPD) has been conducted to produce thin and dense YSZ electrolyte films. Deposition kinetics have been studied in depth and good quality films on conducting substrate are obtained at an applied voltage of 15 V for 3 min. YSZ films are also fabricated on non-conducting NiO-YSZ anode substrate using a steel plate on the reverse side of the substrate. Upon co-firing at 1400 °C for 6 h a dense YSZ film of thickness ∼5 μm is obtained. Such a half cell (anode + electrolyte) can be used to fabricate a solid oxide fuel cell on applying a suitable cathode layer.« less

Generation of colour centres in yttria-stabilized zirconia by heavy ion irradiations in the GeV range.

PubMed

Costantini, Jean-Marc; Beuneu, François; Schwartz, Kurt; Trautmann, Christina

2010-08-11

We have studied the colour centre production in yttria-stabilized zirconia (ZrO(2):Y(3 +)) by heavy ion irradiation in the GeV range using on-line UV-visible optical absorption spectroscopy. Experiments were performed with 11.4 MeV amu(-1) (127)Xe, (197)Au, (208)Pb and (238)U ion irradiations at 8 K or room temperature (RT). A broad and asymmetrical absorption band peaked at a wavelength about 500 nm is recorded regardless of the irradiation parameters, in agreement with previous RT irradiations with heavy ions in the 100 MeV range. This band is de-convoluted into two broad Gaussian-shaped bands centred at photon energies about 2.4 and 3.1 eV that are respectively associated with the F(+)-type centres (involving a singly ionized oxygen vacancy, VO· and T centres (i.e. Zr(3+) in a trigonal symmetry) observed by electron paramagnetic resonance (EPR) spectroscopy. In the case of 8 K Au ion irradiation at low fluences, six bands are used at about 1.9, 2.3, 2.7, 3.1 and 4.0 eV. The three bands near 2.0-2.5 eV can be assigned to oxygen divacancies (i.e. F(2)(+) centres). No significant effect of the irradiation temperature is found on the widths of all absorption bands for the same ion and fluence. This is attributed to the inhomogeneous broadening arising from the static disorder due to the native charge-compensating oxygen vacancies. However, the colour centre production yield is strongly enhanced at 8 K with respect to RT. When heating irradiated samples from 8 K to RT, the extra colour centres produced at low temperature do not recover completely to the level of RT irradiation. The latter results are accounted for by an electronically driven defect recovery process.

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

Corrosion and Wear Response of Oxide-Reinforced Nickel Composite Coatings

NASA Astrophysics Data System (ADS)

Tirlapur, Pradeep; Muniprakash, M.; Srivastava, Meenu

2016-07-01

Various grades of fuels are used in automobiles, as a result the engine components are continuously subjected to simultaneous action of corrosion and wear. Ni-SiC composite coating is the most widely investigated and commercialized wear-resistant coating in the automotive industry. However, this coating cannot be used at temperatures above 450 °C due to the tendency of SiC to react with Ni and form brittle silicides. An alternate approach is to use oxide-reinforced coatings. In the present study, zirconia, ZrO2 and, yttria-stabilized zirconia, YSZ-reinforced Ni composite coatings have been developed by electrodeposition method. It was observed from the microhardness studies that there is no significant difference in the values for Ni-SiC and Ni-ZrO2 coatings. The corrosion behavior was evaluated using polarization and electrochemical impedance studies. The studies showed that oxide particle-reinforced Ni coatings possessed better corrosion resistance due to their lower corrosion current density, I corr. Tribo-corrosion studies were carried out to understand the synergistic effect of wear and corrosion on the performance of Ni-based composite coatings in 0.5 M Na2SO4. Among various composite coatings, Ni-YSZ exhibited less material loss thereby showing better tribo-corrosion behavior.

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

PubMed Central

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

2014-01-01

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. PMID:27877628

Composite Matrix Experimental Combustor

DTIC Science & Technology

1994-04-01

utilized zirconia powder prereacted with 12 weight-percent yt- tria stabilizer (12-YSZ) with good results. Subsequent investigations indicated that...YSZ. The choice of material for the ceramic layer also considered work at Allison using 6-8 w/o yttria-stabi- lized zirconia powder obtained from the

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.

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.; Mitchell, T. E.

1981-01-01

A commercially available bulk 4.5 mole percent yttria-(Y2O3) partially stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging curves were constructed for both the as received and the solution annealed and quenched materials; the curves showed hardness peaks at 1397 and 1517 Kg/sq mm respectively. The rectangular plate shaped tetragonal precipitates were found to have a 110 habit plane. A total of twelve different types of tetragonal precipitates were found. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinc phase, thus indicating that transformation toughening is not a significant mechanism for the material.

Effect of Suspension Plasma-Sprayed YSZ Columnar Microstructure and Bond Coat Surface Preparation on Thermal Barrier Coating Properties

NASA Astrophysics Data System (ADS)

Bernard, Benjamin; Quet, Aurélie; Bianchi, Luc; Schick, Vincent; Joulia, Aurélien; Malié, André; Rémy, Benjamin

2017-08-01

Suspension plasma spraying (SPS) is identified as promising for the enhancement of thermal barrier coating (TBC) systems used in gas turbines. Particularly, the emerging columnar microstructure enabled by the SPS process is likely to bring about an interesting TBC lifetime. At the same time, the SPS process opens the way to a decrease in thermal conductivity, one of the main issues for the next generation of gas turbines, compared to the state-of-the-art deposition technique, so-called electron beam physical vapor deposition (EB-PVD). In this paper, yttria-stabilized zirconia (YSZ) coatings presenting columnar structures, performed using both SPS and EB-PVD processes, were studied. Depending on the columnar microstructure readily adaptable in the SPS process, low thermal conductivities can be obtained. At 1100 °C, a decrease from 1.3 W m-1 K-1 for EB-PVD YSZ coatings to about 0.7 W m-1 K-1 for SPS coatings was shown. The higher content of porosity in the case of SPS coatings increases the thermal resistance through the thickness and decreases thermal conductivity. The lifetime of SPS YSZ coatings was studied by isothermal cyclic tests, showing equivalent or even higher performances compared to EB-PVD ones. Tests were performed using classical bond coats used for EB-PVD TBC coatings. Thermal cyclic fatigue performance of the best SPS coating reached 1000 cycles to failure on AM1 substrates with a β-(Ni,Pt)Al bond coat. Tests were also performed on AM1 substrates with a Pt-diffused γ-Ni/γ'-Ni3Al bond coat for which more than 2000 cycles to failure were observed for columnar SPS YSZ coatings. The high thermal compliance offered by both the columnar structure and the porosity allowed the reaching of a high lifetime, promising for a TBC application.

[Effects of colorants on yttria stabilized tetragonal zirconia polycrystals powder].

PubMed

Wang, Bo; Chen, Jianfeng; Zhang, Yanchun; Wang, Ru

2015-10-01

To evaluate the effect of Fe2O3 and CeO2 as colorants on yttria stabilized tetragonal zirconia poly-crystals (Y-TZP) powder. The spray granulation slurry of colored zirconia was prepared with different concentrations of Fe2O3 (0.15%) and CeO2 (4%), which were added in Y-TZP. Zirconia powder was made by spray granulation. The powder specimens were divided into three groups: uncolored zirconia, Fe2O3 (0.15%) zirconia, and CeO2 (4%) zirconia. The particle morphologies of the powder specimens were measured with a laser particle size analyzer and an optical microscope. The differences in D50 among the three groups were statistically significant (P<0.05). Group Fe2O3 showed a significant difference from groups CeO2 and uncolored zirconia (P<0.05). Group uncolored zirconia showed no significant difference from group CeO2 (P>0.05). Mostly spherical powder was observed in the three groups. Fe2O3 as a colorant can affect particles, whereas CeO2 has no effect.

Failure Analysis of Multilayered Suspension Plasma-Sprayed Thermal Barrier Coatings for Gas Turbine Applications

NASA Astrophysics Data System (ADS)

Gupta, M.; Markocsan, N.; Rocchio-Heller, R.; Liu, J.; Li, X.-H.; Östergren, L.

2018-02-01

Improvement in the performance of thermal barrier coatings (TBCs) is one of the key objectives for further development of gas turbine applications. The material most commonly used as TBC topcoat is yttria-stabilized zirconia (YSZ). However, the usage of YSZ is limited by the operating temperature range which in turn restricts the engine efficiency. Materials such as pyrochlores, perovskites, rare earth garnets are suitable candidates which could replace YSZ as they exhibit lower thermal conductivity and higher phase stability at elevated temperatures. The objective of this work was to investigate different multilayered TBCs consisting of advanced topcoat materials fabricated by suspension plasma spraying (SPS). The investigated topcoat materials were YSZ, dysprosia-stabilized zirconia, gadolinium zirconate, and ceria-yttria-stabilized zirconia. All topcoats were deposited by TriplexPro-210TM plasma spray gun and radial injection of suspension. Lifetime of these samples was examined by thermal cyclic fatigue and thermal shock testing. Microstructure analysis of as-sprayed and failed specimens was performed with scanning electron microscope. The failure mechanisms in each case have been discussed in this article. The results show that SPS could be a promising route to produce multilayered TBCs for high-temperature applications.

Improved Epitaxy and Surface Morphology in YBa2Cu3Oy Thin Films Grown on Double Buffered Si Wafers

NASA Astrophysics Data System (ADS)

Gao, J.; Kang, L.; Wong, H. Y.; Cheung, Y. L.; Yang, J.

Highly epitaxial thin films of YBCO have been obtained on silicon wafers using a Eu2CuO4/YSZ (yttrium-stabilized ZrO2) double buffer. Our results showed that application of such a double buffer can significantly enhance the epitaxy of grown YBCO. It also leads to an excellent surface morphology. The average surface roughness was found less than 5 nm in a large range. The results of X-ray small angle reflection and positron spectroscpy demonstrate a very clear and flat interface between YBCO and buffer layers. The Eu2CuO4/YSZ double buffer could be promising for coating high-TC superconducting films on various reactive substrates.

Ion beam synthesis of Fe nanoparticles in MgO and yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Potzger, K.; Reuther, H.; Zhou, Shengqiang; Mücklich, A.; Grötzschel, R.; Eichhorn, F.; Liedke, M. O.; Fassbender, J.; Lichte, H.; Lenk, A.

2006-04-01

To form embedded Fe nanoparticles, MgO(001) and YSZ(001) single crystals have been implanted at elevated temperatures with Fe ions at energies of 100 keV and 110 keV, respectively. The ion fluence was fixed at 6×1016 cm-2. As a result, γ- and α-phase Fe nanoparticles were synthesized inside MgO and YSZ, respectively. A synthesis efficiency of 100% has been achieved for implantation at 1273 K into YSZ. The ferromagnetic behavior of the α-Fe nanoparticles is reflected by a magnetic hyperfine field of 330 kOe and a hysteretic magnetization reversal. Electron holography showed a fringing magnetic field around some, but not all of the particles.

(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.

YSZ thin films with minimized grain boundary resistivity

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

Mills, Edmund M.; Kleine-Boymann, Matthias; Janek, Juergen

2016-03-31

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e. g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here we report that the ionic conductivity ofmore » yttria stabilized zirconia thin films with nano-­ columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500°C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film- substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.« less

YSZ thin films with minimized grain boundary resistivity

DOE PAGES

Mills, Edmund M.; Kleine-Boymann, Matthias; Janek, Juergen; ...

2016-03-31

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e.g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here in this paper, we report that the ionicmore » conductivity of yttria stabilized zirconia thin films with nano-columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500 °C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film–substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg 2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.« less

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.

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.; Mitchell, T. E.

1981-01-01

A commercially available bulk 4.5 mole percent yttria-Y2O3)-partially-stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging cuves were constructed for both the as-received and the solution-annealed-and-quenched materials; the curves showed hardness peaks at 1397 and 1517 kg/sq mm, respectively. A total of twelve different types of tetragonal precipitates were found. The rectangular plate-shaped tetragonal precipitates were found to have a (110) habit plane. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinic phase, thus indicating that transformation toughening is not a significant mechanism for the material. The fracture toughness of the aged and of the unaged solution-annealed-and-quenched PSZ was found to be between 2 and 3 MN/cu m/2.

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

Environmental Barrier Coatings for Silicon-Based Ceramics

NASA Technical Reports Server (NTRS)

Lee, Kang N.; Fox, Dennis S.; Robinson, Raymond C.; Bansal, Narottam P.

2001-01-01

Silicon-based ceramics, such as SiC fiber-reinforced SiC (SiC/SiC ceramic matrix composites (CMC) and monolithic silicon nitride (Si3N4), are prime candidates for hot section structural components of next generation gas turbine engines. Silicon-based ceramics, however, suffer from rapid surface recession in combustion environments due to volatilization of the silica scale via reaction with water vapor, a major product of combustion. Therefore, application of silicon-based ceramic components in the hot section of advanced gas turbine engines requires development of a reliable method to protect the ceramic from environmental attack. An external environmental barrier coating (EBC) is considered a logical approach to achieve protection and CP long-term stability. The first generation EBC consisted of two layers, mullite (3Al2O3-2SiO2) bond coat and yttria-stabilized zirconia (YSZ, ZrO2-8 Wt.% Y2O3) top coat. Second generation EBCs, with substantially improved performance compared with the first generation EBC, were developed in the NASA High Speed Research-Enabling Propulsion Materials (HSR-EPM) Program. The first generation EBC consisted of two layers, mullite (3Al2O3-2SiO2) bond coat and yttria-stabilized zirconia (YSZ, ZrO2-8 wt.% Y2O3) top coat. Second generation EBCs, with substantially improved performance compared with the first generation EBC, were developed in the NASA High Speed Research-Enabling Propulsion Materials (HSR-EPM) Program (5). They consist of three layers, a silicon first bond coat, a mullite or a mullite + BSAS (BaO(1-x)-SrO(x)-Al2O3-2SiO2) second bond coat, and a BSAS top coat. The EPM EBCs were applied on SiC/SiC CMC combustor liners in three Solar Turbines (San Diego, CA) Centaur 50s gas turbine engines. The combined operation of the three engines has accumulated over 24,000 hours without failure (approximately 1,250 C maximum combustor liner temperature), with the engine in Texaco, Bakersfield, CA, accumulating about 14,000 hours. As the

Diamagnetic to ferromagnetic switching in VO2 epitaxial thin films by nanosecond excimer laser treatment

NASA Astrophysics Data System (ADS)

Molaei, R.; Bayati, R.; Nori, S.; Kumar, D.; Prater, J. T.; Narayan, J.

2013-12-01

VO2(010)/NiO(111) epitaxial heterostructures were integrated with Si(100) substrates using a cubic yttria-stabilized zirconia (c-YSZ) buffer. The epitaxial alignment across the interfaces was determined to be VO2(010)‖NiO(111)‖c-YSZ(001)‖Si(001) and VO2[100]‖NiO⟨110⟩‖c-YSZ⟨100⟩‖Si⟨100⟩. The samples were subsequently treated by a single shot of a nanosecond KrF excimer laser. Pristine as-deposited film showed diamagnetic behavior, while laser annealed sample exhibited ferromagnetic behavior. The population of majority charge carriers (e-) and electrical conductivity increased by about two orders of magnitude following laser annealing. These observations are attributed to the introduction of oxygen vacancies into the VO2 thin films and the formation of V3+ defects.

Intermediate coating layer for high temperature rubbing seals for rotary regenerators

DOEpatents

Schienle, James L.; Strangman, Thomas E.

1995-01-01

A metallic regenerator seal is provided having multi-layer coating comprising a NiCrAlY bond layer, a yttria stabilized zirconia (YSZ) intermediate layer, and a ceramic high temperature solid lubricant surface layer comprising zinc oxide, calcium fluoride, and tin oxide. Because of the YSZ intermediate layer, the coating is thermodynamically stable and resists swelling at high temperatures.

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.

Cubic zirconia as a species permeable coating for zinc diffusion in gallium arsenide

NASA Astrophysics Data System (ADS)

Bisberg, J. E.; Dabkowski, F. P.; Chin, A. K.

1988-10-01

Diffusion of zinc into GaAs through an yttria-stabilized cubic zirconia (YSZ) passivation layer has been demonstrated with an open-tube diffusion method. Pure zinc or GaAs/Zn2As3 sources produced high quality planar p-n junctions. The YSZ layer protects the GaAs surface from excessive loss of arsenic, yet is permeable to zinc, allowing its diffusion into the semiconductor. The YSZ films, deposited by electron beam evaporation, were typically 2000 Å thick. Zinc diffusion coefficients (DT) at 650 °C in the YSZ passivated GaAs ranged from 3.6×10-10 cm2/min for the GaAs/Zn2As3 source to 1.9×10-9 cm2/min for the pure zinc source. Doping concentrations for both YSZ passivated and uncapped samples were approximately 5×1019 cm-3.

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.

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.

Characterization of ZrO2 and (ZrO2)x(Al2O3)1-X thin films on Si substrates: effect of the Al2O3 component

NASA Astrophysics Data System (ADS)

Vitanov, P.; Harizanova, A.; Ivanova, T.

2014-05-01

ZrO2 and (ZrO2)x(Al2O3)1-x films were deposited by the sol-gel technique on Si substrates. The effect of the Al2O3 additive on the film surface morphology was studied by atomic force microscopy (AFM). The mixed oxide films showed a smoother morphology and lower values of the root-mean-square (RMS) roughness compared to ZrO2. Further, FTIR spectra indicated that ZrO2 underwent crystallization. The electrical measurements of the MIS structure revealed that the presence of Al2O3 and the amorphization affects its dielectric properties. The MIS structure with (ZrO2)x(Al2O3)1-x showed a lower fixed charge (~ 6×1010 cm-2) and an interface state density in the middle of the band gap of 6×1011 eV-1 cm-2). The dielectric constant measured was 22, with the leakage current density decreasing to 2×10-8 A cm-2 at 1×106 V cm-1.

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.

Effect of SiO 2-ZrO 2 supports prepared by a grafting method on hydrogen production by steam reforming of liquefied natural gas over Ni/SiO 2-ZrO 2 catalysts

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Song, In Kyu

SiO 2-ZrO 2 supports with various zirconium contents are prepared by grafting a zirconium precursor onto the surface of commercial Carbosil silica. Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of SiO 2-ZrO 2 supports on the performance of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts is investigated. SiO 2-ZrO 2 prepared by a grafting method serves as an efficient support for the nickel catalyst in the steam reforming of LNG. Zirconia enhances the resistance of silica to steam significantly and increases the interaction between nickel and the support, and furthermore, prevents the growth of nickel oxide species during the calcination process through the formation of a ZrO 2-SiO 2 composite structure. The crystalline structures and catalytic activities of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are strongly influenced by the amount of zirconium grafted. The conversion of LNG and the yield of hydrogen show volcano-shaped curves with respect to zirconium content. Among the catalysts tested, the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) sample shows the best catalytic performance in terms of both LNG conversion and hydrogen yield. The well-developed and pure tetragonal phase of ZrO 2-SiO 2 (Zr/Si = 0.54) appears to play an important role in the adsorption of steam and subsequent spillover of steam from the support to the active nickel. The small particle size of the metallic nickel in the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) catalyst is also responsible for its high performance.

Validating the technological feasibility of yttria-stabilized zirconia-based semiconducting-ionic composite in intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Cai, Yixiao; Wang, Baoyuan; Wang, Yi; Xia, Chen; Qiao, Jinli; van Aken, Peter A.; Zhu, Bin; Lund, Peter

2018-04-01

YSZ as the electrolyte of choice has dominated the progressive development of solid oxide fuel cell (SOFC) technologies for many years. To enable SOFCs operating at intermediate temperatures of 600 °C or below, major technical advances were built on a foundation of a thin-film YSZ electrolyte, NiO anode, and perovskite cathode, e.g. La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF). Inspired by functionalities in engineered heterostructure interfaces, the present work uses the components from state-of-the-art SOFCs, i.e, the anode NiO-YSZ and the cathode LSCF-YSZ, or the convergence of all three components, i.e., NiO-YSZ-LSCF, to fabricate semiconductor-ionic membranes (SIMs) and devices. A series of proof-of-concept fuel cell devices are designed by using each of the above SIMs sandwiched between two semiconducting Ni0.8Co0.15Al0.05LiO2-δ (NCAL) layers. We systematically compare these novel designs at 600 °C with two reference fuel cells: a commercial product of anode-supported YSZ electrolyte thin-film cell, and a lab-assembled fuel cell with a conventional configuration of NiO-YSZ (anode)/YSZ (electrolyte)/LSCF-YSZ (cathode). In comparison to the reference cells, the SIM device in a configuration of NCAL/NiO-YSZ-LSCF/NCAL reaches more than 3-fold enhancement of the maximum power output. By using spherical aberration-corrected transmission electron microscopy and spectroscopy approaches, this work offers insight into the mechanisms underlying SIM-associated SOFC performance enhancement.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

Suspensions Plasma Spraying of Ceramics with Hybrid Water-Stabilized Plasma Technology

NASA Astrophysics Data System (ADS)

Musalek, Radek; Medricky, Jan; Tesar, Tomas; Kotlan, Jiri; Pala, Zdenek; Lukac, Frantisek; Chraska, Tomas; Curry, Nicholas

2017-01-01

Technology of water-stabilized plasma torch was recently substantially updated through introduction of a so-called hybrid concept that combines benefits of water stabilization and gas stabilization principles. The high-enthalpy plasma provided by the WSP-H ("hybrid") torch may be used for thermal spraying of powders as well as liquid feedstocks with high feed rates. In this study, results from three selected experiments with suspension plasma spraying with WSP-H technology are presented. Possibility of deposition of coatings with controlled microstructures was demonstrated for three different ceramics (YSZ—yttria-stabilized zirconia, YAG—yttrium aluminum garnet and Al2O3) introduced into ethanol-based suspensions. Shadowgraphy was used for optimization of suspension injection and visualization of the liquid fragmentation in the plasma jet. Coatings were deposited onto substrates attached to the rotating carousel with integrated temperature monitoring and air cooling, which provided an excellent reproducibility of the deposition process. Deposition of columnar-like YSZ and dense YAG and Al2O3 coatings was successfully achieved. Deposition efficiency reached more than 50%, as evaluated according to EN ISO 17 836 standard.

Synthesis of Zr2WP2O12/ZrO2 Composites with Adjustable Thermal Expansion.

PubMed

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

2017-01-01

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

Characterization and durability testing of plasma-sprayed zirconia-yttria and hafnia-yttria thermal barrier coatings. Part 2: Effect of spray parameters on the performance of several hafnia-yttria and zirconia-yttria coatings

NASA Technical Reports Server (NTRS)

Miller, Robert A.; Leissler, George W.

1993-01-01

This is the second of two reports which discuss initial experiments on thermal barrier coatings prepared and tested in newly upgraded plasma spray and burner rig test facilities at LeRC. The first report, part 1, describes experiments designed to establish the spray parameters for the baseline zirconia-yttria coating. Coating quality was judged primarily by the response to burner rig exposure, together with a variety of other characterization approaches including thermal diffusivity measurements. That portion of the study showed that the performance of the baseline NASA coating was not strongly sensitive to processing parameters. In this second part of the study, new hafnia-yttria coatings were evaluated with respect to both baseline and alternate zirconia-yttria coatings. The hafnia-yttria and the alternate zirconia-yttria coatings were very sensitive to plasma-spray parameters in that high-quality coatings were obtained only when specific parameters were used. The reasons for this important observation are not understood.

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

Effect of synthesis process on the microstructure and electrical conductivity of nickel/yttria-stabilized zirconia powders prepared by urea hydrolysis

NASA Astrophysics Data System (ADS)

Lin, Jyung-Dong; Wu, Zhao-Lun

In this study, NiO/YSZ composite powders were synthesized using hydrolysis on two solutions, one contains YSZ particles and Ni 2+ ion, and the other contains NiO particles, Zr 4+, and Y 3+ ions, with the aid of urea. The microstructure of the powders and sintered bulks was further characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicated that various synthesis processes yielded NiO/YSZ powders with different morphologies. The NiO precursors would deposit onto the surface of YSZ particles, and NiO-deposited YSZ composite powders were obtained. Alternatively, it was not observed that YSZ precursors deposited onto the surface of NiO particles, thus, a uniform powder mixture of fine NiO and fine YSZ particles was produced. After sintering and subsequent reduction, these powders would lead to the variations of Ni distribution in the YSZ matrix and conductivity of cermets. Owing to the core-shell structure of the powders and the higher size ratio of YSZ and NiO particles, the conductivity of cermet with NiO-deposited YSZ powders containing 23 wt% NiO is comparable to those with a NiO/YSZ powder mixture containing 50 wt% NiO.

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%.

Reactions of yttria-stabilized zirconia with oxides and sulfates of various elements

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1978-01-01

The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).

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.

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet and magnesium oxide.

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet, and magnesium oxide.

Advanced study of thermal behaviour of CSZ comparing with the classic YSZ coating

NASA Astrophysics Data System (ADS)

Dragomirescu, A.; Constantin, N.; Ştefan, A.; Manoliu, V.; Truşcă, R.

2017-01-01

Thermal barrier coatings (TBC) are advanced materials typically applied to metal surfaces subjected to extreme temperatures to protect them and increase their lifetime. Ceria stabilized zirconia ceramic layer (CSZ) is increasingly used as an alternative improved as replace for classical TBC system - yttria stabilized zirconia - thanks to superior properties, including mechanical and high resistance to thermal corrosion. The paper describes the thermal shock testing of two types of thermal barrier coatings used to protect a nickel super alloy. For the experimental procedure, it was used plate samples from nickel super alloy with a bond coat and a ceramic top coat. The top coat was different: on some samples, it was used YSZ and on others CSZ. Ni based super alloys have good corrosion resistance in reducing environments action, but poor in oxidizing conditions. Extreme environments can lead to loss of material by oxidation / corrosion, along with decreased mechanical properties of the substrate due to damaging elements which diffuses into the substrate at high temperatures. Using laboratory equipment, the TBC systems were exposed repeatedly to extreme high temperatures for a short time and then cooled. After the thermal shock tests, the samples were morph-structured characterized using electronic microscopy to analyze the changes. The experimental results were compared to rank the TBC systems in order of performance.

Small stack performance of intermediate temperature-operating solid oxide fuel cells using stainless steel interconnects and anode-supported single cell

NASA Astrophysics Data System (ADS)

Bae, Joongmyeon; Lim, Sungkwang; Jee, Hyunjin; Kim, Jung Hyun; Yoo, Young-Sung; Lee, Taehee

We are developing 1 kW class solid oxide fuel cell (SOFC) system for residential power generation (RPG) application supported by Korean Government. Anode-supported single cells with thin electrolyte layer of YSZ (yttria-stabilized zirconia) or ScSZ (scandia-stabilized zirconia) for intermediate temperature operation (650-750 °C), respectively, were fabricated and small stacks were built and evaluated. The LSCF/ScSZ/Ni-YSZ single cell showed performance of 543 mW cm -2 at 650 °C and 1680 mW cm -2 at 750 °C. The voltage of 15-cell stack based on 5 cm × 5 cm single cell (LSM/YSZ/Ni-YSZ) at 150 mW was 12.5 V in hydrogen as fuel of 120 sccm per cell at 750 °C and decreased to about 10.9 V at 500 h operation time. A 5-cell stack based on the LSCF/YSZ/FL/Ni-YSZ showed the maximum power density of 30 W, 25 W and 20 W at 750 °C, 700 °C and 650 °C, respectively. LSCF/ScSZ/Ni-YSZ-based stack showed better performance than LSCF/YSZ/Ni-YSZ stack from the experiment temperature range. I- V characteristics by using hydrogen gas and reformate gas of methane as fuel were investigated at 750 °C in LSCF/ScSZ/FL/Ni-YSZ-based 5-cell stack.

Flexible Mixed-Potential-Type (MPT) NO2 Sensor Based on An Ultra-Thin Ceramic Film

PubMed Central

You, Rui; Jing, Gaoshan; Yu, Hongyan; Cui, Tianhong

2017-01-01

A novel flexible mixed-potential-type (MPT) sensor was designed and fabricated for NO2 detection from 0 to 500 ppm at 200 °C. An ultra-thin Y2O3-doped ZrO2 (YSZ) ceramic film 20 µm thick was sandwiched between a heating electrode and reference/sensing electrodes. The heating electrode was fabricated by a conventional lift-off process, while the porous reference and the sensing electrodes were fabricated by a two-step patterning method using shadow masks. The sensor’s sensitivity is achieved as 58.4 mV/decade at the working temperature of 200 °C, as well as a detection limit of 26.7 ppm and small response time of less than 10 s at 200 ppm. Additionally, the flexible MPT sensor demonstrates superior mechanical stability after bending over 50 times due to the mechanical stability of the YSZ ceramic film. This simply structured, but highly reliable flexible MPT NO2 sensor may lead to wide application in the automobile industry for vehicle emission systems to reduce NO2 emissions and improve fuel efficiency. PMID:28758933

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.

Effects of compositional changes on the performance of a thermal barrier coating system. [yttria-stabilized zirconia coatings on gas turbine engine blades

NASA Technical Reports Server (NTRS)

Stecura, S.

1978-01-01

Currently proposed thermal barrier systems for aircraft gas turbine engines consist of NiCrAlY bond coating covered with an insulating oxide layer of yttria-stabilized zirconia. The effect of yttrium concentration (from 0.15 to 1.08 w/o) in the bond coating and the yttria concentration (4 to 24.4 w/o) in the oxide layer were evaluated. Furnace, natural gas-oxygen torch, and Mach 1.0 burner rig cyclic tests on solid specimens and air-cooled blades were used to identify trends in coating behavior. Results indicate that the combinations of yttrium levels between 0.15 - 0.35 w/o in the bond coating and the yttria concentration between 6 - 8 w/o in the zirconium oxide layer were the most adherent and resistant to high temperature cyclic exposure.

Adsorption as a method of doping 3-mol%-yttria-stabilized zirconia powder with copper oxides

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

Seidensticker, J.R.; Mayo, M.J.; Osseo-Asare, K.

The adsorption behavior of Cu[sup 2+] on 3-mol%-yttria-stabilized tetragonal zirconia polycrystalline (3Y-TZP) powder was studied. There is a window of pH values (10 < pH < 11) where adsorption may be used as a method of doping 3Y-TZP with Cu[sup 2+]. The maximum mole percent of the CuO additions is determined by the specific surface area of the 3Y-TZP powder; a powder with a specific surface area of 16.1 m[sup 2]/g is limited to about 1 mol% CuO. Compacts made from powders doped with CuO using this method exhibited an enhancement in superplasticity comparable to that observed in other studiesmore » using samples doped with CuO by attrition milling.« less

Calculations of single crystal elastic constants for yttria partially stabilised zirconia from powder diffraction data

NASA Astrophysics Data System (ADS)

Lunt, A. J. G.; Xie, M. Y.; Baimpas, N.; Zhang, S. Y.; Kabra, S.; Kelleher, J.; Neo, T. K.; Korsunsky, A. M.

2014-08-01

Yttria Stabilised Zirconia (YSZ) is a tough, phase-transforming ceramic that finds use in a wide range of commercial applications from dental prostheses to thermal barrier coatings. Micromechanical modelling of phase transformation can deliver reliable predictions in terms of the influence of temperature and stress. However, models must rely on the accurate knowledge of single crystal elastic stiffness constants. Some techniques for elastic stiffness determination are well-established. The most popular of these involve exploiting frequency shifts and phase velocities of acoustic waves. However, the application of these techniques to YSZ can be problematic due to the micro-twinning observed in larger crystals. Here, we propose an alternative approach based on selective elastic strain sampling (e.g., by diffraction) of grain ensembles sharing certain orientation, and the prediction of the same quantities by polycrystalline modelling, for example, the Reuss or Voigt average. The inverse problem arises consisting of adjusting the single crystal stiffness matrix to match the polycrystal predictions to observations. In the present model-matching study, we sought to determine the single crystal stiffness matrix of tetragonal YSZ using the results of time-of-flight neutron diffraction obtained from an in situ compression experiment and Finite Element modelling of the deformation of polycrystalline tetragonal YSZ. The best match between the model predictions and observations was obtained for the optimized stiffness values of C11 = 451, C33 = 302, C44 = 39, C66 = 82, C12 = 240, and C13 = 50 (units: GPa). Considering the significant amount of scatter in the published literature data, our result appears reasonably consistent.

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.

Characterization and durability testing of plasma-sprayed zirconia-yttria and hafnia-yttria thermal barrier coatings. Part 1: Effect of spray parameters on the performance of several lots of partially stabilized zirconia-yttria powder

NASA Technical Reports Server (NTRS)

Miller, Robert A.; Leissler, George W.; Jobe, J. Marcus

1993-01-01

Initial experiments conducted on thermal barrier coatings prepared in the newly upgraded research plasma spray facility and the burner rig test facilities are discussed. Part 1 discusses experiments which establish the spray parameters for three baseline zirconia-yttria coatings. The quality of five similar coating lots was judged primarily by their response to burner rig exposure supplemented by data from other sources such as specimen characterizations and thermal diffusivity measurements. After allowing for burner rig variability, although there appears to be an optimum density (i.e., optimum microstructure) for maximum burner rig life, the distribution tends to be rather broad about the maximum. In Part 2, new hafnia-yttria-based coatings were evaluated against both baseline and alternate zirconia-yttria coatings. The hafnia-yttria coatings and the zirconia-yttria coatings that were prepared by an alternate powder vendor were very sensitive to plasma spray parameters, in that high-quality coatings were only obtained when certain parameters were employed. The reasons for this important observation are not understood. Also not understood is that the first of two replicate specimens sprayed for Part 1 consistently performed better than the second specimen. Subsequent experiments did not display this spray order affect, possibly because a chiller was installed in the torch cooling water circuit. Also, large changes in coating density were observed after switching to a new lot of electrodes. Analyses of these findings were made possible, in part, because of the development of a sensitive density measurement technique described herein in detail. The measured thermal diffusivities did not display the expected strong relationship with porosity. This surprising result was believed to have been caused by increased microcracking of the denser coatings on the stainless steel substrates.

Perovskite Sr2Fe1.5Mo0.5O6-δ as electrode materials for symmetrical solid oxide electrolysis cells

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

Liu, Qiang; Yang, Chenghao; Dong, Xihui

2010-10-01

Perovskite Sr2Fe1.5Mo0.5O6-δ (SFM) has been successfully prepared by a microwave-assisted combustion method in air and employed as both anode and cathode in symmetrical solid oxide electrolysis cells (SOECs) for hydrogen production for the first time in this work. Influence of cell operating temperature, absolute humidity (AH) as well as applied direct current (DC) on the impedance of single cells with the configuration of SFM|La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM)|SFM has been evaluated. Under open circuit conditions and 60 vol.% AH, the cell polarization resistance, RP is as low as 0.26 Ω cm2 at 900 °C. An electrolysis current of 0.88 A cm-2 and amore » hydrogen production rate as high as 380 mL cm-2 h have been achieved at 900 °C with an electrolysis voltage of 1.3 V and 60 vol.% AH. Further, the cell has demonstrated good stability in the long-term steam electrolysis test. The results showed that the cell electrolysis performance was even better than that of the reported strontium doped lanthanum manganite (LSM) – yttria stabilized zirconia (YSZ)|YSZ|Ni–YSZ cell, indicating that SFM could be a very promising electrode material for the practical application of SOEC technology.« less

Grain Boundary Resistivity of Yttria-Stabilized Zirconia at 1400°C

DOE PAGES

Wang, J.; Du, A.; Yang, Di; ...

2013-01-01

Tmore » he grain size dependence of the bulk resistivity of 3 mol% yttria-stabilized zirconia at 1400°C was determined from the effect of a dc electric field E a = 18.1  V/cm on grain growth and the corresponding electric current during isothermal annealing tests. Employing the brick layer model, the present annealing test results were in accordance with extrapolations of the values obtained at lower temperature employing impedance spectroscopy and 4-point-probe dc. he combined values give that the magnitude of the grain boundary resistivity ρ b = 133  ohm-cm. he electric field across the grain boundary width was 28–43 times the applied field for the grain size and current ranges in the present annealing test.« less

Phenol-photodegradation on ZrO2. Enhancement by semiconductors.

PubMed

Karunakaran, C; Dhanalakshmi, R; Gomathisankar, P

2012-06-15

On illumination with light of wavelength 365 nm phenol undergoes degradation on the surface of ZrO(2). The rate of degradation enhances linearly with the concentration of phenol and also the light intensity but decreases with increase of pH. The photonic efficiency of degradation is higher with illumination at 254 nm than with 365 nm. The diffuse reflectance spectral study suggests phenol-sensitized activation of ZrO(2) with 365 nm light. TiO(2), Fe(2)O(3), CuO, ZnO, ZnS, Nb(2)O(5) and CdO particles enhance the photodegradation on ZrO(2), indicating inter-particle charge-transfer. Determination of size of the particles under suspension, by light scattering technique, shows agglomeration of particles supporting the proposition of charge-transfer between particles. Copyright © 2012 Elsevier B.V. All rights reserved.

Effect of La0.6 Sr0.4 Co0.2 Fe0.8O3 - δ air electrode-electrolyte interface on the short-term stability under high-current electrolysis in solid oxide electrolyzer cells

NASA Astrophysics Data System (ADS)

Pan, Zehua; Liu, Qinglin; Lyu, Renzhi; Li, Ping; Chan, Siew Hwa

2018-02-01

In this work, the effects of the La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) electrode-yttria stabilized zirconia (YSZ) electrolyte interface on the stability of LSCF electrodes under high-current electrolysis are studied. Six different half-cells with different configurations are tested at 800 °C for 264 h under an electrolysis current of 1 A cm-2. A few concluding remarks can be drawn by comparing the behaviors of different cells. Firstly, it is confirmed that the formation of SrZrO3 at the interface will lead to the delamination of air electrode. Thus, the formation of SrZrO3 should be strictly prevented. Secondly, increasing sintering temperature can decrease the degradation rate of polarization resistance, RP, for LSCF electrodes. Thirdly, the increase of ohmic resistance, RS, comes from structural changes as the degradation rate in percentage is similar for cells with different electrolytes and electrodes. Fourthly, the LSCF electrode after the electrolysis test shows recrystallization and lattice shrink which could be the reason for the degradation of LSCF electrodes on Gd0.1Ce0.9O2-δ (GDC) electrolytes. Lastly, comparing all the samples, the cell composed of YSZ electrolyte, dense GDC interlayer and LSCF electrode sintered at 1000 °C can be used for future study on the degradation mechanisms of the LSCF air electrode and the electrolyte.

Consolidation of Partially Stabilized ZrO2 in the Presence of a Noncontacting Electric Field

NASA Astrophysics Data System (ADS)

Majidi, Hasti; van Benthem, Klaus

2015-05-01

Electric field-assisted sintering techniques demonstrate accelerated densification at lower temperatures than the conventional sintering methods. However, it is still debated whether the applied field and/or resulting currents are responsible for the densification enhancement. To distinguish the effects of an applied field from current flow, in situ scanning transmission electron microscopy experiments with soft agglomerates of partially stabilized yttria-doped zirconia particles are carried out. A new microelectromechanical system-based sample support is used to heat particle agglomerates while simultaneously exposing them to an externally applied noncontacting electric field. Under isothermal condition at 900 °C , an electric field strength of 500 V /cm shows a sudden threefold enhancement in the shrinkage of the agglomerates. The applied electrostatic potential lowers the activation energy for point defect formation within the space charge zone and therefore promotes consolidation. Obtaining similar magnitudes of shrinkage in the absence of any electric field requires a higher temperature and longer time.

Multilayer ceramic oxide solid electrolyte for fuel cells and electrolysis cells and method for fabrication thereof

NASA Technical Reports Server (NTRS)

Schroeder, James E. (Inventor); Anderson, Harlan U. (Inventor)

1990-01-01

An unitary layered ceramic structure is disclosed which comprises co-sintered layers. The co-sintered structure comprises a sintered central layer of yttria stabilized zirconia (YSZ) which is about 8 mole percent yttria and having a density of at least about 95% of theoretical, and sintered outer layers of strontium lanthanum manganite (LSM) having the approximate molecular composition La.sub.0.8 Sr.sub.0.2 MnO.sub.3, having a density from about 50 to about 60% of theoretical, and having interconnected porosity from about 40 to 50% with an interconnected pore diameter from about one micron to about five microns. The sintered central layer is sandwiched by and bonded and sintered to the outer layers and is essentially free of significant amounts of manganese. A process for making the unitary composition-of-matter is also disclosed which involves tape casting a LSM tape and then on top thereof casting a YSZ tape. The process comprises presintering LSM powder at 1250.degree. F., crushing the presintered commercially available LSM powder, forming a slurry with the crushed LSM, a binder and solvent, tape casting the slurry and allowing the slurry to air dry. A mixture of commercially available submicron size particle YSZ powder is milled with a dispersant and solvent to disperse the YSZ particles thereby forming a dispersed YSZ slurry. The YSZ slurry is then tape cast on the dried LSM tape. If desired, a third layer of LSM can be cast on top of the dried YSZ layer. After drying the composite LSM/YSZ and LSM/YSZ/LSM tapes are fired at 1300.degree. C. No migration of manganese into the YSZ layer was observed with scanning electron microscope/edax in the sintered multilayer tape.

Multilayer ceramic oxide solid electrolyte for fuel cells and electrolysis cells

NASA Technical Reports Server (NTRS)

Schroeder, James E. (Inventor); Anderson, Harlan U. (Inventor)

1991-01-01

A unitary layered ceramic structure is disclosed which comprises co-sintered layers. The co-sintered structure comprises a sintered central layer of yttria stabilized zirconia (YSZ) which is about 8 mole percent yttria and having a density of at least about 95% of theoretical, and sintered outer layers of strontium lanthanum manganite (LSM) having the approximate molecular composition La.sub.0.8 Sr.sub.0.2 MnO.sub.3, having a density from about 50 to about 60% of theoretical, and having interconnected porosity from about 40 to 50% with an interconnected pore diameter from about one micron to about five microns. The sintered central layer is sandwiched by and bonded and sintered to the outer layers and is essentially free of significant amounts of manganese. A process for making the unitary composition-of-matter is also disclosed which involves tape casting a LSM tape and then on top thereof casting a YSZ tape. The process comprises presintering LSM powder at 1250.degree. F., crushing the presintered commercially available LSM powder, forming a slurry with the crushed LSM, a binder and solvent, tape casting the slurry and allowing the slurry to air dry. A mixture of commercially available submicron size particle YSZ powder is milled with a dispersant and solvent to disperse the YSZ particles thereby forming a dispersed YSZ slurry. The YSZ slurry is then tape cast on the dried LSM tape. If desired, a third layer of LSM can be cast on top of the dried YSZ layer. After drying the composite LSM/YSZ and LSM/YSZ/LSM tapes are fired at 1300.degree. C. No migration of manganese into the YSZ layer was observed with scanning electron microscope/edax in the sintered multilayer tape.

Calculations of single crystal elastic constants for yttria partially stabilised zirconia from powder diffraction data

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

Lunt, A. J. G., E-mail: alexander.lunt@eng.ox.ac.uk; Xie, M. Y.; Baimpas, N.

2014-08-07

Yttria Stabilised Zirconia (YSZ) is a tough, phase-transforming ceramic that finds use in a wide range of commercial applications from dental prostheses to thermal barrier coatings. Micromechanical modelling of phase transformation can deliver reliable predictions in terms of the influence of temperature and stress. However, models must rely on the accurate knowledge of single crystal elastic stiffness constants. Some techniques for elastic stiffness determination are well-established. The most popular of these involve exploiting frequency shifts and phase velocities of acoustic waves. However, the application of these techniques to YSZ can be problematic due to the micro-twinning observed in larger crystals.more » Here, we propose an alternative approach based on selective elastic strain sampling (e.g., by diffraction) of grain ensembles sharing certain orientation, and the prediction of the same quantities by polycrystalline modelling, for example, the Reuss or Voigt average. The inverse problem arises consisting of adjusting the single crystal stiffness matrix to match the polycrystal predictions to observations. In the present model-matching study, we sought to determine the single crystal stiffness matrix of tetragonal YSZ using the results of time-of-flight neutron diffraction obtained from an in situ compression experiment and Finite Element modelling of the deformation of polycrystalline tetragonal YSZ. The best match between the model predictions and observations was obtained for the optimized stiffness values of C11 = 451, C33 = 302, C44 = 39, C66 = 82, C12 = 240, and C13 = 50 (units: GPa). Considering the significant amount of scatter in the published literature data, our result appears reasonably consistent.« less

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.

Thermal barrier coatings

DOEpatents

Alvin, Mary Anne [Pittsburg, PA

2010-06-22

This disclosure addresses the issue of providing a metallic-ceramic overlay coating that potentially serves as an interface or bond coat layer to provide enhanced oxidation resistance to the underlying superalloy substrate via the formation of a diffusion barrier regime within the supporting base material. Furthermore, the metallic-ceramic coating is expected to limit the growth of a continuous thermally grown oxide (TGO) layer that has been primarily considered to be the principal cause for failure of existing TBC systems. Compositional compatibility of the metallic-ceramic with traditional yttria-stabilized zirconia (YSZ) top coats is provided to further limit debond or spallation of the coating during operational use. A metallic-ceramic architecture is disclosed wherein enhanced oxidation resistance is imparted to the surface of nickel-based superalloy or single crystal metal substrate, with simultaneous integration of the yttria stabilized zirconia (YSZ) within the metallic-ceramic overlayer.

Heterogeneous electrolyte (YSZ-Al 2O 3) based direct oxidation solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Thokchom, J. S.; Xiao, H.; Rottmayer, M.; Reitz, T. L.; Kumar, B.

Bilayers comprised of dense and porous YSZ-Al 2O 3 (20 wt%) composite were tape cast, processed, and then fabricated into working solid oxide fuel cells (SOFCs). The porous part of the bilayer was converted into anode for direct oxidation of fuels by infiltrating CeO 2 and Cu. The cathode side of the bilayer was coated with an interlayer [YSZ-Al 2O 3 (20 wt%)]: LSM (1:1) and LSM as cathode. Several button cells were evaluated under hydrogen/air and propane/air atmospheres in intermediate temperature range and their performance data were analyzed. For the first time the feasibility of using YSZ-Al 2O 3 material for fabricating working SOFCs with high open circuit voltage (OCV) and power density is demonstrated. AC impedance spectroscopy and scanning electron microscopy (SEM) techniques were used to characterize the membrane and cell.

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.

Orientation control and domain structure analysis of {100}-oriented epitaxial ferroelectric orthorhombic HfO{sub 2}-based thin films

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

Katayama, Kiliha; Shimizu, Takao; Sakata, Osami

2016-04-07

Orientation control of {100}-oriented epitaxial orthorhombic 0.07YO{sub 1.5}-0.93HfO{sub 2} films grown by pulsed laser deposition was investigated. To achieve in-plane lattice matching, indium tin oxide (ITO) and yttria-stabilized zirconia (YSZ) were selected as underlying layers. We obtained (100)- and (001)/(010)-oriented films on ITO and YSZ, respectively. Ferroelastic domain formation was confirmed for both films by X-ray diffraction using the superlattice diffraction that appeared only for the orthorhombic symmetry. The formation of ferroelastic domains is believed to be induced by the tetragonal–orthorhombic phase transition upon cooling the films after deposition. The present results demonstrate that the orientation of HfO{sub 2}-based ferroelectricmore » films can be controlled in the same manner as that of ferroelectric films composed of conventional perovskite-type material such as Pb(Zr, Ti)O{sub 3} and BiFeO{sub 3}.« less

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.

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.

Evaluation of self-adhesive resin cement bond strength to yttria-stabilized zirconia ceramic (Y-TZP) using four surface treatments.

PubMed

Miragaya, Luciana; Maia, Luciane Cople; Sabrosa, Carlos Eduardo; de Goes, Mário Fernando; da Silva, Eduardo Moreira

2011-10-01

To evaluate the influence of four surface treatments on the bond strength of a self-adhesive resin cement to an yttria-stabilized zirconia (Y-TZP) ceramic material (Lava Frame zirconia). Forty plates (8 x 6 x 1 mm) of a Y-TZP ceramic restorative material were randomly assigned to four groups (n = 10) according to the surface treatments: control, no treatment; airborne-particle abrasion with 50-μm Al2O3; coating with an MDP-based primer; conditioning with Rocatec System. The ceramic plates treated with each of the four methods were further divided into 2 subgroups according to the resin cement tested: RelyXTM ARC (ARC, conventional) and RelyXTM Unicem (Ucem, self-adhesive). The resin cements were put into PVC tubes (diameter 0.75 mm, 0.5 mm height) placed on the ceramic plate surfaces. After water storage at 37°C for 24 h, the specimens were submitted to a microshear bond strength (μSBS) test at a crosshead speed of 1.0 mm/min. The surface treatments significantly influenced the μSBS (p < 0.05). For the four surface treatments, UCem presented significantly higher μSBS than ARC (p < 0.05). For both resin cements, the best result was produced by the MDP-based primer: ARC 15.9 ± 5.0 MPa and UCem 36.2 ± 2.1 MPa. The highest μSBS values were presented by UCem on ceramic plates treated with the MDP-based primer (36.2 ± 2.1 MPa) and Rocatec system (37.4 ± 2.3 MPa). Irrespective of the surface treatment, the self-adhesive resin cement performed better in terms of bond strength to yttria-stabilized zirconia ceramic than did conventional resin cement.

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.

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.

Reversible operation of microtubular solid oxide cells using La0.6Sr0.4Co0.2Fe0.8O3-δ-Ce0.9Gd0.1O2-δ oxygen electrodes

NASA Astrophysics Data System (ADS)

López-Robledo, M. J.; Laguna-Bercero, M. A.; Larrea, A.; Orera, V. M.

2018-02-01

Yttria stabilized zirconia (YSZ) based microtubular solid oxide fuel cells (mT-SOFCs) using La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) and Ce0.9Gd0.1O2-δ (GDC) as the oxygen electrode, along with a porous GDC electrolyte-electrode barrier layer, were fabricated and characterized in both fuel cell (SOFC) and electrolysis (SOEC) operation modes. The cells were anode-supported, the NiO-YSZ microtubular supports being made by Powder Extrusion Moulding (PEM). The cells showed power densities of 695 mW cm-2 at 800 °C and 0.7 V in SOFC mode, and of 845 mA cm-2 at 800 °C and 1.3 V in SOEC mode. AC impedance experiments performed under different potential loads demonstrated the reversibility of the cells. These results showed that these cells, prepared with a method suitable for using on an industrial scale, are highly reproducible and reliable, as well as very competitive as reversible SOFC-SOEC devices operating at intermediate temperatures.

Initial Bacterial Adhesion on Different Yttria-Stabilized Tetragonal Zirconia Implant Surfaces in Vitro.

PubMed

Karygianni, Lamprini; Jähnig, Andrea; Schienle, Stefanie; Bernsmann, Falk; Adolfsson, Erik; Kohal, Ralf J; Chevalier, Jérôme; Hellwig, Elmar; Al-Ahmad, Ali

2013-12-04

Bacterial adhesion to implant biomaterials constitutes a virulence factor leading to biofilm formation, infection and treatment failure. The aim of this study was to examine the initial bacterial adhesion on different implant materials in vitro . Four implant biomaterials were incubated with Enterococcus faecalis , Staphylococcus aureus and Candida albicans for 2 h: 3 mol % yttria-stabilized tetragonal zirconia polycrystal surface (B1a), B1a with zirconium oxide (ZrO₂) coating (B2a), B1a with zirconia-based composite coating (B1b) and B1a with zirconia-based composite and ZrO₂ coatings (B2b). Bovine enamel slabs (BES) served as control. The adherent microorganisms were quantified and visualized using scanning electron microscopy (SEM); DAPI and live/dead staining. The lowest bacterial count of E. faecalis was detected on BES and the highest on B1a. The fewest vital C. albicans strains (42.22%) were detected on B2a surfaces, while most E. faecalis and S. aureus strains (approximately 80%) were vital overall. Compared to BES; coated and uncoated zirconia substrata exhibited no anti-adhesive properties. Further improvement of the material surface characteristics is essential.

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.

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.

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.

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

Effects of artificial aging conditions on yttria-stabilized zirconia implant abutments.

PubMed

Basílio, Mariana de Almeida; Cardoso, Kátia Vieira; Antonio, Selma Gutierrez; Rizkalla, Amin Sami; Santos Junior, Gildo Coelho; Arioli Filho, João Neudenir

2016-08-01

Most ceramic abutments are fabricated from yttria-stabilized tetragonal zirconia (Y-TZP). However, Y-TZP undergoes hydrothermal degradation, a process that is not well understood. The purpose of this in vitro study was to assess the effects of artificial aging conditions on the fracture load, phase stability, and surface microstructure of a Y-TZP abutment. Thirty-two prefabricated Y-TZP abutments were screwed and tightened down to external hexagon implants and divided into 4 groups (n = 8): C, control; MC, mechanical cycling (1×10(6) cycles; 10 Hz); AUT, autoclaving (134°C; 5 hours; 0.2 MPa); and TC, thermal cycling (10(4) cycles; 5°/55°C). A single-load-to-fracture test was performed at a crosshead speed of 0.5 mm/min to assess the assembly's resistance to fracture (ISO Norm 14801). X-ray diffraction (XRD) analysis was applied to observe and quantify the tetragonal-monoclinic (t-m) phase transformation. Representative abutments were examined with high-resolution scanning electron microscopy (SEM) to observe the surface characteristics of the abutments. Load-to-fracture test results (N) were compared by ANOVA and Tukey test (α=.05). XRD measurements revealed the monoclinic phase in some abutments after each aging condition. All the aging conditions reduced the fracture load significantly (P<.001). Mechanical cycling reduced the fracture load more than autoclaving (P=.034). No differences were found in the process of surface degradation among the groups; however, the SEM detected grinding-induced surface flaws and microcracks. The resistance to fracture and the phase stability of Y-TZP implant abutments were susceptible to hydrothermal and mechanical conditions. The surface microstructure of Y-TZP abutments did not change after aging conditions. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

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.

A sputtered zirconia primer for improved thermal shock resistance of plasma sprayed ceramic turbine seals

NASA Technical Reports Server (NTRS)

Bill, R. C.; Sovey, J.; Allen, G. P.

1981-01-01

The development of plasma-sprayed yttria stabilized zirconia (YSZ) ceramic turbine blade tip seal components is discussed. The YSZ layers are quite thick (0.040 to 0.090 in.). The service potential of seal components with such thick ceramic layers is cyclic thermal shock limited. The most usual failure mode is ceramic layer delamination at or very near the interface between the plasma sprayed YSZ layer and the NiCrAlY bondcoat. Deposition of a thin RF sputtered YSZ primer to the bondcoat prior to deposition of the thick plasma sprayed YSZ layer was found to reduce laminar cracking in cyclic thermal shock testing. The cyclic thermal shock life of one ceramic seal design was increased by a factor of 5 to 6 when the sputtered YSZ primer was incorporated. A model based on thermal response of plasma sprayed YSZ particles impinging on the bondcoat surface with and without the sputtered YSZ primer provides a basis for understanding the function of the primer.

Performance of iron-chromium-aluminum alloy surface coatings on Zircaloy 2 under high-temperature steam and normal BWR operating conditions

NASA Astrophysics Data System (ADS)

Zhong, Weicheng; Mouche, Peter A.; Han, Xiaochun; Heuser, Brent J.; Mandapaka, Kiran K.; Was, Gary S.

2016-03-01

Iron-chromium-aluminum (FeCrAl) coatings deposited on Zircaloy 2 (Zy2) and yttria-stabilized zirconia (YSZ) by magnetron sputtering have been tested with respect to oxidation weight gain in high-temperature steam. In addition, autoclave testing of FeCrAl-coated Zy2 coupons under pressure-temperature-dissolved oxygen coolant conditions representative of a boiling water reactor (BWR) environment has been performed. Four different FeCrAl compositions have been tested in 700 °C steam; compositions that promote alumina formation inhibited oxidation of the underlying Zy2. Parabolic growth kinetics of alumina on FeCrAl-coated Zy2 is quantified via elemental depth profiling. Autoclave testing under normal BWR operating conditions (288 °C, 9.5 MPa with normal water chemistry) up to 20 days demonstrates observable weight gain over uncoated Zy2 simultaneously exposed to the same environment. However, no FeCrAl film degradation was observed. The 900 °C eutectic in binary Fe-Zr is addressed with the FeCrAl-YSZ system.

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

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.

Influence of low temperature ageing on optical and mechanical properties of transparent yittria stabilized-zirconia cranial prosthesis

NASA Astrophysics Data System (ADS)

Davoodzadeh, Nami; Uahengo, Gottlieb; Halaney, David; Garay, Javier E.; Aguilar, Guillermo

2018-02-01

Laser-based diagnostics and therapeutics show promise for many neurological disorders. However, the poor transparency of cranial bone limits the spatial resolution and interaction depth that can be achieved. We addressed this limitation previously, by introducing a novel cranial prosthesis made of a transparent nanocrystalline yttria-stabilized zirconia (nc-YSZ) which aims to enhance the diagnosis and treatment of neurological diseases by providing chronic optical access to the brain. By using optical coherence tomography, we have demonstrated the initial feasibility of ncYSZ implants for cortical imaging in an acute murine model. Although zirconia-based implants have been known for their excellent mechanical properties, the in vivo application was found to be affected by long-term failures, due to low temperature degradation. Accelerated aging simulations in humid environments at slightly elevated temperatures and over long periods typically transforms the ceramic surface into a monoclinic structure through a stress-corrosion-type mechanism. It was expected that the new nc-YSZ would show sufficient resistance to humid environments in comparison to the conventional zirconia implant. However, even a modest amount of transformation can change optical characteristics such as transparency. Herein we present the results of a simulated ageing study following the guidelines from the ISO 13356:2008 on aging of surgical zirconia ceramics. Comparison of %monoclinic transformation, optical transparency and mechanical hardness of nc-YSZ samples at baseline and following 25 and 100 h hydrothermal treatments shows our implant can withstand these extended ageing treatments.

Single-Crystal Elastic Constants of Yttria (Y2O3) Measured to High Temperatures

NASA Technical Reports Server (NTRS)

Sayir, Ali; Palko, James W.; Kriven, Waltraud M.; Sinogeikin, Sergey V.; Bass, Jay D.

2001-01-01

Yttria, or yttrium sesquioxide (Y2O3), has been considered for use in nuclear applications and has gained interest relatively recently for use in infrared optics. Single crystals of yttria have been grown successfully at the NASA Glenn Research Center using a laser-heated float zone technique in a fiber and rod. Such samples allow measurement of the single-crystal elastic properties, and these measurements provide useful property data for the design of components using single crystals. They also yield information as to what degree the elastic properties of yttria ceramics are a result of the intrinsic properties of the yttria crystal in comparison to characteristics that may depend on processing, such as microstructure and intergranular phases, which are common in sintered yttria. The single-crystal elastic moduli are valuable for designing such optical components. In particular, the temperature derivatives of elastic moduli allow the dimensional changes due to heating under physical constraints, as well as acoustic excitation, to be determined. The single-crystal elastic moduli of yttria were measured by Brillouin spectroscopy up to 1200 C. The room-temperature values obtained were C(sub 11) = 223.6 + 0.6 GPa, C(sub 44) = 74.6 + 0.5 GPa, and C(sub 12) = 112.4 + 1.0 GPa. The resulting bulk and (Voigt-Reuss-Hill) shear moduli were K = 149.5 + 1.0 GPa and G(sub VRH) = 66.3 + 0.8 GPa, respectively. Linear least-squares regressions to the variation of bulk and shear moduli with temperature resulted in derivatives of dK/dT = -17 + 2 MPa/C and dG(sub VRH)/dT = -8 + 2 MPa/ C. Elastic anisotropy was found to remain essentially constant over the temperature range studied.

Creep of plasma sprayed zirconia

NASA Technical Reports Server (NTRS)

Firestone, R. F.; Logan, W. R.; Adams, J. W.

1982-01-01

Specimens of plasma-sprayed zirconia thermal barrier coatings with three different porosities and different initial particle sizes were deformed in compression at initial loads of 1000, 2000, and 3500 psi and temperatures of 1100 C, 1250 C, and 1400 C. The coatings were stabilized with lime, magnesia, and two different concentrations of yttria. Creep began as soon as the load was applied and continued at a constantly decreasing rate until the load was removed. Temperature and stabilization had a pronounced effect on creep rate. The creep rate for 20% Y2O3-80% ZrO2 was 1/3 to 1/2 that of 8% Y2O3-92% ZrO2. Both magnesia and calcia stabilized ZrO2 crept at a rate 5 to 10 times that of the 20% Y2O3 material. A near proportionality between creep rate and applied stress was observed. The rate controlling process appeared to be thermally activated, with an activation energy of approximately 100 cal/gm mole K. Creep deformation was due to cracking and particle sliding.

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.

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.

Highly stable ceria-zirconia-yttria supported Ni catalysts for syngas production by CO2 reforming of methane

NASA Astrophysics Data System (ADS)

Muñoz, M. A.; Calvino, J. J.; Rodríguez-Izquierdo, J. M.; Blanco, G.; Arias, D. C.; Pérez-Omil, J. A.; Hernández-Garrido, J. C.; González-Leal, J. M.; Cauqui, M. A.; Yeste, M. P.

2017-12-01

Ni/CeO2/YSZ and Ni/Ce0.15Zr0.85O2 have been investigated as catalysts for the dry reforming of methane at 750 °C. Ni was incorporated by the impregnation method. The supports were previously activated by using a thermo-chemical protocol consisting on a severe reduction (H2/Ar) at 950 °C followed by a mild oxidation (O2/He) at 500 °C. According to TPR results, this protocol leads to the development of unique redox properties in the case of the CeO2/YSZ oxide. Two types of CO2 + CH4 (1:1) mixtures (helium-diluted and undiluted) were used to feed the reactor. When using the Ni/Ce0.15Zr0.85O2 catalyst with undiluted feed, the reactor became plugged by coke. By contrast, Ni/CeO2/YSZ behaved as an active and stable catalyst even under the most severe operation conditions. The characterization of the spent Ni/CeO2/YSZ using TGA, TEM, Raman and XPS spectroscopy revealed that only a limited amount of graphitic carbon, in form of nanotubes, was formed. No evidences of deactivating carbonaceous forms were obtained. The singular redox properties of the activated CeO2/YSZ oxides are proposed as a key for designing Ni catalysts highly stable in reforming processes.

Enhanced structural stability of nanoporous zirconia under irradiation of He

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

Yang, Tengfei; Huang, Xuejun; Wang, Chenxu

2012-01-01

This work reports a greatly enhanced tolerance for He irradiation-induced swelling in nanocrystalline zirconia film with interconnected nanoporous structure (hereinafter referred as to NC-C). Compared to bulk yttria-stabilized zirconia (YSZ) and another nanocrystalline zirconia film only with discrete nano voids (hereinafter referred as to NC-V), the NC-C film reveals good tolerance for irradiation of high-fluence He. No appreciable surface blistering can be found even at the highest fluence of 6 1017 cm2 in NCC film. From TEM analysis of as-irradiated samples, the enhanced tolerance for volume swelling in NCC film is attributed to the enhanced diffusion mechanism of deposited Hemore » via widely distributed nano channels. Furthermore, the growth of grain size is quite small for both nanocrystalline zirconia films after irradiation, which is ascribed to the decreasing of area of grain boundary due to loose structure and low energy of primary knock-on atoms for He ions.« less

Fabrication of low-temperature solid oxide fuel cells with a nanothin protective layer by atomic layer deposition

PubMed Central

2013-01-01

Anode aluminum oxide-supported thin-film fuel cells having a sub-500-nm-thick bilayered electrolyte comprising a gadolinium-doped ceria (GDC) layer and an yttria-stabilized zirconia (YSZ) layer were fabricated and electrochemically characterized in order to investigate the effect of the YSZ protective layer. The highly dense and thin YSZ layer acted as a blockage against electron and oxygen permeation between the anode and GDC electrolyte. Dense GDC and YSZ thin films were fabricated using radio frequency sputtering and atomic layer deposition techniques, respectively. The resulting bilayered thin-film fuel cell generated a significantly higher open circuit voltage of approximately 1.07 V compared with a thin-film fuel cell with a single-layered GDC electrolyte (approximately 0.3 V). PMID:23342963

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.

The effect of Al intermediate layer on thermal resistance of EB-PVD yttria-stabilized zirconia coatings on titanium substrate

NASA Astrophysics Data System (ADS)

Panin, Alexey; Panin, Victor; Kazachenok, Marina; Shugurov, Artur; Sinyakova, Elena; Martynov, Sergey; Rusyaev, Andrey; Kasterov, Artur

2017-12-01

The yttria-stabilized zirconia coatings sprayed on titanium substrates by the electron beam physical vapor deposition were subjected to thermal annealing in air at 1000°C for 1, 30 and 60 min. The delamination and fracture of the coatings are studied by the scanning electron microscopy and X-ray diffraction. It is shown that a magnetron sputtered Al interlayer between the coating and the substrate considerably improves the thermal resistance of ceramic coatings.

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.

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.

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.

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.

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.

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.

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.

High performance anode-supported tubular solid oxide fuel cells fabricated by a novel slurry-casting method

PubMed Central

Duan, Nan-Qi; Yan, Dong; Chi, Bo; Pu, Jian; Jian, Li

2015-01-01

Tubular solid oxide fuel cells were fabricated and evaluated for their microstructure and electrochemical performance. The tubular substrate was prepared by casting NiO-Y2O3 stabilized ZrO2 (YSZ) slurry on the inner wall of a plastic mold (tube). The wall thickness and uniformity were controlled by slurry viscosity and rotation speed of the tube. The cells consisted of Ni-YSZ functional anode, YSZ electrolyte and (La0.8Sr0.2)0.95MnO3-δ (LSM)-YSZ cathode prepared in sequence on the substrate by dip-coating and sintering. Their dimension was 50 mm in length, 0.8 mm in thickness and 10.5 mm in outside diameter. The peak power density of the cell at temperatures between 650 and 850°C was in the range from 85 to 522 mW cm−2 and was greatly enhanced to the range from 308 to 1220 mW cm−2 by impregnating PdO into LSM-YSZ cathode. During a cell testing at 0.7 A cm−2 and 750°C for 282 h, the impregnated PdO particles grew by coalescence, which increased the cathode polarization resistance and so that decreased the cell performance. According to the degradation tendency, the cell performance will be stabilized in a longer run. PMID:25640168

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.

Orientation-dependent hydration structures at yttria-stabilized cubic zirconia surfaces

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-11-30

Water interaction with surfaces is very important and plays key roles in many natural and technological processes. Because the experimental challenges that arise when studying the interaction water with specific crystalline surfaces, most studies on metal oxides have focused on powder samples, which averaged the interaction over different crystalline surfaces. As a result, studies on the crystal orientation-dependent interaction of water with metal oxides are rarely available in the literature. In this work, water adsorption at 8 mol % yttria-stabilized cubic single crystal zirconia (100) and (111) surfaces was studied in terms of interfacial hydration structures using high resolution X-raymore » reflectivity measurements. The interfacial electron density profiles derived from the structure factor analysis of the measured data show the existence of multiple layers of adsorbed water with additional peculiar metal adsorption near the oxide surfaces.Surface relaxation, depletion, and interaction between the adsorbed layers and bulk water are found to vary greatly between the two surfaces and are also different when compared to the previously studied (110) surface. The fractional ratio between chemisorbed and physisorbed water species were also quantitatively estimated, which turned out to vary dramatically from surface to surface. Finally, the result gives us a unique opportunity to reconsider the simplified 2:1 relation between chemisorption and physisorption, originally proposed by Morimoto et al. based on the adsorption isotherms of water on powder metal oxide samples.« less

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.

High-Tc thermal bridges for space-borne cryogenic infrared detectors

NASA Technical Reports Server (NTRS)

Wise, S. A.; Buckley, J. D.; Nolt, I.; Hooker, M. W.; Haertling, G. H.; Selim, R.; Caton, R.; Buoncristiani, A. M.

1993-01-01

The potential for using high-temperature superconductive elements, screen-printed onto ceramic substrates, as thermal bridges to replace the currently employed manganin wires is studied at NASA-LaRC. Substrate selection is considered to be the most critical parameter in device production. Due to the glass-like thermal behavior of yttria-stabilized-zirconia (YSZ) and fused silica substrates, these materials are found to reduce the heat load significantly. The estimated thermal savings for superconductive leads printed onto YSZ or fused silica substrates range from 6 to 14 percent.

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

Kirby, Brent W.

The crucibles used currently for microwave melting of U-Mo alloy at the Y-12 Complex contain silicon carbide (SiC) in a mullite (3Al 2O 3-2SiO 2) matrix with an erbia coating in contact with the melt. Due to observed silicon contamination, Pacific Northwest National Laboratory has investigated alternative crucible materials that are susceptible to microwave radiation and are chemically compatible with molten U-Mo at 1400 1500C. Recommended crucibles for further testing are: 1) high-purity alumina (Al 2O 3); 2) yttria-stabilized zirconia (ZrO 2); 3) a composite of alumina and yttria-stabilized zirconia; 4) aluminum nitride (AlN). Only AlN does not require anmore » erbia coating. The recommended secondary susceptor, for heating at low temperature, is SiC in a “picket fence” arrangement.« less

Hot Corrosion of Yttrium Stabilized Zirconia Coatings Deposited by Air Plasma Spray on a Nickel-Based Superalloy

NASA Astrophysics Data System (ADS)

Vallejo, N. Diaz; Sanchez, O.; Caicedo, J. C.; Aperador, W.; Zambrano, G.

In this research, the electrochemical impedance spectroscopy (EIS) and Tafel analysis were utilized to study the hot corrosion performance at 700∘C of air plasma-sprayed (APS) yttria-stabilized zirconia (YSZ) coatings with a NiCrAlY bond coat grown by high velocity oxygen fuel spraying (HVOF), deposited on an INCONEL 625 substrate, in contact with corrosive solids salts as vanadium pentoxide V2O5 and sodium sulfate Na2SO4. The EIS data were interpreted based on proposed equivalent electrical circuits using a suitable fitting procedure performed with Echem AnalystTM Software. Phase transformations and microstructural development were examined using X-ray diffraction (XRD), with Rietveld refinement for quantitative phase analysis, scanning electron microscopy (SEM) was used to determinate the coating morphology and corrosion products. The XRD analysis indicated that the reaction between sodium vanadate (NaVO3) and yttrium oxide (Y2O3) produces yttrium vanadate (YVO4) and leads to the transformation from tetragonal to monoclinic zirconia phase.

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.

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

Environmental degradation of oxidation resistant and thermal barrier coatings for fuel-flexible gas turbine applications

NASA Astrophysics Data System (ADS)

Mohan, Prabhakar

The development of thermal barrier coatings (TBCs) has been undoubtedly the most critical advancement in materials technology for modern gas turbine engines. TBCs are widely used in gas turbine engines for both power-generation and propulsion applications. Metallic oxidation-resistant coatings (ORCs) are also widely employed as a stand-alone protective coating or bond coat for TBCs in many high-temperature applications. Among the widely studied durability issues in these high-temperature protective coatings, one critical challenge that received greater attention in recent years is their resistance to high-temperature degradation due to corrosive deposits arising from fuel impurities and CMAS (calcium-magnesium-alumino-silicate) sand deposits from air ingestion. The presence of vanadium, sulfur, phosphorus, sodium and calcium impurities in alternative fuels warrants a clear understanding of high-temperature materials degradation for the development of fuel-flexible gas turbine engines. Degradation due to CMAS is a critical problem for gas turbine components operating in a dust-laden environment. In this study, high-temperature degradation due to aggressive deposits such as V2O5, P2O 5, Na2SO4, NaVO3, CaSO4 and a laboratory-synthesized CMAS sand for free-standing air plasma sprayed (APS) yttria stabilized zirconia (YSZ), the topcoat of the TBC system, and APS CoNiCrAlY, the bond coat of the TBC system or a stand-alone ORC, is examined. Phase transformations and microstructural development were examined by using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. This study demonstrated that the V2O5 melt degrades the APS YSZ through the formation of ZrV2O7 and YVO 4 at temperatures below 747°C and above 747°C, respectively. Formation of YVO4 leads to the depletion of the Y2O 3 stabilizer and the deleterious transformation of the YSZ to the monoclinic ZrO2 phase. The investigation on the YSZ degradation by Na 2SO4 and a Na2SO4 + V2

JT90 thermal barrier coated vanes

NASA Technical Reports Server (NTRS)

Sheffler, K. D.; Graziani, R. A.; Sinko, G. C.

1982-01-01

The technology of plasma sprayed thermal barrier coatings applied to turbine vane platforms in modern high temperature commercial engines was advanced to the point of demonstrated feasibility for application to commercial aircraft engines. The three thermal barrier coatings refined under this program are zirconia stabilized with twenty-one percent magnesia (21% MSZ), six percent yttria (6% YSZ), and twenty percent yttria (20% YSZ). Improvement in thermal cyclic endurance by a factor of 40 times was demonstrated in rig tests. A cooling system evolved during the program which featured air impingement cooling for the vane platforms rather than film cooling. The impingement cooling system, in combination with the thermal barrier coatings, reduced platform cooling air requirements by 44% relative to the current film cooling system. Improved durability and reduced cooling air requirements were demonstrated in rig and engine endurance tests. Two engine tests were conducted, one of 1000 cycles and the other of 1500 cycles. All three coatings applied to vanes fabricated with the final cooling system configuration completed the final 1500 cycle engine endurance test. Results of this test clearly demonstrated the durability of the 6% YSZ coating which was in very good condition after the test. The 21% MSZ and 20% YSZ coatings had numerous occurrences of significant spalling in the test.

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.

Yttria-Stabilized Zirconia Ceramic Deposition on SS430 Ferritic Steel Grown by PLD - Pulsed Laser Deposition Method

NASA Astrophysics Data System (ADS)

Khalid Rivai, Abu; Mardiyanto; Agusutrisno; Suharyadi, Edi

2017-01-01

Development of high temperature materials are one of the key issues for the deployment of advanced nuclear reactors due to higher temperature operation. One of the candidate materials for that purpose is ceramic-coated ferritic steel that one of the functions is to be a thermal barrier coating (TBC). Thin films of YSZ (Ytrria-Stabilized Zirconia) ceramic have been deposited on a SS430 ferritic steel using Pulsed Laser Deposition (PLD) at Center For Science and Technology of Advanced Materials laboratory - National Nuclear Energy Agency of Indonesia (BATAN). The thin film was deposited with the chamber pressure range of 200-225 mTorr, the substrate temperature of 800oC, and the number of laser shots of 3×104, 6×104 and 9×104. Afterward, the samples were analyzed using Scanning Electron Microscope - Energy Dispersive X-ray Spectroscope (SEM-EDS), X-Ray Diffractometer (XRD), Atomic Force Microscope (AFM) and Vickers hardness tester. The results showed that the YSZ could homogeneously and sticky deposited on the surface of the ferritic steel. The surfaces were very smoothly formed with the surface roughness was in the range of 70 nm. Furthermore, thickness, composition of Zr4+ dan Y3+, the crystallinity, and hardness property was increased with the increasing the number of the shots.

[Mechanical property of tooth-like yttria-stabilized tetragonal zirconia polycrystal by adding rare earth oxide].

PubMed

Gao, Yan; Zhang, Fuqiang; Gao, Jianhua

2012-02-01

To evaluate the influence of mechanical property of tooth-like yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) by adding rare earth oxide as colorants. Six kinds of tooth-like Y-TZP were made by introducing internal coloration technology. The colorants included rare earth oxide (Pr6O11, CeO2, Er2O3) and transition element oxide (MnO2). Mechanical properties (flexural strength, vickers hardness and fracture toughness) were tested. Microstructure was examined by scanning electron microscope(SEM), and the fracture model was analyzed. The range of flexural strength of the six kinds of tooth-like Y-TZP were (792 +/- 20)-(960 +/- 17) MPa, the fracture toughness were (4.72 +/- 0.31)-(5.64 +/- 0.38) MPam(1/2), and the vickers hardness were (1332 +/- 19)-(1380 +/- 17) MPa. SEM observation on the cross section of the six kinds of sintered composites showed a relatively dense polycrystal structure, and the fracture models was mixed type. Tooth-like Y-TZP is acquired with better mechanical properties (fracture toughness and vickers hardness) by adding rare earth oxide as colorants. It is available for clinical application.

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.

High yttria ferritic ODS steels through powder forging

NASA Astrophysics Data System (ADS)

Kumar, Deepak; Prakash, Ujjwal; Dabhade, Vikram V.; Laha, K.; Sakthivel, T.

2017-05-01

Oxide dispersion strengthened (ODS) steels are being developed for future nuclear reactors. ODS Fe-18%Cr-2%W-0.2%Ti steels with 0, 0.35, 0.5, 1 and 1.5% Y2O3 (all compositions in weight%) dispersion were fabricated by mechanical alloying of elemental powders. The powders were placed in a mild steel can and forged in a stream of hydrogen gas at 1473 K. The steels were forged again to final density. The strength of ODS steel increased with yttria content. Though this was accompanied by a decrease in tensile elongation, all the steels showed significant ductility. The ductility in high yttria alloys may be attributed to improved inter-particle bonding between milled powders due to reduction of surface oxides by hydrogen. This may permit development of ODS steels with yttria contents higher than the conventional limit of 0.5%. It is suggested that powder forging is a promising route to fabricate ODS steels with high yttria contents and improved ductility.

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.

A novel highly porous ceramic foam with efficient thermal insulation and high temperature resistance properties fabricated by gel-casting process

NASA Astrophysics Data System (ADS)

Yu, Jiahong; Wang, Guixiang; Tang, Di; Qiu, Ya; Sun, Nali; Liu, Wenqiao

2018-01-01

The design of super thermal insulation and high-temperature resistant materials for high temperature furnaces is crucial due to the energy crisis and the huge wasting. Although it is told that numerous studies have been reported about various of thermal insulation materials prepared by different methods, the applications of yttria-stabilized zirconia (YSZ) ceramic foams fabricated through tert-butyl alcohol (TBA)-based gel-casting process in bulk thermal isolators were barely to seen. In this paper, highly porous yttria-stabilized zirconia (YSZ) ceramic foams were fabricated by a novel gel-casting method using tert-butyl alcohol (TBA) as solvent and pore-forming agent. Different raw material ratio, sintering temperature and soaking time were all investigated to achieve optimal thermal insulation and mechanical properties. We can conclude that porosity drops gradually while compressive strength increases significantly with the rising temperature from 1000-1500°C. With prolonged soaking time, there is no obvious change in porosity but compressive strength increases gradually. All specimens have uniformly distributed pores with average size of 0.5-2μm and show good structural stability at high temperature. The final obtained ceramic foams displayed an outstanding ultra-low thermal conductivity property with only 200.6 °C in cold surface while the hot side was 1000 °C (hold 60 min to keep thermal balance before testing) at the thickness of 10 mm.

Long-time aging in 3 mol.% yttria-stabilized tetragonal zirconia polycrystals at human body temperature.

PubMed

Keuper, Melanie; Berthold, Christoph; Nickel, Klaus Georg

2014-02-01

We present new findings on the low-temperature degradation of yttria-stabilized zirconia at 37°C over several years and at high and low partial pressures of water. With the aid of focused ion beam cross-section confirmation studies we are able to show an extensive linear, continuous degradation without retardation, even at low temperatures and low water pressures. The characteristic layer growth and its inferred rate constant imply a lifetime of tens of years under simple tension and open the possibility of studying the longevity of these ceramics more rigorously. In addition, we show reproducibility complications of accelerated aging tests by the use of different autoclaves and possible implications for standardized procedures. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

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.

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.

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.

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.

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.

Atomic layer deposition of ultrathin blocking layer for low-temperature solid oxide fuel cell on nanoporous substrate

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

Yu, Wonjong; Cho, Gu Young; Noh, Seungtak

2015-01-15

An ultrathin yttria-stabilized zirconia (YSZ) blocking layer deposited by atomic layer deposition (ALD) was utilized for improving the performance and reliability of low-temperature solid oxide fuel cells (SOFCs) supported by an anodic aluminum oxide substrate. Physical vapor-deposited YSZ and gadolinia-doped ceria (GDC) electrolyte layers were deposited by a sputtering method. The ultrathin ALD YSZ blocking layer was inserted between the YSZ and GDC sputtered layers. To investigate the effects of an inserted ultrathin ALD blocking layer, SOFCs with and without an ultrathin ALD blocking layer were electrochemically characterized. The open circuit voltage (1.14 V) of the ALD blocking-layered SOFC was visiblymore » higher than that (1.05 V) of the other cell. Furthermore, the ALD blocking layer augmented the power density and improved the reproducibility.« less

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.

Er0.4Bi1.6O3-δ - La0.8Sr0.2MnO3-δ nano-composite as a low-temperature firing cathode of solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Kim, Sun Jae; Dayaghi, Amir Masoud; Kim, Kun Joong; Choi, Gyeong Man

2017-03-01

Er0.4Bi1.6O3-δ (ESB) composited with La0.8Sr0.2MnO3-δ (LSM) (2:3 or 3:2 wt:wt) with a bonding aid to decrease firing temperature TF are screen-printed on symmetric single cells composed of a Gd0.2Ce0.8O2-δ (GDC) interlayer/yttria-stabilized zirconia (YSZ) electrolyte/GDC interlayer, and their impedance spectra are compared. Addition of 5 wt % CuO to ESB-LSM (3:2 wt:wt) decreases the cathode TF to 650 °C without increasing cathodic polarization resistance (Rp ∼0.19 Ω cm2 at 650 °C). This ESB-LSM composite can be used as a cathode that can be fired at low temperature.

Rapid, cool sintering of wet processed yttria-stabilized zirconia ceramic electrolyte thin films.

PubMed

Park, Jun-Sik; Kim, Dug-Joong; Chung, Wan-Ho; Lim, Yonghyun; Kim, Hak-Sung; Kim, Young-Beom

2017-09-29

Here we report a photonic annealing process for yttria-stabilized zirconia films, which are one of the most well-known solid-state electrolytes for solid oxide fuel cells (SOFCs). Precursor films were coated using a wet-chemical method with a simple metal-organic precursor solution and directly annealed at standard pressure and temperature by two cycles of xenon flash lamp irradiation. The residual organics were almost completely decomposed in the first pre-annealing step, and the fluorite crystalline phases and good ionic conductivity were developed during the second annealing step. These films showed properties comparable to those of thermally annealed films. This process is much faster than conventional annealing processes (e.g. halogen furnaces); a few seconds compared to tens of hours, respectively. The significance of this work includes the treatment of solid-state electrolyte oxides for SOFCs and the demonstration of the feasibility of other oxide components for solid-state energy devices.

High strength yttria-reinforced HA scaffolds fabricated via honeycomb ceramic extrusion.

PubMed

Elbadawi, M; Shbeh, M

2018-01-01

The present study investigated the effects of hydroxyapatite (HA) reinforced with yttria on porous scaffolds fabricated via honeycomb ceramic extrusion. Yttria was selected as it has been demonstrated to toughen other ceramics. Moreover, yttria has been surmised to suppress dehydroxylation in HA, a characteristic that prefigures decomposition thereof during sintering into mechanically weaker phases. However, the compressive strength of yttria-reinforced hydroxyapatite (Y-HA) porous scaffolds has hitherto not been reported. Y-HA was synthesised by calcining a commercially available HA with 10wt% yttria at 1000°C. Y-HA was then fabricated into porous scaffolds using an in-house honeycomb extruder, and subsequently sintered at 1200 and 1250°C. The results were compared to the uncalcined as-received commercial powder (AR-HA) and calcined pure HA powder at 1000°C (C-HA). It was discovered that calcination alone caused marked improvements to the stoichiometry, thermal stability, porosity and compressive strength of scaffolds. The improvements were ascribed to the calcined powders with less susceptibility to both agglomeration and enhanced densification. Still, differences were observed between C-HA and Y-HA at 1250°C. The compressive strength increased from 105.9 to 127.3MPa, a larger microporosity was descried and the HA matrix in Y-HA was more stoichiometric. The latter was confirmed by XRD and EDS analyses. Therefore, it was concluded that the reinforcing of hydroxyapatite with yttria improved the compressive strength and suppressed dehydroxylation of porous HA scaffolds. In addition, the compressive strength achieved demonstrated great potential for load-bearing application. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Re-activation of degraded nickel cermet anodes - Nano-particle formation via reverse current pulses

NASA Astrophysics Data System (ADS)

Hauch, A.; Marchese, M.; Lanzini, A.; Graves, C.

2018-02-01

The Ni/yttria-stabilized-zirconia (YSZ) cermet is the most commonly applied fuel electrode for solid oxide cells (SOCs). Loss of Ni/YSZ electrode activity is a key life-time limiting factor of the SOC. Developing means to mitigate this loss of performance or re-activate a fuel electrode is therefore important. In this work, we report a series of five tests on state-of-the-art Ni/YSZ-YSZ-CGObarrier-LSC/CGO cells. All cells were deliberately degraded via gas stream impurities in CO2/CO or harsh steam electrolysis operation. The cells were re-activated via a variety of reverse current treatments (RCTs). Via electrochemical impedance spectroscopy, we found that the Ni/YSZ electrode performance could be recovered via RCT, but not via constant fuel cell operation. For optimized RCT, we obtained a lower Ni/YSZ electrode resistance than the initial resistance. E.g. at 700 °C we measured fuel electrode resistance of 180 mΩ cm2, 390 mΩ cm2, and 159 mΩ cm2 before degradation, after degradation and after re-activation via RCT, respectively. Post-test SEM revealed that the RCT led to formation of nano-particles in the fuel electrode. Besides the remarkable improvement, the results also showed that RCTs can weaken Ni/YSZ interfaces and the electrode/electrolyte interface. This indicates that finding an optimum RCT profile is crucial for achieving maximum benefit.

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

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.

Zircon-Based Ceramics Composite Coating for Environmental Barrier Coating

NASA Astrophysics Data System (ADS)

Suzuki, M.; Sodeoka, S.; Inoue, T.

2008-09-01

Studies on plasma spraying of zircon (ZrSiO4) have been carried out by the authors as one of the candidates for an environmental barrier coating (EBC) application, and had reported that substrate temperature is one of the most important factors to obtain crack-free and highly adhesive coating. In this study, several amounts of yttria were added to zircon powder, and the effect of the yttria addition on the structure and properties of the coatings were evaluated to improve the stability of the zircon coating structure at elevated temperature. The coatings obtained were composed of yttria-stabilized zirconia (YSZ), glassy silica, whereas the one prepared from monolithic zircon powder was composed of the metastable high temperature tetragonal phase of zirconia and glassy silica. After the heat treatment over 1200 °C, silica and zirconia formed zircon in all coatings. However, coatings with higher amounts of yttria exhibited lower amounts of zircon. This resulted in the less open porosity of the coating at elevated temperature. These yttria-added coatings also showed good adhesion even after the heat treatment, while monolithic zircon coating pealed off.

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.