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

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

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.

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.

Epitaxial growth of YBa2Cu3O7 - delta films on oxidized silicon with yttria- and zirconia-based buffer layers

NASA Astrophysics Data System (ADS)

Pechen, E. V.; Schoenberger, R.; Brunner, B.; Ritzinger, S.; Renk, K. F.; Sidorov, M. V.; Oktyabrsky, S. R.

1993-09-01

A study of epitaxial growth of YBa2Cu3O7-δ films on oxidized Si with yttria- and zirconia-based buffer layers is reported. Using substrates with either SiO2 free or naturally oxidized (100) surfaces of Si it was found that a thin SiO2 layer on top of the Si favors high-quality superconducting film formation. Compared to yttria-stabilized ZrO2 (YSZ) single layers, YSZY2O3 double and YSZ/Y2O3YSZ triple layers allows the deposition of thin YBa2Cu3O7-δ films with improved properties including reduced aging effects. In epitaxial YBa2Cu3O7-δ films grown on the double buffer layers a critical temperature Tc(R=0)=89.5 K and critical current densities of 3.5×106 A/cm2 at 77 K and 1×107 A/cm2 at 66 K were reached.

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).

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.

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.

Superconductivity devices: Commercial use of space

NASA Technical Reports Server (NTRS)

Haertling, Gene; Hsi, Chi-Shiung; Li, Guang

1992-01-01

High T sub C superconducting thick film were prepared by a screen printing process. Y-based (YBa2Cu3O(7-x) superconducting thick film were printed on 211/Al2O3, SNT/Al2O3, and YSZ substrates. Because of poor adhesion of the superconductor thick films to 211/Al2O3 and SNT/Al2O3 substrates, relatively low T sub C and J sub C values were obtained from the films printed on these substrates. Critical temperatures (T sub C) of YBa2Cu3O(7-x) thick films deposited on 211/Al2O3 and SNT/Al2O3 substrates were about 80 K. The critical current densities (J sub C) of these films were less than 2 A/sq cm. Higher T sub C and J sub C YBa2Cu3O(7-x) thick films were printed on YSZ substrates. A YBa2Cu3O(7-x) thick film with T sub C=86.4 and J sub C= 50.4 A/sq cm was prepared by printing the film on YSZ substrate and firing at 990 C for 10 minutes. Multiple-lead samples were also prepared on the YSZ substrates. The multiple-lead samples showed lower T sub C and/or J sub C values than those of the plain samples. The electrical properties of YBa2Cu3O(7-x) thick films were determined by the microstructures of the films. The YBa2Cu3O(7-x) thick films printed on the YSZ substrates, which had the best properties among the films printed on the three different kinds of substrates, had the highest density and the best particle interconnection. The YBa2Cu3O(7-x) thick films with preferred orientation in (001) direction were obtained on the YSZ substrates. Cracks, which retard the properties of the films, were found from the films deposited on the YSZ substrates. Currently, a MSZ (Magnesium Stabilized Zirconia) substrate, which had higher thermal expansion coefficient than the YSZ substrate, is used as substrate for the YBa2Cu3O(7-x) thick film in order to eliminate the cracks on the film. Bi-based superconductor thick films were printed on polycrystalline MgO and YSZ substrates. Interactions between BSCCO thick films and the YSZ substrates were observed. Various buffer layer materials were applied onto the substrates in order to avoid the interactions between the BSCCO thick films and the ZrO2-based substrates. So far, a BSCCO printed on MgO substrate with T Sub C=89K was obtained. The J sub C of the film was lower than 0.1 A/sq cm by reason of poor interconnectivity of the BSCCO particles.

Zirconia toughened mica glass ceramics for dental restorations.

PubMed

Gali, Sivaranjani; K, Ravikumar; Murthy, B V S; Basu, Bikramjit

2018-03-01

The objective of the present study is to understand the role of yttria stabilized zirconia (YSZ) in achieving the desired spectrum of clinically relevant mechanical properties (hardness, elastic modulus, fracture toughness and brittleness index) and chemical solubility of mica glass ceramics. The glass-zirconia mixtures with varying amounts of YSZ (0, 5, 10, 15 and 20wt.%) were ball milled, compacted and sintered to obtain pellets of glass ceramic-YSZ composites. Phase analysis was carried out using X-ray diffraction and microstructural characterization with SEM revealed the crystal morphology of the composites. Mechanical properties such as Vickers hardness, elastic modulus, indentation fracture toughness and chemical solubility were assessed. Phase analysis of sintered pellets of glass ceramic-YSZ composites revealed the characteristic peaks of fluorophlogopite (FPP) and tetragonal zirconia. Microstructural investigation showed plate and lath-like interlocking mica crystals with embedded zirconia. Vickers hardness of 9.2GPa, elastic modulus of 125GPa, indentation toughness of 3.6MPa·m 1/2 , and chemical solubility of 30μg/cm 2 (well below the permissible limit) were recorded with mica glass ceramics containing 20wt.% YSZ. An increase in hardness and toughness of the glass ceramic-YSZ composites with no compromise on their brittleness index and chemical solubility has been observed. Such spectrum of properties can be utilised for developing a machinable ceramic for low stress bearing inlays, onlays and veneers. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

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

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

Nanosecond laser switching of surface wettability and epitaxial integration of c-axis ZnO thin films with Si(111) substrates.

PubMed

Molaei, R; Bayati, M R; Alipour, H M; Estrich, N A; Narayan, J

2014-01-08

We have achieved integration of polar ZnO[0001] epitaxial thin films with Si(111) substrates where cubic yttria-stabilized zirconia (c-YSZ) was used as a template on a Si(111) substrate. Using XRD (θ-2θ and φ scans) and HRTEM techniques, the epitaxial relationship between the ZnO and the c-YSZ layers was shown to be [0001]ZnO || [111]YSZ and [21¯1¯0]ZnO || [1¯01](c-YSZ), where the [21¯1¯0] direction lies in the (0001) plane, and the [1¯01] direction lies in the (111) plane. Similar studies on the c-YSZ/Si interface revealed epitaxy as (111)YSZ || (111)Si and in-plane (110)YSZ || (110)Si. HRTEM micrographs revealed atomically sharp and crystallographically continuous interfaces. The ZnO epilayers were subsequently laser annealed by a single pulse of a nanosecond excimer KrF laser. It was shown that the hydrophobic behavior of the pristine sample became hydrophilic after laser treatment. XPS was employed to study the effect of laser treatment on surface stoichiometry of the ZnO epilayers. The results revealed the formation of oxygen vacancies, which are envisaged to control the observed hydrophilic behavior. Our AFM studies showed surface smoothing due to the coupling of the high energy laser beam with the surface. The importance of integration of c-axis ZnO with Si(111) substrates is emphasized using the paradigm of domain matching epitaxy on the c-YSZ[111] buffer platform along with their out-of-plane orientation, which leads to improvement of the performance of the solid-state devices. The observed ultrafast response and switching in photochemical characteristics provide new opportunities for application of ZnO in smart catalysts, sensors, membranes, DNA self-assembly and multifunctional devices.

Portable Oxygen Generation for Medical Applications.

DTIC Science & Technology

1997-07-01

stabilized zirconia; these include scandia- stabilized zirconia, lanthanum gallate , ceria, and bismuth oxide. Scandia-stabilized zirconia [1] exhibits...uncertainty of using doped ceria is its high thermal expansion coefficient (ceria -13-14 ppm/°C, YSZ -10.5 ppm/°C). Lanthanum gallate (LaGa03) [2-4...the conductivity of lanthanum gallate approximately 2-3 times that of YSZ in the 600- 1000°C temperature range. The enhanced conductivity in lanthanum

Positron annihilation studies of zirconia doped with metal cations of different valence

NASA Astrophysics Data System (ADS)

Prochazka, I.; Cizek, J.; Melikhova, O.; Konstantinova, T. E.; Danilenko, I. A.; Yashchishyn, I. A.; Anwand, W.; Brauer, G.

2013-06-01

New results obtained by applying positron annihilation spectroscopy to the investigation of zirconia-based nanomaterials doped with metal cations of different valence are reported. The slow-positron implantation spectroscopy combined with Doppler broadening measurements was employed to study the sintering of pressure-compacted nanopowders of tetragonal yttria-stabilised zirconia (t-YSZ) and t-YSZ with chromia additive. Positronium (Ps) formation in t-YSZ was proven by detecting 3γ-annihilations of ortho-Ps and was found to gradually decrease with increasing sintering temperature. A subsurface layer with enhanced 3γ-annihilations, compared to the deeper regions, could be identified. Addition of chromia was found to inhibit Ps formation. In addition, first results of positron lifetime measurements on nanopowders of zirconia phase-stabilised with MgO and CeO2 are presented.

Health Monitoring of Thermal Barrier Coatings by Mid-Infrared Reflectance

NASA Technical Reports Server (NTRS)

Eldridge, J. I.; Spuckler, C. M.; Nesbitt, J. A.; Street, K. W.

2002-01-01

Mid-infrared (MIR) reflectance is shown to be a powerful tool for monitoring the integrity of 8wt% yttria-stabilized zirconia (8YSZ) thermal barrier coatings (TBCs). Because of the translucent nature of plasma-sprayed 8YSZ TBCs, particularly at MIR wavelengths (3 to 5 microns), measured reflectance does not only originate from the TBC surface, but contains strong contributions from internal scattering within the coating as well as reflectance from the underlying TBC/substrate interface. Therefore, changes in MIR reflectance measurements can be used to monitor the progression of TBC delamination. In particular, MIR reflectance is shown to reproducibly track the progression of TBC delamination produced by repeated thermal cycling (to 1163 C) of plasma-sprayed 8YSZ TBCs on Rene N5 superalloy substrates. To understand the changes in MIR reflectance with the progression of a delamination crack network, a four-flux scattering model is used to predict the increase in MIR reflectance produced by the introduction of these cracks.

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.

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.

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 stable in enthalpy than monoclinic zirconia. The difference between the surface energies of amorphous and tetragonal zirconia phases is ˜1.19 +/- 0.05 J/m2, with a lower surface energy for the amorphous material.

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

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

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

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.

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

Fabrication and Characterization of Functionally Graded Cathodes for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Simonet, J.; Kapelski, G.; Bouvard, D.

2008-02-01

Solid oxide fuel cells are multi-layered designed. The most prevalent structure is an anode supported cell with a thick porous layer of nickel oxide NiO and yttrium stabilized zirconia (YSZ) composite acting as an anode, a thin dense layer of YSZ as an electrolyte, a composite thin porous layer of lanthanum strontium manganate LSM and YSZ and a current collector layer of porous LSM. Regular operating temperature is 1000 °C. The industrial development requires designing cathodes with acceptable electrochemical and mechanical properties at a lower temperature, typically between 700 and 800 °C. A solution consists in designing composite bulk cathodes with more numerous electro-chemical reaction sites. This requirement could be met by grading the composition of the cathode in increasing the YSZ volume fraction near the electrolyte and the LSM volume fraction near the current collector layer so that the repartition of reaction sites and the interfacial adhesion between the cathode and electrolyte layers are optimal. The fabrication of graded composite cathode has been investigated using a sedimentation process that consists of preparing a suspension containing the powder mixture and allowing the particles to fall by gravity upon a substrate. Different composite cathodes with continuous composition gradient have been obtained by sedimentation of LSM and YSZ powder mixture upon a dense YSZ substrate and subsequent firing. Their compositions and microstructures have been analysed with Scanning Electron Microscope (SEM) and Electron Dispersive Spectrometry (EDS).

Lower-Conductivity Ceramic Materials for Thermal-Barrier Coatings

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Zhu, Dongming

2006-01-01

Doped pyrochlore oxides of a type described below are under consideration as alternative materials for high-temperature thermal-barrier coatings (TBCs). In comparison with partially-yttria-stabilized zirconia (YSZ), which is the state-of-the-art TBC material now in commercial use, these doped pyrochlore oxides exhibit lower thermal conductivities, which could be exploited to obtain the following advantages: For a given difference in temperature between an outer coating surface and the coating/substrate interface, the coating could be thinner. Reductions in coating thicknesses could translate to reductions in weight of hot-section components of turbine engines (e.g., combustor liners, blades, and vanes) to which TBCs are typically applied. For a given coating thickness, the difference in temperature between the outer coating surface and the coating/substrate interface could be greater. For turbine engines, this could translate to higher operating temperatures, with consequent increases in efficiency and reductions in polluting emissions. TBCs are needed because the temperatures in some turbine-engine hot sections exceed the maximum temperatures that the substrate materials (superalloys, Si-based ceramics, and others) can withstand. YSZ TBCs are applied to engine components as thin layers by plasma spraying or electron-beam physical vapor deposition. During operation at higher temperatures, YSZ layers undergo sintering, which increases their thermal conductivities and thereby renders them less effective as TBCs. Moreover, the sintered YSZ TBCs are less tolerant of stress and strain and, hence, are less durable.

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.

Stability of yttria-stabilized zirconia during pyroprocessing tests

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Lee, Jeong; Lee, Sung-Jai; Kim, Sung-Wook; Jeon, Sang-Chae; Cho, Soo Haeng; Oh, Seung Chul; Jeon, Min Ku; Lee, Sang Kwon; Kang, Hyun Woo; Hur, Jin-Mok

2016-07-01

In this study, the feasibility of yttria-stabilized zirconia (YSZ) was investigated for use as a ceramic material, which can be commonly used for both electrolytic reduction and electrorefining. First, the stability of YSZ in salts for electrolytic reduction and electrorefining was examined. Then, its stability was demonstrated by a series of pyroprocessing tests, such as electrolytic reduction, LiCl distillation, electrorefining, and LiClsbnd KCl distillation, using a single stainless steel wire mesh basket containing fuel and YSZ. A single basket was used by its transportation from one test to subsequent tests without the requirements for unloading.

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.

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.

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. The different thermal conduction behaviors were linked to the porosity and compositional properties of the coatings using immersion density, SEM, and synchrotron radiation characterization techniques.

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

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.

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.

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

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

Senabulya, Nancy; Jones, Christina M.; Mathis, James

We report on the crystal structure of epitaxial ZnSnN{sub 2} films synthesized via plasma-assisted vapor deposition on (111) yttria stabilized zirconia (YSZ) and (001) lithium gallate (LiGaO{sub 2}) substrates. X-ray diffraction measurements performed on ZnSnN{sub 2} films deposited on LiGaO{sub 2} substrates show evidence of single-crystal, phase-pure orthorhombic structure in the Pn2{sub 1}a symmetry [space group (33)], with lattice parameters in good agreement with theoretically predicted values. This Pn2{sub 1}a symmetry is imposed on the ZnSnN{sub 2} films by the LiGaO{sub 2} substrate, which also has orthorhombic symmetry. A structural change from the wurtzite phase to the orthorhombic phase inmore » films grown at high substrate temperatures ∼550°C and low values of nitrogen flux ∼10{sup −5} Torr is observed in ZnSnN{sub 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

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.

Brazing of Stainless Steels to Yttria Stabilized Zirconia (YSZ) Using Silver -Base Brazes

NASA Technical Reports Server (NTRS)

Singh, Mrityunjay; Shpargel, Tarah P.; Asthana, Rajiv

2005-01-01

Three silver-base brazes containing either noble metal palladium (Palcusil-10 and Palcusil-15) or active metal titanium (Ticusil) were evaluated for high-temperature oxidation resistance, and their effectiveness in joining yttria stabilized zirconia (YSZ) to a corrosion-resistant ferritic stainless steel. Thermogravimetric analysis (TGA), and optical- and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) were used to evaluate the braze oxidation behavior and the structure and chemistry of the YSZ/braze/steel joints. The effect of the braze type and processing conditions on the interfacial microstructure and composition of the joint regions is discussed with reference to the chemical changes that occur at the interface. It was found that chemical interdiffusion of the constituents of YSZ, steel and the brazes led to compositional changes and/or interface reconstruction, and metallurgically sound joints.

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.

Microstructure evolution determined by the crystalline phases competition in self-assembled WO3-BiVO4 hetero nanostructures

NASA Astrophysics Data System (ADS)

Song, Haili; Li, Chao; Nguyen Van, Chien; Dong, Wenxia; Qi, Ruijuan; Zhang, Yuanyuan; Huang, Rong; Chu, Ying-Hao; Duan, Chun-Gang

2018-02-01

A series of self-assembled WO3-BiVO4 nanostructured thin films were grown on the (001) yttria-stabilized zirconia (YSZ) substrate at the substrate temperatures of 400 °C, 500 °C, 550 °C, 600 °C, 650 °C and 700 °C by a pulsed laser deposition method. The microstructures including crystalline phases, epitaxial relationships, surface morphologies and interface structures were investigated by a combination of x-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy. The sample grown at 400 °C was amorphous due to the low driving forces for nucleation and diffusion. For the samples made at 500 °C, 550 °C and 600 °C, the monoclinic BiVO4 matrix epitaxially grew on YSZ, forming the matrix, where the WO3 nanopillars were embedded in with a specific orientation relationship among BiVO4, WO3 and YSZ. However, in thin films deposited at 650 °C and 700 °C, the WO3 grains randomly grew on the YSZ substrate, which dominated the microstructures of the resultant thin films. Quantitative analyses of the microstructures revealed that the lateral grain sizes of BiVO4 and WO3 increased and the volume fraction of BiVO4 in the thin films decreased with the increase of the deposition temperature. A three-regime growth mechanism of the WO3-BiVO4 composite thin film was proposed based on the growth dynamics determined by the competition between BiVO4 and WO3.

Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

DOE PAGES

Park, Joong Sun; An, Jihwan; Lee, Min Hwan; ...

2015-11-01

In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

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.

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.

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.

Resistance of Nanostructured Environmental Barrier Coatings to the Movement of Molten Salts

NASA Astrophysics Data System (ADS)

Rao, S.; Frederick, L.; McDonald, A.

2012-09-01

Corrosion of components in a recovery boiler is a major problem faced by the pulp and paper industry. The superheater tubes become severely corroded due to the presence of sulfidic gases in the boiler and molten salts which are deposited on the surface of the tubes. As a result, the boiler must be decommissioned for expensive maintenance and repairs. Yttria-stabilized zirconia (YSZ) coatings have been shown to provide corrosion resistance when applied on gas turbines operating at high temperatures. Air plasma-sprayed YSZ environmental barrier coatings on Type 309 stainless steel were exposed to three different corrosive environments: Test A—600 °C, salt vapors, flue gases, 168 h; Test B—600 °C, molten salt, air, 168 h; and Test C—600 °C, molten salt, flue gases, 168 h. Two different types of YSZ coatings—conventional YSZ and nanostructured YSZ—were tested to study their resistance to corrosion and molten salt penetration. The performances of both types of coatings were evaluated, and a comparative study was conducted. It was found that the nanostructured YSZ samples protected the stainless steel substrate better than their conventional counterparts. This superior performance was attributed to the presence of semi-molten nano-agglomerates present in the coating microstructure, which acted as collection points for the penetrating molten salts.

High temperature gradient cobalt based clad developed using microwave hybrid heating

NASA Astrophysics Data System (ADS)

Prasad, C. Durga; Joladarashi, Sharnappa; Ramesh, M. R.; Sarkar, Anunoy

2018-04-01

The development of cobalt based cladding on a titanium substrate using microwave cladding technique is benchmark in coating area. The developed cladding would serve the function of a corrosion resistant coating under high temperatures. Clads of thickness 500 µm have been developed by microwave hybrid heating. A microwave furnace of 2.45GHz frequency was used at a 900W power level for processing. Impact of processing time on melting and adhesion of clad has been discussed. The study also extended to static thermal analysis of simple parts with cladding using commercial Finite Element analysis (FEA) software. A comparative study is explored between four variants of the clad being developed. The analysis has been conducted using a square sample. Similar temperature gradient is also shown for a proposed multi-layer coating, which includes a thermal barrier coating yttria stabilized zirconia (YSZ) on top of the corrosion resistant clad. The YSZ coating would protect the corrosion resistant cladding and substrate from high temperatures.

Processing of Alumina-Toughened Zirconia Composites

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Choi, Sung R.

2003-01-01

Dense and crack-free 10-mol%-yttria-stabilized zirconia (10YSZ)-alumina composites, containing 0 to 30 mol% of alumina, have been fabricated by hot pressing. Release of pressure before onset of cooling was crucial in obtaining crack-free material. Hot pressing at 1600 C resulted in the formation of ZrC by reaction of zirconia with grafoil. However, no such reaction was observed at 1500 C. Cubic zirconia and -alumina were the only phases detected from x-ray diffraction indicating no chemical reaction between the composite constituents during hot pressing. Microstructure of the composites was analyzed by scanning electron microscopy and transmission electron microscopy. Density and elastic modulus of the composites followed the rule-of-mixtures. Addition of alumina to 10YSZ resulted in lighter, stronger, and stiffer composites by decreasing density and increasing strength and elastic modulus.

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.

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

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.

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.

APS TBC performance on directionally-solidified superalloy substrates with HVOF NiCoCrAlYHfSi bond coatings

DOE PAGES

Lance, Michael J.; Unocic, Kinga A.; Haynes, James A.; ...

2015-09-04

Directionally-solidified (DS) superalloy components with advanced thermal barrier coatings (TBC) to lower the metal operating temperature have the potential to replace more expensive single crystal superalloys for large land-based turbines. In order to assess relative TBC performance, furnace cyclic testing was used with superalloys 1483, X4 and Hf-rich DS 247 substrates and high velocity oxygen fuel (HVOF)-NiCoCrAlYHfSi bond coatings at 1100 °C with 1-h cycles in air with 10% H 2O. With these coating and test conditions, there was no statistically-significant effect of substrate alloy on the average lifetime of the air plasma sprayed (APS) yttria-stabilized zirconia (YSZ) top coatingsmore » on small coupons. Using photo-stimulated luminescence piezospectroscopy maps at regular cycling intervals, the residual compressive stress in the α-Al 2O 3 scale underneath the YSZ top coating and on a bare bond coating was similar for all three substrates and delaminations occurred at roughly the same rate and frequency. As a result, x-ray fluorescence (XRF) measurements collected from the bare bond coating surface revealed higher Ti interdiffusion occurring with the 1483 substrate, which contained the highest Ti content.« less

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.

Monitoring Delamination of Plasma-Sprayed Thermal Barrier Coatings by Reflectance-Enhanced Luminescence

NASA Technical Reports Server (NTRS)

Eldridge, Jeffrey I.; Bencic, Timothy J.

2006-01-01

Highly scattering plasma-sprayed thermal barrier coatings (TBCs) present a challenge for optical diagnostic methods to monitor TBC delamination because scattering attenuates light transmitted through the TBC and usually degrades contrast between attached and delaminated regions of the TBC. This paper presents a new approach where reflectance-enhanced luminescence from a luminescent sublayer incorporated along the bottom of the TBC is used to identify regions of TBC delamination. Because of the higher survival rate of luminescence reflecting off the back surface of a delaminated TBC, the strong scattering exhibited by plasma-sprayed TBCs actually accentuates contrast between attached and delaminated regions by making it more likely that multiple reflections of luminescence off the back surface occur before exiting the top surface of the TBC. A freestanding coating containing sections designed to model an attached or delaminated TBC was prepared by depositing a luminescent Eu-doped or Er-doped yttria-stabilized zirconia (YSZ) luminescent layer below a plasma-sprayed undoped YSZ layer and utilizing a NiCr backing layer to represent an attached substrate. For specimens with a Eu-doped YSZ luminescent sublayer, luminescence intensity maps showed excellent contrast between unbacked and NiCr-backed sections even at a plasma-sprayed overlayer thickness of 300 m. Discernable contrast between unbacked and NiCr-backed sections was not observed for specimens with a Er-doped YSZ luminescent sublayer because luminescence from Er impurities in the undoped YSZ layer overwhelmed luminescence originating form the Er-doped YSZ sublayer.

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.

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.

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.

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.

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.

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.

Deposition, Heat Treatment And Characterization of Two Layer Bioactive Coatings on Cylindrical PEEK

PubMed Central

Durham, John W.; Rabiei, Afsaneh

2015-01-01

Polyether ether ketone (PEEK) rods were coated via ion beam asssited deposition (IBAD) at room temperature. The coating consists of a two-layer design of yttria-stabilized zirconia (YSZ) as a heat-protection layer, and hydroxyapatite (HA) as a top layer to increase bioactivity. A rotating substrate holder was designed to deposit an even coating on the cylindrical surface of PEEK rods; the uniformity is verified by cross-sectional measurements using scanning electron microscopy (SEM). Deposition is followed by heat treatment of the coating using microwave annealing and autoclaving. Transmission electron microscopy (TEM) showed a dense, uniform columnar grain structure in the YSZ layer that is well bonded to the PEEK substrate, while the calcium phosphate layer was amorphous and pore-free in its as-deposited state. Subsequent heat treatment via microwave energy introduced HA crystallization in the calcium phosphate layer and additional autoclaving further expanded the crystallization of the HA layer. Chemical composition evaluation of the coating indicated the Ca/P ratios of the HA layer to be near that of stoichiometric HA, with minor variations through the HA layer thickness. The adhesion strength of as-deposited HA/YSZ coatings on smooth, polished PEEK surfaces was mostly unaffected by microwave heat treatment, but decreased with additional autoclave treatment. Increasing surface roughness showed improvement of bond strength. PMID:27713592

Polycrystalline Superconducting Thin Films: Texture Control and Critical Current Density

NASA Astrophysics Data System (ADS)

Yang, Feng

1995-01-01

The growth processes of polycrystalline rm YBa_2CU_3O_{7-X} (YBCO) and yttria-stabilized-zirconia (YSZ) thin films have been developed. The effectiveness of YSZ buffer layers on suppression of the reaction between YBCO thin films and metallic substrates was carefully studied. Grown on the chemically inert surfaces of YSZ buffer layers, YBCO thin films possessed good quality of c-axis alignment with the c axis parallel to the substrate normal, but without any preferred in-plane orientations. This leads to the existence of a large percentage of the high-angle grain boundaries in the YBCO films. The critical current densities (rm J_{c}'s) found in these films were much lower than those in single crystal YBCO thin films, which was the consequence of the weak -link effect of the high-angle grain boundaries in these films. It became clear that the in-plane alignment is vital for achieving high rm J_{c }s in polycrystalline YBCO thin films. To induce the in-plane alignment, ion beam-assisted deposition (IBAD) technique was integrated into the conventional pulsed laser deposition process for the growth of the YSZ buffer layers. It was demonstrated that using IBAD the in-plane orientations of the YSZ grains could be controlled within a certain range of a common direction. This ion -bombardment induced in-plane texturing was explained using the anisotropic sputtering yield theory. Our observations and analyses have provided valuable information on the optimization of the IBAD process, and shed light on the texturing mechanism in YSZ. With the in-plane aligned YSZ buffer layers, YBCO thin films grown on metallic substrates showed improved rm J_{c}s. It was found that the in-plane alignment of YSZ and that of YBCO were closely related. A direct correlation was revealed between the rm J_{c} value and the degree of the in-plane alignment for the YBCO thin films. To explain this correlation, a numerical model was applied to multi-grain superconducting paths with different textures to determine the expected rm J_{c}s. The good agreement between the experimental data and numerical results confirmed that the rm J_{c} improvement directly resulted from the reduction of the number of high-angle grain boundaries in the in-plane aligned polycrystalline YBCO thin films, and provided a guideline on the further improvement of the rm J_ {c}s of polycrystalline YBCO thin films.

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.

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.

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

A Theoretical Model for Predicting Residual Stress Generation in Fabrication Process of Double-Ceramic-Layer Thermal Barrier Coating System.

PubMed

Song, Yan; Wu, Weijie; Xie, Feng; Liu, Yilun; Wang, Tiejun

2017-01-01

Residual stress arisen in fabrication process of Double-Ceramic-Layer Thermal Barrier Coating System (DCL-TBCs) has a significant effect on its quality and reliability. In this work, based on the practical fabrication process of DCL-TBCs and the force and moment equilibrium, a theoretical model was proposed at first to predict residual stress generation in its fabrication process, in which the temperature dependent material properties of DCL-TBCs were incorporated. Then, a Finite Element method (FEM) has been carried out to verify our theoretical model. Afterwards, some important geometric parameters for DCL-TBCs, such as the thickness ratio of stabilized Zirconia (YSZ, ZrO2-8%Y2O3) layer to Lanthanum Zirconate (LZ, La2Zr2O7) layer, which is adjustable in a wide range in the fabrication process, have a remarkable effect on its performance, therefore, the effect of this thickness ratio on residual stress generation in the fabrication process of DCL-TBCs has been systematically studied. In addition, some thermal spray treatment, such as the pre-heating treatment, its effect on residual stress generation has also been studied in this work. It is found that, the final residual stress mainly comes from the cooling down process in the fabrication of DCL-TBCs. Increasing the pre-heating temperature can obviously decrease the magnitude of residual stresses in LZ layer, YSZ layer and substrate. With the increase of the thickness ratio of YSZ layer to LZ layer, magnitudes of residual stresses arisen in LZ layer and YSZ layer will increase while residual stress in substrate will decrease.

A Theoretical Model for Predicting Residual Stress Generation in Fabrication Process of Double-Ceramic-Layer Thermal Barrier Coating System

PubMed Central

Song, Yan; Wu, Weijie; Xie, Feng; Liu, Yilun; Wang, Tiejun

2017-01-01

Residual stress arisen in fabrication process of Double-Ceramic-Layer Thermal Barrier Coating System (DCL-TBCs) has a significant effect on its quality and reliability. In this work, based on the practical fabrication process of DCL-TBCs and the force and moment equilibrium, a theoretical model was proposed at first to predict residual stress generation in its fabrication process, in which the temperature dependent material properties of DCL-TBCs were incorporated. Then, a Finite Element method (FEM) has been carried out to verify our theoretical model. Afterwards, some important geometric parameters for DCL-TBCs, such as the thickness ratio of stabilized Zirconia (YSZ, ZrO2-8%Y2O3) layer to Lanthanum Zirconate (LZ, La2Zr2O7) layer, which is adjustable in a wide range in the fabrication process, have a remarkable effect on its performance, therefore, the effect of this thickness ratio on residual stress generation in the fabrication process of DCL-TBCs has been systematically studied. In addition, some thermal spray treatment, such as the pre-heating treatment, its effect on residual stress generation has also been studied in this work. It is found that, the final residual stress mainly comes from the cooling down process in the fabrication of DCL-TBCs. Increasing the pre-heating temperature can obviously decrease the magnitude of residual stresses in LZ layer, YSZ layer and substrate. With the increase of the thickness ratio of YSZ layer to LZ layer, magnitudes of residual stresses arisen in LZ layer and YSZ layer will increase while residual stress in substrate will decrease. PMID:28103275

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.

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.

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.

The sol-gel route: A versatile process for up-scaling the fabrication of gas-tight thin electrolyte layers

NASA Astrophysics Data System (ADS)

Viazzi, Céline; Rouessac, Vincent; Lenormand, Pascal; Julbe, Anne; Ansart, Florence; Guizard, Christian

2011-03-01

Sol-gel routes are often investigated and adapted to prepare, by suitable chemical modifications, submicronic powders and derived materials with controlled morphology, which cannot be obtained by conventional solid state chemistry paths. Wet chemistry methods provide attractive alternative routes because mixing of species occurs at the atomic scale. In this paper, ultrafine powders were prepared by a novel synthesis method based on the sol-gel process and were dispersed into suspensions before processing. This paper presents new developments for the preparation of functional materials like yttria-stabilized-zirconia (YSZ, 8% Y2O3) used as electrolyte for solid oxide fuel cells. YSZ thick films were coated onto porous Ni-YSZ substrates using a suspension with an optimized formulation deposited by either a dip-coating or a spin-coating process. The suspension composition is based on YSZ particles encapsulated by a zirconium alkoxide which was added with an alkoxide derived colloidal sol. The in situ growth of these colloids increases significantly the layer density after an appropriated heat treatment. The derived films were continuous, homogeneous and around 20 μm thick. The possible up-scaling of this process has been also considered and the suitable processing parameters were defined in order to obtain, at an industrial scale, homogeneous, crack-free, thick and adherent films after heat treatment at 1400 °C.

Columnar-Structured Mg-Al-Spinel Thermal Barrier Coatings (TBCs) by Suspension Plasma Spraying (SPS)

NASA Astrophysics Data System (ADS)

Schlegel, N.; Ebert, S.; Mauer, G.; Vaßen, R.

2015-01-01

The suspension plasma spraying (SPS) process has been developed to permit the feeding of sub-micrometer-sized powder into the plasma plume. In contrast to electron beam-physical vapor deposition and plasma spray-physical vapor deposition, SPS enables the cost-efficient deposition of columnar-structured coatings. Due to their strain tolerance, these coatings play an important role in the field of thermal barrier coatings (TBCs). In addition to the cost-efficient process, attention was turned to the TBC material. Nowadays, yttria partially stabilized zirconia (YSZ) is used as standard TBC material. However, its long-term application at temperatures higher than 1200 °C is problematic. At these high temperatures, phase transitions and sintering effects lead to the degradation of the TBC system. To overcome those deficits of YSZ, Mg-Al-spinel was chosen as TBC material. Even though it has a lower melting point (~2135 °C) and a higher thermal conductivity (~2.5 W/m/K) than YSZ, Mg-Al-spinel provides phase stability at high temperatures in contrast to YSZ. The Mg-Al-spinel deposition by SPS resulted in columnar-structured coatings, which have been tested for their thermal cycling lifetime. Furthermore, the influence of substrate cooling during the spraying process on thermal cycling behavior, phase composition, and stoichiometry of the Mg-Al-spinel has been investigated.

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

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, Ti alloy and YSZ components.

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.

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.

Abradable dual-density ceramic turbine seal system

NASA Technical Reports Server (NTRS)

Clingman, D. L.; Schechter, B.; Cross, K. R.; Cavanagh, J. R.

1981-01-01

A plasma sprayed dual density ceramic abradable seal system for direct application to the HPT seal shroud of small gas turbine engines. The system concept is based on the thermal barrier coating and depends upon an additional layer of modified density ceramic material adjacent to the gas flow path to provide the desired abradability. This is achieved by codeposition of inert fillers with yttria stabilized zirconia (YSZ) to interrupt the continuity of the zirconia struture. The investigation of a variety of candidate fillers, with hardness values as low as 2 on Moh's scale, led to the conclusion that solid filler materials in combination with a YSZ matrix, regardless of their hardness values, have a propensity for compacting rather than shearing as originally expected. The observed compaction is accompanied by high energy dissipation in the rub interaction, usually resulting in the adhesive transfer of blade material to the stationary seal member. Two YSZ based coating systems which incorported hollow alumino silicate spheres as density reducing agents were surveyed over the entire range of compositions from 100 percent filler to 100 percent YSZ. Abradability and erosion characteristics were determined, hardness and permeability characterized, and engine experience acquired with several system configurations.

Permeability and Microstructure of Suspension Plasma-Sprayed YSZ Electrolytes for SOFCs on Various Substrates

NASA Astrophysics Data System (ADS)

Marr, Michael; Kesler, Olivera

2012-12-01

Yttria-stabilized zirconia electrolyte coatings for solid oxide fuel cells were deposited by suspension plasma spraying using a range of spray conditions and a variety of substrates, including finely structured porous stainless steel disks and cathode layers on stainless steel supports. Electrolyte permeability values and trends were found to be highly dependent on which substrate was used. The most gas-tight electrolyte coatings were those deposited directly on the porous metal disks. With this substrate, permeability was reduced by increasing the torch power and reducing the stand-off distance to produce dense coating microstructures. On the substrates with cathodes, electrolyte permeability was reduced by increasing the stand-off distance, which reduced the formation of segmentation cracks and regions of aligned and concentrated porosity. The formation mechanisms of the various permeability-related coating features are discussed and strategies for reducing permeability are presented. The dependences of electrolyte deposition efficiency and surface roughness on process conditions and substrate properties are also presented.

The Influence of Process Equipment on the Properties of Suspension Plasma Sprayed Yttria-Stabilized Zirconia Coatings

NASA Astrophysics Data System (ADS)

Marr, Michael; Waldbillig, David; Kesler, Olivera

2013-03-01

Suspension plasma-sprayed YSZ coatings were deposited at lab-scale and production-type facilities to investigate the effect of process equipment on coating properties. The target application for these coatings is solid oxide fuel cell (SOFC) electrolytes; hence, dense microstructures with low permeability values were preferred. Both facilities had the same torch but different suspension feeding systems, torch robots, and substrate holders. The lab-scale facility had higher torch-substrate relative speeds compared with the production-type facility. On porous stainless steel substrates, permeabilities and microstructures were comparable for coatings from both facilities, and no segmentation cracks were observed. Coating permeability was further reduced by increasing substrate temperatures during deposition or reducing suspension feed rates. On SOFC cathode substrates, coatings made in the production-type facility had higher permeabilities and more segmentation cracks compared with coatings made in the lab-scale facility. Increased cracking in coatings from the production-type facility was likely caused mainly by its lower torch-substrate relative speed.

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.

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.

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.

Magneto-optical characterizations of FeTe₀̣₅Se₀̣₅ thin films with critical current density over 1 MA/cm²

DOE PAGES

Sun, Yue; Li, Qiang; Tsuchiya, Yuji; ...

2014-12-03

We performed magneto-optical (MO) measurements on FeTe₀̣₅Se₀̣₅ thin films grown on LaAlO₃ (LAO) and Yttria-stabilized zirconia (YSZ) single-crystalline substrates. These thin films show superconducting transition temperature T c ~19 K, 4 K higher than the bulk sample. Typical roof-top patterns can be observed in the MO images of thin films grown on LAO and YSZ, from which a large and homogeneous critical current density J c ~ 3 - 4 x 10⁶ A/cm² at 5 K was obtained. In this study, magnetic flux penetration measurement reveals that the current is almost isotropically distributed in the two thin films. Compared withmore » bulk crystals, FeTe₀̣₅Se₀̣₅ thin film demonstrates not only higher T c, but also much larger J c, which is attractive for applications.« less

Zirconia and Pyrochlore Oxides for Thermal Barrier Coatings in Gas Turbine Engines

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

2014-06-01

One of the important applications of yttria-stabilized zirconia (YSZ) is as a thermal barrier coating for gas turbine engines. While YSZ performs well in this function, the need for increased operating temperatures to achieve higher energy conversion efficiencies, requires the development of improved materials. To meet this challenge, some rare-earth zirconates that form the cubic fluorite-derived pyrochlore structure are being developed for use in thermal barrier coatings due to their low thermal conductivity, excellent chemical stability, and other suitable properties. In this paper, the thermal conductivities of current and prospective oxides for use in thermal barrier coatings are reviewed. The factors affecting the variations and differences in the thermal conductivities and the degradation behaviors of these materials are discussed.

High T(sub c) superconductor/ferroelectric heterostructures

NASA Astrophysics Data System (ADS)

Ryder, Daniel F., Jr.

1994-12-01

Thin films of the ferroelectric perovskite, Ba(x) Sr(1-x) TiO3 (BST), were deposited on superconducting (100)YBa2Cu3O(x)(YBCO)/ (100)Yttria-stabilized zirconia(YSZ) substrates and (100)Si by ion-beam sputtering. Microstructural and compositional features of the ceramic bilayer were assessed by a combination of x-ray diffraction (XRD) and scanning electron microscopy. The films were smooth and featureless, and energy dispersive x-ray spectroscopy (EDX) data indicated that film composition closely matched target composition. XRD analysis showed that films deposited on YBCO substrates were highly c-axis textured, while the films deposited on (100)Si did not exhibit any preferred growth morphology. The superconducting properties of the YBCO substrate layer were maintained throughout the processing stages and, as such, it was demonstrated that ion beam sputtering is a viable method for the deposition of Ferroelectric/YBCO heterostructures.

Erosion Performance of Gadolinium Zirconate-Based Thermal Barrier Coatings Processed by Suspension Plasma Spray

NASA Astrophysics Data System (ADS)

Mahade, Satyapal; Curry, Nicholas; Björklund, Stefan; Markocsan, Nicolaie; Nylén, Per; Vaßen, Robert

2017-01-01

7-8 wt.% Yttria-stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used by the gas turbines industry due to its excellent thermal and thermo-mechanical properties up to 1200 °C. The need for improvement in gas turbine efficiency has led to an increase in the turbine inlet gas temperature. However, above 1200 °C, YSZ has issues such as poor sintering resistance, poor phase stability and susceptibility to calcium magnesium alumino silicates (CMAS) degradation. Gadolinium zirconate (GZ) is considered as one of the promising top coat candidates for TBC applications at high temperatures (>1200 °C) due to its low thermal conductivity, good sintering resistance and CMAS attack resistance. Single-layer 8YSZ, double-layer GZ/YSZ and triple-layer GZdense/GZ/YSZ TBCs were deposited by suspension plasma spray (SPS) process. Microstructural analysis was carried out by scanning electron microscopy (SEM). A columnar microstructure was observed in the single-, double- and triple-layer TBCs. Phase analysis of the as-sprayed TBCs was carried out using XRD (x-ray diffraction) where a tetragonal prime phase of zirconia in the single-layer YSZ TBC and a cubic defect fluorite phase of GZ in the double and triple-layer TBCs was observed. Porosity measurements of the as-sprayed TBCs were made by water intrusion method and image analysis method. The as-sprayed GZ-based multi-layered TBCs were subjected to erosion test at room temperature, and their erosion resistance was compared with single-layer 8YSZ. It was shown that the erosion resistance of 8YSZ single-layer TBC was higher than GZ-based multi-layered TBCs. Among the multi-layered TBCs, triple-layer TBC was slightly better than double layer in terms of erosion resistance. The eroded TBCs were cold-mounted and analyzed by SEM.

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

Challenge for lowering concentration polarization in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shimada, Hiroyuki; Suzuki, Toshio; Yamaguchi, Toshiaki; Sumi, Hirofumi; Hamamoto, Koichi; Fujishiro, Yoshinobu

2016-01-01

In the scope of electrochemical phenomena, concentration polarization at electrodes is theoretically inevitable, and lowering the concentration overpotential to improve the performance of electrochemical cells has been a continuing challenge. Electrodes with highly controlled microstructure, i.e., high porosity and uniform large pores are therefore essential to achieve high performance electrochemical cells. In this study, state-of-the-art technology for controlling the microstructure of electrodes has been developed for realizing high performance support electrodes of solid oxide fuel cells (SOFCs). The key is controlling the porosity and pore size distribution to improve gas diffusion, while maintaining the integrity of the electrolyte and the structural strength of actual sized electrode supports needed for the target application. Planar anode-supported SOFCs developed in this study realize 5 μm thick dense electrolyte (yttria-stabilized zirconia: YSZ) and the anode substrate (Ni-YSZ) of 53.6 vol.% porosity with a large median pore diameter of 0.911 μm. Electrochemical measurements reveal that the performance of the anode-supported SOFCs improves with increasing anode porosity. This Ni-YSZ anode minimizes the concentration polarization, resulting in a maximum power density of 3.09 W cm-2 at 800 °C using humidified hydrogen fuel without any electrode functional layers.

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.

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.

Thermal Conductivity and Erosion Durability of Composite Two-Phase Air Plasma Sprayed Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Schmitt, Michael P.; Rai, Amarendra K.; Zhu, Dongming; Dorfman, Mitchell R.; Wolfe, Douglas E.

2015-01-01

To enhance efficiency of gas turbines, new thermal barrier coatings (TBCs) must be designed which improve upon the thermal stability limit of 7 wt% yttria stabilized zirconia (7YSZ), approximately 1200 C. This tenant has led to the development of new TBC materials and microstructures capable of improved high temperature performance. This study focused on increasing the erosion durability of cubic zirconia based TBCs, traditionally less durable than the metastable t' zirconia based TBCs. Composite TBC microstructures composed of a low thermal conductivity/high temperature stable cubic Low-k matrix phase and a durable t' Low-k secondary phase were deposited via APS. Monolithic coatings composed of cubic Low-k and t' Low-k were also deposited, in addition to a 7YSZ benchmark. The thermal conductivity and erosion durability were then measured and it was found that both of the Low-k materials have significantly reduced thermal conductivities, with monolithic t' Low-k and cubic Low-k improving upon 7YSZ by approximately 13 and approximately 25%, respectively. The 40 wt% t' Low-k composite (40 wt% t' Low-k - 60 wt% cubic Low-k) showed a approximately 22% reduction in thermal conductivity over 7YSZ, indicating even at high levels, the t' Low-k secondary phase had a minimal impact on thermal in the composite coating. It was observed that a mere 20 wt% t' Low-k phase addition can reduce the erosion of a cubic Low-k matrix phase composite coating by over 37%. Various mixing rules were then investigated to assess this non-linear composite behavior and suggestions were made to further improve erosion durability.

Comparison of candidate materials for a synthetic osteo-odonto keratoprosthesis device.

PubMed

Tan, Xiao Wei; Perera, A Promoda P; Tan, Anna; Tan, Donald; Khor, K A; Beuerman, Roger W; Mehta, Jodhbir S

2011-01-05

Osteo-odonto keratoprosthesis is one of the most successful forms of keratoprosthesis surgery for end-stage corneal and ocular surface disease. There is a lack of detailed comparison studies on the biocompatibilities of different materials used in keratoprosthesis. The aim of this investigation was to compare synthetic bioinert materials used for keratoprosthesis surgery with hydroxyapatite (HA) as a reference. Test materials were sintered titanium oxide (TiO(2)), aluminum oxide (Al(2)O(3)), and yttria-stabilized zirconia (YSZ) with density >95%. Bacterial adhesion on the substrates was evaluated using scanning electron microscopy and the spread plate method. Surface properties of the implant discs were scanned using optical microscopy. Human keratocyte attachment and proliferation rates were assessed by cell counting and MTT assay at different time points. Morphologic analysis and immunoblotting were used to evaluate focal adhesion formation, whereas cell adhesion force was measured with a multimode atomic force microscope. The authors found that bacterial adhesion on the TiO(2), Al(2)O(3), and YSZ surfaces were lower than that on HA substrates. TiO(2) significantly promoted keratocyte proliferation and viability compared with HA, Al(2)O(3,) and YSZ. Immunofluorescent imaging analyses, immunoblotting, and atomic force microscope measurement revealed that TiO(2) surfaces enhanced cell spreading and cell adhesion compared with HA and Al(2)O(3). TiO(2) is the most suitable replacement candidate for use as skirt material because it enhanced cell functions and reduced bacterial adhesion. This would, in turn, enhance tissue integration and reduce device failure rates during keratoprosthesis surgery.

Effect of thermally growth oxides (TGO) on adhesion strength for high purity yitria stabilised zirconia (YSZ) and rare - Earth lanthanum zirconates (LZ) multilayer thermal barrier coating before and after isothermal heat treatment

NASA Astrophysics Data System (ADS)

Yunus, Salmi Mohd; Johari, Azril Dahari; Husin, Shuib

2017-12-01

Investigation on the effect of Thermally Growth Oxides (TGO) on the adhesion strength for thermal barrier coating (TBC) was carried out. The TBC under studied was the multilayer systems which consist of NiCrAlY bond coat and YSZ/LZ ceramic coating deposited on Ni-based superalloy substrates. The development of thermally growth oxides (TGO) for both TBC systems after isothermal heat treatment was measured. Isothermal heat treatment was carried out at 1100 ˚C for 100 hours to age the samples. ASTM D4541: Standard Test Method for Pull-off Strength of Coatings using Portable Adhesion Tester was used to measure the adhesion strength of both TBC systems before and after heat treatment. The effect of the developed TGO on the measured adhesion strength was examined and correlation between them was established individually for both TBC systems. The failure mechanism of the both system was also identified; either cohesive or adhesive or the combination of both. The results showed that TGO has more than 50% from the bond coat layer for rare-earth LZ system compared to the typical YSZ system, which was less than 10 % from the bond coat layer. This leads to the lower adhesion strength of rare-earth LZ coating system compared to typical YSZ system. Failure mechanism during the pull-off test also was found to be different for both TBC systems. The typical YSZ system experienced cohesive failure whereas the rare-earth LZ system experienced the combination of cohesive and adhesive failure.

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.

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.

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

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

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

2011-02-15

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

Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics

NASA Technical Reports Server (NTRS)

Lee, Kang N.

1999-01-01

Plasma-sprayed mullite (3Al2O3 central dot 2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon-based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface, Thus modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.

Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics

NASA Technical Reports Server (NTRS)

Lee, Kang N.

2000-01-01

Plasma-sprayed mullite (3Al2O3.2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon -based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface. Thus the modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while a weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause a premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.

Role of indium tin oxide electrode on the microstructure of self-assembled WO3-BiVO4 hetero nanostructures

NASA Astrophysics Data System (ADS)

Song, Haili; Li, Chao; Van, Chien Nguyen; Dong, Wenxia; Qi, Ruijuan; Zhang, Yuanyuan; Huang, Rong; Chu, Ying-Hao; Duan, Chun-Gang

2017-11-01

Self-assembled WO3-BiVO4 nanostructured thin films were grown on a (001) yttrium stabilized zirconia (YSZ) substrate by the pulsed laser deposition method with and without the indium tin oxide (ITO) bottom electrode. Their microstructures including surface morphologies, crystalline phases, epitaxial relationships, interface structures, and composition distributions were investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray energy dispersive spectroscopy. In both samples, WO3 formed nanopillars embedded into the monoclinic BiVO4 matrix with specific orientation relationships. In the sample with the ITO bottom electrode, an atomically sharp BiVO4/ITO interface was formed and the orthorhombic WO3 nanopillars were grown on a relaxed BiVO4 buffer layer with a mixed orthorhombic and hexagonal WO3 transition layer. In contrast, a thin amorphous layer appears at the interfaces between the thin film and the YSZ substrate in the sample without the ITO electrode. In addition, orthorhombic Bi2WO6 lamellar nanopillars were formed between WO3 and BiVO4 due to interdiffusion. Such a WO3-Bi2WO6-BiVO4 double heterojunction photoanode may promote the photo-generated charge separation and further improve the photoelectrochemical water splitting properties.

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 a single tetragonal phase. Thus, compositions are of single phase tetragonal phase, theoretically, should not undergo high temperature partitioning. Single Tetragonal phase oxides of Ti-YSZ also offer the possibility of enhanced toughness and higher temperature stability akin to those observed in yttria partially stabilized zirconia. Many pyrochlore oxides are under review because they have shown to have lower thermal conductivity than YSZ oxides. This study focused on chemically synthesizing homogeneous starting material compositions in a metastable state (preferably amorphous), following its evolution according to the phase hierarchy under conditions of kinetic constraints. The current equilibrium diagram of YO1.5-TiO2-ZrO 2 is based on theoretical calculations. One of the contributions of this work is the redefined phase fields in YO1.5-TiO2-ZrO 2 based on our experimental results. Investigated compositions were based on tie lines of Y2-xTi2ZrxO7+x/2 and Y2Ti2-yZryO7 representing substitution of Zr4+ for Y3+ and Zr4+ for Ti4+ respectively. More notably, we observed extended metastable phases in pyrochlore and fluorite oxides at low temperature. The significance of this result is that it offers a larger compositional range for investing pyrochlore oxides with associated high temperature phase stability for TBC applications. In tetragonal oxides, our results showed that Ti-YSZ results have slower partitioning kinetics in comparison to YSZ at high temperature. This study also emphasized the deposition of advanced ceramic coatings by plasma spray for tetragonal and pyrochlore systems, compositionally complex functional oxides that may potentially have lower thermal conductivity values compared to current YSZ oxides. Next generation thermal barrier coatings require powders with high chemical purity, chemical homogeneity, controlled particle size/shape and pertinent phase state. Thermal spray offers an avenue to create novel materials and deposits directly from the precursor and compositionally controlled powder feedstock. This study contributed to investigating an unexplored field that offers a variety of opportunities in materials synthesis that would not be possible by conventional methods. Understanding processing-microstructure-property correlations is of considerable importance in thermal spray of functional oxide materials. This thesis demonstrated by radio-frequency thermal spray that the complex pyrochlore oxide Y 2Ti2O7 could be deposited by directly injecting molecularly mixed precursors to form oxide coatings. Structural analysis revealed the metastable fluorite phase; however, with thermal treatments at relatively low temperature of 700°C the pyrochlore phase was obtained. For Ti-YSZ coatings, the tetragonal phase oxides were obtained with unique microstructures, however, the tetragonal prime destabilized at 1200°C. This dissertation explored novel oxide compositions through detailed structural analysis. The approach presented a comprehensive and integrated investigation as it pertains to phase evolution of oxides in powder feedstock to coating characteristics (phase/properties).

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.

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.

Functionally Graded Bismuth Oxide/Zirconia Bilayer Electrolytes for High-Performance Intermediate-Temperature Solid Oxide Fuel Cells (IT-SOFCs).

PubMed

Joh, Dong Woo; Park, Jeong Hwa; Kim, Doyeub; Wachsman, Eric D; Lee, Kang Taek

2017-03-15

A functionally graded Bi 1.6 Er 0.4 O 3 (ESB)/Y 0.16 Zr 0.84 O 1.92 (YSZ) bilayer electrolyte is successfully developed via a cost-effective screen printing process using nanoscale ESB powders on the tape-cast NiO-YSZ anode support. Because of the highly enhanced oxygen incorporation process at the cathode/electrolyte interface, a novel bilayer solid oxide fuel cell (SOFC) yields extremely high power density of ∼2.1 W cm -2 at 700 °C, which is a 2.4 times increase compared to that of the YSZ single electrolyte SOFC.

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

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.

Subsurface segregation of yttria in yttria stabilized zirconia

NASA Astrophysics Data System (ADS)

de Ridder, M.; van Welzenis, R. G.; van der Gon, A. W. Denier; Brongersma, H. H.; Wulff, S.; Chu, W.-F.; Weppner, W.

2002-09-01

The segregation behavior in 3 and 10 mol % polycrystalline yttria stabilized zirconia (YSZ), calcined at temperatures ranging from 300 to 1600 degC, is characterized using low-energy ion scattering (LEIS). In order to be able to separate the Y and Zr LEIS signals, YSZ samples have been prepared using isotopically enriched 94ZrO2 instead of natural zirconia. The samples are made via a special precipitation method at a low temperature. The segregation to the outermost surface layer is dominated by impurities. The increased impurity levels are restricted to this first layer, which underlines the importance of the use of LEIS for this study. For temperatures of 1000 degC and higher, the oxides of the impurities Na, Si, and Ca even cover the surface completely. The performance of a device like the solid oxide fuel cell which has an YSZ electrolyte and a working temperature around 1000 degC, will, therefore, be strongly hampered by these impurities. The reduction of impurities, to prevent accumulation at the surface, will only be effective if the total impurity bulk concentration can be reduced below the 10 ppm level. Due to the presence of the impurities, yttria cannot accumulate in the outermost layer. It does so, in contrast to the general belief, in the subsurface layer and to much higher concentrations than the values reported previously. The difference in the interfacial free energies of Y2O3 and ZrO2 is determined to be -21plus-or-minus3 kJ/mol.

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.

Design and fabrication of segmented-in-series solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lai, Tammy S.

Segmented-in-series solid oxide fuel cells (SS-SOFC) consist of several thick film cells deposited onto a porous, flattened tubular substrate. SS-SOFCs have a reduced need for gas-tight seals relative to planar SOFCs and can have a short current path compared to tubular SOFCs, limiting electrode ohmic resistance. Like tubular SOFCs, SS-SOFCs are suitable for stationary power generation. Their potentially small cell size makes them candidates for portable applications as well. The goals of this thesis project were to develop SS-SOFCs with 1-2 mm cell lengths and to analyze the effects of cell geometry and support current shunting on performance. Standard SOFC materials were chosen for the active components: yttria stabilized zirconia (YSZ) electrolyte; Ni-YSZ cermet anode; and (La,Sr)MnO 3-based cathode. A Pt-YSZ cermet was used as the interconnect material. Screen printing was the deposition method for all layers due to its low cost and patterning ability. A power density of >900 mW/cm2 was achieved with a cathode sheet resistance of ≈3 O/□ (≈90 mum LSM thickness). A D-optimal study was conducted to find processing conditions yielding substrates with ≥30 vol% porosity and high strength. Uniaxially pressed partially stabilized zirconia (PSZ) with 15 wt% starch pore former met the requirements, though 20 wt% graphite pore former was later found to give a smoother surface that improved screen printed layer quality. Calculations presented in this thesis take into account losses due to cell resistances, electrode ohmic resistances, interconnect resistance, and shunting by a weakly-conductive support material. Power density was maximized at an optimal cell length---it decreased at larger cell lengths due to electrode lateral resistance loss and at smaller cell lengths due to a decreasing fraction of cell active area. Assuming dimensions expected for screen printing and typical area specific resistances (RAS), optimal cell lengths typically ranged from 1 to 3 mm. The calculated and experimental values for the array RAS (active and inactive areas) showed similar dependences on cathode sheet resistance. The impact of shunting current increased with decreasing cell lengths. Shunting current was predicted to decrease array current by ˜10% for a 1.5 mm active cell length, though experimental measurements suggest that the calculation may overestimate the shunting effect.

Growth of highly strained CeO 2 ultrathin films

DOE PAGES

Shi, Yezhou; Lee, Sang Chul; Monti, Matteo; ...

2016-11-07

Large biaxial strain is a promising route to tune the functionalities of oxide thin films. However, large strain is often not fully realized due to the formation of misfit dislocations at the film/substrate interface. In this work, we examine the growth of strained ceria (CeO 2) thin films on (001)-oriented single crystal yttria-stabilized zirconia (YSZ) via pulsed-laser deposition. By varying the film thickness systematically between 1 and 430 nm, we demonstrate that ultrathin ceria films are coherently strained to the YSZ substrate for thicknesses up to 2.7 nm, despite the large lattice mismatch (~5%). The coherency is confirmed by bothmore » X-ray diffraction and high-resolution transmission electron microscopy. This thickness is several times greater than the predicted equilibrium critical thickness. Partial strain relaxation is achieved by forming semirelaxed surface islands rather than by directly nucleating dislocations. In situ reflective high-energy electron diffraction during growth confirms the transition from 2-D (layer-by-layer) to 3-D (island) at a film thickness of ~1 nm, which is further supported by atomic force microscopy. We propose that dislocations likely nucleate near the surface islands and glide to the film/substrate interface, as evidenced by the presence of 60° dislocations. Finally, an improved understanding of growing oxide thin films with a large misfit lays the foundation to systematically explore the impact of strain and dislocations on properties such as ionic transport and redox chemistry.« less

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.

Color center annealing and ageing in electron and ion-irradiated yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Costantini, Jean-Marc; Beuneu, François

2005-04-01

We have used X-band electron paramagnetic resonance (EPR) measurements at room-temperature (RT) to study the thermal annealing and RT ageing of color centers induced in yttria-stabilized zirconia (YSZ), i.e. ZrO2:Y with 9.5 mol% Y2O3, by swift electron and ion-irradiations. YSZ single crystals with the <1 0 0> orientation were irradiated with 2.5 MeV electrons, and implanted with 100 MeV 13C ions. Electron and ion beams produce the same two color centers, namely an F+-type center (singly ionized oxygen vacancy) and the so-called T-center (Zr3+ in a trigonal oxygen local environment) which is also produced by X-ray irradiations. Isochronal annealing was performed in air up to 973 K. For both electron and ion irradiations, the defect densities are plotted versus temperature or time at various fluences. The influence of a thermal treatment at 1373 K of the YSZ single crystals under vacuum prior to the irradiations was also investigated. In these reduced samples, color centers are found to be more stable than in as-received samples. Two kinds of recovery processes are observed depending on fluence and heat treatment.

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.

Processing and Mechanical Properties of Various Zirconia/Alumina Composites for Fuel Cell Applications

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Bansal, Narottam P.

2002-01-01

Various electrolyte materials for solid oxide fuel cells were fabricated by hot pressing 10 mol% yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina, particulates and platelets, each containing 0 to 30 mol% alumina. Flexure strength and fracture toughness of both particulate and platelet composites at ambient temperature increased with increasing alumina content, reaching a maximum at 30 mot% alumina. For a given alumina content, strength of particulate composites was greater than that of platelet composites, whereas, the difference in fracture toughness between the two composite systems was negligible. No virtual difference in elastic modulus and density was observed for a given alumina content between particulate and platelet composites. Thermal cycling up to 10 cycles between 200 to 1000 C did not show any effect on strength degradation of the 30 mol% platelet composites, indicative of negligible influence of CTE mismatches between YSZ matrix and alumina grains.

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.

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.

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.

Mechanical reliability, fatigue strength and survival analysis of new polycrystalline translucent zirconia ceramics for monolithic restorations.

PubMed

Pereira, Gabriel K R; Guilardi, Luís F; Dapieve, Kiara S; Kleverlaan, Cornelis J; Rippe, Marília P; Valandro, Luiz Felipe

2018-05-23

This study characterized the mechanical properties (static and under fatigue), the crystalline microstructure (monoclinic - m, tetragonal - t and cubic - c phase contents) and the surface topography of three yttrium-stabilized zirconia (YSZ) materials with different translucent properties, before and after aging in an autoclave (low temperature degradation). Disc-shaped specimens were produced from second generation (Katana ML/HT - high-translucent) and third generations (Katana STML - super-translucent and UTML - ultra-translucent) YSZ ceramics (Kuraray Noritake Dental Inc.), following ISO 6872-2015 guidelines for biaxial flexural strength testing (final dimensions: 15 mm in diameter and 1.2 ± 0.2 mm in thickness), and then subjected to the respective tests and analyses. ML was mainly composed of tetragonal crystals, while STML and UTML presented cubic content. Aging increased the monoclinic content for ML and did not affect STML and UTML. Topographical analysis highlights different grain sizes on the ceramic surface (UTML > STML > ML) and aging had no effect on this outcome. Weibull analysis showed the highest characteristic strength for ML both before and after aging, and statistically similar Weibull moduli for all groups. ML material also obtained the highest survival rates (ML > STML > UTML) for both fatigue strength and number of cycles to failure. All fractures originated from surface defects on the tensile side. Third generation zirconia (Katana STML and UTML) are fully stabilized materials (with tetragonal and cubic crystals), being totally inert to the autoclave aging, and presented lower mechanical properties than the second-generation zirconia (Katana ML - metastable zirconia). Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

PubMed

Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

2015-03-11

Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode.

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.

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.

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.

Investigations in the mechanism of carbothermal reduction of yttria stabilized zirconia for ultra-high temperature ceramics application and its influence on yttria contained in it

NASA Astrophysics Data System (ADS)

Sondhi, Anchal

Zirconium carbide (ZrC) is a high modulus ceramic with an ultra-high melting temperature and, consequently, is capable of withstanding extreme environments. Carbon-carbon composites (CCCs) are important structural materials in current commercial and future hypersonic aircraft; however, these materials may be susceptible to degradation when exposed to elevated temperatures during extreme velocities. At speeds of exceeding Mach 5, intense heating of leading edges of the aircraft triggers rapid oxidation of carbon in CCCs resulting in degradation of the structure and probable failure. Environmental/thermal barrier coatings (EBC/TBC) are employed to protect airfoil structures from extreme conditions. Yttria stabilized zirconia (YSZ) is a well-known EBC/TBC material currently used to protect metallic turbine blades and other aerospace structures. In this work, 3 mol% YSZ has been studied as a potential EBC/TBC on CCCs. However, YSZ is an oxygen conductor and may not sufficiently slow the oxidation of the underlying CCC. Under appropriate conditions, ZrC can form at the interface between CCC and YSZ. Because ZrC is a poor oxygen ion conductor in addition to its stability at high temperatures, it can reduce the oxygen transport to the CCC and thus increase the service lifetime of the structure. This dissertation investigates the thermodynamics and kinetics of the YSZ/ZrC/CCC system and the resulting structural changes across multiple size scales. A series of experiments were conducted to understand the mechanisms and species involved in the carbothermal reduction of ZrO2 to form ZrC. 3 mol% YSZ and graphite powders were uniaxially pressed into pellets and reacted in a graphite (C) furnace. Rietveld x-ray diffraction phase quantification determined that greater fractions of ZrC were formed when carbon was the majority mobile species. These results were validated by modeling the process thermochemically and were confirmed with additional experiments. Measurements were conducted to examine the effect of carbothermal reduction on the bond lengths in YSZ and ZrC. Subsequent extended x-ray absorption fine structure (EXAFS) measurements and calculations showed Zr-O, Zr-C and Zr-Zr bond lengths to be unchanged after carbothermal reduction. Energy dispersive spectroscopy (EDS) line scan and mapping were carried out on carbothermaly reduced 3 mol% YSZ and 10 mol% YSZ powders. Results revealed Y2O3 stabilizer forming agglomerates with a very low solubility in ZrC.

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

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

Chen, Yun; Chen, Song; Hackett, Gregory

The interaction of trace (ppm) phosphine with the nickel/yttria stabilized zirconia (YSZ) anode of commercial solid oxide fuel cells has been investigated and evaluated for both synthesis gas and hydrogen fuels in an effort to examine P–Y reactions. The Ni poisoning effects reported in literature were confirmed and degradation was examined by electrochemical methods and post-test microstructural and chemical analyses. The results indicate that P-induced degradation rates and mechanisms are fuel dependent and that degradation of cells operated in synthesis gas (syngas) with phosphine is more severe than that of cells operated in hydrogen with phosphine. As reported in publishedmore » literature, a cell operated in syngas containing 10 ppm phosphine demonstrated significant microstructural degradation within the Ni phase, including formation of Ni–P phases concentrated on the outer layer of the anode and significant pitting corrosion in the Ni grains. In this research, a previously undetected YPO{sub 4} phase is observed at the YSZ/YSZ/Ni triple grain junctions located at the interface with the YSZ electrolyte. Tetragonal YSZ (t-YSZ) and cubic-YSZ (c-YSZ) domains with sizes of several tens of nanometers are also newly observed along the Ni/YSZ interface. These observations contrast with data obtained for a cell operated in dry hydrogen with phosphine, where no YPO{sub 4} phase is observed and the alternating t-YSZ and c-YSZ domains at the Ni/YSZ interface are smaller with typical sizes of 5–10 nm. The data imply that electrolyte attack by P is a potentially debilitating mode of degradation in SOFC anodes, and that the associated reaction mechanisms and rates are worthy of further examination.« less

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.

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."

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.

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

Tribological characterization of zirconia coatings deposited on Ti6Al4V components for orthopedic applications.

PubMed

Berni, M; Lopomo, N; Marchiori, G; Gambardella, A; Boi, M; Bianchi, M; Visani, A; Pavan, P; Russo, A; Marcacci, M

2016-05-01

One of the most important issues leading to the failure of total joint arthroplasty is related to the wear of the plastic components, which are generally made of ultra high molecular weight polyethylene (UHMWPE). Therefore, the reduction of joint wear represents one of the main challenges the research in orthopedics is called to address nowadays. Surface treatments and coatings have been recognized as innovative methods to improve tribological properties, also in the orthopedic field. This work investigated the possibility to realize hard ceramic coatings on the metal component of a prosthesis, by means of Pulsed Plasma Deposition, in order to reduce friction and wear in the standard coupling against UHMWPE. Ti6Al4V substrates were coated with a 2 μm thick yttria-stabilized zirconia (YSZ) layer. The mechanical properties of the YSZ coatings were assessed by nanoindentation tests performed on flat Ti6Al4V substrates. Tribological performance was evaluated using a ball-on-disk tribometer in dry and lubricated (i.e. with fetal bovine serum) highly-stressing conditions, up to an overall distance of 10 km. Tribology was characterized in terms of coefficient of friction (CoF) and wear rate of the UHMWPE disk. After testing, specimens were analyzed through optical microscopy and SEM images, in order to check the wear degradation mechanisms. Progressive loading scratch tests were also performed in dry and wet conditions to determine the effects of the environment on the adhesion of the coating. Our results supported the beneficial effect of YSZ coating on metal components. In particular, the proposed solution significantly reduced UHMWPE wear rate and friction. At 10 km of sliding distance, a wear rate reduction of about 18% in dry configuration and of 4% in presence of serum, was obtained by the coated group compared to the uncoated group. As far as friction in dry condition is concerned, the coating allowed to maintain low CoF values until the end of the tests, with an overall difference of about 40% compared to the uncoated balls. In wet conditions, the friction values were found to be comparable between coated and uncoated materials, mainly due to a premature delamination of the coating. Scratch tests in wet showed in fact a reduction of the critical load required to a complete delamination due to a formation of blister, although no change or damage occurred at the coating during the soaking period. Although conditions of high values of contact pressure were considered, further analyses are however required to fully understand the behavior of YSZ coatings in wet environment and additional research on the deposition process will be mandatory in order to improve the coating tribological performance at long distances addressing orthopedic applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Densification kinetics of nanocrystalline zirconia powder using microwave and spark plasma sintering--a comparative study.

PubMed

Vasylkiv, Oleg; Demirskyi, Dmytro; Sakka, Yoshio; Ragulya, Andrey; Borodianska, Hanna

2012-06-01

Two-stage densification process of nanosized 3 mol% yttria-stabilized zirconia (3Y-SZ) polycrystalline compacts during consolidation via microwave and spark-plasma sintering have been observed. The values of activation energies obtained for microwave and spark-plasma sintering 260-275 kJ x mol(-1) are quite similar to that of conventional sintering of zirconia, suggesting that densification during initial stage is controlled by the grain-boundary diffusion mechanism. The sintering behavior during microwave sintering was significantly affected by preliminary pressing conditions, as the surface diffusion mechanism (230 kJ x mol(-1)) is active in case of cold-isostatic pressing procedure was applied.

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.

Investigation for surface resistance of yttrium-barium-copper-oxide thin films on various substrates for microwave applications

NASA Astrophysics Data System (ADS)

Yao, Hongjun

High temperature superconducting (HTS) materials such as YBCO (Yttrium-Barium-Copper-Oxide) are very attractive in microwave applications because of their extremely low surface resistance. In the proposed all-HTS tunable filter, a layer of HTS thin film on a very thin substrate (100 mum) is needed to act as the toractor that can be rotated to tune the frequency. In order to provide more substrate candidates that meet both electrical and mechanical requirements for this special application, surface resistance of YBCO thin films on various substrates was measured using microstrip ring resonator method. For alumina polycrystalline substrate, a layer of YSZ (Yttrium stabilized Zirconia) was deposited using IBAD (ion beam assisted deposition) method prior to YBCO deposition. The surface resistance of the YBCO thin film on alumina was found to be 22 mO due to high-angle grain boundary problem caused by the mixed in-plane orientations and large FWHM (full width at half maximum) of the thin film. For YBCO thin films on a YSZ single crystal substrate, the surface resistance showed even higher value of 30 mO because of the mixed in-plane orientation problem. However, by annealing the substrate in 200 Torr oxygen at 730°C prior to deposition, the in-plane orientation of YBCO thin films can be greatly improved. Therefore, the surface resistance decreased to 1.4 mO, which is still more than an order higher than the reported best value. The YBCO thin films grown on LaAlO3 single crystal substrate showed perfect in-plane orientation with FWHM less 1°. The surface resistance was as low as 0.032 mO. A tunable spiral resonator made of YBCO thin film on LaAlO3 single crystal substrate demonstrated that the resonant frequency can be tuned in a rang as large as 500 MHz by changing the gap between toractor and substrate. The Q-factor was more than 12,000, which ensured the extraordinarily high sensitivity for the proposed all-HTS tunable filter.

Strength and Fracture Toughness of Solid Oxide Fuel Cell Electrolyte Material Improved

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Choi, Sung R.

2002-01-01

Solid oxide fuel cells (SOFC) are being developed for various applications in the automobile, power-generation, and aeronautics industries. Recently, the NASA Glenn Research Center has been exploring the possibility of using SOFC's for aeropropulsion under its Zero Carbon Dioxide Emission Technology (ZCET) Program. 10-mol% yttriastabilized zirconia (10YSZ) is a very good anionic conductor at high temperatures and is, therefore, used as an oxygen solid electrolyte in SOFC. However, it has a high thermal expansion coefficient, low thermal shock resistance, low fracture toughness, and poor mechanical strength. For aeronautic applications, the thin ceramic electrolyte membrane of the SOFC needs to be strong and tough. Therefore, we have been investigating the possibility of enhancing the strength and fracture toughness of the 10YSZ electrolyte without degrading its electrical conductivity to an appreciable extent. We recently demonstrated that the addition of alumina to zirconia electrolyte increases its strength as well as its fracture toughness. Zirconia-alumina composites containing 0 to 30 mol% of alumina were fabricated by hot pressing. The hot pressing procedure was developed and various hot pressing parameters were optimized, resulting in dense, crackfree panels of composite materials. Cubic zirconia and a-alumina were the only phases detected, indicating that there was no chemical reaction between the constituents during hot pressing at elevated temperatures. Flexure strength sf and fracture toughness K(sub IC) of the various zirconia-alumina composites were measured at room temperature as well as at 1000 C in air. Both properties showed systematic improvement with increased alumina addition at room temperature and at 1000 C. Use of these modified electrolytes with improved strength and fracture toughness should prolong the life and enhance the performance of SOFC in aeronautics and other applications.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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.

The early growth and interface of YBa 2Cu 3O y thin films deposited on YSZ substrates

NASA Astrophysics Data System (ADS)

Gao, J.; Tang, W. H.; Yau, C. Y.

2001-11-01

Epitaxial thin films of YBa 2Cu 3O y (YBCO) have been prepared on yttrium-stabilized zirconia substrates with and without a buffer layer. The early growth, crystallinity and surface morphology of these thin films have been characterized by X-ray diffraction, rocking curves, scanning electron microscope, in situ conductance measurements, and surface step profiler. The full width at half maximum of the ( 0 0 5 ) peak of rocking curve was found to be less than 0.1°. Over a wide scanning range of 2000 μm the average surface roughness is just 5 nm, indicating very smooth films. Grazing incident X-ray reflection and positron annihilation spectroscopy shows well-defined interfaces between layers and substrate. By applying a new Eu 2CuO 4 (ECO) buffer layer the initial formation of YBCO appears to grow layer-by-layer rather than the typical island growth mode. The obtained results reveal significant improvements at the early formation and crystallinity of YBCO by using the 214-T ‧ ECO as a buffer layer.

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

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.

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.

Thermal Barrier Coatings Resistant to Glassy Deposits

NASA Astrophysics Data System (ADS)

Drexler, Julie Marie

Engineering of alloys has for years allowed aircraft turbine engines to become more efficient and operate at higher temperatures. As advancements in these alloy systems have become more difficult, ceramic thermal barrier coatings (TBCs), often yttria (7 wt %) stabilized zirconia (7YSZ), have been utilized for thermal protection. TBCs have allowed for higher engine operating temperatures and better fuel efficiency but have also created new engineering problems. Specifically, silica based particles such as sand and volcanic ash that enter the engine during operation form glassy deposits on the TBCs. These deposits can cause the current industrial 7YSZ thermal barrier coatings to fail since the glass formed penetrates and chemically interacts with the TBC. When this occurs, coating failure may occur due to a loss of strain tolerance, which can lead to fracture, and phase changes of the TBC material. There have been several approaches used to stop calcium-magnesium aluminio-silcate (CMAS) glasses (molten sand) from destroying the entire TBC, but overall there is still limited knowledge. In this thesis, 7YSZ and new TBC materials will be examined for thermochemical and thermomechanical performance in the presence of molten CMAS and volcanic ash. Two air plasma sprayed TBCs will be shown to be resistant to volcanic ash and CMAS. The first type of coating is a modified 7YSZ coating with 20 mol% Al2O3 and 5 mol% TiO2 in solid solution (YSZ+20Al+5Ti). The second TBC is made of gadolinium zirconate. These novel TBCs impede CMAS and ash penetration by interacting with the molten CMAS or ash and drastically changing the chemistry. The chemically modified CMAS or ash will crystallize into an apatite or anorthite phase, blocking the CMAS or ash from further destroying the coating. A presented mechanism study will show these coatings are effective due to the large amount of solute (Gd, Al) in the zirconia structure, which is the key to creating the crystalline apatite or anorthite phases. In fact, it will be shown that if the industrial standard 7YSZ coatings contained more Y2O3 they would be very effective in stopping CMAS penetration. Lastly, thermal cyclic testing of 7YSZ and YSZ+20Al+5Ti TBCs reveals that partially CMAS-impregnated TBCs can survive mechanically if cycled in thermal gradient while in most isothermal tests they would fail. Since parts in a jet engine are in a thermal gradient, this type of testing should be performed on future CMAS resistant TBCs.

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

PubMed Central

2014-01-01

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

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.

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.

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

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

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

Influence of Laser Glazing on the Characterization of Plasma-Sprayed YSZ Coatings

NASA Astrophysics Data System (ADS)

Wang, Yan; Liu, Jiangwei; Liao, Hanlin; Darut, Geoffrey; Stella, Jorge; Poirier, Thierry; Planche, Marie-Pierre

2017-01-01

In this study, 8 wt.% yttria-stabilized zirconia powder was deposited on the substrates by atmospheric plasma spray. The coatings were post-treated by laser glazing under different parameters in order to densify them. The characterization of the laser molten pools under different laser treatment conditions was studied. Preheating processes were also employed. Scanning electron microscopy observations of the surface and cross section of as-sprayed and laser-glazed coatings were carried out to investigate the influence of laser glazing on the microstructure on laser-glazed coatings. The results show that preheating processes improve the coating in terms of deepening the laser-glazed layer, reducing the number of vertical cracks and surface density of cracks and widening the molten pool. Finally, the influences of linear energy density on the characterization of the glazed layer are discussed.

Thermal Barrier Coatings Chemically and Mechanically Resistant to High Temperature Attack by Molten Ashes

NASA Astrophysics Data System (ADS)

Gledhill, Andrew

Thermal barrier coatings (TBCs) are ceramic coatings used on component in the hottest sections of gas turbine engines, used for power generation and aviation. These coatings insulate the underlying metal components and allow for much higher engine operating temperatures, improving the engine efficiency. These increase temperatures engender a new set of materials problems for TBCs. Operating temperatures in engines are now high enough for silicate impurities, either present in the fuel or ingested into the engines, to melt and adhere to the surface of the TBCs. The effects of four such impurities, two coal fly ashes, a petroleum coke-fly ash blend, and volcanic ash from the Eyjafjallajokull volcano were tested with conventional yttria-stabilized zirconia (YSZ) coatings, and found to penetrate through the entire thickness of the coating. This penetration reduces the strain tolerance of the coatings, and can result in premature failure. Testing on a newly built thermal gradient burner rig with simultaneous injection of ash impurities has shown a reduction of life up to 99.6% in these coatings when ash is present. Coatings of an alternative ceramic, gadolinium zirconate (Gd2Zr 2O7), were found to form a dense reaction layer with each of these impurities, preventing further penetration of the molten ash. This dense layer also reduces the strain tolerance, but these coatings were found to have a significantly higher life than the YSZ coatings. Testing with a small amount of ash baked onto the samples showed thirteen times the life of YSZ coatings. When the ash is continuously sprayed onto the hot sample, the life of the Gd2Zr2O7 coatings was nearly twice that of the YSZ. Finally, a delamination model was employed to explain the degradation of both types of coatings. This elastic model that takes into account the degree of penetration, differential cooling in thermal gradient testing, and thermal expansion mismatch with the underlying substrate, predicted the failure of YSZ coatings with the observed degree of penetration. The model shows that deposition optimization can be employed to further enhance the life of Gd 2Zr2O7coatings.

High temperature mechanical properties of zirconia tapes used for electrolyte supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Fleischhauer, Felix; Bermejo, Raul; Danzer, Robert; Mai, Andreas; Graule, Thomas; Kuebler, Jakob

2015-01-01

Solid-Oxide-Fuel-Cell systems are efficient devices to convert the chemical energy stored in fuels into electricity. The functionality of the cell is related to the structural integrity of the ceramic electrolyte, since its failure can lead to drastic performance losses. The mechanical property which is of most interest is the strength distribution at all relevant temperatures and how it is affected with time due to the environment. This study investigates the impact of the temperature on the strength and the fracture toughness of different zirconia electrolytes as well as the change of the elastic constants. 3YSZ and 6ScSZ materials are characterised regarding the influence of sub critical crack growth (SCCG) as one of the main lifetime limiting effects for ceramics at elevated temperatures. In addition, the reliability of different zirconia tapes is assessed with respect to temperature and SCCG. It was found that the strength is only influenced by temperature through the change in fracture toughness. SCCG has a large influence on the strength and the lifetime for intermediate temperature, while its impact becomes limited at temperatures higher than 650 °C. In this context the tetragonal 3YSZ and 6ScSZ behave quite different than the cubic 10Sc1CeSZ, so that at 850 °C it can be regarded as competitive compared to the tetragonal compounds.

Radiation damage in cubic ZrO 2 and yttria-stabilized zirconia from molecular dynamics simulations

DOE PAGES

Aidhy, Dilpuneet S.; Zhang, Yanwen; Weber, William J.

2014-11-20

Here, we perform molecular dynamics simulation on cubic ZrO 2 and yttria-stabilized zirconia (YSZ) to elucidate defect cluster formation resulting from radiation damage, and evaluate the impact of Y-dopants. Interstitial clusters composed of split-interstitial building blocks, i.e., Zr-Zr or Y-Zr are formed. Moreover, oxygen vacancies control cation defect migration; in their presence, Zr interstitials aggregate to form split-interstitials whereas in their absence Zr interstitials remain immobile, as isolated single-interstitials. Y-doping prevents interstitial cluster formation due to sequestration of oxygen vacancies.

Thermal Conductivity of Alumina-Toughened Zirconia Composites

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Zhu, Dong-Ming

2003-01-01

10-mol% yttria-stabilized zirconia (10YSZ)-alumina composites containing 0 to 30 mol% alumina were fabricated by hot pressing at 1500 C in vacuum. Thermal conductivity of the composites, determined at various temperatures using a steady-state laser heat flux technique, increased with increase in alumina content. Composites containing 0, 5, and 10-mol% alumina did not show any change in thermal conductivity with temperature. However, those containing 20 and 30-mol% alumina showed a decrease in thermal conductivity with increase in temperature. The measured values of thermal conductivity were in good agreement with those calculated from simple rule of mixtures.

Fracture Behaviour of Plasma Sprayed Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Malzbender, Jürgen; Wakui, Takashi; Wessel, Egbert; Steinbrech, Rolf W.

Thermal barrier coatings (TBCs) of plasma sprayed yttria stabilised zirconia (YSZ) are increasingly utilised for heat exposed components of advanced gas turbines1,2. An important reason for the application of zirconia coatings is the low thermal conductivity of this ceramic material which is further diminished in a TBC by the high concentration of spraying induced microstructural defects, e.g. crack-shaped defects between and within the spraying splats. Thus with TBCs on gas cooled turbine components stiff temperature gradients can be realised as an important prerequisite for an increased thermal efficiency of the energy conversion process.

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.

Delamination-Indicating Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Eldridge, Jeffrey I.

2007-01-01

The risk of premature failure of thermal barrier coatings (TBCs), typically composed of yttria-stabilized zirconia (YSZ), compromises the reliability of TBCs used to provide thermal protection for turbine engine components. Unfortunately, TBC delamination proceeds well beneath the TBC surface and cannot be monitored by visible inspection. Nondestructive diagnostic tools that could reliably probe the subsurface damage state of TBCs would alleviate the risk of TBC premature failure by indicating when the TBC needs to be replaced before the level of TBC damage threatens engine performance or safety. To meet this need, a new coating design for thermal barrier coatings (TBCs) that are self-indicating for delamination has been successfully implemented by incorporating a europium-doped luminescent sublayer at the base of a TBC composed of YSZ. The luminescent sublayer has the same YSZ composition as the rest of the TBC except for the addition of low-level europium doping and therefore does not alter TBC performance.

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.

Ceramic Top Coats of Plasma-Sprayed Thermal Barrier Coatings: Materials, Processes, and Properties

NASA Astrophysics Data System (ADS)

Bakan, Emine; Vaßen, Robert

2017-08-01

The ceramic top coat has a major influence on the performance of the thermal barrier coating systems (TBCs). Yttria-partially-stabilized zirconia (YSZ) is the top coat material frequently used, and the major deposition processes of the YSZ top coat are atmospheric plasma spraying and electron beam physical vapor deposition. Recently, also new thermal spray processes such as suspension plasma spraying or plasma spray-physical vapor deposition have been intensively investigated for TBC top coat deposition. These new processes and particularly the different coating microstructures that can be deposited with them will be reviewed in this article. Furthermore, the properties and the intrinsic-extrinsic degradation mechanisms of the YSZ will be discussed. Following the TBC deposition processes and standard YSZ material, alternative ceramic materials such as perovskites and hexaaluminates will be summarized, while properties of pyrochlores with regard to their crystal structure will be discussed more in detail. The merits of the pyrochlores such as good CMAS resistance as well as their weaknesses, e.g., low fracture toughness, processability issues, will be outlined.

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.

The effect of environment on thermal barrier coating lifetime

DOE PAGES

Pint, Bruce A.; Unocic, Kinga A.; Haynes, James Allen

2016-03-15

While the water vapor content of the combustion gas in natural gas-fired land-based turbines is ~10%, it can be 20–85% with coal-derived (syngas or H 2) fuels or innovative turbine concepts for more efficient carbon capture. Additional concepts envisage working fluids with high CO 2 contents to facilitate carbon capture and sequestration. To investigate the effects of changes in the gas composition on thermal barrier coating (TBC) lifetime, furnace cycling tests (1-h and 100-h cycles) were performed in air with 10, 50, and 90 vol. % water vapor and CO 2-10% H 2O and compared to prior results in drymore » air or O 2. Two types of TBCs were investigated: (1) diffusion bond coatings (Pt-diffusion or Pt-modified aluminide) with commercial electron-beam physical vapor-deposited yttria-stabilized zirconia (YSZ) top coatings on second-generation superalloy N5 and N515 substrates and (2) high-velocity oxygen fuel (HVOF) sprayed MCrAlYHfSi bond coatings with air plasma-sprayed YSZ top coatings on superalloys X4, 1483, or 247 substrates. For both types of coatings exposed in 1-h cycles, the addition of water vapor resulted in a decrease in coating lifetime, except for Pt-diffusion coatings which were unaffected by the environment. In 100-h cycles, environment was less critical, perhaps because coating failure was chemical (i.e., due to interdiffusion) rather than mechanical. As a result, in both 1-h and 100-h cycles, CO 2 did not appear to have any negative effect on coating lifetime.« less

Alumina-Reinforced Zirconia Composites

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Bansal, Narottam P.

2003-01-01

Alumina-reinforced zirconia composites, used as electrolyte materials for solid oxide fuel cells, were fabricated by hot pressing 10 mol percent yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol percent alumina. Major mechanical and physical properties of both particulate and platelet composites including flexure strength, fracture toughness, slow crack growth, elastic modulus, density, Vickers microhardness, thermal conductivity, and microstructures were determined as a function of alumina content either at 25 C or at both 25 and 1000 C. Flexure strength and fracture toughness at 1000 C were maximized with 30 particulate and 30 mol percent platelet composites, respectively, while resistance to slow crack growth at 1000 C in air was greater for 30 mol percent platelet composite than for 30 mol percent particulate composites.

Grain growth simulation of [001] textured YBCO films grown on (001) substrates with large lattice misfit: Prediction of misorientations of the remaining boundaries

NASA Astrophysics Data System (ADS)

Tsai, Jack W. H.; Ling, Shiun; Rodriguez, Julio C.; Mustapha, Zarina; Chan, Siu-Wai

2001-04-01

We study the effects of (1) the variation of grain boundary energy with misorientation and (2) the large lattice misfit (>3%) between the films and substrates on grain growth in films by method of Monte Carlo simulations. The results from the grain growth simulation in YBa2Cu3O7-x (YBCO) films was found to concur with previous experimental observation of preferred grain orientations for YBCO films deposited on various substrates such as (001) magnesium oxide (MgO) and (001) yttria stabilized zirconia (YSZ). The simulation has helped us to identify three factors influencing the competition of these [001] tilt boundaries. They are: (1) the relative depths of local minima in the boundary energy vs. misorientation curve, (2) the number of combinations of coincidence epitaxy (CE) orientations contributing to the exact misorientation for each of the high-angle-but-low-energy (HABLE) boundaries, and (3) the number of combinations of CE orientations within the angular ranges bracketing each of the exact HABLE boundaries. Hence, these factors can be applied to clarify the origin of special misorientations observed experimentally.

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.

Tailoring the electrode-electrolyte interface of Solid Oxide Fuel Cells (SOFC) by laser micro-patterning to improve their electrochemical performance

NASA Astrophysics Data System (ADS)

Cebollero, J. A.; Lahoz, R.; Laguna-Bercero, M. A.; Larrea, A.

2017-08-01

Cathode activation polarisation is one of the main contributions to the losses of a Solid Oxide Fuel Cell. To reduce this loss we use a pulsed laser to modify the surface of yttria stabilized zirconia (YSZ) electrolytes to make a corrugated micro-patterning in the mesoscale. The beam of the laser source, 5 ns pulse width and emitting at λ = 532 nm (green region), is computer-controlled to engrave the selected micro-pattern on the electrolyte surface. Several laser scanning procedures and geometries have been tested. Finally, we engrave a square array with 28 μm of lattice parameter and 7 μm in depth on YSZ plates. With these plates we prepare LSM-YSZ/YSZ/LSM-YSZ symmetrical cells (LSM: La1-xSrxMnO3) and determine their activation polarisation by Electrochemical Impedance Spectroscopy (EIS). To get good electrode-electrolyte contact after sintering it is necessary to use pressure-assisted sintering with low loads (about 5 kPa), which do not modify the electrode microstructure. The decrease in polarisation with respect to an unprocessed cell is about 30%. EIS analysis confirms that the reason for this decrease is an improvement in the activation processes at the electrode-electrolyte interface.

Phosphor-Doped Thermal Barrier Coatings Deposited by Air Plasma Spray for In-Depth Temperature Sensing

PubMed Central

Peng, Di; Yang, Lixia; Cai, Tao; Liu, Yingzheng; Zhao, Xiaofeng; Yao, Zhiqi

2016-01-01

Yttria-stabilized zirconia (YSZ)-based thermal barrier coating (TBC) has been integrated with thermographic phosphors through air plasma spray (APS) for in-depth; non-contact temperature sensing. This coating consisted of a thin layer of Dy-doped YSZ (about 40 µm) on the bottom and a regular YSZ layer with a thickness up to 300 µm on top. A measurement system has been established; which included a portable; low-cost diode laser (405 nm); a photo-multiplier tube (PMT) and the related optics. Coating samples with different topcoat thickness were calibrated in a high-temperature furnace from room temperature to around 900 °C. The results convincingly showed that the current sensor and the measurement system was capable of in-depth temperature sensing over 800 °C with a YSZ top layer up to 300 µm. The topcoat thickness was found to have a strong effect on the luminescent signal level. Therefore; the measurement accuracy at high temperatures was reduced for samples with thick topcoats due to strong light attenuation. However; it seemed that the light transmissivity of YSZ topcoat increased with temperature; which would improve the sensor’s performance at high temperatures. The current sensor and the measurement technology have shown great potential in on-line monitoring of TBC interface temperature. PMID:27690037

Preparation and Properties of High-T(sub c) Bi-Pb-Sr-Ca-Cu-O Thick Film Superconductors on YSZ Substrates

NASA Technical Reports Server (NTRS)

Hooker, Matthew W.

1996-01-01

An evaluation of four firing profiles was performed to determine the optimum processing conditions for producing high-T(sub c) Bi-Pb-Sr-Ca-Cu-O thick films on yttria-stabilized zirconia substrates. Using these four profiles, the effects of sintering temperatures of 830-850 C and soak times of 0.5 to 12 hours were examined. In this study, T-c, zero values of 100 K were obtained using a firing profile in which the films were sintered for 1.5 to 2 hours at 840 to 845 C and then quenched to room temperature. X-ray diffraction analyses of these specimens confirmed the presence of the high-T(sub c) phase. Films which were similarly fired and furnace cooled from the peak processing temperature exhibited a two-step superconductive transition to zero resistance, with T-c,zero values ranging from 85 to 92 K. The other firing profiles evaluated in this investigation yielded specimens which either exhibited critical transition temperatures below 90 K or did not exhibit a superconductive transition above 77 K.

High-Temperature Creep Degradation of the AM1/NiAlPt/EBPVD YSZ System

NASA Astrophysics Data System (ADS)

Riallant, Fanny; Cormier, Jonathan; Longuet, Arnaud; Milhet, Xavier; Mendez, José

2014-01-01

The failure mechanisms of a NiAlPt/electron beam physical vapor deposition yttria-stabilized-zirconia thermal barrier coating system deposited on the AM1 single crystalline substrate have been investigated under pure creep conditions in the temperature range from 1273 K to 1373 K (1000 °C to 1100 °C) and for durations up to 1000 hours. Doubly tapered specimens were used allowing for the analysis of different stress states and different accumulated viscoplastic strains for a given creep condition. Under such experiments, two kinds of damage mechanisms were observed. Under low applied stress conditions ( i.e., long creep tests), microcracking is localized in the vicinity of the thermally grown oxide (TGO). Under high applied stress conditions, an unconventional failure mechanism at the substrate/bond coat interface is observed because of large creep strains and fast creep deformation, hence leading to a limited TGO growth. This unconventional failure mechanism is observed although the interfacial bond coat/top coat TGO thickening is accelerated by the mechanical applied stress beyond a given stress threshold.

The Effects of Grain Boundaries on the Current Transport Properties in YBCO-Coated Conductors

NASA Astrophysics Data System (ADS)

Yang, Chao; Xia, Yudong; Xue, Yan; Zhang, Fei; Tao, Bowan; Xiong, Jie

2015-10-01

We report a detailed study of the grain orientations and grain boundary (GB) networks in Y2O3 films grown on Ni-5 at.%W substrates. Electron back scatter diffraction (EBSD) exhibited different GB misorientation angle distributions, strongly decided by Y2O3 films with different textures. The subsequent yttria-stabilized zirconia (YSZ) barrier and CeO2 cap layer were deposited on Y2O3 layers by radio frequency sputtering, and YBa2Cu3O7-δ (YBCO) films were deposited by pulsed laser deposition. For explicating the effects of the grain boundaries on the current carry capacity of YBCO films, a percolation model was proposed to calculate the critical current density ( J c) which depended on different GB misorientation angle distributions. The significantly higher J c for the sample with sharper texture is believed to be attributed to improved GB misorientation angle distributions.

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.

Carbon tolerance of Ni-Cu and Ni-Cu/YSZ sub-μm sized SOFC thin film model systems

NASA Astrophysics Data System (ADS)

Götsch, Thomas; Schachinger, Thomas; Stöger-Pollach, Michael; Kaindl, Reinhard; Penner, Simon

2017-04-01

Thin films of YSZ, unsupported Ni-Cu 1:1 alloy phases and YSZ-supported Ni-Cu 1:1 alloy solutions have been reproducibly prepared by magnetron sputter deposition on Si wafers and NaCl(001) single crystal facets at two selected substrate temperatures of 298 K and 873 K. Subsequently, the layer properties of the resulting sub-μm thick thin films as well as the tendency towards carbon deposition following treatment in pure methane at 1073 K has been tested comparatively. Well-crystallized structures of cubic YSZ, cubic NiCu and cubic NiCu/YSZ have been obtained following deposition at 873 K on both substrates. Carbon is deposited on all samples following the trend Ni-Cu (1:1) = Ni-Cu (1:1)/YSZ > pure YSZ, indicating that at least the 1:1 composition of layered Ni-Cu alloy phases is not able to suppress the carbon deposition completely, rendering it unfavorable for usage as anode component in sub-μm sized fuel cells. It is shown that surfaces with a high Cu/Ni ratio nevertheless prohibit any carbon deposition.

Surface Modification of Zirconia Substrate by Calcium Phosphate Particles Using Sol-Gel Method.

PubMed

Jin, So Dam; Um, Sang Cheol; Lee, Jong Kook

2015-08-01

Surface modification with a biphasic composition of hydroxyapatite (HA) and tricalcium phosphate (TCP) was performed on a zirconia substrate using a sol-gel method. An initial calcium phosphate sol was prepared by mixing a solution of Ca(NO3)2 · 4H20 and (C2H5O)3P(O), while both porous and dense zirconia were used as substrates. The sol-gel coating was performed using a spin coater. The coated porous zirconia substrate was re-sintered at 1350 °C 2 h, while coated dense zirconia substrate was heat-treated at 750 °C 1 h. The microstructure of the resultant HA/TCP coatings was found to be dependent on the type of zirconia substrate used. With porous zirconia as a starting substrate, numerous isolated calcium phosphate particles (TCP and HA) were uniformly dispersed on the surface, and the particle size and covered area were dependent on the viscosity of the calcium phosphate sol. Conversely, when dense zirconia was used as a starting substrate, a thick film of nano-sized HA particles was obtained after heat treatment, however, substantial agglomeration and cracking was also observed.

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°C) with approximately 5.5 mum h-1 growth rate. In metal-organic CVD (MOCVD), liquid precursor solutions of Y- and Zr-beta-diketonate and Y- and Zr-n-butoxide precursors were used as the metal sources and O2 gas was used as the oxidation source. Using the Y- and Zr-beta-diketonate liquid precursor solution, tetragonal YSZ was deposited with a layered microstructure apparent and a maximum growth rate of approximately 14 mum h-1 (activation energy (E a) of 50.9 +/- 4.3 kJ mol-1). The growth rate (approximately 43 mum h-1 with Ea = 53.8 +/- 7.9 kJ mol-1) was improved using Y- and Zr- n-butoxide liquid precursor solutions, and the microstructure was columnar. Yet, two-phase deposition of monoclinic ZrO2 and tetragonal YSZ occurred. Results of electron-probe micro-analysis showed that the nY/(nY + nZr ) ratio was less than 45% of the nY/( nY + nZr) ratio in the liquid precursor solution.

SrZrO 3 Formation at the Interlayer/Electrolyte Interface during (La 1-xSr x) 1-δCo 1-yFe yO 3 Cathode Sintering

DOE PAGES

Lu, Zigui; Darvish, Shadi; Hardy, John; ...

2017-07-19

This work probes the formation of SrZrO 3 at the SDC/YSZ interface (Sm doped ceria, SDC; Y stabilized zirconia, YSZ) during (La 1-xSr x) 1-δCo1 -yFe yO 3 (LSCF) cathode sintering. SEM/EDS and grazing incidence X-ray diffraction results of annealed LSCF and YSZ samples reveal that even without physical contact between LSCF and YSZ, SrZrO 3 was formed on the surface of YSZ, preferentially at the grain boundaries. It was suspected that the SrZrO 3 formation is due to the Sr-containing gas species diffused through the pores of the SDC layer and reacted with the YSZ electrolyte. Computational thermodynamics wasmore » adopted to predict the gas species formed in air during sintering by using the La-Sr-Co-Fe-O-H thermodynamic database. Sr(OH) 2 is identified as the dominant Sr-containing gas species under the experimental conditions. In addition, it was found that A-site deficiency in LSCF could effectively suppress the SrZrO 3 formation while a dense and pore-free SDC interlayer is required to totally block the SrZrO 3 formation. As a result, cell performance was significantly improved for a cell with a dense SDC interlayer fabricated by pulsed laser deposition, due to elimination of SrZrO 3 formation and therefore reduced interfacial resistance.« less

SrZrO 3 Formation at the Interlayer/Electrolyte Interface during (La 1-xSr x) 1-δCo 1-yFe yO 3 Cathode Sintering

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

Lu, Zigui; Darvish, Shadi; Hardy, John

This work probes the formation of SrZrO 3 at the SDC/YSZ interface (Sm doped ceria, SDC; Y stabilized zirconia, YSZ) during (La 1-xSr x) 1-δCo1 -yFe yO 3 (LSCF) cathode sintering. SEM/EDS and grazing incidence X-ray diffraction results of annealed LSCF and YSZ samples reveal that even without physical contact between LSCF and YSZ, SrZrO 3 was formed on the surface of YSZ, preferentially at the grain boundaries. It was suspected that the SrZrO 3 formation is due to the Sr-containing gas species diffused through the pores of the SDC layer and reacted with the YSZ electrolyte. Computational thermodynamics wasmore » adopted to predict the gas species formed in air during sintering by using the La-Sr-Co-Fe-O-H thermodynamic database. Sr(OH) 2 is identified as the dominant Sr-containing gas species under the experimental conditions. In addition, it was found that A-site deficiency in LSCF could effectively suppress the SrZrO 3 formation while a dense and pore-free SDC interlayer is required to totally block the SrZrO 3 formation. As a result, cell performance was significantly improved for a cell with a dense SDC interlayer fabricated by pulsed laser deposition, due to elimination of SrZrO 3 formation and therefore reduced interfacial resistance.« less

Operando X-ray Investigation of Electrode/Electrolyte Interfaces in Model Solid Oxide Fuel Cells

PubMed Central

2016-01-01

We employed operando anomalous surface X-ray diffraction to investigate the buried interface between the cathode and the electrolyte of a model solid oxide fuel cell with atomic resolution. The cell was studied under different oxygen pressures at elevated temperatures and polarizations by external potential control. Making use of anomalous X-ray diffraction effects at the Y and Zr K-edges allowed us to resolve the interfacial structure and chemical composition of a (100)-oriented, 9.5 mol % yttria-stabilized zirconia (YSZ) single crystal electrolyte below a La0.6Sr0.4CoO3−δ (LSC) electrode. We observe yttrium segregation toward the YSZ/LSC electrolyte/electrode interface under reducing conditions. Under oxidizing conditions, the interface becomes Y depleted. The yttrium segregation is corroborated by an enhanced outward relaxation of the YSZ interfacial metal ion layer. At the same time, an increase in point defect concentration in the electrolyte at the interface was observed, as evidenced by reduced YSZ crystallographic site occupancies for the cations as well as the oxygen ions. Such changes in composition are expected to strongly influence the oxygen ion transport through this interface which plays an important role for the performance of solid oxide fuel cells. The structure of the interface is compared to the bare YSZ(100) surface structure near the microelectrode under identical conditions and to the structure of the YSZ(100) surface prepared under ultrahigh vacuum conditions. PMID:27346923

Wear studies on plasma-sprayed Al2O3 and 8mole% of Yttrium-stabilized ZrO2 composite coating on biomedical Ti-6Al-4V alloy for orthopedic joint application

PubMed Central

Ganapathy, Perumal; Manivasagam, Geetha; Rajamanickam, Asokamani; Natarajan, Alagumurthi

2015-01-01

This paper presents the wear characteristics of the composite ceramic coating made with Al2O3-40wt%8YSZ on the biomedical grade Ti-6Al-4V alloy (grade 5) used for total joint prosthetic components, with the aim of improving their tribological behavior. The coatings were deposited using a plasma spraying technique, and optimization of plasma parameters was performed using response surface methodology to obtain dense coating. The tribological behaviors of the coated and uncoated substrates were evaluated using a ball-on-plate sliding wear tester at 37°C in simulated body-fluid conditions. The microstructure of both the titanium alloy and coated specimen were examined using an optical microscope and scanning electron microscope. The hardness of the plasma-sprayed alumina–zirconia composite coatings was 2.5 times higher than that of the Ti-6Al-4V alloy, while the wear rate of Ti-6Al-4V alloy was 253 times higher than that of the composite-coated Ti-6Al-4V alloy. The superior wear resistance of the alumina–zirconia coated alloy is attributed to its enhanced hardness and intersplat bonding strength. Wear-track examination showed that the predominant wear mechanism of Ti-6Al-4V alloy was abrasive and adhesive wear, whereas, in the case of alumina–zirconia composite coated alloy, the wear was dominated by microchipping and microcracking. PMID:26491323

Strain-tolerant ceramic coated seal

DOEpatents

Schienle, James L.; Strangman, Thomas E.

1994-01-01

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. An array of discontinuous grooves is laser machined into the outer surface of the solid lubricant surface layer making the coating strain tolerant.

Strength, Fracture Toughness, and Slow Crack Growth of Zirconia/alumina Composites at Elevated Temperature

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Bansal, Narottam P.

2003-01-01

Various electrolyte materials for solid oxide fuel cells were fabricated by hot pressing 10 mol% yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol% alumina. Flexure strength and fracture toughness of platelet composites were determined as a function of alumina content at 1000 C in air and compared with those of particulate composites determined previously. In general, elevated-temperature strength and fracture toughness of both composite systems increased with increasing alumina content. For a given alumina content, flexure strength of particulate composites was greater than that of platelet composites at higher alumina contents (greater than or equal to 20 mol%), whereas, fracture toughness was greater in platelet composites than in particulate composites, regardless of alumina content. The results of slow crack growth (SCG) testing, determined at 1000 C via dynamic fatigue testing for three different composites including 0 mol% (10-YSZ matrix), 30 mol % particulate and 30 mol% platelet composites, showed that susceptibility to SCG was greatest with SCG parameter n = 6 to 8 for both 0 and 30 mol% particulate composites and was least with n = 33 for the 30 mol% platelet composite.

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.

Mueller matrix polarimetry on plasma sprayed thermal barrier coatings for porosity measurement.

PubMed

Luo, David A; Barraza, Enrique T; Kudenov, Michael W

2017-12-10

Yttria-stabilized zirconia (YSZ) is the most widely used material for thermal plasma sprayed thermal barrier coatings (TBCs) used to protect gas turbine engine parts in demanding operation environments. The superior material properties of YSZ coatings are related to their internal porosity level. By quantifying the porosity level, tighter control on the spraying process can be achieved to produce reliable coatings. Currently, destructive measurement methods are widely used to measure the porosity level. In this paper, we describe a novel nondestructive approach that is applicable to classify the porosity level of plasma sprayed YSZ TBCs via Mueller matrix polarimetry. A rotating retarder Mueller matrix polarimeter was used to measure the polarization properties of the plasma sprayed YSZ coatings with different porosity levels. From these measurements, it was determined that a sample's measured depolarization ratio is dependent on the sample's surface roughness and porosity level. To this end, we correlate the depolarization ratio with the samples' surface roughness, as measured by a contact profilometer, as well as the total porosity level, in percentage measured using a micrograph and stereological analysis. With the use of this technique, a full-field and rapid measurement of porosity level can be achieved.

Investigation of aluminosilicate as a solid oxide fuel cell refractory

NASA Astrophysics Data System (ADS)

Gentile, Paul S.; Sofie, Stephen W.

2011-05-01

Aluminosilicate represents a potential low cost alternative to alumina for solid oxide fuel cell (SOFC) refractory applications. The objectives of this investigation are to study: (1) changes of aluminosilicate chemistry and morphology under SOFC conditions, (2) deposition of aluminosilicate vapors on yttria stabilized zirconia (YSZ) and nickel, and (3) effects of aluminosilicate vapors on SOFC electrochemical performance. Thermal treatment of aluminosilicate under high temperature SOFC conditions is shown to result in increased mullite concentrations at the surface due to diffusion of silicon from the bulk. Water vapor accelerates the rate of surface diffusion resulting in a more uniform distribution of silicon. The high temperature condensation of volatile gases released from aluminosilicate preferentially deposit on YSZ rather than nickel. Silicon vapor deposited on YSZ consists primarily of aluminum rich clusters enclosed in an amorphous siliceous layer. Increased concentrations of silicon are observed in enlarged grain boundaries indicating separation of YSZ grains by insulating glassy phase. The presence of aluminosilicate powder in the hot zone of a fuel line supplying humidified hydrogen to an SOFC anode impeded peak performance and accelerated degradation. Energy dispersive X-ray spectroscopy detected concentrations of silicon at the interface between the electrolyte and anode interlayer above impurity levels.

Air Plasma-Sprayed Yttria and Yttria-Stabilized Zirconia Thermal Barrier Coatings Subjected to Calcium-Magnesium-Alumino-Silicate (CMAS)

NASA Astrophysics Data System (ADS)

Li, Wenshuai; Zhao, Huayu; Zhong, Xinghua; Wang, Liang; Tao, Shunyan

2014-08-01

Yttria (Y2O3) and zirconia (ZrO2) stabilized by 8 and 20 wt.%Y2O3 thermal barrier coatings (TBCs) subjected to calcium-magnesium-alumino-silicate (CMAS) have been investigated. Free-standing Y2O3, 8 and 20 wt.%YSZ coatings covered with synthetic CMAS slurry were heated at 1300 °C in air for 24 h in order to assess the effect of Y2O3 on the corrosion resistance of the coatings subjected to CMAS. The microstructures and phase compositions of the coatings were characterized by SEM, EDS, XRD, RS, and TEM. TBCs with higher Y2O3 content exhibited better CMAS corrosion resistance. Phase transformation of ZrO2 from tetragonal (t) to monoclinic (m) occurred during the interaction of 8YSZ TBCs and CMAS, due to the depletion of Y2O3 in the coating. Some amounts of original c-ZrO2 still survived in 20YSZ TBCs along with a small amount of m-ZrO2 that appeared after reaction with CMAS. Furthermore, Y2O3 coating was found to be particularly highly effective in resisting the penetration of molten CMAS glass at high temperature (1300 °C). This may be ascribed to the formation of sealing layers composed of Y-apatite phase [based on Ca4Y6 (SiO4)6O and Y4.67(SiO4)3O] by the high-temperature chemical interactions of Y2O3 coating and CMAS glass.

Synthesis of zirconium oxynitride in air under DC electric fields

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

Morisaki, Nobuhiro; Tokunaga, Tomoharu; Sasaki, Katsuhiro

We synthesized zirconium oxynitride from yttria-stabilized zirconia (YSZ) in air by applying DC electric fields that produced a controlled electric current in the specimen. When YSZ was heated under an applied DC electric field, the electric current of the specimen steeply increased at a critical temperature, called a flash event, during flash sintering. By keeping the electric current of the specimen constant during the flash event and then holding the specimen at the critical temperature, YSZ was transformed into zirconium oxynitride under the optimal conditions of 50 V/cm, 500 mA, and 1000 °C. We confirmed that zirconium oxynitride formed using high-resolution transmission electronmore » microscopy, electron energy-loss spectroscopy, and energy-dispersive spectrometry. To convert oxides to nitrides, reducing conditions are necessary to form excess oxygen vacancies. Our technique produced the strong reducing conditions necessary to form nitrides from the oxides by delivering a controlled electric current to the specimen.« less

Effect of Electrode Configuration on Nitric Oxide Gas Sensor Behavior.

PubMed

Cui, Ling; Murray, Erica P

2015-09-23

The influence of electrode configuration on the impedancemetric response of nitric oxide (NO) gas sensors was investigated for solid electrochemical cells [Au/yttria-stabilized zirconia (YSZ)/Au)]. Fabrication of the sensors was carried out at 1050 °C in order to establish a porous YSZ electrolyte that enabled gas diffusion. Two electrode configurations were studied where Au wire electrodes were either embedded within or wrapped around the YSZ electrolyte. The electrical response of the sensors was collected via impedance spectroscopy under various operating conditions where gas concentrations ranged from 0 to 100 ppm NO and 1%-18% O₂ at temperatures varying from 600 to 700 °C. Gas diffusion appeared to be a rate-limiting mechanism in sensors where the electrode configuration resulted in longer diffusion pathways. The temperature dependence of the NO sensors studied was independent of the electrode configuration. Analysis of the impedance data, along with equivalent circuit modeling indicated the electrode configuration of the sensor effected gas and ionic transport pathways, capacitance behavior, and NO sensitivity.

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.

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 in the SSA associated with void systems due to sintering, specifically the closing and healing of intralamellar cracks perpendicular to the applied stress, and (3) A compaction and closure of void systems under the applied load. These anisotropic changes in microstructure result in distinguishable changes in thermo-mechanical properties, with very minute changes to the overall bulk density.

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.

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

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.

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

Zirconia-based mixed potential sensor with Pt electrode prepared by spin-coating of polymeric precursor

NASA Astrophysics Data System (ADS)

Chrzan, A.; Woźniak, Ł.; Szymczewska, D.; Jasiński, P.

2016-11-01

Many types of yttria-stabilized zirconia (YSZ) based gas sensors have been explored extensively in recent years. Great attention have been directed to mixed-potential-type gas sensors. It is due to growing concerns with environmental issues. Not without a significance is the fact of very attractive performance of this type of sensor allowing to detect low concentration of pollutant gases. In this paper two types of YSZ based mixed-potential planar sensors were investigated, with platinum electrode painted using commercial paste and with spin coated platinum layer. Both types had second electrode in the form of porous gold. Measurements were performed at 400 °C in synthetic air and different concentrations of SO2. Gas flow was set to 100 cm3min-1 and the concentration of 50 ppm SO2 was tested. During this measurements the sensor was sintered in-situ at increasing temperatures. Sensor with 100 nm spin-coated platinum layer sintered at 700 °C was shown to exhibit two times smaller response than sensor with 5 μm porous electrode, while consisting of over 20 times smaller amount of Pt. The influence of sintering temperature on electrical conductivity of platinum films was also examined. Moreover, the platinum microstructure was investigated using SEM microscopy.

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

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.

Hot Corrosion Resistance and Mechanical Behavior of Atmospheric Plasma Sprayed Conventional and Nanostructured Zirconia Coatings

NASA Astrophysics Data System (ADS)

Saremi, Mohsen; Keyvani, Ahmad; Heydarzadeh Sohi, Mahmoud

Conventional and nanostructured zirconia coatings were deposited on In-738 Ni super alloy by atmospheric plasma spray technique. The hot corrosion resistance of the coatings was measured at 1050°C using an atmospheric electrical furnace and a fused mixture of vanadium pent oxide and sodium sulfate respectively. According to the experimental results nanostructured coatings showed a better hot corrosion resistance than conventional ones. The improved hot corrosion resistance could be explained by the change of structure to a dense and more packed structure in the nanocoating. The evaluation of mechanical properties by nano indentation method showed the hardness (H) and elastic modulus (E) of the YSZ coating increased substantially after hot corrosion.

Preparation, characterization and in vitro response of bioactive coatings on polyether ether ketone.

PubMed

Durham, John W; Allen, Matthew J; Rabiei, Afsaneh

2017-04-01

Polyether ether ketone (PEEK) is a highly heat-resistant thermoplastic with excellent strength and elastic modulus similar to human bone, making it an attractive material for orthopedic implants. However, the hydrophobic surface of PEEK implants induces fibrous encapsulation which is unfavorable for stable implant anchorage. In this study, PEEK was coated via ion-beam-assisted deposition (IBAD) using a two-layer design of yttria-stabilized zirconia (YSZ) as a heat-protection layer, and hydroxyapatite (HA) as a top layer to improve osseointegration. Microstructural analysis of the coatings showed a dense, uniform columnar grain structure in the YSZ layer and no delamination from the substrate. The HA layer was found to be amorphous and free of porosities in its as-deposited state. Subsequent heat treatment via microwave energy followed by autoclaving crystallized the HA layer, confirmed by SEM and XRD analysis. An in vitro study using MC3T3 preosteoblast cells showed improved bioactivity in heat-treated sample groups. Cell proliferation, differentiation, and mineralization were analyzed by MTT assay and DNA content, osteocalcin expression, and Alizarin Red S (AR-S) content, respectively. Initial cell growth was increased, and osteogenic maturation and mineralization were accelerated most on coatings that underwent a combined microwave and autoclave heat treatment process as compared to uncoated PEEK and amorphous HA surfaces. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 560-567, 2017. © 2015 Wiley Periodicals, Inc.

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.

A porous ceramic membrane tailored high-temperature supercapacitor

NASA Astrophysics Data System (ADS)

Zhang, Xin; He, Benlin; Zhao, Yuanyuan; Tang, Qunwei

2018-03-01

The supercapacitor that can operate at high-temperature are promising for markedly increase in capacitance because of accelerated charge movement. However, the state-of-the-art polymer-based membranes will decompose at high temperature. Inspired by solid oxide fuel cells, we present here the experimental realization of high-temperature supercapacitors (HTSCs) tailored with porous ceramic separator fabricated by yttria-stabilized zirconia (YSZ) and nickel oxide (NiO). Using activated carbon electrode and supporting electrolyte from potassium hydroxide (KOH) aqueous solution, a category of symmetrical HTSCs are built in comparison with a conventional polymer membrane based device. The dependence of capacitance performance on temperature is carefully studied, yielding a maximized specific capacitance of 272 F g-1 at 90 °C for the optimized HTSC tailored by NiO/YSZ membrane. Moreover, the resultant HTSC has relatively high durability when suffer repeated measurement over 1000 cycles at 90 °C, while the polymer membrane based supercapacitor shows significant reduction in capacitance at 60 °C. The high capacitance along with durability demonstrates NiO/YSZ membrane tailored HTSCs are promising in future advanced energy storage devices.

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.

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 supply of the "fuel" (oxygen and hydrogen gas), the performance of an SOFC device is primarily limited by the Ohmic resistance of the electrolyte and the electrochemical reaction kinetics at the electrode/electrolyte interfaces. While the former constraint may be substantially diminished by reducing the electrolyte's physical dimension into nanoscale thin films, the incorporation of oxygen ions into YSZ from the cathode side remains a relatively sluggish process. In order to study how structural modifications influence the effectiveness of the oxygen transfer at the cathode/YSZ boundary, ion implantation at different energies and doses was performed on the electrolyte, prior to the deposition of platinum (Pt) electrodes. Xenon ions (Xe+) were used as the implant species, and the irradiation was done on atomic layer deposited (ALD) YSZ films and monocrystalline YSZ (001) substrates. From direct electrochemical measurements on fuel cell structures made on the ALD layers, an improvement by a factor of two was witnessed in the peak power density with relatively low implantation dose (10 13 cm-2) as compared to no irradiation. However the fuel cell properties worsened significantly with elevated dosage. Cross sectional TEM images of xenon implanted YSZ single crystals demonstrated the evidence of considerable defect accumulation (dislocation loops and extended dislocation lines) at 1015 and 1016 cm-2 doses. It is speculated that the bombardment with a relatively low concentration of xenon generates an optimum density of structural defects in the electrolyte that facilitate the incorporation or diffusion of O2- ions, whereas at higher radiation fluences the associated buildup of the imperfections or the implanted elements themselves may act as impediments to the anion transfer and conduction.

Comparison of edge chipping resistance of PFM and veneered zirconia specimens

PubMed Central

Quinn, Janet B.; Sundar, Veeraraghavan; Parry, Edward E.; Quinn, George D.

2011-01-01

Objectives To investigate the chipping resistance of veneered zirconia specimens and compare it to the chipping resistance of porcelain fused to metal (PFM) specimens. Methods Veneered zirconia and PFM bar specimens were prepared in clinically relevant thicknesses. The specimen edges were chipped with different magnitude forces, producing chips of various sizes. The range of sizes included small chips that did not penetrate all the way through the veneers to the substrates, and also chips that were very large and reached the zirconia or metal substrates. The relationship between force magnitude and chip size (edge distance) was graphed. The resulting curves were compared for the veneered zirconia and PFM specimens. Knoop hardness vs. force graphs for the veneers and substrates were also obtained. Results The zirconia and PFM veneer chipping data followed a power law (coefficient of determination, R2 > 0.93) as expected from the literature. The curves overlapped within the combined data scatter, indicating similar resistance to chipping. The chips made in both types of specimens detached and did not penetrate into the substrate when they reached the veneer/substrate intersections. The hardness–load curves for the veneers and substrates all exhibited an indentation size effect (ISE) at low loads. The Knoop hardness values with uncertainties of ±one standard deviation at 4 N loads for the metal, zirconia, and the metal and zirconia veneers are: (2.02 ± 0.08, 12.01 ± 0.39, 4.24 ± 0.16 and 4.36 ± 0.02 GPa), respectively, with no statistically significant difference between the veneers (Tukey pairwise comparison at 0.95 family confidence). Significance This work indicates that a similar resistance to chipping might be expected for veneered zirconia and PFM restorations, in spite of the large difference in substrate hardness. Differences in susceptibility to chip spalling were not detected, but the chips in both specimen types detached off the sides in a similar manner instead of extending into the substrates. PMID:19748115

Enhanced thermoelectric performance of Nb-doped SrTiO3 by nano-inclusion with low thermal conductivity

PubMed Central

Wang, Ning; Chen, Haijun; He, Hongcai; Norimatsu, Wataru; Kusunoki, Michiko; Koumoto, Kunihito

2013-01-01

Authors reported an effective path to increase the electrical conductivity while to decrease the thermal conductivity, and thus to enhance the ZT value by nano-inclusions. By this method, the ZT value of Nb-doped SrTiO3 was enhanced 9-fold by yttria stabilized zirconia (YSZ) nano-inclusions. YSZ inclusions, located inside grain and in triple junction, can reduce the thermal conductivity by effective interface phonon scattering, enhance the electrical conductivity by promoting the abnormal grain growth, and thus lead to the obvious enhancement of ZT value, which strongly suggests that, it is possible to not only reduce the thermal conductivity, but also increase the electrical conductivity by nano-inclusions with low thermal conductivity. This study will give some useful enlightenment to the preparation of high-performance oxide thermoelectric materials. PMID:24316665

CHEMICAL SOLUTION DEPOSITION BASED OXIDE BUFFERS AND YBCO COATED CONDUCTORS

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

Paranthaman, Mariappan Parans

We have reviewed briefly the growth of buffer and high temperature superconducting oxide thin films using a chemical solution deposition (CSD) method. In the Rolling-Assisted Biaxially Textured Substrates (RABiTS) process, developed at Oak Ridge National Laboratory, utilizes the thermo mechanical processing to obtain the flexible, biaxially oriented copper, nickel or nickel-alloy substrates. Buffers and Rare Earth Barium Copper Oxide (REBCO) superconductors have been deposited epitaxially on the textured nickel alloy substrates. The starting substrate serves as a template for the REBCO layer, which has substantially fewer weak links. Buffer layers play a major role in fabricating the second generation REBCOmore » wire technology. The main purpose of the buffer layers is to provide a smooth, continuous and chemically inert surface for the growth of the REBCO film, while transferring the texture from the substrate to the superconductor layer. To achieve this, the buffer layers need to be epitaxial to the substrate, i.e. they have to nucleate and grow in the same bi-axial texture provided by the textured metal foil. The most commonly used RABiTS multi-layer architectures consist of a starting template of biaxially textured Ni-5 at.% W (Ni-W) substrate with a seed (first) layer of Yttrium Oxide (Y2O3), a barrier (second) layer of Yttria Stabilized Zirconia (YSZ), and a Cerium Oxide (CeO2) cap (third) layer. These three buffer layers are generally deposited using physical vapor deposition (PVD) techniques such as reactive sputtering. On top of the PVD template, REBCO film is then grown by a chemical solution deposition. This article reviews in detail about the list of oxide buffers and superconductor REBCO films grown epitaxially on single crystal and/or biaxially textured Ni-W substrates using a CSD method.« less

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

DOE PAGES

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

2015-07-28

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

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.

Preparation of functional layers for anode-supported solid oxide fuel cells by the reverse roll coating process

NASA Astrophysics Data System (ADS)

Mücke, R.; Büchler, O.; Bram, M.; Leonide, A.; Ivers-Tiffée, E.; Buchkremer, H. P.

The roll coating technique represents a novel method for applying functional layers to solid oxide fuel cells (SOFCs). This fast process is already used for mass production in other branches of industry and offers a high degree of automation. It was utilized for coating specially developed anode (NiO + 8YSZ, 8YSZ: 8 mol% yttria-stabilized zirconia) and electrolyte (8YSZ) suspensions on green and pre-sintered tape-cast anode supports (NiO + 8YSZ). The layers formed were co-fired in a single step at 1400 °C for 5 h. As a result, the electrolyte exhibited a thickness of 14-18 μm and sufficient gas tightness. Complete cells with a screen-printed and sintered La 0.65Sr 0.3MnO 3- δ (LSM)/8YSZ cathode yielded a current density of 0.9-1.1 A cm -2 at 800 °C and 0.7 V, which is lower than the performance of non-co-fired slip-cast or screen-printed Jülich standard cells with thinner anode and electrolyte layers. The contribution of the cell components to the total area-specific resistance (ASR) was calculated by analyzing the distribution function of the relaxation times (DRTs) of measured electrochemical impedance spectra (EIS) and indicates the potential improvement in the cell performance achievable by reducing the thickness of the roll-coated layers. The results show that the anode-supported planar half-cells can be fabricated cost-effectively by combining roll coating with subsequent co-firing.

Preconditioning of the YSZ-NiO Fuel Cell Anode in Hydrogenous Atmospheres Containing Water Vapor.

PubMed

Vasyliv, Bogdan; Podhurska, Viktoriya; Ostash, Orest

2017-12-01

The YSZ-NiO ceramics for solid oxide fuel cells (SOFCs) anode have been investigated. A series of specimens were singly reduced in a hydrogenous atmosphere (Ar-5 vol% H 2 mixture) at 600 °C under the pressure of 0.15 MPa or subjected to 'reduction in the mixture-oxidation in air' (redox) cycling at 600 °C. The YSZ-Ni cermets formed in both treatment conditions were then aged in 'water vapor in Ar-5 vol% H 2 mixture' atmosphere at 600 °C under the pressure of 0.15 MPa. Additionally, the behaviour of the as-received material in this atmosphere was studied. It was revealed that small amount of water vapor in Ar-5 vol% H 2 mixture (water vapor pressure below 0.03 MPa) does not affect the reduction of the nickel phase in the YSZ-NiO ceramics, but causes some changes in the YSZ-Ni cermet structure. In particular, nanopore growth in tiny Ni particles takes place. At higher concentration of water vapor in the mixture (water vapor pressure above 0.03-0.05 MPa), converse changes in the kinetics of reduction occur. The best physical and mechanical properties were revealed for the material treated by redox cycling after holding at 600 °C in water depleted gas mixture. The dual effect of water vapor on nickel-zirconia anode behaviour is discussed basing on scanning electron microscopy analysis data, material electrical conductivity, and strength.

Development of in-situ control diagnostics for application of epitaxial superconductor and buffer layers

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

B.C. Winkleman; T.V. Giel; Jason Cunningham

1999-07-30

The recent achievements of critical currents in excess of 1 x 10{sup 6} amp/cm{sup 2} at 77 K in YBCO deposited over suitably textured buffer/substrate composites have stimulated interest in the potential fabrication of these coated conductors as wire. Numerous approaches and manufacturing schemes for producing coated conductor wire are currently being developed. Recently, under the US DOE's sponsorship, the University of Tennessee Space Institute performed an extensive evaluation of leading coated conductor processing options. In general, it is their feeling that the science and chemistry that are being developed in the coated conductor wire program now need proper engineeringmore » evaluation to define the most viable options for a commercial fabrication process. All fabrication processes will need process control measurements. This report provides a specific review of the needs and available technologies for process control for many of the coated conductor processing options. This report also addresses generic process monitoring areas in which additional research and development is needed. The concentration is on the two different approaches for obtaining the textured substrates that have been identified as viable candidates. These are the Los Alamos National Laboratory's ion-beam assisted deposition, called IBAD, to obtain a highly textured yttria-stabilized zirconia (YSZ) buffer on nickel alloy strips, and Oak Ridge National Laboratory's rolling assisted, bi-axially textured substrate option called RABiTS{trademark}.« less

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.

Durability test on irradiated rock-like oxide fuels

NASA Astrophysics Data System (ADS)

Kuramoto, K.; Nitani, N.; Yamashita, T.

2003-06-01

For a profitable use of Pu, Japan Atomic Energy Research Institute has been promoting researches for once-through type fuels. The strategy consists of stable rock-like oxide fuel fabrication in conventional fuel facilities followed by almost complete Pu burning in LWR and disposal of chemically stable spent fuel without further processing. Because leach rates of hazardous nuclides, such as TRU and β-emitters, that have long half-lives, are very important for the evaluation of geological safety, leaching tests in deionized water at 363 K were performed with reference to the MCC-1 method. Five irradiated fuel pellets, a single phase fuel of a yttria-stabilized zirconia (YSZ) containing UO 2 (U-YSZ), two fuels of U-YSZ particle dispersed in MgAl 2O 4 (SPI) or Al 2O 3 (COR) matrix, two homogeneous-blended fuels of U-YSZ and SPI or COR powders, were submitted to the tests. Stainless steel containers with Au coating and ethylene propylene diene monomer were used as leaching vessels and packing, respectively. The evaluated normalized leach rates of Zr, U and Pu were obviously lower than those of the other important elements and nuclides. Americium, Np and especially Y showed unexpectedly high evaluated normalized leach rates. The volatile elements, Cs and I, showed enhanced leaching within particle-dispersed type fuels because of crack formation around the particle.

Electrochemical properties of composite cathodes using Sm doped layered perovskite for intermediate temperature-operating solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Baek, Seung-Wook; Azad, Abul K.; Irvine, John T. S.; Choi, Won Seok; Kang, Hyunil; Kim, Jung Hyun

2018-02-01

SmBaCo2O5+d (SBCO) showed the lowest observed Area Specific Resistance (ASR) value in the LnBaCo2O5+d (Ln: Pr, Nd, Sm, and Gd) oxide system for the overall temperature ranges tested. The ASR of a composite cathode (mixture of SBCO and Ce0.9Gd0.1O2-d) on a Ce0.9Gd0.1O2-d (CGO91) electrolyte decreased with respect to the CGO91 content; the percolation limit was also achieved for a 50 wt% SBCO and 50 wt% CGO91 (SBCO50) composite cathode. The ASRs of SBCO50 on the dense CGO91 electrolyte in the overall temperature range of 500-750 °C were relatively lower than those of SBCO50 on the CGO91 coated dense 8 mol% yttria-stabilized zirconia (8YSZ) electrolyte for the same temperature range. From 750 °C and for all higher temperatures tested, however, the ASRs of SBCO50 on the CGO91 coated dense 8YSZ electrolyte were lower than those of the CGO91 electrolyte. The maximum power densities of SBCO50 on the Ni-8YSZ/8YSZ/CGO91 buffer layer were 1.034 W cm-2 and 0.611 W cm-2 at 800 °C and 700 °C.

Shear bond strength of veneering porcelain to zirconia: Effect of surface treatment by CNC-milling and composite layer deposition on zirconia.

PubMed

Santos, R L P; Silva, F S; Nascimento, R M; Souza, J C M; Motta, F V; Carvalho, O; Henriques, B

2016-07-01

The purpose of this study was to evaluate the shear bond strength of veneering feldspathic porcelain to zirconia substrates modified by CNC-milling process or by coating zirconia with a composite interlayer. Four types of zirconia-porcelain interface configurations were tested: RZ - porcelain bonded to rough zirconia substrate (n=16); PZ - porcelain bonded to zirconia substrate with surface holes (n=16); RZI - application of a composite interlayer between the veneering porcelain and the rough zirconia substrate (n=16); PZI - application of a composite interlayer between the porcelain and the zirconia substrate treated by CNC-milling (n=16). The composite interlayer was composed of zirconia particles reinforced porcelain (30%, vol%). The mechanical properties of the ceramic composite have been determined. The shear bond strength test was performed at 0.5mm/min using a universal testing machine. The interfaces of fractured and untested specimens were examined by FEG-SEM/EDS. Data was analyzed with Shapiro-Wilk test to test the assumption of normality. The one-way ANOVA followed by Tukey HSD multiple comparison test was used to compare shear bond strength results (α=0.05). The shear bond strength of PZ (100±15MPa) and RZI (96±11MPa) specimens were higher than that recorded for RZ (control group) specimens (89±15MPa), although not significantly (p>0.05). The highest shear bond strength values were recorded for PZI specimens (138±19MPa), yielding a significant improvement of 55% relative to RZ specimens (p<0.05). This study shows that it is possible to highly enhance the zirconia-porcelain bond strength - even by ~55% - by combining surface holes in zirconia frameworks and the application of a proper ceramic composite interlayer. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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.

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 depends on both laser fluence and operation mode (CW or PW). The results demonstrate that while CW laser reduces the biofilm formation more than PW laser with the same power, the higher surface temperature of the implant generated by CW laser limits its medical efficacy. In contrast, with the right parameters, PW laser produces a more moderate photothermal effect which can be equally effective at controlling bacterial growth. Our results show that E. coli biofilm formation across the thickness of the nc-YSZ implant can be disrupted using NIR laser treatment. The results of this in vitro study suggest that using nc-YSZ as a cranial implant in vivo may also allow for locally selective, non-invasive, chronic treatment of bacterial layers (fouling) that might form under cranial implants, without causing adverse thermal damage to the underlying host tissue when appropriate laser parameters are used. Lasers Surg. Med. 48:782-789, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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.

Screen printed Y and Bi-based superconductors

NASA Technical Reports Server (NTRS)

Haertling, Gene H.; Hsi, Chi-Shiung

1992-01-01

High T(sub c) superconducting thick film was prepared by screen printing process. Y-based (YBa2Cu3O(7 - x)) superconducting thick films were printed on 211/Al2O3, SNT/Al2O3, and YSZ substrates. Because of poor adhesion of the superconducting thick films to 211/Al2O3 and SNT/Al2O3 substrates, relatively low T(sub c) and J(sub c) values were obtained from the films printed on these substrates. Critical temperatures of YBa2Cu3O(7 - x) thick films deposited on 211/Al2O3 and SNT/Al2O3 substrates were about 80 K. The critical current densities of these films were less than 2 A/cm(exp 2). Higher T(sub c) and J(sub c) films were printed on the YSZ substrates; T(sub c) = 86.4 K and J(sub c) = 50.4 A/cm(exp 2). Multiple lead samples were also prepared on the YSZ substrates. These showed lower T(sub c) and J(sub c) values than plain samples. The heat treatment conditions of the multiple lead samples are still under investigation. Bi-based superconductor thick films have been obtained so far. Improving the superconducting properties of the BSCCO screen printed thick films will be emphasized in future work.

Evaluation of pulsed laser deposited SrNb0.1Co0.9O3-δ thin films as promising cathodes for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Chen, Dengjie; Chen, Chi; Gao, Yang; Zhang, Zhenbao; Shao, Zongping; Ciucci, Francesco

2015-11-01

SrNb0.1Co0.9O3-δ (SNC) thin films prepared on single-crystal yttria-stabilized zirconia (YSZ) electrolytes are evaluated as promising cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Geometrically well-defined polycrystalline SNC thin films with low surface roughness and high surface oxygen vacancy concentration are successfully fabricated by pulsed laser deposition. The thin films are characterized by basic techniques, e.g., X-ray diffraction for phase structure identification, scanning electron microscopy and atomic force microscopy for microstructures measurement, and X-ray photoelectron spectroscopy for elements quantification. Electrochemical impedance spectroscopy (EIS) is used to investigate oxygen reduction reaction activities of SNC thin films in symmetric electrochemical cells. Current collectors (Ag paste, Ag strip, and Au strip) are found to have negligible impact on polarization resistances. A slight decrease of the electrode polarization resistances is observed after adding a samarium doped ceria (SDC) buffer layer between SNC and YSZ. SNC thin-film electrodes exhibit low electrode polarization resistances, e.g., 0.237 Ω cm2 (SNC/SDC/YSZ/SDC/SNC) and 0.274 Ω cm2 (SNC/YSZ/SNC) at 700 °C and 0.21 atm, demonstrating the promise of SNC materials for IT-SOFCs. An oxygen reduction reaction mechanism of SNC thin films is also derived by analyzing EIS at temperature of 550-700 °C under oxygen partial pressure range of 0.04-1 atm.

Correlative tomography at the cathode/electrolyte interfaces of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Wankmüller, Florian; Szász, Julian; Joos, Jochen; Wilde, Virginia; Störmer, Heike; Gerthsen, Dagmar; Ivers-Tiffée, Ellen

2017-08-01

This paper introduces a correlative tomography technique. It visualizes the spatial organization of primary and secondary phases at the interface of La0.58Sr0.4Co0.2Fe0.8O3-δ cathode/10 mol% Gadolinia doped Ceria/8 mol% Yttria stabilized Zirconia electrolyte. It uses focused ion beam/scanning electron microscope tomography (FIB/SEM), and combines data sets from Everhart-Thornley and Inlens detector differentiating four primary and two secondary material phases. In addition, grayscale information is correlated to elemental distribution gained by energy dispersive X-ray spectroscopy in a scanning transmission electron microscope. Interdiffusion of GDC into YSZ and SrZrO3 as secondary phases depend (in both amount and spatial organization) on the varied co-sintering temperature of the GDC/YSZ electrolyte. The ion-blocking SrZrO3 forms a continuous layer on top of the temperature-dependent GDC/YSZ interdiffusion zone (ID) at and below a co-sintering temperature of 1200 °C; above it becomes intermittent. 2D FIB/SEM images of primary and secondary phases at 1100, 1200, 1300 and 1400 °C were combined with a 3D FIB/SEM reconstruction (1300 °C). This reveals that ;preferred; oxygen ion transport pathways from the LSCF cathode through GDC and the ID into the YSZ electrolyte only exist in samples sintered above 1200 °C. The applied correlative technique expands our understanding of this multiphase cathode/electrolyte interface region.

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.

Magnetic properties of epitaxial hexagonal HoFeO3 thin films

NASA Astrophysics Data System (ADS)

Wang, Xiao; Xiao, Zhuyun; Xu, Xiaoshan; Wang, Wenbin; Keavney, David; Liu, Yaohua; Cheng, X. M.

2014-03-01

Multiferroic materials exhibit multiple ferroic orders simultaneously and thus have great potential applications in information technology, sensing and actuation. Epitaxial hexagonal HoFeO3 (h-HFO) films are very promising candidates as multiferroic materials with room temperature ferromagnetism, because magnetic Ho3+ ions are expected to have stronger exchange interactions with Fe3+ ions than the well-studied h-LuFeO3 films. We report study of magnetic properties of epitaxial h-HFO thin films deposited using laser molecular beam epitaxy on Yttria-stabilized zirconia (YSZ) substrates. X-ray diffraction measurements confirmed the epitaxial registry and six-fold symmetry of the film. Temperature dependence of magnetization of the film measured by a Quantum Design SQUID magnetometer shows dominating paramagnetic characteristic. Element specific x-ray magnetic circular dichroism measurements performed at beamline 4-ID-C of the Advanced Photon Source show a ferromagnetic ordering of Fe and an exchange coupling between Ho3+ and Fe3+ ions. Work at BMC is supported by NSF Career award (DMR 1053854). Work at ANL is supported by US-DOE, Office of Science, BES (No. DE-AC02-06CH11357).

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 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.

DEVELOPMENT OF IN-SITU CONTROL DIAGNOSTICS FOR APPLICATION OF EPITAXIAL SUPERCONDUCTOR AND BUFFER LAYERS

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

B.C. Winkleman; T.V. Giel, Jr.; J. Cunningham

1999-06-30

The recent achievements of critical currents in excess of 1x10{sup 6}amp/cm{sup 2} at 77K in YBCO deposited over suitably textured buffer/substrate composites have stimulated interest in the potential fabrication of these coated conductors as wire. Numerous approaches and manufacturing schemes for producing coated conductor wire are currently being developed. Recently, under the U. S. Department of Energy (DOE's) sponsorship, the University of Tennessee Space Institute (UTSI) performed an extensive evaluation of leading coated conductor processing options. In general, it is our feeling that the science and chemistry that are being developed in the coated conductor wire program now need propermore » engineering evaluation to define the most viable options for a commercial fabrication process. All fabrication processes will need process control measurements. This report provides a specific review of the needs and available technologies for process control for many of the coated conductor processing options. This report also addresses generic process monitoring areas in which additional research and development is needed. The concentration is on the two different approaches for obtaining the textured substrates that have been identified as viable candidates. These are the Los Alamos National Laboratory's (LANL) ion-beam assisted deposition, called IBAD, to obtain a highly textured yttria-stabilized zirconia (YSZ) buffer on nickel alloy strips, and Oak Ridge National Laboratory's (ORNL) rolling assisted, bi-axially textured substrate option called RABiTS{trademark}.« less

Masking ability of a zirconia ceramic on composite resin substrate shades.

PubMed

Tabatabaian, Farhad; Shabani, Sima; Namdari, Mahshid; Sadeghpour, Koroush

2017-01-01

Masking ability of a restorative material plays an important role to cover discolored tooth structure; however, this ability has not yet been well understood in zirconia-based restorations. This study assessed the masking ability of a zirconia ceramic on composite resin substrates with different shades. Ten zirconia disc specimens, with 0.5 mm thickness and 10 mm diameter, were fabricated by a computer-aided design/computer-aided manufacturing system. A white substrate (control) and six composite resin substrates with different shades including A1, A2, A3, B2, C2, and D3 were prepared. The substrates had a cylindrical shape with 10 mm diameter and height. The specimens were placed onto the substrates for spectrophotometric evaluation. A spectrophotometer measured the L*, a*, and b* values for the specimens. ΔE values were calculated to determine the color differences between the groups and the control and then were compared with a perceptional threshold (ΔE = 2.6). Repeated measures ANOVA and Bonferroni tests were used for data analysis ( P < 0.05). The mean and standard deviation of ΔE values for A1, A2, A3, B2, C2, and D3 groups were 6.78 ± 1.59, 8.13 ± 1.66, 9.81 ± 2.64, 9.61 ± 1.38, 9.59 ± 2.63, and 8.13 ± 1.89, respectively. A significant difference was found among the groups in the ΔE values ( P = 0.006). The ΔE values were more than the perceptional threshold in all the groups ( P < 0.0001). Within the limitations of this study, it can be concluded that the tested zirconia ceramic could not thoroughly mask different shades of the composite resin substrates. Moreover, color masking of zirconia depends on the shade of substrate.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, A.F.; Makowiecki, D.M.; Rambach, G.D.; Randich, E.

1998-05-19

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated. 8 figs.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1999-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1998-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

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.

Solid oxide fuel cell short stack performance testing - Part A: Experimental analysis and μ-combined heat and power unit comparison

NASA Astrophysics Data System (ADS)

Mastropasqua, L.; Campanari, S.; Brouwer, J.

2017-12-01

The need to experimentally understand the detailed performance of SOFC stacks under operating conditions typical of commercial SOFC systems has prompted this two-part study. The steady state performance of a 6-cell short stack of yttria (Y2O3) stabilised zirconia (YSZ) with Ni/YSZ anodes and composite Sr-doped lanthanum manganite (LaMnO3, LSM)/YSZ cathodes is experimentally evaluated. In Part A, the stack characterisation is carried out by means of sensitivity analyses on the fuel utilisation factor and the steam-to-carbon ratio. Electrical and environmental performances are assessed and the results are compared with a commercial full-scale micro-CHP system, which comprises the same cells. The results show that the measured temperature dynamics of the short stack in a test stand environment are on the order of many minutes; therefore, one cannot neglect temperature dynamics for a precise measurement of the steady state polarisation behaviour. The overall polarisation performance is comparable to that of the full stack employed in the micro-CHP system, confirming the good representation that short-stack analyses can give of the entire SOFC module. The environmental performance is measured verifying the negligible values of NO emissions (<10 ppb) across the whole polarisation curve.

Higher Temperature Thermal Barrier Coatings with the Combined Use of Yttrium Aluminum Garnet and the Solution Precursor Plasma Spray Process

NASA Astrophysics Data System (ADS)

Gell, Maurice; Wang, Jiwen; Kumar, Rishi; Roth, Jeffery; Jiang, Chen; Jordan, Eric H.

2018-04-01

Gas-turbine engines are widely used in transportation, energy and defense industries. The increasing demand for more efficient gas turbines requires higher turbine operating temperatures. For more than 40 years, yttria-stabilized zirconia (YSZ) has been the dominant thermal barrier coating (TBC) due to its outstanding material properties. However, the practical use of YSZ-based TBCs is limited to approximately 1200 °C. Developing new, higher temperature TBCs has proven challenging to satisfy the multiple property requirements of a durable TBC. In this study, an advanced TBC has been developed by using the solution precursor plasma spray (SPPS) process that generates unique engineered microstructures with the higher temperature yttrium aluminum garnet (YAG) to produce a TBC that can meet and exceed the major performance standards of state-of-the-art air plasma sprayed YSZ, including: phase stability, sintering resistance, CMAS resistance, thermal cycle durability, thermal conductivity and erosion resistance. The temperature improvement for hot section gas turbine materials (superalloys & TBCs) has been at the rate of about 50 °C per decade over the last 50 years. In contrast, SPPS YAG TBCs offer the near-term potential of a > 200 °C improvement in temperature capability.

Study on component interface evolution of a solid oxide fuel cell stack after long term operation

NASA Astrophysics Data System (ADS)

Yang, Jiajun; Huang, Wei; Wang, Xiaochun; Li, Jun; Yan, Dong; Pu, Jian; Chi, Bo; Li, Jian

2018-05-01

A 5-cell solid oxide fuel cell (SOFC) stack with external manifold structure is assembled and underwent a durability test with an output of 250 W for nearly 4400 h when current density and operating temperature are 355 mA/cm2 and 750 °C. Cells used in the stack are anode-supported cells (ASC) with yttria-stabilized zirconia (YSZ) electrolytes, Ni/YSZ hydrogen electrodes, and YSZ based composite cathode. The dimension of the cell is 150 × 150 mm (active area: 130 × 130 mm). Ceramic-glass sealant is used in the stack to keep the gas tightness between cells, interconnects and manifolds. Pure hydrogen and dry air are used as fuel and oxidant respectively. The stack has a maximum output of 340 W at 562 mA/cm2 current density at 750 °C. The stack shows a degradation of 1.5% per 1000 h during the test with 2 thermal cycles to room temperature. After the test, the stack was dissembled and examined. The relationship between microstructure changes of interfaces and degradation in the stack are discussed. The microstructure evolution of interfaces between electrode, contact material and current collector are unveiled and their relationship with the degradation is discussed.

Synthesis of functional ceramic supports by ice templating and atomic layer deposition

NASA Astrophysics Data System (ADS)

Klotz, Michaela; Weber, Matthieu; Deville, Sylvain; Oison, Didier; Iatsunskyi, Igor; Coy, Emerson; Bechelany, Mikhael

2018-05-01

In this work, we report an innovative route for the manufacturing of functional ceramic supports, by combining ice templating of yttria stabilized zirconia (YSZ) and atomic layer deposition (ALD) of Al2O3 processes. Ceramic YSZ monoliths are prepared using the ice-templating process, which is based on the controlled crystallization of water following a thermal gradient. Sublimation of the ice and the sintering of the material reveal the straight micrometer sized pores shaped by the ice crystal growth. The high temperature sintering allows for the ceramic materials to present excellent mechanical strength and porosities of 67%. Next, the conformality benefit of ALD is used to deposit an alumina coating at the surface of the YSZ pores, in order to obtain a functional material. The Al2O3 thin films obtained by ALD are 100 nm thick and conformally deposited within the macroporous ceramic supports, as shown by SEM and EDS analysis. Mercury intrusion experiments revealed a reduction of the entrance pore diameter, in line with the growth per cycle of 2 Å of the ALD process. In addition to the manufacture of the innovative ceramic nanomaterials, this article also describes the fine characterization of the coatings obtained using mercury intrusion, SEM and XRD analysis.

High-performance electrodes for reduced temperature solid oxide fuel cells with doped lanthanum gallate electrolyte. II. La(Sr)CoO 3 cathode

NASA Astrophysics Data System (ADS)

Inagaki, Toru; Miura, Kazuhiro; Yoshida, Hiroyuki; Maric, Radenka; Ohara, Satoshi; Zhang, Xinge; Mukai, Kazuo; Fukui, Takehisa

The reduced temperature solid oxide fuel cell (SOFC) with 0.5 mm thick La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- α (LSGM) electrolyte, La 0.6Sr 0.4CoO 3- δ (LSCo) cathode, and Ni-(CeO 2) 0.8(SmO 1.5) 0.2 (SDC) cermet anode showed an excellent initial performance, and high maximum power density, 0.47 W/cm 2, at 800°C. The results were comparable to those for the conventional SOFC with yttria-stabilized zirconia (YSZ) electrolyte, La(Sr)MnO 3-YSZ cathode and Ni-YSZ cermet anode at 1000°C. Using an LSCo powder prepared by spray pyrolysis, and selecting appropriate sintering temperatures, the lowest cathodic polarization of about 25 mV at 300 mA/cm 2 was measured for a cathode prepared by sintering at 1000°C. Life time cell test results, however, showed that the polarization of the LSCo cathode increased with operating time. From EPMA results, this behavior was considered to be related to the interdiffusion of the elements at the cathode/electrolyte interface. Calcination of LSCo powder could be a possible way to suppress this interdiffusion at the interface.

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.

Solid Oxide Fuel Cell short stack performance testing - part B: Operation in carbon capture applications and degradation issues

NASA Astrophysics Data System (ADS)

Mastropasqua, L.; Campanari, S.; Brouwer, J.

2017-12-01

The need to experimentally understand the performance of Solid Oxide Fuel Cells (SOFC) stacks under Carbon Capture and Storage (CCS) mode operating conditions, hence with anode recirculation, has prompted this two-part study. The steady state performance of a 6-cell short stack of Y2O3 stabilised Zirconia (YSZ) with Ni/YSZ anodes and composite Sr-doped LaMnO3 (LSM)/YSZ cathodes is experimentally evaluated. In Part A, the electrical and environmental performance are assessed and the results are compared with the commercial full-scale micro-Combined Heat and Power system, which comprises the same cells. In Part B of this work, a specific set of stack operating conditions important to CCS applications is explored. The experimental inlet composition is changed in order to reproduce a simulated syngas in CCS mode operation for different fuel utilisation factors. Operation with the simulated anode recycle syngas leads to lower voltage when the anode recycle is lower, mainly due to higher internal reforming and polarisation losses. A clear voltage trend is observed when the amount of CO content in the inlet fuel is increased, signalling an improvement of the polarisation performance at constant current density and fixed inlet equivalent hydrogen content. Stack degradation is measured and results in line with manufacturer's data.

Structural Characterization Studies on Semiconducting ZnSnN 2 Films using Synchrotron X-ray Diffraction

NASA Astrophysics Data System (ADS)

Senabulya, Nancy

This work is motivated by the need for new visible frequency direct bandgap semiconductor materials that are earth abundant and low-cost to meet the increasing demand for optoelectronic device applications such as solid state lighting and photovoltaics. Zinc-Tin-Nitride (ZnSnN2), a member of the II-IV nitride semiconductor family has been proposed as an alternative to the more common III-nitride semiconductors for use in optoelectronic devices. This material has been synthesized under optimized conditions using plasma assisted molecular beam epitaxy. Though a lot of research has recently been done computationally to predict the electronic and structural properties of ZnSnN2, experimental verification of these theories in single crystal thin films is lacking and warrants investigation because the accurate determination of the crystal structure of ZnSnN2 is a fundamental prerequisite for controlling and optimizing optoelectronic properties. In this synchrotron x-ray diffraction study, we present experimental validation, through unit cell refinement and 3d reciprocal space maps, of the crystal structure of single domain ZnSnN2 films deposited on (111) Yttria stabilized zirconia (YSZ) and (001) Lithium gallate (LGO) substrates. We find that ZnSnN2 films grown on (111) YSZ can attain both the theoretically predicted disordered wurtzite and ordered orthorhombic Pna21 structures under carefully controlled MBE growth conditions, while films grown on (001) LGO have the ordered Pn21a orthorhombic crystal structure. Through a systematic annealing study, a temperature induced first order structural phase transition from the wurtzite to orthorhombic phase is realized, characterized by the appearance of superstructure reflections in.

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

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.

Bonding quality of contemporary dental cements to sandblasted esthetic crown copings.

PubMed

Abdelaziz, Khalid M; Al-Qahtani, Nasser M; Al-Shehri, Abdulrahman S; Abdelmoneam, Adel M

2012-05-01

To evaluate the shear bond strength of current luting cements to sandblasted crown-coping substrates. Specimens of nickel-chromium, pressable glass ceramic, and zirconia crown-coping substrates were sandblasted in three groups (n = 30 each) with 50 (group 1), 110 (group 2), and 250 μm (group 3) alumina particles at a pressure of 250 kPa. Cylinders of glass ionomer, universal resin, and self-adhesive resin cements were then built up on the sandblasted substrate surfaces of each group (n = 10). All bonded specimens were stressed to evaluate the cement-substrate shear bond strength. Both the mode and incidence of bond failure were also considered. No difference was noticed between all test groups in terms of cement-substrate bond strength. In comparison to self-adhesive type, the universal resin cement provided lower bond strengths to both metal and glass-ceramic substrates in group 1. The self-adhesive resin cement provided the highest bond strengths to the zirconia substrates in groups 2 and 3. The adhesive type of bond failure was common in the metal and zirconia substrates in all groups. Cement-substrate bonding quality is not affected by the size of sandblasting particles. Resin cements bond better to different coping substrates. Self-adhesive resin cement is the best choice to bond zirconia-based substrates. © 2011 Blackwell Publishing Asia Pty Ltd.

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

Convection of tin in a Bridgman system. I - Flow characterization by effective diffusivity measurements

NASA Technical Reports Server (NTRS)

Sears, B.; Narayanan, R.; Anderson, T. J.; Fripp, A. L.

1992-01-01

An electrochemical titration method was used to investigate the dynamic states in a cylindrical layer of convecting tin. The liquid tin was contained in a cell, with curved boundaries made of quartz and flat boundaries made of a solid state electrolyte - yttria-stabilized zirconia (YSZ). The electrolyte acted as a window through which a trace amount of oxygen could be pumped in or out by the application of a constant voltage. The concentration at the YSZ interface was monitored by operating the electrochemical cell in the galvanic mode. Experimentally determined effective diffusivities of oxygen were compared with the molecular diffusivity. Dynamic states in the convective flow were thus inferred. Temperature measurements were simultaneously made in order to identify the onset of oscillations from a steady convective regime. The experiments were conducted for two different aspect ratios for various imposed temperature gradients and two different orientations with respect to gravity. Transcritical states were identified and comparison to two-dimensional numerical models were made.

Achieving High Efficiency and Eliminating Degradation in Solid Oxide Electrochemical Cells Using High Oxygen-Capacity Perovskite.

PubMed

Jun, Areum; Kim, Junyoung; Shin, Jeeyoung; Kim, Guntae

2016-09-26

Recently, there have been efforts to use clean and renewable energy because of finite fossil fuels and environmental problems. Owing to the site-specific and weather-dependent characteristics of the renewable energy supply, solid oxide electrolysis cells (SOECs) have received considerable attention to store energy as hydrogen. Conventional SOECs use Ni-YSZ (yttria-stabilized zirconia) and LSM (strontium-doped lanthanum manganites)-YSZ as electrodes. These electrodes, however, suffer from redox-instability and coarsening of the Ni electrode along with delamination of the LSM electrode during steam electrolysis. In this study, we successfully design and fabricate highly efficient SOECs using layered perovskites, PrBaMn2 O5+δ (PBM) and PrBa0.5 Sr0.5 Co1.5 Fe0.5 O5+δ (PBSCF50), as both electrodes for the first time. The SOEC with layered perovskites as both-side electrodes shows outstanding performance, reversible cycling, and remarkable stability over 600 hours. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low-Thermal-Conductivity Pyrochlore Oxide Materials Developed for Advanced Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Zhu, Dong-Ming

2005-01-01

When turbine engines operate at higher temperatures, they consume less fuel, have higher efficiencies, and have lower emissions. The upper-use temperatures of the base materials (superalloys, silicon-based ceramics, etc.) used for the hot-section components of turbine engines are limited by the physical, mechanical, and corrosion characteristics of these materials. Thermal barrier coatings (TBCs) are applied as thin layers on the surfaces of these materials to further increase the operating temperatures. The current state-of-the-art TBC material in commercial use is partially yttria-stabilized zirconia (YSZ), which is applied on engine components by plasma spraying or by electron-beam physical vapor deposition. At temperatures higher than 1000 C, YSZ layers are prone to sintering, which increases thermal conductivity and makes them less effective. The sintered and densified coatings can also reduce thermal stress and strain tolerance, which can reduce the coating s durability significantly. Alternate TBC materials with lower thermal conductivity and better sintering resistance are needed to further increase the operating temperature of turbine engines.

Buffer layers on metal surfaces having biaxial texture as superconductor substrates

DOEpatents

Paranthaman, Mariappan; Lee, Dominic F.; Kroeger, Donald M.; Goyal, Amit

2000-01-01

Buffer layer architectures are epitaxially deposited on biaxially-textured rolled substrates of nickel and/or copper and their alloys for high current conductors, and more particularly buffer layer architectures such as Y.sub.2 O.sub.3 /Ni, YSZ/Y.sub.2 O.sub.3 /Ni, RE.sub.2 O.sub.3 /Ni, (RE=Rare Earth), RE.sub.2 O.sub.3 /Y.sub.2 O.sub.3 /Ni, RE.sub.2 O.sub.3 /CeO.sub.2 /Ni, and RE.sub.2 O.sub.3 /YSZ/CeO.sub.2 /Ni, Y.sub.2 O.sub.3 /Cu, YSZ/Y.sub.2 O.sub.3 /Cu, RE.sub.2 O.sub.3 /Cu, RE.sub.2 O.sub.3 /Y.sub.2 O.sub.3 /Cu, RE.sub.2 O.sub.3 /CeO.sub.2 /Cu, and RE.sub.2 O.sub.3 /YSZ/CeO.sub.2 /Cu. Deposition methods include physical vapor deposition techniques which include electron-beam evaporation, rf magnetron sputtering, pulsed laser deposition, thermal evaporation, and solution precursor approaches, which include chemical vapor deposition, combustion CVD, metal-organic decomposition, sol-gel processing, and plasma spray.

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

DOE PAGES

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

2015-09-03

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

Degradation of TBC Systems in Environments Relevant to Advanced Gas Turbines for IGCC Systems

NASA Astrophysics Data System (ADS)

Bohna, Nathaniel Allan

Plasma sprayed (PS) thermal barrier coatings (TBCs) are used to provide thermal insulation for the hottest components in gas turbines. Zirconia stabilized with 7wt% yttria (7YSZ) is the most common ceramic top coat used for turbine blades. The 7YSZ coating can be degraded by the buildup of fly-ash deposits which can arise from the fuel source (coal/biomass) used in the combustion process in gas turbines. Fly-ash from the integrated gasification combined cycle (IGCC) process can result from coal-based syngas and also from ambient air which passes through the system. TBCs are also exposed to harsh gas environments containing CO2, SO2, and steam. As presented in this thesis, degradation from the combined effects of fly-ash and harsh gas atmosphere can severely limit TBC lifetimes. It is well established that degradation at very high temperatures (≥1250°C) from deposits consisting of the oxides CaO-MgO-Al2O3-SiO 2 results from extensive liquid silicate infiltration into the porous top coat of the YSZ. This infiltration causes early failure resulting from chemical and/or mechanical damage to the ceramic layer. Damage resulting from liquid infiltration, however, is not typically considered at relatively lower temperatures around 1100°C because liquid silicates would not be expected to form from the oxides in the deposit. A key focus of this study is to assess the mode and extent of TBC degradation at 1100°C in cases when some amount of liquid forms owing to the presence of K2SO4 as a minor ash constituent. Two types of liquid infiltrations are observed depending on the principal oxide (i.e., CaO or SiO2) in the deposit. The degradation is primarily the result of mechanical damage, which results from infiltration caused by the interaction of liquid K2SO4 with either the CaO or SiO2. The TBCs used in this work are representative of commonly used coatings used in the hottest sections of land-based gas turbines. The specimens consist of 7YSZ top coats deposited on superalloy (Rene' N5 and PWA 1484) substrates that had been coated with NiCoCrAlY bond coats. Two different top coats are studied: conventional low-density 7YSZ, and also dense vertically cracked coatings. The specific mechanisms of liquid infiltration resulting from CaO and SiO2 are studied by conducting isothermal exposures followed by detailed characterizations. The resulting consequences on cyclic lifetimes are also determined. Further, the cyclic lifetimes are studied in several gas atmospheres to examine the combined effect of deposit and gas atmosphere on TBC lifetime. This work identifies a TBC degradation mechanism which had previously not been considered. It will be clearly shown that deposit-induced attack of TBCs can be highly detrimental at an intermediate temperature like 1100°C.

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

Enhanced electrochemical performance and carbon anti-coking ability of solid oxide fuel cells with silver modified nickel-yttrium stabilized zirconia anode by electroless plating

NASA Astrophysics Data System (ADS)

Wu, Xiaoyan; Tian, Yu; Zhang, Jun; Zuo, Wei; Kong, Xiaowei; Wang, Jinghui; Sun, Kening; Zhou, Xiaoliang

2016-01-01

In this paper, silver (Ag) particles are introduced into the conventional Ni/YSZ anode by utilizing electroless plating method to improve its carbon anti-coking ability in hydrocarbons. The experimental results show that electrochemical performances of the decorated cells in H2, CH4 and C2H6 are all increased as compared to the cell with unmodified Ni/YSZ anode, which are verified by impedance spectrums as well. The durability experiment is carried out for as long as 24 h at the current density of 0.33 A/cm2 where the modified anode is subjected to dry C2H6 indicating the anti-coking ability of the anode is greatly improved. Scanning electron microscope shows that the slight decreasing in the cell terminal voltage can be attributed to the minimized carbon deposition which maybe resulted from the aggregation of silver particles at high temperature. Energy-dispersive X-ray spectroscopy line scanning results after long-term stability operation of the anode suggest that the carbon deposition can be depressed effectively both inside the anode and on the surface of the anode. Therefore, the results show that silver is a promising candidate material for modifying the Ni/YSZ anode with regard to improving electrochemical performance and suppressing the carbon deposition when taking the hydrocarbons as fuels.

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.

Oxidation behavior of thermal barrier coating systems with Al interlayer under isothermal loading

NASA Astrophysics Data System (ADS)

Ali, I.; Sokołowski, P.; Grund, T.; Pawłowski, L.; Lampke, T.

2018-06-01

In the present study, the phenomena related to the Thermally Grown Oxides (TGO) in atmospheric plasma sprayed Thermal Barrier Coatings (TBCs) are discussed. CoNiCrAlY bond coatings were sprayed on Inconel 600 substrates. Subsequently, thin Al layers were deposited by DC-Magnetron sputtering. Finally, yttria-stabilized zirconia (YSZ) top coatings were deposited to form a three-layered TBC system. The thus produced aluminum interlayer containing thermal barrier coatings (Al-TBC) were subjected to isothermal exposure with different holding times at 1150 °C and compared with reference TBCs of the same kind, but without Al interlayers (R-TBC). The oxide film formation in the interface between bond coating (BC) and top coating (TC) was investigated by scanning electron microscope (SEM) after 100 and 300 h of high temperature isothermal exposure. The growth of this oxide film as a function of the isothermal exposure time was studied. As a result, the designed Al-TBC system exhibited better oxidation resistance in the BC/TC interface than the two-layered R-TBC system. This was lead back to the Al enrichment, which slows down the formation rate of transition metal oxides during thermal loading.

Intergranular metal phase increases thermal shock resistance of ceramic coating

NASA Technical Reports Server (NTRS)

Carpenter, H. W.

1966-01-01

Dispersed copper phase increases the thermal shock resistance of a plasma-arc-sprayed coating of zirconia used as a heat barrier on a metal substrate. A small amount of copper is deposited on the granules of the zirconia powder before arc-spraying the resultant powder composite onto the substrate.

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

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.

Investigations on composition and morphology of electrochemical alumina and alumina yttria stabilised zirconia deposits

NASA Astrophysics Data System (ADS)

El Hajjaji, S.; Manov, S.; Roy, J.; Aigouy, T.; Ben Bachir, A.; Aries, L.

2001-08-01

Conversion coatings modified by deposits of electrolytic alumina added or not with yttria and/or zirconia, have been studied which are well known for their resistance to chemical attack and high temperature. Conversion coating, characterised by a particular morphology and strong interfacial adhesion with the substrate, facilitate the electrochemical deposition of ceramic layers and enhance their adhesion to the substrate. Zirconia-alumina coating behaviour at 1000°C is similar to that of alumina coating; from 800°C, the chromium diffuses from the stainless steel through the electrolytic refractory coating up to the external interface, provokes discontinuities and can modify its protective character. Yttrium stabilises the cubic and the tetragonal form of the zirconia; so, during cooling, the phase transformation near 1000°C of tetragonal zirconia to monoclinic form cannot take place.

Preparation and characterization of TiO2 and Si-doped octacalcium phosphate composite coatings on zirconia ceramics (Y-TZP) for dental implant applications

NASA Astrophysics Data System (ADS)

Bao, Lei; Liu, Jingxiao; Shi, Fei; Jiang, Yanyan; Liu, Guishan

2014-01-01

In order to prevent the low temperature degradation and improve the bioactivity of zirconia ceramic implants, TiO2 and Si-doped octacalcium phosphate composite coating was prepared on zirconia substrate. The preventive effect on low temperature degradation and surface morphology of the TiO2 layer were studied. Meanwhile, the structure and property changes of the bioactive coating after doping Si were discussed. The results indicate that the dense TiO2 layer, in spite of some microcracks, inhibited the direct contact of the water vapor with the sample's surface and thus prevented the low temperature degradation of zirconia substrates. The acceleration aging test shows that the ratio of the monoclinic phase transition decreased from 10% for the original zirconia substrate to 4% for the TiO2-coated substrate. As to the Si-doped octacalcium phosphate coating prepared by biomimetic method, the main phase composition of the coating was octacalcium phosphate. The morphology of the coating was lamellar-like, and the surface was uniform and continuous with no cracks being observed. It is suggested that Si was added into the coating both through substituting for PO43- and doping as NaSiO3.

Buffer layers on rolled nickel or copper as superconductor substrates

DOEpatents

Paranthaman, Mariappan; Lee, Dominic F.; Kroeger, Donald M.; Goyal, Amit

2000-01-01

Buffer layer architectures are epitaxially deposited on biaxially-textured rolled substrates of nickel and/or copper and their alloys for high current conductors, and more particularly buffer layer architectures such as Y.sub.2 O.sub.3 /Ni, YSZ/Y.sub.2 O.sub.3 /Ni, Yb.sub.2 O.sub.3 /Ni, Yb.sub.2 O.sub.3 /Y.sub.2 O.sub.3 /Ni, Yb.sub.2 O.sub.3 /CeO.sub.2 /Ni, RE.sub.2 O.sub.3 /Ni (RE=Rare Earth), and Yb.sub.2 O.sub.3 /YSZ/CeO.sub.2 /Ni, Y.sub.2 O.sub.3 /Cu, YSZ/Y.sub.2 O.sub.3 /Cu, Yb.sub.2 O.sub.3 /Cu, Yb.sub.2 O.sub.3 /Y.sub.2 O.sub.3 /Cu, Yb.sub.2 O.sub.3 /CeO.sub.2 /Cu, RE.sub.2 O.sub.3 /Cu, and Yb.sub.2 O.sub.3 /YSZ/CeO.sub.2 /Cu. Deposition methods include physical vapor deposition techniques which include electron-beam evaporation, rf magnetron sputtering, pulsed laser deposition, thermal evaporation, and solution precursor approach, which includes chemical vapor deposition, combustion CVD, metal-organic decomposition, sol-gel processing, and plasma spray.

Atomic Layer Deposited Thin Films for Dielectrics, Semiconductor Passivation, and Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Xu, Runshen

Atomic layer deposition (ALD) utilizes sequential precursor gas pulses to deposit one monolayer or sub-monolayer of material per cycle based on its self-limiting surface reaction, which offers advantages, such as precise thickness control, thickness uniformity, and conformality. ALD is a powerful means of fabricating nanoscale features in future nanoelectronics, such as contemporary sub-45 nm metal-oxide-semiconductor field effect transistors, photovoltaic cells, near- and far-infrared detectors, and intermediate temperature solid oxide fuel cells. High dielectric constant, kappa, materials have been recognized to be promising candidates to replace traditional SiO2 and SiON, because they enable good scalability of sub-45 nm MOSFET (metal-oxide-semiconductor field-effect transistor) without inducing additional power consumption and heat dissipation. In addition to high dielectric constant, high-kappa materials must meet a number of other requirements, such as low leakage current, high mobility, good thermal and structure stability with Si to withstand high-temperature source-drain activation annealing. In this thesis, atomic layer deposited Er2O3 doped TiO2 is studied and proposed as a thermally stable amorphous high-kappa dielectric on Si substrate. The stabilization of TiO2 in its amorphous state is found to achieve a high permittivity of 36, a hysteresis voltage of less than 10 mV, and a low leakage current density of 10-8 A/cm-2 at -1 MV/cm. In III-V semiconductors, issues including unsatisfied dangling bonds and native oxides often result in inferior surface quality that yields non-negligible leakage currents and degrades the long-term performance of devices. The traditional means for passivating the surface of III-V semiconductors are based on the use of sulfide solutions; however, that only offers good protection against oxidation for a short-term (i.e., one day). In this work, in order to improve the chemical passivation efficacy of III-V semiconductors, ultra-thin layer of encapsulating ZnS is coated on the surface of GaSb and GaSb/InAs substrates. The 2 nm-thick ZnS film is found to provide a long-term protection against reoxidation for one order and a half longer times than prior reported passivation likely due to its amorphous structure without pinholes. Finally, a combination of binary ALD processes is developed and demonstrated for the growth of yttria-stabilized zirconia films using alkylamido-cyclopentadiengyls zirconium and tris(isopropyl-cyclopentadienyl)yttrium, as zirconium and yttrium precursors, respectively, with ozone being the oxidant. The desired cubic structure of YSZ films is apparently achieved after post-deposition annealing. Further, platinum is atomic layer deposited as electrode on YSZ (8 mol% of Yttria) within the same system. In order to control the morphology of as-deposited Pt thin structure, the nucleation behavior of Pt on amorphous and cubic YSZ is investigated. Three different morphologies of Pt are observed, including nanoparticle, porous and dense films, which are found to depend on the ALD cycle number and the structure and morphology of they underlying ALD YSZ films.

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.

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.

Performance of Solid Oxide Fuel Cell With La and Cr Co-doped SrTiO3 as Anode.

PubMed

Yi, Fenyun; Chen, Hongyu; Li, He

2014-06-01

The La 0.3 Sr 0.55 Ti 0.9 Cr 0.1 O 3-δ (LSTC10) anode material was synthesized by citric acid-nitrate process. The yttria-stabilized zirconia (YSZ) electrolyte-supported cell was fabricated by screen printing method using LSTC10 as anode and (La 0.75 Sr 0.25 ) 0.95 MnO 3-δ (LSM) as cathode. The electrochemical performance of cell was tested by using dry hydrogen as fuel and air as oxidant in the temperature range of 800-900 °C. At 900 °C, the open circuit voltage (OCV) and the maximum power density of cell are 1.08 V and 13.0 mW·cm -2 , respectively. The microstructures of cell after performance testing were investigated by scanning electron microscope (SEM). The results show that the anode and cathode films are porous and closely attached to the YSZ electrolyte. LSTC10 is believed to be a kind of potential solid oxide fuel cell (SOFC) anode material.

Hydroxyapatite coating on PEEK implants: biomechanical and histological study in a rabbit model

PubMed Central

Durham, John W.; Montelongo, Sergio A.; Ong, Joo L.; Guda, Teja; Allen, Matthew J.; Rabiei, Afsaneh

2016-01-01

A bioactive two-layer coating consisting of hydroxyapatite (HA) and yttria-stabilized zirconia (YSZ) was investigated on cylindrical polyether ether ketone (PEEK) implants using ion beam assisted deposition (IBAD). Post-deposition heat treatments via variable frequency microwave annealing with and without subsequent autoclaving were used to crystallize the as-deposited amorphous HA layer. Microstructural analysis, performed by TEM and EDS, showed that these methods were capable of crystallizing HA coating on PEEK. The in vivo response to cylindrical PEEK samples with and without coating was studied by implanting uncoated PEEK and coated PEEK implants in the lateral femoral condyle of 18 rabbits. Animals were studied in two groups 9 for observation at 6 or 18 weeks post surgery. MicroCT analysis, histology, and mechanical pull-out tests were performed to determine the effect of the coating on osseointegration. The heat-treated HA/YSZ coatings showed improved implant fixation as well as higher bone regeneration and bone-implant contact area compared to uncoated PEEK. The study offers a novel method to coat PEEK implants with improved osseointegration. PMID:27524073

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.

Developmental status and system studies of the monolithic solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Myles, K. M.

The monolithic solid oxide fuel cell (MSOFC) was invented at the Argonne National Laboratory in 1983 and is currently being developed by a team consisting of Argonne National Laboratory and Allied-Signal Aerospace/AiResearch. The MSOFC is an oxide ceramic structure in which appropriate electronic and ionic conductors are fabricated in a honeycomb shape similar to a block of corrugated paperboard. The electrolyte, which conducts oxygens ions from the air side to the fuel side, is yttria-stabilized zirconia (YSZ). All the other materials, that is, the nickel-YSZ anode, the strontium-doped lanthanum manganite cathode, and the doped lanthanum chromite interconnect (bipolar plate), are electronic conductors. These electronic and ionic conductors are arranged to provide short conduction paths to minimize resistive losses. The power density achievable with the MSOFC is expected to be about 8 kW/kg or 4 kW/l at fuel efficiencies over 50 percent, because of small cell size and low resistive losses in the materials. These performances have been approached in laboratory test fuel cell stacks of nominal 125-W capacities.

Hydroxyapatite coating on PEEK implants: Biomechanical and histological study in a rabbit model.

PubMed

Durham, John W; Montelongo, Sergio A; Ong, Joo L; Guda, Teja; Allen, Matthew J; Rabiei, Afsaneh

2016-11-01

A bioactive two-layer coating consisting of hydroxyapatite (HA) and yttria-stabilized zirconia (YSZ) was investigated on cylindrical polyetheretherketone (PEEK) implants using ion beam assisted deposition (IBAD). Post-deposition heat treatments via variable frequency microwave annealing with and without subsequent autoclaving were used to crystallize the as-deposited amorphous HA layer. Microstructural analysis, performed by TEM and EDS, showed that these methods were capable of crystallizing HA coating on PEEK. The in vivo response to cylindrical PEEK samples with and without coating was studied by implanting uncoated PEEK and coated PEEK implants in the lateral femoral condyle of 18 rabbits. Animals were studied in two groups of 9 for observation at 6 or 18weeks post surgery. Micro-CT analysis, histology, and mechanical pull-out tests were performed to determine the effect of the coating on osseointegration. The heat-treated HA/YSZ coatings showed improved implant fixation as well as higher bone regeneration and bone-implant contact area compared to uncoated PEEK. The study offers a novel method to coat PEEK implants with improved osseointegration. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Stechel, Ellen Beth; Ambrosini, Andrea; Coker, Eric Nicholas

The Sunshine to Petrol effort at Sandia aims to convert carbon dioxide and water to precursors for liquid hydrocarbon fuels using concentrated solar power. Significant advances have been made in the field of solar thermochemical CO{sub 2}-splitting technologies utilizing yttria-stabilized zirconia (YSZ)-supported ferrite composites. Conceptually, such materials work via the basic redox reactions: Fe{sub 3}O{sub 4} {yields} 3FeO + 0.5O{sub 2} (Thermal reduction, >1350 C) and 3FeO + CO{sub 2} {yields} Fe{sub 3}O{sub 4} + CO (CO{sub 2}-splitting oxidation, <1200 C). There has been limited fundamental characterization of the ferrite-based materials at the high temperatures and conditions present in thesemore » cycles. A systematic study of these composites is underway in an effort to begin to elucidate microstructure, structure-property relationships, and the role of the support on redox behavior under high-temperature reducing and oxidizing environments. In this paper the synthesis, structural characterization (including scanning electron microscopy and room temperature and in-situ x-ray diffraction), and thermogravimetric analysis of YSZ-supported ferrites will be reported.« less

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.

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.

Solid oxide membrane (SOM) process for ytterbium and silicon production from their oxides

NASA Astrophysics Data System (ADS)

Jiang, Yihong

The Solid oxide membrane (SOM) electrolysis is an innovative green technology that produces technologically important metals directly from their respective oxides. A yttria-stabilized zirconia (YSZ) tube, closed at one end is employed to separate the molten salt containing dissolved metal oxides from the anode inside the YSZ tube. When the applied electric potential between the cathode in the molten salt and the anode exceeds the dissociation potential of the desired metal oxides, oxygen ions in the molten salt migrate through the YSZ membrane and are oxidized at the anode while the dissolved metal cations in the flux are reduced to the desired metal at the cathode. Compared with existing metal production processes, the SOM process has many advantages such as one unit operation, less energy consumption, lower capital costs and zero carbon emission. Successful implementation of the SOM electrolysis process would provide a way to mitigate the negative environmental impact of the metal industry. Successful demonstration of producing ytterbium (Yb) and silicon (Si) directly from their respective oxides utilizing the SOM electrolysis process is presented in this dissertation. During the SOM electrolysis process, Yb2O3 was reduced to Yb metal on an inert cathode. The melting point of the supporting electrolyte (LiF-YbF3-Yb2O3) was determined by differential thermal analysis (DTA). Static stability testing confirmed that the YSZ tube was stable with the flux at operating temperature. Yb metal deposit on the cathode was confirmed by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). During the SOM electrolysis process for silicon production, a fluoride based flux based on BaF2, MgF2, and YF3 was engineered to serve as the liquid electrolyte for dissolving silicon dioxide. YSZ tube was used to separate the molten salt from an anode current collector in the liquid silver. Liquid tin was chosen as cathode to dissolve the reduced silicon during SOM electrolysis. After electrolysis, upon cooling, silicon crystals precipitated out from the Si-Sn liquid alloy. The presence of high-purity silicon crystals in the liquid tin cathode was confirmed by SEM/EDS. The fluoride based flux was also optimized to improve YSZ membrane stability for long-term use.

Ceramic surfaces, interfaces and solid-state reactions

NASA Astrophysics Data System (ADS)

Heffelfinger, Jason Roy

Faceting, the decomposition of a surface into two or more surfaces of different orientation, is studied as a function of annealing time for ceramic surfaces. Single-crystals of Alsb2Osb3\\ (alpha-Alsb2Osb3 or corundum structure) are carefully prepared and characterized by atomic force microscopy, scanning electron microscopy and transmission electron microscopy. The mechanisms by which the originally smooth vicinal surface transforms into either a hill-and-valley or a terrace-and-step structure have been characterized. The progression of faceting is found to have a series of stages: surface smoothing, nucleation and growth of individual facets, formation of facet domains, coalescence of individual and facet domains and facet coarsening. These stages provide a model for the mechanisms of how other ceramic surfaces may facet into hill-and-valley and terrace-and-step surface microstructures. The well characterized Alsb2Osb3 surfaces provide excellent substrates by which to study the effect of surface structure on thin-film growth. Pulsed-laser deposition was used to grow thin films of yttria stabilized zirconia (YSZ) and Ysb2Osb3 onto annealed Alsb2Osb3 substrates. The substrate surface structure, such as surface steps and terraces, was found to have several effects on thin-film growth. Thin-films grown onto single-crystal substrates serve as a model geometry for studying thin-film solid-state reactions. Here, the reaction sequence and orientation relationship between thin films of Ysb2Osb3 and an Alsb2Osb3 substrate were characterized for different reaction temperatures. In a system were multiple reaction phases can form, the yttria aluminum monoclinic phase (YAM) was found to form prior to formation of other phases in this system. In a second system, a titanium alloy was reacted with single crystal Alsb2Osb3 in order to study phase formation in an intermetallic system. Both Tisb3Al and TiAl were found to form as reaction products and their orientation relationships with the Alsb2Osb3 are discussed.

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 + V2O 5 mixture (50-50 mol. %) demonstrated that Na2SO4 itself did not degrade the YSZ, however, in the presence of V2O 5, Na2SO4 formed vanadates such as NaVO3 that degraded the YSZ through YVO4 formation at temperature as low as 700°C. The APS YSZ was found to react with the P2O 5 melt by forming ZrP2O7 at all temperatures. This interaction led to the depletion of ZrO2 in the YSZ (i.e., enrichment of Y2O3 in t'-YSZ) and promoted the formation of the fluorite-cubic ZrO2 phase. Above 1250°C, CMAS deposits were observed to readily infiltrate and significantly dissolve the YSZ coating via thermochemical interactions. Upon cooling, zirconia reprecipitated with a spherical morphology and a composition that depended on the local melt chemistry. The molten CMAS attack destabilized the YSZ through the detrimental phase transformation (t' → t → f + m). Free standing APS CoNiCrAlY was also prone to degradation by corrosive molten deposits. The V2O5 melt degraded the APS CoNiCrAlY through various reactions involving acidic dissolution of the protective oxide scale, which yielded substitutional-solid solution vanadates such as (Co,Ni) 3(VO4)2 and (Cr,Al)VO4. The molten P2O5, on the other hand, was found to consume the bond coat constituents significantly via reactions that formed both Ni/Co rich phosphates and Cr/Al rich phosphates. Sulfate deposits such as Na2SO 4, when tested in encapsulation, damaged the CoNiCrAlY by Type I acidic fluxing hot corrosion mechanisms at 1000°C that resulted in accelerated oxidation and sulfidation. The formation of a protective continuous Al 2O3 oxide scale by preoxidation treatment significantly delayed the hot corrosion of CoNiCrAlY by sulfates. However, CoNiCrAlY in both as-sprayed and preoxidized condition suffered a significant damage by CaSO4 deposits via a basic fluxing mechanism that yielded CaCrO4 and CaAl2O4. The CMAS melt also dissolved the protective Al2O3 oxide scale developed on CoNiCrAlY by forming anorthite platelets and spinel oxides. Based on the detailed investigation on degradation of the APS YSZ and CoNiCrAlY by various corrosive deposits, an experimental attempt was carried out to mitigate the melt-induced deposit attack. Experimental results from this study demonstrate, for the first time, that an oxide overlay produced by electrophoretic deposition (EPD) can effectively perform as an environmental barrier overlay for APS TBCs. The EPD protective overlay has a uniform and easily-controllable thickness, uniformly distributed closed pores and tailored chemistry. The EPD Al2O3 and MgO overlays were successful in protecting the APS YSZ TBCs against CMAS attack and hot corrosion attack (e.g., sulfate and vanadate), respectively. Furnace thermal cyclic oxidation testing of overlay-modified TBCs on bond-coated superalloy also demonstrated the good adhesive durability of the EPD Al2O3 overlay.

Detecting Thermal Barrier Coating Delamination Using Visible and Near-Infrared Luminescence from Erbium-Doped Sublayers

NASA Technical Reports Server (NTRS)

Eldridge, J. I.; Bencic, T. J.; Martin, R. E.; Singh, J.; Wolfe, D. E.

2007-01-01

Nondestructive diagnostic tools are needed to monitor early stages of delamination progression in thermal barrier coatings (TBCs) because the risk of delamination induced coating failure will compromise engine performance and safety. Previous work has demonstrated that for TBCs composed of yttria-stabilized zirconia (YSZ), luminescence from a buried europium-doped sublayer can be utilized to identify the location of TBC delamination from the substantially higher luminescence intensity observed from the delaminated regions of the TBC. Luminescence measurements from buried europium-doped layers depend on sufficient transmittance of the 532 nm excitation and 606 nm emission wavelengths through the attenuating undoped YSZ overlayer to produce easily detected luminescence. In the present work, improved delamination indication is demonstrated using erbium-doped YSZ sublayers. For visible-wavelength luminescence, the erbium-doped sublayer offers the advantage of a very strong excitation peak at 517 nm that can be conveniently excited a 514 nm Ar ion laser. More importantly, the erbium-doped sublayer also produces near-infrared luminescence at 1550 nm that is effectively excited by a 980 nm laser diode. Both the 980 nm excitation and the 1550 nm emission are transmitted through the TBC with much less attenuation than visible wavelengths and therefore show great promise for delamination monitoring through thicker or more highly scattering TBCs. The application of this approach for both electron beam physical vapor deposited (EB-PVD) and plasma-sprayed TBCs is discussed.

Thermal cycling and electrochemical characteristics of solid oxide fuel cell supported on stainless steel with a new 3-phase composite anode

NASA Astrophysics Data System (ADS)

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

2017-06-01

We report design, fabrication method, and fast thermal-cycling ability of solid oxide fuel cells (SOFCs) that use stainless steel (STS) as a support, and a new 3-phase anode. La and Ni co-doped SrTiO3 (La0.2Sr0.8Ti0.9Ni0.1O3-d, LSTN), replaces some of the Ni in conventional Ni-yttria stabilized zirconia (YSZ) anode; the resultant LSTN-YSZ-Ni 3-phase-composite anode is tested as a new reduction (or decomposition)-resistant anode of STS-supported SOFCs that can be co-fired with STS. A multi-layered cell with YSZ electrolyte (thickness ∼5 μm), composite anode, STS-cermet contact-layer, and STS support is designed, then fabricated by tape casting, lamination, and co-firing at 1250 °C in reducing atmosphere. The maximum power density (MPD) is 325 mW cm-2 at 650 °C; this is one of the highest among STS-supported cells fabricated by co-firing. The cell also shows stable open-circuit voltage and Ohmic resistance during 100 rapid thermal cycles between 170 and 600 °C. STS support minimizes stress and avoids cracking of electrolyte during rapid thermal cycling. The excellent MPD and stability during thermal cycles, and promising characteristics of SOFC as a power source for vehicle or mobile devices that requires rapid thermal cycles, are attributed to the new design of the cell with new anode structure.

Antibacterial studies of ZnO nanoparticle coatings on nanocrystalline YSZ irradiated with femtosecond laser light

NASA Astrophysics Data System (ADS)

Alvarez, Crysthal; Garcia, Valeria; Cuando, Natanael; Aguilar, Guillermo

2018-02-01

Recently, efforts have been made to create a transparent ceramic cranial implant comprised of nanocrystalline yttriastabilized zirconia (nc-YSZ) that will provide optical access to the brain. This has been referred to as Window to the Brain (WttB) in the literature. WttB will allow the use of laser and photonic treatments and diagnostics in areas with difficult optical access in the brain. Nevertheless, infection is still one of the frequent cranial implant complications. In most cases a second surgery is required to replace the infected implant. To address potential infections in the WttB platform, we have studied the antibacterial effect of a Zinc Oxide (ZnO) nanoparticles coating on nc-YSZ. After coating with ZnO nanoparticles, the implant was irradiated with infrared femtosecond laser light. We synthesized ZnO nanoparticles through the Laser Ablation of Solids in Liquids (LASL) method, using a Zinc solid target in a liquid medium (water/acetone). Antibacterial coatings were obtained by air brush, using a precursor solution of ZnO nanoparticles in distilled water. Escherichia coli (E. coli) have been used as representative, clinical relevant bacteria to probe the antibacterial effect of the coating. Our previous studies suggested that the use of ZnO nanoparticles inhibit bacterial growth. Laser irradiation treatment alone also offers inhibition of bacterial growth, up to 70%. The incorporation of nanoparticles offers an additional 20% inhibition. Thus, this work represents the next step towards the development of a clinically-oriented transparent cranial implant.

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

Evaluation of thermal barrier coating systems on novel substrates

NASA Astrophysics Data System (ADS)

Pint, B. A.; Wright, I. G.; Brindley, W. J.

2000-06-01

Testing was conducted on both plasma-sprayed (PS) and electron beam-physical vapor deposited (EB-PVD) Y2O3-stabilized ZrO2 (YSZ) thermal barrier coatings (TBCs) applied directly to oxidation-resistant substrates such as β-NiAl, oxide-dispersed FeCrAl, and NiCr. On an alloy that forms a very adherent alumina scale, β-NiAl+Zr, the coating lifetime of YSZ in furnace cyclic tests was 6 or more times longer than on state-of-the-art, YSZ coatings on single-crystal Ni-base superalloys with MCrAlY or Pt aluminide bond coats. Coatings on FeCrAl alloys appear to be a viable option for applications such as the external skin of the X-33, single stage to orbit, reusable launch vehicle. Model chromia-forming bond coat compositions also show promise for power generation applications at temperatures where hot corrosion may be a major problem. In general, while this work examined unique materials systems, many of the same fundamental failure mechanisms observed in conventional TBCs were observed.

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.

Stabilization of metallic catalyst microstructures against high-temperature thermal coarsening

NASA Astrophysics Data System (ADS)

Driscoll, David Robert

The size and shape of metal particulate at high temperature is dictated by surface energy. In systems containing very small metal particles, smaller particles shrink and disappear as they grow into larger particles in a process referred to as coarsening. Coarsening causes irreversible degradation in a number of important systems including automotive catalytic converters and solid oxide fuel cells (SOFC) through a loss of catalyst (metal) surface area. This phenomenon is exemplified by nickel metal catalyst that is supported on ytrria-stabilized zirconia (YSZ) which represents a materials system critical to the function of SOFCs. It has been demonstrated that additions of aluminum titanate (ALT) to the Ni-YSZ system with subsequent thermal treatment can act to stabilize the geometry of Ni on YSZ. In demonstration SOFCs, ALT has increased the time required for the first 10% of degradation by a factor of 115. This work has sought to elucidate the mechanisms by which ALT imparts increased stability. The work contained here demonstrates that ALT easily decomposes to Al 2O3 and TiO2. During thermal treatment, the alumina reacts with NiO to form nickel aluminate and the titania interacts with the YSZ where it can form Zr5Ti7O24--a mixed ion electron conducting phase. In this way, the Al and Ti components of ALT have been determined to act independently where alumina appears to be dominant in microstructural stabilization. During cell operation, the nickel aluminate decomposes to nickel metal decorated with alumina nano-particulate. This geometry forms the basis of "diffusion caging" as a stabilization mechanism which is the subject of Chapter 8. The role of titania appears to be less important except when processing occurs in a way that facilitates formation of the MIEC phase. However, Ni-YSZ cermets have also shown a strength enhancement when doped with ALT. This strength enhancement is likely due to the influence of titania (Chapter 7). Future work has the potential to extend concepts discussed here to a number of high temperature catalytic systems.

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.

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 fitted to the experimental data, and subsequently used to predict the change in anode three-phase boundary density and average particle size for extended times under normal SOFC conditions. Characterization of other anodes (pulsed-laser deposited and micro-tubular geometries) produced by international collaborators is also presented. Finally, a testing setup and protocol for anode life testing with current density and overpotential has been developed and implemented. Early test results are presented.

Raman spectroscopy analysis of air grown oxide scale developed on pure zirconium substrate

NASA Astrophysics Data System (ADS)

Kurpaska, L.; Favergeon, J.; Lahoche, L.; El-Marssi, M.; Grosseau Poussard, J.-L.; Moulin, G.; Roelandt, J.-M.

2015-11-01

Using Raman spectroscopy technique, external and internal parts of zirconia oxide films developed at 500 °C and 600 °C on pure zirconium substrate under air at normal atmospheric pressure have been examined. Comparison of Raman peak positions of tetragonal and monoclinic zirconia phases, recorded during the oxide growth at elevated temperature, and after cooling at room temperature have been presented. Subsequently, Raman peak positions (or shifts) were interpreted in relation with the stress evolution in the growing zirconia scale, especially closed to the metal/oxide interface, where the influence of compressive stress in the oxide is the biggest. Reported results, for the first time show the presence of a continuous layer of tetragonal zirconia phase developed in the proximity of pure zirconium substrate. Based on the Raman peak positions we prove that this tetragonal layer is stabilized by the high compressive stress and sub-stoichiometry level. Presence of the tetragonal phase located in the outer part of the scale have been confirmed, yet its Raman characteristics suggest a stress-free tetragonal phase, therefore different type of stabilization mechanism. Presented study suggest that its stabilization could be related to the lattice defects introduced by highstoichiometry of zirconia or presence of heterovalent cations.

Hydrodynamic and Chemical Modeling of a Chemical Vapor Deposition Reactor for Zirconia Deposition

NASA Astrophysics Data System (ADS)

Belmonte, T.; Gavillet, J.; Czerwiec, T.; Ablitzer, D.; Michel, H.

1997-09-01

Zirconia is deposited on cylindrical substrates by flowing post-discharge enhanced chemical vapor deposition. In this paper, a two dimensional hydrodynamic and chemical modeling of the reactor is described for given plasma characteristics. It helps in determining rate constants of the synthesis reaction of zirconia in gas phase and on the substrate which is ZrCl4 hydrolysis. Calculated deposition rate profiles are obtained by modeling under various conditions and fits with a satisfying accuracy the experimental results. The role of transport processes and the mixing conditions of excited gases with remaining ones are studied. Gas phase reaction influence on the growth rate is also discussed.

Epitaxial growth of metallic buffer layer structure and c-axis oriented Pb(Mn1/3,Nb2/3)O3-Pb(Zr,Ti)O3 thin film on Si for high performance piezoelectric micromachined ultrasonic transducer

NASA Astrophysics Data System (ADS)

Thao, Pham Ngoc; Yoshida, Shinya; Tanaka, Shuji

2017-12-01

This paper reports on the development of a metallic buffer layer structure, (100) SrRuO3 (SRO)/(100) Pt/(100) Ir/(100) yttria-stabilized zirconia (YSZ) layers for the epitaxial growth of a c-axis oriented Pb(Mn1/3,Nb2/3)O3-Pb(Zr,Ti)O3 (PMnN-PZT) thin film on a (100) Si wafer for piezoelectric micro-electro mechanical systems (MEMS) application. The stacking layers were epitaxially grown on a Si substrate under the optimal deposition condition. A crack-free PMnN-PZT epitaxial thin films was obtained at a thickness up to at least 1.7 µm, which is enough for MEMS applications. The unimorph MEMS cantilevers based on the PMnN-PZT thin film were fabricated and characterized. As a result, the PMnN-PZT thin film exhibited -10 to -12 C/m2 as a piezoelectric coefficient e 31,f and ˜250 as a dielectric constants ɛr. The resultant FOM for piezoelectric micromachined ultrasonic transducer (pMUT) is higher than those of general PZT and AlN thin films. This structure has a potential to provide high-performance pMUTs.

Templated electrochemical deposition of zirconia thin films on "recordable CDs.".

PubMed

Yu, Hua-Zhong; Rowe, Aaron W; Waugh, Damien M

2002-11-15

In this paper, we describe a practical method of using gold films constructed from recordable compact disks (CD-Rs) as simple, inexpensive, and micropatterned conductive substrates for the fabrication of inorganic material microstructures. Extending from their application for the fabrication of self-assembled monolayers (SAMs) reported recently, bare and SAM-modified CD-R gold substrates have been used for template-directed electrodeposition of zirconia (ZrO2) thin films (i.e., the controlled formation of zirconia thin films on the different areas of the prefabricated, micrometer mountain-valley CD-R gold substrate surfaces). The present results demonstrate that the variation of the functional groups of the selected SAMs combined with electrodynamic control can be very successful to "customize" the formation and microstructure of functional inorganic thin films, which hold promise for modern technological applications.

Thermal barrier coatings with (Al2O3-Y2O3)/(Pt or Pt-Au) composite bond coat and 8YSZ top coat on Ni-based superalloy

NASA Astrophysics Data System (ADS)

Yao, Junqi; He, Yedong; Wang, Deren; Peng, Hui; Guo, Hongbo; Gong, Shengkai

2013-12-01

Developing new bond coat has been acknowledged as an effective way to extend the service life of thermal barrier coating (TBC) during high temperature. In this study, novel thermal barrier coating system, which is composed with an (Al2O3-Y2O3)/(Pt or Pt-Au) composite bond coat and a YSZ top coat on Ni-based superalloy, has been prepared by magnetron sputtering and EB-PVD, respectively. It is demonstrated, from the cyclic oxidation tests in air at 1100 °C for 200 h, that the YSZ top coat and alloy substrate can be bonded together effectively by the (Al2O3-Y2O3)/(Pt or Pt-Au) composite coating, showing excellent resistance to oxidation, cracking and buckling. These beneficial results can be attributed to the sealing effect of such composite coating, by which the alloy substrate can be protected from oxidation and the interdiffusion between the bond coat and alloy substrate can be avoided; and the toughening effect of noble metals and composite structure of bond coat, by which the micro-cracks propagation can be inhibited and the stress in bond coat can be relaxed. This ceramic/noble metal composite coating can be a considerable structure which would has great application prospect in the TBC.

Solar Thermochemical Energy Storage Through Carbonation Cycles of SrCO3/SrO Supported on SrZrO3.

PubMed

Rhodes, Nathan R; Barde, Amey; Randhir, Kelvin; Li, Like; Hahn, David W; Mei, Renwei; Klausner, James F; AuYeung, Nick

2015-11-01

Solar thermochemical energy storage has enormous potential for enabling cost-effective concentrated solar power (CSP). A thermochemical storage system based on a SrO/SrCO3 carbonation cycle offers the ability to store and release high temperature (≈1200 °C) heat. The energy density of SrCO3/SrO systems supported by zirconia-based sintering inhibitors was investigated for 15 cycles of exothermic carbonation at 1150 °C followed by decomposition at 1235 °C. A sample with 40 wt % of SrO supported by yttria-stabilized zirconia (YSZ) shows good energy storage stability at 1450 MJ m(-3) over fifteen cycles at the same cycling temperatures. After further testing over 45 cycles, a decrease in energy storage capacity to 1260 MJ m(-3) is observed during the final cycle. The decrease is due to slowing carbonation kinetics, and the original value of energy density may be obtained by lengthening the carbonation steps. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Irradiation-induced grain growth and defect evolution in nanocrystalline zirconia with doped grain boundaries

DOE PAGES

Dey, Sanchita; Mardinly, John; Wang, Yongqiang; ...

2016-05-27

Grain boundaries are effective sinks for radiation-induced defects, ultimately impacting the radiation tolerance of nanocrystalline materials (dense materials with nanosized grains) against net defect accumulation. However, irradiation-induced grain growth leads to grain boundary area decrease, shortening potential benefits of nanostructures. A possible approach to mitigate this is the introduction of dopants to target a decrease in grain boundary mobility or a reduction in grain boundary energy to eliminate driving forces for grain growth (using similar strategies as to control thermal growth). Here, in this study, we tested this concept in nanocrystalline zirconia doped with lanthanum. Although the dopant is observedmore » to segregate to the grain boundaries, causing grain boundary energy decrease and promoting dragging forces for thermally activated boundary movement, irradiation induced grain growth could not be avoided under heavy ion irradiation, suggesting a different growth mechanism as compared to thermal growth. Furthermore, it is apparent that reducing the grain boundary energy reduced the effectiveness of the grain boundary as sinks, and the number of defects in the doped material is higher than in undoped (La-free) YSZ.« less

Voltage and partial pressure dependent defect chemistry in (La,Sr)FeO3–δ thin films investigated by chemical capacitance measurements

PubMed Central

Rupp, Ghislain M.; Fleig, Jürgen

2018-01-01

La0.6Sr0.4FeO3–δ (LSF) thin films of different thickness were prepared by pulsed laser deposition on yttria stabilized zirconia (YSZ) and characterized by using three electrode impedance spectroscopy. Electrochemical film capacitance was analyzed in relation to oxygen partial pressure (0.25 mbar to 1 bar), DC polarization (0 m to –600 m) and temperature (500 to 650 °C). For most measurement parameters, the chemical bulk capacitance dominates the overall capacitive properties and the corresponding defect chemical state depends solely on the oxygen chemical potential inside the film, independent of atmospheric oxygen pressure and DC polarization. Thus, defect chemical properties (defect concentrations and defect formation enthalpies) could be deduced from such measurements. Comparison with LSF defect chemical bulk data from the literature showed good agreement for vacancy formation energies but suggested larger electronic defect concentrations in the films. From thickness-dependent measurements at lower oxygen chemical potentials, an additional capacitive contribution could be identified and attributed to the LSF|YSZ interface. Deviations from simple chemical capacitance models at high pressures are most probably due to defect interactions. PMID:29671421

Voltage and partial pressure dependent defect chemistry in (La,Sr)FeO3-δ thin films investigated by chemical capacitance measurements.

PubMed

Schmid, Alexander; Rupp, Ghislain M; Fleig, Jürgen

2018-05-03

La0.6Sr0.4FeO3-δ (LSF) thin films of different thickness were prepared by pulsed laser deposition on yttria stabilized zirconia (YSZ) and characterized by using three electrode impedance spectroscopy. Electrochemical film capacitance was analyzed in relation to oxygen partial pressure (0.25 mbar to 1 bar), DC polarization (0 m to -600 m) and temperature (500 to 650 °C). For most measurement parameters, the chemical bulk capacitance dominates the overall capacitive properties and the corresponding defect chemical state depends solely on the oxygen chemical potential inside the film, independent of atmospheric oxygen pressure and DC polarization. Thus, defect chemical properties (defect concentrations and defect formation enthalpies) could be deduced from such measurements. Comparison with LSF defect chemical bulk data from the literature showed good agreement for vacancy formation energies but suggested larger electronic defect concentrations in the films. From thickness-dependent measurements at lower oxygen chemical potentials, an additional capacitive contribution could be identified and attributed to the LSF|YSZ interface. Deviations from simple chemical capacitance models at high pressures are most probably due to defect interactions.

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.

Ultrasonic Detection of Delamination and Material Characterization of Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Chen, Hung-Liang Roger; Zhang, Binwei; Alvin, Mary Anne; Lin, Yun

2012-12-01

This article describes ultrasonic nondestructive evaluation (NDE) to detect the changes of material properties and provide early warning of delamination in thermal barrier coating (TBC) systems. NDE tests were performed on single-crystal René N5 superalloy coupons that were coated with a commercially available MCrAlY bond coat and an air plasma sprayed 7% yttria-stabilized zirconia (YSZ) top coat deposited by Air Plasma Spray method, as well as Haynes 230 superalloy coupons coated with MCrA1Y bond coat, and an electron beam physical vapor deposit of 7% YSZ top coat. The TBC coupons were subjected to either cyclic or isothermal exposure for various lengths of time at temperatures ranging from 900 to 1100 °C. The ultrasonic measurements performed on the coupons had provided an early warning of delamination along the top coat/TGO interface before exposure time, when delamination occurred. The material's property (Young's modulus) of the top coat was estimated using the measured wave speeds. Finite element analysis (FEA) of the ultrasonic wave propagation was conducted on a simplified TBC system to verify experimental observations. The technique developed was also demonstrated on an as-manufactured turbine blade to estimate normalized top coat thickness measurements.

High-temperature Raman spectroscopy of solid oxide fuel cell materials and processes.

PubMed

Pomfret, Michael B; Owrutsky, Jeffrey C; Walker, Robert A

2006-09-07

Chemical and material processes occurring in high temperature environments are difficult to quantify due to a lack of experimental methods that can probe directly the species present. In this letter, Raman spectroscopy is shown to be capable of identifying in-situ and noninvasively changes in material properties as well as the formation and disappearance of molecular species on surfaces at temperatures of 715 degrees C. The material, yttria-stabilized zirconia or YSZ, and the molecular species, Ni/NiO and nanocrystalline graphite, factor prominently in the chemistry of solid oxide fuel cells (SOFCs). Experiments demonstrate the ability of Raman spectroscopy to follow reversible oxidation/reduction kinetics of Ni/NiO as well as the rate of carbon disappearance when graphite, formed in-situ, is exposed to a weakly oxidizing atmosphere. In addition, the Raman active phonon mode of YSZ shows a temperature dependent shift that correlates closely with the expansion of the lattice parameter, thus providing a convenient internal diagnostic for identifying thermal gradients in high temperature systems. These findings provide direct insight into processes likely to occur in operational SOFCs and motivate the use of in-situ Raman spectroscopy to follow chemical processes in these high-temperature, electrochemically active environments.

High Temperature Electrolysis using Electrode-Supported Cells

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

J. E. O'Brien; C. M. Stoots

2010-07-01

An experimental study is under way to assess the performance of electrode-supported solid-oxide cells operating in the steam electrolysis mode for hydrogen production. The cells currently under study were developed primarily for the fuel cell mode of operation. Results presented in this paper were obtained from single cells, with an active area of 16 cm2 per cell. The electrolysis cells are electrode-supported, with yttria-stabilized zirconia (YSZ) electrolytes (~10 µm thick), nickel-YSZ steam/hydrogen electrodes (~1400 µm thick), and manganite (LSM) air-side electrodes (~90 µm thick). The purpose of the present study was to document and compare the performance and degradation ratesmore » of these cells in the fuel cell mode and in the electrolysis mode under various operating conditions. Initial performance was documented through a series of DC potential sweeps and AC impedance spectroscopy measurements. Degradation was determined through long-duration testing, first in the fuel cell mode, then in the electrolysis mode over more than 500 hours of operation. Results indicate accelerated degradation rates in the electrolysis mode compared to the fuel cell mode, possibly due to electrode delamination. The paper also includes details of the single-cell test apparatus developed specifically for these experiments.« less

Performance Assessment of Single Electrode-Supported Solid Oxide Cells Operating in the Steam Electrolysis Mode

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

X. Zhang; J. E. O'Brien; R. C. O'Brien

2011-11-01

An experimental study is under way to assess the performance of electrode-supported solid-oxide cells operating in the steam electrolysis mode for hydrogen production. Results presented in this paper were obtained from single cells, with an active area of 16 cm{sup 2} per cell. The electrolysis cells are electrode-supported, with yttria-stabilized zirconia (YSZ) electrolytes ({approx}10 {mu}m thick), nickel-YSZ steam/hydrogen electrodes ({approx}1400 {mu}m thick), and modified LSM or LSCF air-side electrodes ({approx}90 {mu}m thick). The purpose of the present study is to document and compare the performance and degradation rates of these cells in the fuel cell mode and in the electrolysismore » mode under various operating conditions. Initial performance was documented through a series of voltage-current (VI) sweeps and AC impedance spectroscopy measurements. Degradation was determined through long-term testing, first in the fuel cell mode, then in the electrolysis mode. Results generally indicate accelerated degradation rates in the electrolysis mode compared to the fuel cell mode, possibly due to electrode delamination. The paper also includes details of an improved single-cell test apparatus developed specifically for these experiments.« less

Separation of Hydrogen from Carbon Dioxide through Porous Ceramics

PubMed Central

Shimonosono, Taro; Imada, Hikari; Maeda, Hikaru; Hirata, Yoshihiro

2016-01-01

The gas permeability of α-alumina, yttria-stabilized zirconia (YSZ), and silicon carbide porous ceramics toward H2, CO2, and H2–CO2 mixtures were investigated at room temperature. The permeation of H2 and CO2 single gases occurred above a critical pressure gradient, which was smaller for H2 gas than for CO2 gas. When the Knudsen number (λ/r ratio, λ: molecular mean free path, r: pore radius) of a single gas was larger than unity, Knudsen flow became the dominant gas transportation process. The H2 fraction for the mixed gas of (20%–80%) H2–(80%–20%) CO2 through porous Al2O3, YSZ, and SiC approached unity with decreasing pressure gradient. The high fraction of H2 gas was closely related to the difference in the critical pressure gradient values of H2 and CO2 single gas, the inlet mixed gas composition, and the gas flow mechanism of the mixed gas. Moisture in the atmosphere adsorbed easily on the porous ceramics and affected the critical pressure gradient, leading to the increased selectivity of H2 gas. PMID:28774051

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

NASA Astrophysics Data System (ADS)

Zhang, Long-shan; Gao, Jian-feng; Tian, Rui-fen; Xia, Chang-rong

2009-08-01

A porous NiO/yttria-stabilized zirconia anode substrate for tubular solid oxide fuel cells was prepared by gel casting technique. Nano-scale samaria-doped ceria (SDC) particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm(NO3)3 and Ce(NO3)3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm2 when it was fed with H2 fuel at 700 °C, but the power density increased to 400 mW/cm2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 °C. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

Iron on mixed zirconia-titania substrate Fischer-Tropsch catalyst and method of making same

DOEpatents

Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

Development of zirconia based phosphors for application in lighting and as luminescent bioprobes =

NASA Astrophysics Data System (ADS)

Soares, Maria Rosa Nunes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure sensors are explored taking into account their studied characteristics.

Highly Segmented Thermal Barrier Coatings Deposited by Suspension Plasma Spray: Effects of Spray Process on Microstructure

NASA Astrophysics Data System (ADS)

Chen, Xiaolong; Honda, Hiroshi; Kuroda, Seiji; Araki, Hiroshi; Murakami, Hideyuki; Watanabe, Makoto; Sakka, Yoshio

2016-12-01

Effects of the ceramic powder size used for suspension as well as several processing parameters in suspension plasma spraying of YSZ were investigated experimentally, aiming to fabricate highly segmented microstructures for thermal barrier coating (TBC) applications. Particle image velocimetry (PIV) was used to observe the atomization process and the velocity distribution of atomized droplets and ceramic particles travelling toward the substrates. The tested parameters included the secondary plasma gas (He versus H2), suspension injection flow rate, and substrate surface roughness. Results indicated that a plasma jet with a relatively higher content of He or H2 as the secondary plasma gas was critical to produce highly segmented YSZ TBCs with a crack density up to 12 cracks/mm. The optimized suspension flow rate played an important role to realize coatings with a reduced porosity level and improved adhesion. An increased powder size and higher operation power level were beneficial for the formation of highly segmented coatings onto substrates with a wider range of surface roughness.

Parallel Large-Scale Molecular Dynamics Simulation Opens New Perspective to Clarify the Effect of a Porous Structure on the Sintering Process of Ni/YSZ Multiparticles.

PubMed

Xu, Jingxiang; Higuchi, Yuji; Ozawa, Nobuki; Sato, Kazuhisa; Hashida, Toshiyuki; Kubo, Momoji

2017-09-20

Ni sintering in the Ni/YSZ porous anode of a solid oxide fuel cell changes the porous structure, leading to degradation. Preventing sintering and degradation during operation is a great challenge. Usually, a sintering molecular dynamics (MD) simulation model consisting of two particles on a substrate is used; however, the model cannot reflect the porous structure effect on sintering. In our previous study, a multi-nanoparticle sintering modeling method with tens of thousands of atoms revealed the effect of the particle framework and porosity on sintering. However, the method cannot reveal the effect of the particle size on sintering and the effect of sintering on the change in the porous structure. In the present study, we report a strategy to reveal them in the porous structure by using our multi-nanoparticle modeling method and a parallel large-scale multimillion-atom MD simulator. We used this method to investigate the effect of YSZ particle size and tortuosity on sintering and degradation in the Ni/YSZ anodes. Our parallel large-scale MD simulation showed that the sintering degree decreased as the YSZ particle size decreased. The gas fuel diffusion path, which reflects the overpotential, was blocked by pore coalescence during sintering. The degradation of gas diffusion performance increased as the YSZ particle size increased. Furthermore, the gas diffusion performance was quantified by a tortuosity parameter and an optimal YSZ particle size, which is equal to that of Ni, was found for good diffusion after sintering. These findings cannot be obtained by previous MD sintering studies with tens of thousands of atoms. The present parallel large-scale multimillion-atom MD simulation makes it possible to clarify the effects of the particle size and tortuosity on sintering and degradation.

High Tc YBCO superconductor deposited on biaxially textured Ni substrate

DOEpatents

Budai, John D.; Christen, David K.; Goyal, Amit; He, Qing; Kroeger, Donald M.; Lee, Dominic F.; List, III, Frederick A.; Norton, David P.; Paranthaman, Mariappan; Sales, Brian C.; Specht, Eliot D.

1999-01-01

A superconducting article includes a biaxially-textured Ni substrate, and epitaxial buffer layers of Pd (optional), CeO.sub.2 and YSZ, and a top layer of in-plane aligned, c-axis oriented YBCO having a critical current density (J.sub.c) in the range of at least 100,000 A/cm.sup.2 at 77 K.

Study of deposition of YBa2Cu3O7-x on cubic zirconia

NASA Technical Reports Server (NTRS)

Warner, Joseph D.; Meola, Joseph E.; Jenkins, Kimberly A.

1989-01-01

Films of YBa2Cu3O7-x were grown on (100) cubic zirconia with 8 percent yttria by laser ablation from sintered targets of YBa2Cu3O7-x. The temperature of the zirconia substrate during growth was varied between 700 and 780 C. The atmosphere during growth was 170 mtorr of O2. The films were subsequently slowly cooled in-situ in 1 atm of O2. The best films were c-axis aligned and had a transition temperature of 87.7 K. The superconducting transition temperature and the X-ray diffraction analysis is reported as a function of the substrate temperature and of the angle between the laser beam and the target's normal.

The color masking ability of a zirconia ceramic on the substrates with different values.

PubMed

Tabatabaian, Farhad; Javadi Sharif, Mahdiye; Massoumi, Farhood; Namdari, Mahshid

2017-01-01

Background. The color masking ability of a restoration plays a significant role in coveringa discolored substructure; however, this optical property of zirconia ceramics has not been clearly determined yet. The aim of this in vitro study was to evaluate the color masking ability of a zirconia ceramic on substrates with different values. Methods. Ten zirconia disk specimens,0.5 mm in thickness and 10 mm in diameter, were fabricated by a CAD/CAM system. Four substrates with different values were prepared, including: white (control), light grey, dark grey, and black. The disk specimens were placed over the substratesfor spectrophotometric measurements. A spectrophotometer measured the L * , a * , and b * color attributes of the specimens. Additionally, ΔE values were calculated to determine the color differences between each group and the control,and were then compared with the perceptional threshold of ΔE=2.6. Repeated-measures ANOVA, Bonferroni, and one-sample t-test were used to analyze data. All the tests were carried out at 0.05 level of significance. Results. The means and standard deviations of ΔE values for the three groups of light grey, dark grey and black were 9.94±2.11, 10.40±2.09, and 13.34±1.77 units, respectively.Significant differences were detected between the groups in the ΔE values (P<0.0001).The ΔE values in all the groups were more than the predetermined perceptional threshold(ΔE>2.6) (P<0.0001). Conclusion. Within the limitations of this study, it was concluded that the tested zirconia ceramic did not exhibit sufficient color masking ability to hide the grey and black substrates.

Polarization-Induced Interfacial Reactions between Nickel and Selenium in Ni/Zirconia SOFC Anodes and Comparison with Sulfur Poisoning

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

Marina, Olga A.; Pederson, Larry R.; Coyle, Christopher A.

2011-01-10

Three distinctly different characteristic responses of a nickel/yttria-stabilized zirconia (Ni/YSZ) cermet anode to the presence of hydrogen selenide in synthetic coal gas were observed, depending on temperature (650-800oC), H2Se concentration (0-40 ppm), and especially on the extent of anodic polarization (0 to ~0.5 V). The first level of response was characterized by a rapid but modest decrease in power density to a new steady state, with no further degradation observed in tests up to 700 hours in duration. Mostly observed at high temperatures, low H2Se concentrations, and low anodic polarizations, this response level was similar to effects caused by themore » presence of H2S, but with slower onset and lower reversibility. Higher anodic polarization at a constant current could trigger a second level of response characterized by oscillatory behavior involving cycles of rapid performance loss followed by rapid recovery. Oscillations at the constant current density were accompanied by the appearance and disappearance of a new feature in the electrochemical impedance spectrum with a summit frequency of ~100 Hz. Oscillatory behavior ceased when the current density was lowered. Such behavior was not observed for cells operated at a constant potential of similar magnitude, though. A third level of response, irreversible cell failure, could be induced by further increases in anodic polarization, additionally favored by low temperature and high H2Se concentration. Post-test analyses of failed cells by electron microscopy revealed the extensive microstructural changes including the appearance of nickel oxide and nickel selenide alteration phases, only at the anode/electrolyte interface. From bulk thermochemical considerations the formation of nickel selenides could not be expected. Local chemical conditions created at the anode/electrolyte interface appear to be of overriding importance with respect to the extent of Ni/YSZ anode interactions with H2Se in coal gas.« less

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

DTIC Science & Technology

1999-05-05

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

Metal oxide nanorod arrays on monolithic substrates

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

Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can includemore » a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.« less

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

PubMed

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

2016-05-25

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

Development of sputtering process to deposit stoichiometric zirconia coatings for the inside wall of regeneratively cooled rocket thrust chambers

NASA Technical Reports Server (NTRS)

Busch, R.

1978-01-01

Thermal barrier coatings of yttria stabilized zirconia and zirconia-ceria mixtures were deposited by RF reactive sputtering. Coatings were 1-2 mils thick, and were deposited on copper cylinders intended to simulate the inner wall of a regeneratively cooled thrust chamber. Coating stoichiometry and adherence were investigated as functions of deposition parameters. Modest deposition rates (approximately 0.15 mil/hr) and subambient sustrate temperatures (-80 C) resulted in nearly stoichiometric coatings which remained adherent through thermal cycles between -196 and 400 C. Coatings deposited at higher rates or substrates temperatures exhibited greater oxygen deficiences, while coatings deposited at lower temperatures were not adherent. Substrate bias resulted in structural changes in the coating and high krypton contents; no clear effect on stoichiometry was observed.

Cerium reduction at the interface between ceria and yttria-stabilised zirconia and implications for interfacial oxygen non-stoichiometry

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

Song, Kepeng; Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Wenhua Road 72, 110016 Shenyang; Schmid, Herbert

2014-03-01

Epitaxial CeO{sub 2} films with different thickness were grown on Y{sub 2}O{sub 3} stabilised Zirconia substrates. Reduction of cerium ions at the interface between CeO{sub 2} films and yttria stabilised zirconia substrates is demonstrated using aberration-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy. It is revealed that most of the Ce ions were reduced from Ce{sup 4+} to Ce{sup 3+} at the interface region with a decay of several nanometers. Several possibilities of charge compensations are discussed. Irrespective of the details, such local non-stoichiometries are crucial not only for understanding charge transport in such hetero-structures but also formore » understanding ceria catalytic properties.« less

Plasma Spray-Physical Vapor Deposition (PS-PVD) of Ceramics for Protective Coatings

NASA Technical Reports Server (NTRS)

Harder, Bryan J.; Zhu, Dongming

2011-01-01

In order to generate advanced multilayer thermal and environmental protection systems, a new deposition process is needed to bridge the gap between conventional plasma spray, which produces relatively thick coatings on the order of 125-250 microns, and conventional vapor phase processes such as electron beam physical vapor deposition (EB-PVD) which are limited by relatively slow deposition rates, high investment costs, and coating material vapor pressure requirements. The use of Plasma Spray - Physical Vapor Deposition (PS-PVD) processing fills this gap and allows thin (< 10 microns) single layers to be deposited and multilayer coatings of less than 100 microns to be generated with the flexibility to tailor microstructures by changing processing conditions. Coatings of yttria-stabilized zirconia (YSZ) were applied to NiCrAlY bond coated superalloy substrates using the PS-PVD coater at NASA Glenn Research Center. A design-of-experiments was used to examine the effects of process variables (Ar/He plasma gas ratio, the total plasma gas flow, and the torch current) on chamber pressure and torch power. Coating thickness, phase and microstructure were evaluated for each set of deposition conditions. Low chamber pressures and high power were shown to increase coating thickness and create columnar-like structures. Likewise, high chamber pressures and low power had lower growth rates, but resulted in flatter, more homogeneous layers

Structure and Oxidation Behavior of Nickel Nanoparticles Supported by YSZ(111)

PubMed Central

2017-01-01

Nickel nanoparticles supported by the yttria-stabilized zirconia (111) surface show several preferential epitaxial relationships, as revealed by in situ X-ray diffraction. The two main nanoparticle orientations are found to have their [111] direction parallel to the substrate surface normal and ∼41.3 degrees tilted from this direction. The former orientation is described by a cube-on-cube stacking at the oxide–metal interface and the latter by a so-called coherent tilt strain-relieving mechanism, which is hitherto unreported for nanoparticles in literature. A modified Wulff construction used for the 111-oriented particles results in a value of the adhesion energy ranging from 1.4 to 2.2 Jm2, whereby the lower end corresponds to more rounded particles and the upper to relatively flat geometries. Upon oxidation at 10–3 Pa of molecular oxygen and 673 K, a NiO shell forms epitaxially on the [111]-oriented particles. Only a monolayer of metallic nickel of the top (111) facets oxidizes, whereas the side facets seem to react more severely. An apparent size increase of the remaining metallic Ni core is discussed in relation to a size-dependent oxidation mechanism, whereby smaller nanoparticles react at a faster rate. We argue that such a preferential oxidation mechanism, which inactivates the smallest and most reactive metal nanoparticles, might play a role for the long-term degradation of solid oxide fuel cells. PMID:28217243

Atomic-Level Properties of Thermal Barrier Coatings: Characterization of Metal-Ceramic Interfaces

DTIC Science & Technology

2001-01-01

these cases metal - metal bonds were stronger than metal - substrate bonds, thus predicting a 3D (cluster) growth mode as opposed to layer-by-layer...coat layer must be deposited. The top coat serves as the insulator and the bond coat mediates contact between the top coat and metal alloy substrate ...in thermomechanical properties between a YSZ top coat and a metal -alloy substrate is enough to require the introduction of an intermediate layer. This

Fracture toughness of plasma-sprayed thermal barrier ceramics: Influence of processing, microstructure, and thermal aging

DOE PAGES

Dwivedi, Gopal; Viswanathan, Vaishak; Sampath, Sanjay; ...

2014-06-09

Fracture toughness has become one of the dominant design parameters that dictates the selection of materials and their microstructure to obtain durable thermal barrier coatings (TBCs). Much progress has been made in characterizing the fracture toughness of relevant TBC compositions in bulk form, and it has become apparent that this property is significantly affected by process-induced microstructural defects. In this investigation, a systematic study of the influence of coating microstructure on the fracture toughness of atmospheric plasma sprayed (APS) TBCs has been carried out. Yttria partially stabilized zirconia (YSZ) coatings were fabricated under different spray process conditions inducing different levelsmore » of porosity and interfacial defects. Fracture toughness was measured on free standing coatings in as-processed and thermally aged conditions using the double torsion technique. Results indicate significant variance in fracture toughness among coatings with different microstructures including changes induced by thermal aging. Comparative studies were also conducted on an alternative TBC composition, Gd 2Zr 2O 7 (GDZ), which as anticipated shows significantly lower fracture toughness compared to YSZ. Furthermore, the results from these studies not only point towards a need for process and microstructure optimization for enhanced TBC performance but also a framework for establishing performance metrics for promising new TBC compositions.« less

Air plasma spray processing and electrochemical characterization of SOFC composite cathodes

NASA Astrophysics Data System (ADS)

White, B. D.; Kesler, O.; Rose, Lars

Air plasma spraying has been used to produce porous composite cathodes containing (La 0.8Sr 0.2) 0.98MnO 3- y (LSM) and yttria-stabilized zirconia (YSZ) for use in solid oxide fuel cells (SOFCs). Preliminary investigations focused on determining the range of plasma conditions under which each of the individual materials could be successfully deposited. A range of conditions was thereby determined that was suitable for the deposition of a composite cathode from pre-mixed LSM and YSZ powders. A number of composite cathodes were produced using different combinations of parameter values within the identified range according to a Uniform Design experimental grid. Coatings were then characterized for composition and microstructure using EDX and SEM. As a result of these tests, combinations of input parameter values were identified that are best suited to the production of coatings with microstructures appropriate for use in SOFC composite cathodes. A selection of coatings representative of the types of observed microstructures were then subjected to electrochemical testing to evaluate the performance of these cathodes. From these tests, it was found that, in general, the coatings that appeared to have the most suitable microstructures also had the highest electrochemical performances, provided that the deposition efficiency of both phases was sufficiently high.

Process-Property Relationship for Air Plasma-Sprayed Gadolinium Zirconate Coatings

NASA Astrophysics Data System (ADS)

Dwivedi, Gopal; Tan, Yang; Viswanathan, Vaishak; Sampath, Sanjay

2015-02-01

The continuous need of elevating operating temperature of gas turbine engines has introduced several challenges with the current state-of-the-art yttria-stabilized zirconia (YSZ)-based thermal barrier coatings (TBCs), requiring examination of new TBC material with high temperature phase stability, lower thermal conductivity, and resistance to environmental ash particles. Gadolinium zirconate (Gd2Zr2O7) (GDZ) has been shown to meet many of these requirements, and has, in fact, been successfully implemented in to engine components. However, several fundamental issues related to the process-ability, toughness, and microstructural differences for GDZ when compared to equivalent YSZ coating. This study seeks to critically address the process-structure-property correlations for plasma-sprayed GDZ coating subjected to controlled parametric exploration. Use of in-flight diagnostics coupled with in situ and ex situ coating property monitoring allows examination and comparison of the process-property interplay and the resultant differences between the two TBC compositions. The results indicate that it is feasible to retain material chemistry and fabricate relevant microstructures of interest with GDZ with concomitant performance advantages such as low conductivity, mechanical compliance, sintering resistance, and suppression of environmentally induced damage from ash particles. This study provides a framework for optimal design and manufacturing of emergent multi-layer and multi-material TBCs.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Atomic Resolution Imaging of Nanoscale Chemical Expansion in PrxCe1-xO2-δ during In Situ Heating.

PubMed

Swallow, Jessica G; Lee, Ja Kyung; Defferriere, Thomas; Hughes, Gareth M; Raja, Shilpa N; Tuller, Harry L; Warner, Jamie H; Van Vliet, Krystyn J

2018-02-27

Thin film nonstoichiometric oxides enable many high-temperature applications including solid oxide fuel cells, actuators, and catalysis. Large concentrations of point defects (particularly, oxygen vacancies) enable fast ionic conductivity or gas exchange kinetics in these materials but also manifest as coupling between lattice volume and chemical composition. This chemical expansion may be either detrimental or useful, especially in thin film devices that may exhibit enhanced performance through strain engineering or decreased operating temperatures. However, thin film nonstoichiometric oxides can differ from bulk counterparts in terms of operando defect concentrations, transport properties, and mechanical properties. Here, we present an in situ investigation of atomic-scale chemical expansion in Pr x Ce 1-x O 2-δ (PCO), a mixed ionic-electronic conducting oxide relevant to electrochemical energy conversion and high-temperature actuation. Through a combination of electron energy loss spectroscopy and transmission electron microscopy with in situ heating, we characterized chemical strains and changes in oxidation state in cross sections of PCO films grown on yttria-stabilized zirconia (YSZ) at temperatures reaching 650 °C. We quantified, both statically and dynamically, the nanoscale chemical expansion induced by changes in PCO redox state as a function of position and direction relative to the film-substrate interface. Additionally, we observed dislocations at the film-substrate interface, as well as reduced cation localization to threading defects within PCO films. These results illustrate several key aspects of atomic-scale structure and mechanical deformation in nonstoichiometric oxide films that clarify distinctions between films and bulk counterparts and that hold several implications for operando chemical expansion or "breathing" of such oxide films.

Modulation of human dermal microvascular endothelial cell and human gingival fibroblast behavior by micropatterned silica coating surfaces for zirconia dental implant applications

PubMed Central

Laranjeira, Marta S; Carvalho, Ângela; Pelaez-Vargas, Alejandro; Hansford, Derek; Ferraz, Maria Pia; Coimbra, Susana; Costa, Elísio; Santos-Silva, Alice; Fernandes, Maria Helena; Monteiro, Fernando Jorge

2014-01-01

Dental ceramic implants have shown superior esthetic behavior and the absence of induced allergic disorders when compared to titanium implants. Zirconia may become a potential candidate to be used as an alternative to titanium dental implants if surface modifications are introduced. In this work, bioactive micropatterned silica coatings were produced on zirconia substrates, using a combined methodology of sol–gel processing and soft lithography. The aim of the work was to compare the in vitro behavior of human gingival fibroblasts (HGFs) and human dermal microvascular endothelial cells (HDMECs) on three types of silica-coated zirconia surfaces: flat and micropatterned (with pillars and with parallel grooves). Our results showed that cells had a higher metabolic activity (HGF, HDMEC) and increased gene expression levels of fibroblast-specific protein-1 (FSP-1) and collagen type I (COL I) on surfaces with pillars. Nevertheless, parallel grooved surfaces were able to guide cell growth. Even capillary tube-like networks of HDMEC were oriented according to the surface geometry. Zirconia and silica with different topographies have shown to be blood compatible and silica coating reduced bacteria adhesion. All together, the results indicated that microstructured bioactive coating seems to be an efficient strategy to improve soft tissue integration on zirconia implants, protecting implants from peri-implant inflammation and improving long-term implant stabilization. This new approach of micropatterned silica coating on zirconia substrates can generate promising novel dental implants, with surfaces that provide physical cues to guide cells and enhance their behavior. PMID:27877662

Modulation of human dermal microvascular endothelial cell and human gingival fibroblast behavior by micropatterned silica coating surfaces for zirconia dental implant applications

NASA Astrophysics Data System (ADS)

Laranjeira, Marta S.; Carvalho, Ângela; Pelaez-Vargas, Alejandro; Hansford, Derek; Ferraz, Maria Pia; Coimbra, Susana; Costa, Elísio; Santos-Silva, Alice; Fernandes, Maria Helena; Monteiro, Fernando Jorge

2014-04-01

Dental ceramic implants have shown superior esthetic behavior and the absence of induced allergic disorders when compared to titanium implants. Zirconia may become a potential candidate to be used as an alternative to titanium dental implants if surface modifications are introduced. In this work, bioactive micropatterned silica coatings were produced on zirconia substrates, using a combined methodology of sol-gel processing and soft lithography. The aim of the work was to compare the in vitro behavior of human gingival fibroblasts (HGFs) and human dermal microvascular endothelial cells (HDMECs) on three types of silica-coated zirconia surfaces: flat and micropatterned (with pillars and with parallel grooves). Our results showed that cells had a higher metabolic activity (HGF, HDMEC) and increased gene expression levels of fibroblast-specific protein-1 (FSP-1) and collagen type I (COL I) on surfaces with pillars. Nevertheless, parallel grooved surfaces were able to guide cell growth. Even capillary tube-like networks of HDMEC were oriented according to the surface geometry. Zirconia and silica with different topographies have shown to be blood compatible and silica coating reduced bacteria adhesion. All together, the results indicated that microstructured bioactive coating seems to be an efficient strategy to improve soft tissue integration on zirconia implants, protecting implants from peri-implant inflammation and improving long-term implant stabilization. This new approach of micropatterned silica coating on zirconia substrates can generate promising novel dental implants, with surfaces that provide physical cues to guide cells and enhance their behavior.

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).

Effect of Three Different Core Materials on Masking Ability of a Zirconia Ceramic.

PubMed

Tabatabaian, Farhad; Masoomi, Faeze; Namdari, Mahshid; Mahshid, Minoo

2016-09-01

Masking ability of a restorative material plays a role in hiding colored substructures; however, the masking ability of zirconia ceramic (ZRC) has not yet been clearly understood in zirconia-based restorations. This study evaluated the effect of three different core materials on masking ability of a ZRC. Ten zirconia disc samples, 0.5mm in thickness and 10mm in diameter, were fabricated. A white (W) substrate (control) and three substrates of nickel-chromium alloy (NCA), non-precious gold alloy (NPGA), and ZRC were prepared. The zirconia discs were placed on the four types of substrates for spectrophotometry. The L*, a*, and b* values of the specimens were measured by a spectrophotometer and color change (ΔE) values were calculated to determine color differences between the test and control groups and were then compared with the perceptual threshold. Randomized block ANOVA and Bonferroni test analyzed the data. A significance level of 0.05 was considered. The mean and standard deviation values of ΔE for NCA, NPGA, and ZRC groups were 10.26±2.43, 9.45±1.74, and 6.70±1.91 units, respectively. Significant differences were found in the ΔE values between ZRC and the other two experimental groups (NCA and NPGA; P<0.0001 and P=0.001, respectively). The ΔE values for the groups were more than the predetermined perceptual threshold. Within the limitations of this study, it was concluded that the tested ZRC could not well mask the examined core materials.

Ceramic electrolyte coating and methods

DOEpatents

Seabaugh, Matthew M [Columbus, OH; Swartz, Scott L [Columbus, OH; Dawson, William J [Dublin, OH; McCormick, Buddy E [Dublin, OH

2007-08-28

Aqueous coating slurries useful in depositing a dense coating of a ceramic electrolyte material (e.g., yttrium-stabilized zirconia) onto a porous substrate of a ceramic electrode material (e.g., lanthanum strontium manganite or nickel/zirconia) and processes for preparing an aqueous suspension of a ceramic electrolyte material and an aqueous spray coating slurry including a ceramic electrolyte material. The invention also includes processes for depositing an aqueous spray coating slurry including a ceramic electrolyte material onto pre-sintered, partially sintered, and unsintered ceramic substrates and products made by this process.

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.

Adhesion/cementation to zirconia and other non-silicate ceramics: Where are we now?

PubMed Central

Thompson, Jeffrey Y; Stoner, Brian R.; Piascik, Jeffrey R.; Smith, Robert

2010-01-01

Non-silicate ceramics, especially zirconia, have become a topic of great interest in the field of prosthetic and implant dentistry. A clinical problem with use of zirconia-based components is the difficulty in achieving suitable adhesion with intended synthetic substrates or natural tissues. Traditional adhesive techniques used with silica-based ceramics do not work effectively with zirconia. Currently, several technologies are being utilized clinically to address this problem, and other approaches are under investigation. Most focus on surface modification of the inert surfaces of high strength ceramics. The ability to chemically functionalize the surface of zirconia appears to be critical in achieving adhesive bonding. This review will focus on currently available approaches as well as new advanced technologies to address this problem. PMID:21094526

Advanced zirconia-coated carbonyl-iron particles for acidic magnetorheological finishing of chemical-vapor-deposited ZnS and other IR materials

NASA Astrophysics Data System (ADS)

Salzman, S.; Giannechini, L. J.; Romanofsky, H. J.; Golini, N.; Taylor, B.; Jacobs, S. D.; Lambropoulos, J. C.

2015-10-01

We present a modified version of zirconia-coated carbonyl-iron (CI) particles that were invented at the University of Rochester in 2008. The amount of zirconia on the coating is increased to further protect the iron particles from corrosion when introduced to an acidic environment. Five low-pH, magnetorheological (MR) fluids were made with five acids: acetic, hydrochloric, nitric, phosphoric, and hydrofluoric. All fluids were based on the modified zirconia-coated CI particles. Off-line viscosity and pH stability were measured for all acidic MR fluids to determine the ideal fluid composition for acidic MR finishing of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and other infrared (IR) optical materials, such as hot-isostatic-pressed (HIP) ZnS, CVD zinc selenide (ZnSe), and magnesium fluoride (MgF2). Results show significant reduction in surface artifacts (millimeter-size, pebble-like structures on the finished surface) for several standard-grade CVD ZnS substrates and good surface roughness for the non-CVD MgF2 substrate when MR finished with our advanced acidic MR fluid.

Fabrication and Properties of Cr2O3 and La0.7Sr0.3MnO3 Thin Film Heterostructures Integrated on Si(001)

NASA Astrophysics Data System (ADS)

Punugupati, Sandhyarani

Spintronics that utilizes both the spin and charge degrees of freedom of an electron is emerged as an alternate memory technology to conventional CMOS electronics. Many proposed spintronic devices require multifunctional properties in a single material. The oxides Cr2O3 and La0.7Sr0.3MnO3 are such materials which exhibit unique physical properties at room temperature. The Cr2O3 is an antiferromagnetic and magnetoelectric material below its Neel temperature 307K. The La0.7Sr0.3MnO3 is a ferromagnetic half metal with a Curie temperature of 360K and exhibits colossal magnetoresistance. However, the reach of this spintronic technology into more device applications is possible only when these materials in epitaxial thin film form are integrated with Si(001) which is the mainstay substrate in semiconductor industry. The primary objective of this dissertation was to integrate epitaxial Cr2O3, La0.7Sr0.3MnO3 and Cr2O3/La0.7Sr0.3MnO3 thin film heterostructure on Si(001) and, study their physical properties to investigate structure-processing-property relationship in these heterostructures. The epitaxial integration of Cr2O3 thin films on Si(001) was done using epitaxial cubic yttria stabilized zirconia (c-YSZ) buffer layer by pulsed laser deposition. Detailed structural characterizations XRD (2theta and phi) and TEM confirm the epitaxial nature of the films. Though bulk Cr2O3 is antiferromagnetic along the c-axis, the in-plane magnetization measurements on Cr2O3(0001) thin films showed ferromagnetic behavior up to 400K. The thickness dependent magnetization together with oxygen annealing results suggested that the in-plane ferromagnetism in Cr2O3 was due to the oxygen related defects whose concentration is controlled by strain in the films. The out-of-plane magnetic measurements on Cr2O3(0001) films showed magnetic behavior indicative of antiferromagnetic nature. To verify whether ferromagnetism can be induced by strain in Cr 2O3 thin films with orientation other than (0001), epitaxial thin films were prepared on r-Al2O3 substrate and their magnetic properties were studied. The XRD (2theta and phi) and TEM confirm that the films were grown epitaxially. The epitaxial relations were given as: [011¯2]Cr2O3 || [011¯2]Al2O 3 and [1¯1¯20]Cr2O3 || [1¯1¯20]Al 2O3. The as-deposited films showed ferromagnetic behavior up to 400K but it almost vanished with oxygen annealing. The Raman spectroscopy data together with strain measurements using XRD indicated that ferromagnetism in r-Cr2O3 thin films was due to the strain caused by defects such as oxygen vacancies. Bi-epitaxial La0.7Sr0.3MnO3(110) thin films were integrated on Si(100) with c-YSZ/SrTiO3(STO) buffer layers by pulsed laser deposition. The La0.7Sr0.3MnO 3 and STO thin films had a single [110] out-of-plane orientation but with two in-plane domain variants as confirmed from XRD and TEM study. The growth of STO on c-YSZ was explained by the domain matching epitaxy paradigm. The epitaxial relationship between STO and c-YSZ were written as [110](001)c-YSZ || [1¯11¯](110)STO (or) [110](001)c-YSZ || [1¯12¯](110)STO. The La0.7Sr0.3MnO3 thin films were ferromagnetic with Curie temperature 324K. They also exhibited hysteresis in magnetoresistance under both in-plane and out-of-plane magnetic fields. The highest magnetoresistance in this study was -32% at 50K and 50 kOe for in-plane configuration. Lastly, the epitaxial La0.7Sr0.3MnO3-delta -d(LSMO)/Cr2O3 bilayer structure was integrated with Si(001) using c-YSZ by pulsed laser deposition. The XRD (2theta and phi) and TEM characterizations confirm that the films were grown epitaxially. The epitaxial relations were written as [0001]Cr2O3 || [111]LSMO and [112¯0]Cr2O3 || [101¯]LSMO. Interestingly, when the LSMO thickness was increased from 66 to 528 nm (Cr2O 3=55nm), the magnetization increased by 2-fold and the magnetic nature changed from ferromagnetic to super paramagnetic. In addition, LSMO/Cr 2O3 showed in-plane exchange bias. We believe that the change in the magnetic anisotropy as a function of LSMO layer thickness could cause the change in magnetization and magnetic nature. The magnetic phase separation in oxygen deficient LSMO layer could lead to in-plane exchange bias as Cr 2O3 is not expected to show in-plane exchange.

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

Buffer layers for high-Tc thin films on sapphire

NASA Technical Reports Server (NTRS)

Wu, X. D.; Foltyn, S. R.; Muenchausen, R. E.; Cooke, D. W.; Pique, A.; Kalokitis, D.; Pendrick, V.; Belohoubek, E.

1992-01-01

Buffer layers of various oxides including CeO2 and yttrium-stabilized zirconia (YSZ) have been deposited on R-plane sapphire. The orientation and crystallinity of the layers were optimized to promote epitaxial growth of YBa2Cu3O(7-delta) (YBCO) thin films. An ion beam channeling minimum yield of about 3 percent was obtained in the CeO2 layer on sapphire, indicating excellent crystallinity of the buffer layer. Among the buffer materials used, CeO2 was found to be the best one for YBCO thin films on R-plane sapphire. High Tc and Jc were obtained in YBCO thin films on sapphire with buffer layers. Surface resistances of the YBCO films were about 4 mOmega at 77 K and 25 GHz.

Cermet electrode

DOEpatents

Maskalick, Nicholas J.

1988-08-30

Disclosed is a cermet electrode consisting of metal particles of nickel, cobalt, iron, or alloys or mixtures thereof immobilized by zirconia stabilized in cubic form which contains discrete deposits of about 0.1 to about 5% by weight of praseodymium, dysprosium, terbium, or a mixture thereof. The solid oxide electrode can be made by covering a substrate with particles of nickel, cobalt, iron, or mixtures thereof, growing a stabilized zirconia solid oxide skeleton around the particles thereby immobilizing them, contacting the skeleton with a compound of praseodymium, dysprosium, terbium, or a mixture thereof, and heating the skeleton to a temperature of at least 500.degree. C. The electrode can also be made by preparing a slurry of nickel, cobalt, iron, or mixture and a compound of praseodymium, dysprosium, terbium, or a mixture thereof, depositing the slurry on a substrate, heating the slurry to dryness, and growing a stabilized zirconia skeleton around the metal particles.

Ca-P spots modified zirconia by liquid precursor infiltration and the effect on osteoblast-like cell responses.

PubMed

Li, Yongmei; Liu, Yan; Zhang, Zutai; Zhuge, Ruishen; Ding, Ning; Tian, Yueming

2018-01-26

Ca-P spots modified zirconia by liquid precursor infiltration and the cell responses were investigated. Pre-sintered zirconia specimens were immersed in Ca-P precursor solution. After dense sintering, scanning electron microscopy showed Ca-P spots were formed on the zirconia and anchored with zirconia substrates. The distribution density was increased with the extension of immersion time. Energy dispersive spectrometer confirmed the stoichiometric Ca/P ratio was about 1.67. After hydrothermal treatment, Ca-P spots turned into rod crystals where diffraction peaks of tricalcium phosphate and hydroxyapatite were detected by X-ray diffraction, and Ca 2+ and PO 4 3- release decreased slightly (p>0.05). There was no significant decrease on three-point bending strength (p>0.05). Osteoblast-like MC3T3-E1 cells attached and spread well and showed higher proliferation on Ca-P spots modified zirconia (p<0.05), though its initial alkaline phosphatase activity was not significant high (p>0.05). In conclusion, Ca-P liquid precursor infiltration is a potential method to modify the zirconia ceramics for improving bioactivity.

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 proportions of scandia. The criterion used to judge these specimens was whether they retained the non-transformable tetragonal phase after a severe heat treatment of 140 hours at 1,400 C.

Bioactive and thermally compatible glass coating on zirconia dental implants.

PubMed

Kirsten, A; Hausmann, A; Weber, M; Fischer, J; Fischer, H

2015-02-01

The healing time of zirconia implants may be reduced by the use of bioactive glass coatings. Unfortunately, existing glasses are either bioactive like Bioglass 45S5 but thermally incompatible with the zirconia substrate, or they are thermally compatible but exhibit only a very low level of bioactivity. In this study, we hypothesized that a tailored substitution of alkaline earth metals and alkaline metals in 45S5 can lead to a glass composition that is both bioactive and thermally compatible with zirconia implants. A novel glass composition was analyzed using x-ray fluorescence spectroscopy, dilatometry, differential scanning calorimetry, and heating microscopy to investigate its chemical, physical, and thermal properties. Bioactivity was tested in vitro using simulated body fluid (SBF). Smooth and microstructured glass coatings were applied using a tailored spray technique with subsequent thermal treatment. Coating adhesion was tested on implants that were inserted in bovine ribs. The cytocompatibility of the coating was analyzed using L929 mouse fibroblasts. The coefficient of thermal expansion of the novel glass was shown to be slightly lower (11.58 · 10(-6) K(-1)) than that of the zirconia (11.67 · 10(-6) K(-1)). After storage in SBF, the glass showed reaction layers almost identical to the bioactive glass gold standard, 45S5. A process window between 800 °C and 910 °C was found to result in densely sintered and amorphous coatings. Microstructured glass coatings on zirconia implants survived a minimum insertion torque of 60 Ncm in the in vitro experiment on bovine ribs. Proliferation and cytotoxicity of the glass coatings was comparable with the controls. The novel glass composition showed a strong adhesion to the zirconia substrate and a significant bioactive behavior in the SBF in vitro experiments. Therefore, it holds great potential to significantly reduce the healing time of zirconia dental implants. © International & American Associations for Dental Research 2014.

Bioactive and Thermally Compatible Glass Coating on Zirconia Dental Implants

PubMed Central

Kirsten, A.; Hausmann, A.; Weber, M.; Fischer, J.

2015-01-01

The healing time of zirconia implants may be reduced by the use of bioactive glass coatings. Unfortunately, existing glasses are either bioactive like Bioglass 45S5 but thermally incompatible with the zirconia substrate, or they are thermally compatible but exhibit only a very low level of bioactivity. In this study, we hypothesized that a tailored substitution of alkaline earth metals and alkaline metals in 45S5 can lead to a glass composition that is both bioactive and thermally compatible with zirconia implants. A novel glass composition was analyzed using x-ray fluorescence spectroscopy, dilatometry, differential scanning calorimetry, and heating microscopy to investigate its chemical, physical, and thermal properties. Bioactivity was tested in vitro using simulated body fluid (SBF). Smooth and microstructured glass coatings were applied using a tailored spray technique with subsequent thermal treatment. Coating adhesion was tested on implants that were inserted in bovine ribs. The cytocompatibility of the coating was analyzed using L929 mouse fibroblasts. The coefficient of thermal expansion of the novel glass was shown to be slightly lower (11.58·10–6 K–1) than that of the zirconia (11.67·10–6 K–1). After storage in SBF, the glass showed reaction layers almost identical to the bioactive glass gold standard, 45S5. A process window between 800 °C and 910 °C was found to result in densely sintered and amorphous coatings. Microstructured glass coatings on zirconia implants survived a minimum insertion torque of 60 Ncm in the in vitro experiment on bovine ribs. Proliferation and cytotoxicity of the glass coatings was comparable with the controls. The novel glass composition showed a strong adhesion to the zirconia substrate and a significant bioactive behavior in the SBF in vitro experiments. Therefore, it holds great potential to significantly reduce the healing time of zirconia dental implants. PMID:25421839

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

Varela, Maria; Scigaj, Mateusz; Gazquez, Jaume

Interfaces between (110) and (111)SrTiO 3 (STO) single crystalline substrates and amorphous oxide layers, LaAlO 3 (a-LAO), Y:ZrO 2 (a-YSZ), and SrTiO 3 (a-STO) become conducting above a critical thickness t c. Here we show that t c for a-LAO does not depend on the substrate orientation, i.e. t c (a-LAO/(110)STO) ≈ t c(a-LAO/(111)STO) interfaces, whereas it strongly depends on the composition of the amorphous oxide: t c(a-LAO/(110)STO) < t c(a-YSZ/(110)STO) < t c(a-STO/(110)STO). It is concluded that the formation of oxygen vacancies in amorphous-type interfaces is mainly determined by the oxygen affinity of the deposited metal ions, rather thanmore » orientation-dependent enthalpy vacancy formation and diffusion. Furthermore, scanning transmission microscopy characterization of amorphous and crystalline LAO/STO(110) interfaces shows much higher amount of oxygen vacancies in the former, providing experimental evidence of the distinct mechanism of conduction in these interfaces.« less

Infrared wire-grid polarizer with sol-gel zirconia grating

NASA Astrophysics Data System (ADS)

Yamada, Itsunari; Ishihara, Yoshiro

2017-05-01

The infrared wire-grid polarizer consisting of an Al grating, Si, and sol-gel derived zirconia grating film was fabricated by soft imprint process and Al shadow coating processes. A silicone mold was used because of its low surface energy, flexibility, and capability of transferring submicrosized patterns. As a result, the Al grating with a pitch of 400 nm and a depth of 100 nm was obtained on the zirconia grating film. The fabricated polarizer exhibited a polarization function with the TM transmittance greater than that of the Si substrate in the specific wavelength range of 3.6-8.5 μm, because the zirconia film acted as an antireflection film. The maximum value was 63% at a wavelength of 5.2 μm. This increment of the TM transmission spectrum results in interference within the zirconia film. Also, the extinction ratio exceeded almost 20 dB in the 3-8.8 μm wavelength range.

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.

Evolution of atomic structure during nanoparticle formation

DOE PAGES

Tyrsted, Christoffer; Lock, Nina; Jensen, Kirsten M. Ø.; ...

2014-04-14

Understanding the mechanism of nanoparticle formation during synthesis is a key prerequisite for the rational design and engineering of desirable materials properties, yet remains elusive due to the difficulty of studying structures at the nanoscale under real conditions. Here, the first comprehensive structural description of the formation of a nanoparticle, yttria-stabilized zirconia (YSZ), all the way from its ionic constituents in solution to the final crystal, is presented. The transformation is a complicated multi-step sequence of atomic reorganizations as the material follows the reaction pathway towards the equilibrium product. Prior to nanoparticle nucleation, reagents reorganize into polymeric species whose structuremore » is incompatible with the final product. Instead of direct nucleation of clusters into the final product lattice, a highly disordered intermediate precipitate forms with a local bonding environment similar to the product yet lacking the correct topology. During maturation, bond reforming occurs by nucleation and growth of distinct domains within the amorphous intermediary. The present study moves beyond kinetic modeling by providing detailed real-time structural insight, and it is demonstrated that YSZ nanoparticle formation and growth is a more complex chemical process than accounted for in conventional models. This level of mechanistic understanding of the nanoparticle formation is the first step towards more rational control over nanoparticle synthesis through control of both solution precursors and reaction intermediaries.« less

High-Temperature Carbon Deposition on Oxide Surfaces by CO Disproportionation

PubMed Central

2016-01-01

Carbon deposition due to the inverse Boudouard reaction (2CO → CO2 + C) has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 in comparison to CH4 by a variety of different chemical, structural, and spectroscopic characterization techniques, including electrochemical impedance spectroscopy (EIS), Fourier-transform infrared (FT-IR) spectroscopy and imaging, Raman spectroscopy, and electron microscopy. Consentaneously, all experimental methods prove the formation of a more or less conducting carbon layer (depending on the used oxide) of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in flowing CO at temperatures above ∼1023 K. All measurements show that during carbon deposition, a more or less substantial surface reduction of the oxides takes place. These results, therefore, reveal that the studied pure oxides can act as efficient nonmetallic substrates for CO-induced growth of highly distorted graphitic carbon with possible important technological implications especially with respect to treatment in pure CO or CO-rich syngas mixtures. Compared to CH4, more carbon is generally deposited in CO under otherwise similar experimental conditions. Although Raman and electron microscopy measurements do not show substantial differences in the structure of the deposited carbon layers, in particular, electrochemical impedance measurements reveal major differences in the dynamic growth process of the carbon layer, eventually leading to less percolated islands and suppressed metallic conductivity in comparison to CH4-induced graphite. PMID:26877828

Growth and surface modification of LaFeO3 thin films induced by reductive annealing

NASA Astrophysics Data System (ADS)

Flynn, Brendan T.; Zhang, Kelvin H. L.; Shutthanandan, Vaithiyalingam; Varga, Tamas; Colby, Robert J.; Oleksak, Richard P.; Manandhar, Sandeep; Engelhard, Mark H.; Chambers, Scott A.; Henderson, Michael A.; Herman, Gregory S.; Thevuthasan, Suntharampillai

2015-03-01

The mixed electronic and ionic conductivity of perovskite oxides has enabled their use in diverse applications such as automotive exhaust catalysts, solid oxide fuel cell cathodes, and visible light photocatalysts. The redox chemistry at the surface of perovskite oxides is largely dependent on the oxidation state of the metal cations as well as the oxide surface stoichiometry. In this study, LaFeO3 (LFO) thin films grown on yttria-stabilized zirconia (YSZ) was characterized using both bulk and surface sensitive techniques. A combination of in situ reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), and Rutherford backscattering spectrometry (RBS) demonstrated that the film is primarily textured in the [1 0 0] direction and is stoichiometric. High-resolution transmission electron microscopy measurements show regions that are dominated by [1 0 0] oriented LFO grains that are oriented with respect to the substrates lattice. However, selected regions of the film show multiple domains of grains that are not [1 0 0] oriented. The film was annealed in an ultra-high vacuum chamber to simulate reducing conditions and studied by angle-resolved X-ray photoelectron spectroscopy (XPS). Iron was found to exist as Fe(0), Fe(II), and Fe(III) depending on the annealing conditions and the depth within the film. A decrease in the concentration of surface oxygen species was correlated with iron reduction. These results should help guide and enhance the design of LFO materials for catalytic applications.

Sol-gel derived fluor-hydroxyapatite biocoatings on zirconia substrate.

PubMed

Kim, Hae-Won; Kong, Young-Min; Bae, Chang-Jun; Noh, Yoon-Jung; Kim, Hyoun-Ee

2004-07-01

Fluor-hydroxyapatite (FHA) film was coated on a zirconia (ZrO(2)) substrate by a sol-gel method. An appropriate amount of F ions was incorporated into the hydroxyapatite (HA) during the preparation of the sols. The apatite phase began to crystallize after heat treatment at 400 degrees C, and increased in intensity above 500 degrees C. No decomposition was detected by X-ray diffraction analyses up to 800 degrees C, which illustrates the high thermal stability of the FHA films. The films showed a uniform and dense morphology with a thickness of approximately 1 microm after a precisely controlled heat treatment process. These FHA films adhered firmly to the zirconia substrate, representing notable adhesion strengths of approximately 70 MPa after heat treatment above 500 degrees C. The dissolution rate of the FHA coating layer varied according to the heat treatment temperature, which was closely related to the film crystallinity. The dissolution rate of the FHA film was lower than that of the HA film, suggesting the possibility of a functional gradient coating of HA and FHA. The MG63 cells seeded onto the FHA films proliferated in a similar manner to those seeded onto pure HA ceramic and a plastic control.

Growth of biaxially textured template layers using ion beam assisted deposition

NASA Astrophysics Data System (ADS)

Park, Seh-Jin

A two-step IBAD (ion beam assisted deposition) method is investigated, and compared to the conventional IBAD methods. The two step method uses surface energy anisotropy to achieve uniaxial texture and ion beam irradiation for biaxial texture. The biaxial texture was achieved by selective surface etching and enhanced by grain overgrowth. In this method, biaxial texture alignment is performed on a (001) uniaxially textured buffer layer. The material selected for achieving uniaxial texture, YBCO (YBa2Cu3O7-x), has strong surface energy anisotropy. YBCO is chemically susceptible to the reaction with the adjacent layer. Yttria stabilized zirconia (YSZ) was used to prevent the reaction between YBCO and the substrates (polycrystalline Ni alloy [Hastelloy] and amorphous SiNx/Si). A SrTiO3 layer was deposited on the uniaxially textured YBCO layer to retard stoichiometry change with subsequent processing. STO is well lattice matched with YBCO. A top layer of Ni was then deposited. The Ni layer was used for studying the effect of grain overgrowth. The obtained uniaxial Ni films were used for subsequent ion beam processing. Ar ion beam irradiation onto the uniaxially textured Ni film was used to study the effect of selective grain etching in achieving in-plane aligned Ni grains. Additional Ni deposition induces the overgrowth of the in-plane aligned Ni grains and, finally, the overall in-plane alignment. The in-plane alignment is examined with XRD phi scan. The effect of surface polarity of insulating oxide substrates on the epitaxial growth behavior was investigated. The lattice strain energy was the most important factor for determining the orientation of Ni films on a non-polar surface. However, for a polar surface, the surface energy plays an important role in determining the final orientation of the Ni films based on the experimental and theoretical results. Y2O3 growth behavior was also studied. The lattice strain energy is the most important factor for Y2O3 growth on single crystalline substrates. The surface energy anisotropy is the most important factor for the growth on amorphous substrates. The XRD phi scan study shows that Ar ion beam irradiation with favorable angle of incidence enhances the in-plane alignment of Y2O3 films grown on randomly oriented substrates due to the ion channeling.

Improvements to Zirconia Thick-Film Oxygen Sensors

NASA Astrophysics Data System (ADS)

Maskell, William C.; Brett, Daniel J. L.; Brandon, Nigel P.

2013-06-01

Thick-film zirconia gas sensors are normally screen-printed onto a planar substrate. A sandwich of electrode-electrolyte-electrode is fired at a temperature sufficient to instigate sintering of the zirconia electrolyte. The resulting porous zirconia film acts as both the electrolyte and as the diffusion barrier through which oxygen diffuses. The high sintering temperature results in de-activation of the electrodes so that sensors must be operated at around 800 °C for measurements in the percentage range of oxygen concentration. This work shows that the use of cobalt oxide as a sintering aid allows reduction of the sensor operating temperature by 100-200 °C with clear benefits. Furthermore, an interesting and new technique is presented for the investigation of the influence of dopants and of the through-porosity of ionically-conducting materials.

Solid oxide fuel cell having a glass composite seal

DOEpatents

De Rose, Anthony J.; Mukerjee, Subhasish; Haltiner, Jr., Karl Jacob

2013-04-16

A solid oxide fuel cell stack having a plurality of cassettes and a glass composite seal disposed between the sealing surfaces of adjacent cassettes, thereby joining the cassettes and providing a hermetic seal therebetween. The glass composite seal includes an alkaline earth aluminosilicate (AEAS) glass disposed about a viscous glass such that the AEAS glass retains the viscous glass in a predetermined position between the first and second sealing surfaces. The AEAS glass provides geometric stability to the glass composite seal to maintain the proper distance between the adjacent cassettes while the viscous glass provides for a compliant and self-healing seal. The glass composite seal may include fibers, powders, and/or beads of zirconium oxide, aluminum oxide, yttria-stabilized zirconia (YSZ), or mixtures thereof, to enhance the desirable properties of the glass composite seal.

Performance evaluation of tubular fuel cells fuelled by pulverized graphite

NASA Astrophysics Data System (ADS)

Kim, Jong-Pil; Lim, Ho; Jeon, Chung-Hwan; Chang, Young-June; Koh, Kwang-Nak; Choi, Soon-Mok; Song, Ju-Hun

A fuel cell fuelled by carbonaceous graphite is proposed. The tubular fuel cell, with the carbon in a fixed-bed form on the anode side, is employed to convert directly the chemical energy of carbon into electricity. Surface platinum electrodes are coated on the cell electrolyte, which is a yttria-stabilized zirconia (YSZ) tube of 1.5 mm thickness. The effect of using different sizes of graphite powder (in the range 0-180 μm) as fuel is analyzed. Power density and actual open-circuit voltage (OCV) values are measured as the temperature is varied from 0 to 950 °C. The cell provides a maximum power density of 16.8 mW cm -2 and an OCV of 1.115 V at the highest temperature condition (950 °C) tested in this study.

Nanocomposite tribological coatings with "chameleon" surface adaptation

NASA Astrophysics Data System (ADS)

Voevodin, A. A.; Fitz, T. A.; Hu, J. J.; Zabinski, J. S.

2002-07-01

Nanocomposite tribological coatings were designed to respond to changing environmental conditions by self-adjustment of their surface properties to maintain good tribological performance in any environment. These smart coatings have been dubbed "chameleon" because, analogous to a chameleon changing its skin color to avoid predators, the coating changes its "skin" chemistry and structure to avoid wear. The concept was originally developed using WC, diamondlike carbon, and WS2 material combination for adaptation to a humid/dry environment cycling. In order to address temperature variation, nanocomposite coatings made of yttria-stabilized zirconia (YSZ) in a gold matrix were developed with encapsulated nanosized reservoirs of MoS2 and diamondlike carbon (DLC). Coatings were produced using a combination of laser ablation and magnetron sputtering. They were characterized by x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, x-ray energy dispersive spectroscopy, and micro-Raman spectroscopy. Results were correlated with mechanical and tribological characterization. Coating hardness was evaluated using nanoindentation, while coating adhesion and toughness were estimated using scratch and Vickers indentation tests. Friction and wear endurance measurements of YSZ/Au/MoS2/DLC coatings against steel and Si3N4 balls were performed at room temperature in controlled humidity air, dry nitrogen, and vacuum environments, as well as at 500 degC in air. Depending on the environment, coating friction surface changed its chemistry and structure between (i) graphitic carbon for sliding in humid air [coating friction coefficients (c.o.f. 0.10-0.15)], (ii) hexagonal MoS2 for sliding in dry N2 and vacuum (c.o.f. 0.02-0.05), and (iii) metallic Au for sliding in air at 500 degC (c.o.f. 0.10-0.20). The unique coating skin adaptation realized with YSZ/Au/MoS2/DLC and WC/DLC/WS composites proves a universal applicability of the chameleon design concept. copyright 2002 American Vacuum Society.

[Research on bond durability among different core materials and zirconia ceramic cemented by self-adhesive resin cements].

PubMed

Xinyu, Luo; Xiangfeng, Meng

2017-02-01

This research estimated shear bond durability of zirconia and different substrates cemented by two self-adhesive resin cements (Clearfil SA Luting and RelyX U100) before and after aging conditioning. Machined zirconia ceramic discs were cemented with four kinds of core material (cobalt-chromium alloy, flowable composite resin core material, packable composite resin, and dentin) with two self-adhesive resin cements (Clearfil SA Luting and RelyX U100). All specimens were divided into eight test groups, and each test group was divided into two subgroups. Each subgroup was subjected to shear test before and after 10 000 thermal cycles. All factors (core materials, cements, and thermal cycle) significantly influenced bond durability of zirconia ceramic (P<0.00 1). After 10 000 thermal cycles, significant decrease was not observed in shear bond strength of cobalt-chromium alloy luted with Clearfil SA Luting (P>0.05); observed shear bond strength was significantly higher than those of other substrates (P<0.05). Significantly higher shear bond strength was noted in Clearfil SA Luting luted with cobalt-chromium alloy, flowable composite resin core material, and packable composite resin than that of RelyX U100 (P<0.05). However, significant difference was not observed in shear bond strength of dentin luted with Clearfil SA Luting and RelyX U100 (P>0.05). Different core materials and self-adhesive resin cements can significantly affect bond durability of zirconia ceramic. 
.

Study on the neotype zirconia's implant coated nanometer hydroxyapatite ceramics

NASA Astrophysics Data System (ADS)

Zhu, J. W.; Yang, D. W.

2007-07-01

In recent years, biologic ceramics is a popular material of implants and bioactive surface modification of dental implant became a research emphasis, which aims to improve bioactivity of implants materials and acquire firmer implants-bone interface. The zirconia ceramic has excellent mechanical properties and nanometer HA ceramics is a bioceramic well known for its bioactivity, therefore, nanometer HA ceramics coating on zirconia, allows combining the excellent mechanical properties of zirconia substrates with its bioactivity. This paper shows a new method for implant shape design and bioactive modification of dental implants surface. Zirconia's implant substrate was prepared by sintered method, central and lateral tunnels were drilled in the zirconia hollow porous cylindrical implants by laser processing. The HA powders and needle-like HA crystals were made by a wet precipitation and calcining method. Its surface was coated with nanometer HA ceramics which was used brush HA slurry and vacuum sintering. Mechanical testing results revealed that the attachment strength of nanometer HA ceramics coated zirconia samples is high. SEM and interface observation after inserted experiment indicated that calcium and phosphor content increased and symmetrically around coated implant-bone tissue interface. A significantly higher affinity index was demonstrated in vivo by histomorphometric evaluation in coated versus uncoated implants. SEM analysis demonstrated better bone adhesion to the material in coated implant at any situation. In addition, the hollow porous cylindrical implant coated with nanometer HA ceramics increase the interaction of bone and implant, the new bone induced into the surface of hollow porous cylindrical implant and through the most tunnels filled into central hole. The branch-like structure makes the implant and bone a body, which increased the contact area and decreased elastic ratio. Therefore, the macroscopical and microcosmic nested structure of implant coated nanometer HA ceramics had increased biocompatibility and improved the osteointegration. It endows the implants with new vital activity.

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.

Fabrication and Microstructure of Hydroxyapatite Coatings on Zirconia by Room Temperature Spray Process.

PubMed

Seo, Dong Seok; Chae, Hak Cheol; Lee, Jong Kook

2015-08-01

Hydroxyapatite coatings were fabricated on zirconia substrates by a room temperature spray process and were investigated with regards to their microstructure, composition and dissolution in water. An initial hydroxyapatite powder was prepared by heat treatment of bovine-bone derived powder at 1100 °C for 2 h, while dense zirconia substrates were fabricated by pressing 3Y-TZP powder and sintering it at 1350 °C for 2 h. Room temperature spray coating was performed using a slit nozzle in a low pressure-chamber with a controlled coating time. The phase composition of the resultant hydroxyapatite coatings was similar to that of the starting powder, however, the grain size of the hydroxyapatite particles was reduced to about 100 nm due to their formation by particle impaction and fracture. All areas of the coating had a similar morphology, consisting of reticulated structure with a high surface roughness. The hydroxyapatite coating layer exhibited biostability in a stimulated body fluid, with no severe dissolution being observed during in vitro experimentation.

Oriented conductive oxide electrodes on SiO2/Si and glass

DOEpatents

Jia, Quanxi; Arendt, Paul N.

2001-01-01

A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

Conduction in In 2O 3/YSZ heterostructures: Complex interplay between electrons and ions, mediated by interfaces

DOE PAGES

Veal, B. W.; Eastman, J. A.

2017-03-01

Thin film In 2O 3/YSZ heterostructures exhibit significant increases in electrical conductance with time when small in-plane electric fields are applied. Contact resistances between the current electrodes and film, and between current electrodes and substrate are responsible for the behavior. With an in-plane electric field, different field profiles are established in the two materials, with the result that oxygen ions can be driven across the heterointerface, altering the doping of the n-type In 2O 3. Furthermore, a low frequency inductive feature observed in AC impedance spectroscopy measurements under DC bias conditions was found to be due to frequency-dependent changes inmore » the contact resistance.« less

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.

Epitaxial Fe/Y2O3 interfaces as a model system for oxide-dispersion-strengthened ferritic alloys

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

Kaspar, Tiffany C.; Bowden, Mark E.; Wang, Chong M.

2015-02-01

The fundamental mechanisms underlying the superior radiation tolerance properties of oxide-dispersion-strengthened ferritic steels and nanostructured ferritic alloys are poorly understood. Thin film heterostructures of Fe/Y2O3 can serve as a model system for fundamental studies of radiation damage. Epitaxial thin films of Y2O3 were deposited by pulsed laser deposition on 8% Y:ZrO2 (YSZ) substrates with (100), (110), and (111) orientation. Metallic Fe was subsequently deposited by molecular beam epitaxy. Characterization by x-ray diffraction and Rutherford backscattering spectrometry in the channeling geometry revealed a degree of epitaxial or axiotaxial ntation for Fe(211) deposited on Y2O3(110)/YSZ(110). In contrast, Fe on Y2O3(111)/YSZ(111) was fullymore » polycrystalline, and Fe on Y2O3(100)/YSZ(100) exhibited out-of-plane texture in the [110] direction with little or no preferential in-plane orientation. Scanning transmission electron microscopy imaging of Fe(211)/Y2O3(110)/YSZ(110) revealed a strongly islanded morphology for the Fe film, with no epitaxial grains visible in the cross-sectional sample. Well-ordered Fe grains with no orientation to the underlying Y2O3 were observed. Well-ordered crystallites of Fe with both epitaxial and non-epitaxial orientations on Y2O3 are a promising model system for fundamental studies of radiation damage phenomena. This is illustrated with preliminary results of He bubble formation following implantation with a helium ion microscope. He bubble formation is shown to preferentially occur at the Fe/Y2O3 interface.« less

High-T(sub c) Edge-geometry SNS Weak Links on Silicon-on-sapphire Substrates

NASA Technical Reports Server (NTRS)

Hunt, B.; Foote, M.; Pike, W.; Barner, J.; Vasquez, R.

1994-01-01

High-quality superconductor/normal-metal/superconductor(SNS) edge-geometry weak links have been produced on silicon-on-sapphire (SOS) substrates using a new SrTiO(sub 3)/'seed layer'/cubic-zirconia (YS2) buffer system.

Degradation of thermal barrier coatings on an Integrated Gasification Combined Cycle (IGCC) simulated film-cooled turbine vane pressure surface due to particulate fly ash deposition

NASA Astrophysics Data System (ADS)

Luo, Kevin

Coal synthesis gas (syngas) can introduce contaminants into the flow of an Integrated Gasification Combined Cycle (IGCC) industrial gas turbine which can form molten deposits onto components of the first stage of a turbine. Research is being conducted at West Virginia University (WVU) to study the effects of particulate deposition on thermal barrier coatings (TBC) employed on the airfoils of an IGCC turbine hot section. WVU had been working with U.S. Department of Energy, National Energy Technology Laboratory (NETL) to simulate deposition on the pressure side of an IGCC turbine first stage vane to study the effects on film cooling. To simulate the particulate deposition, TBC coated, angled film-cooled test articles were subjected to accelerated deposition injected into the flow of a combustor facility with a pressure of approximately 4 atm and a gas temperature of 1560 K. The particle characteristics between engine conditions and laboratory are matched using the Stokes number and particulate loading. To investigate the degradation on the TBC from the particulate deposition, non-destructive evaluations were performed using a load-based multiple-partial unloading micro-indentation technique and were followed by scanning electron microscopy (SEM) evaluation and energy dispersive X-ray spectroscopy (EDS) examinations. The micro-indentation technique used in the study was developed by Kang et al. and can quantitatively evaluate the mechanical properties of materials. The indentation results found that the Young's Modulus of the ceramic top coat is higher in areas with deposition formation due to the penetration of the fly ash. The increase in the modulus of elasticity has been shown to result in a reduction of strain tolerance of the 7% yttria-stabilized zirconia (7YSZ) TBC coatings. The increase in the Young's modulus of the ceramic top coat is due to the stiffening of the YSZ columnar microstructure from the cooled particulate fly ash. SEM evaluation was used to evaluate the microstructure of the layers within the TBC system, and the SEM micrographs showed that the TBC/fly ash deposition interaction zone made the YSZ coating more susceptible to delamination and promoted a dissolution-reprecipitation mechanism that changes the YSZ morphology and composition. EDS examination provided elemental maps which showed a shallow infiltration depth of the fly ash deposits and an elemental distribution spectrum analysis showed yttria migration from the YSZ top coating into the molten deposition. This preliminary work should lead to future studies in gas turbine material coating systems and their interaction with simulated fly ash and potentially CMAS or volcanic ash deposition.

Synthesis of zirconia (ZrO2) nanowires via chemical vapor deposition

NASA Astrophysics Data System (ADS)

Baek, M. K.; Park, S. J.; Choi, D. J.

2017-02-01

Monoclinic zirconia nanowires were synthesized by chemical vapor deposition using ZrCl4 powder as a starting material at 1200 °C and 760 Torr. Graphite was employed as a substrate, and an Au thin film was pre-deposited on the graphite as a catalyst. The zirconia nanostructure morphology was observed through scanning electron microscopy and transmission electron microscopy. Based on X-ray diffraction, selected area electron diffraction, and Raman spectroscopy data, the resulting crystal structure was found to be single crystalline monoclinic zirconia. The homogeneous distributions of Zr, O and Au were studied by scanning transmission electron microscopy with energy dispersive X-ray spectroscopy mapping, and there was no metal droplet at the nanowire tips despite the use of an Au metal catalyst. This result is apart from that of conventional metal catalyzed nanowires.

Investigation of Nd xY 0.25-xZr 0.75O 1.88 inert matrix fuel materials made by a co-precipitation synthetic route

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

Hayes, John R.; Grosvenor, Andrew P.

Yttria-stabilized zirconia (YSZ) is a material that we are considering in our inert matrix fuel nuclear reactors, but a complete characterization of these materials is required for them to be licensed for use. A series of NdxY0.25–xZr0.75O1.88 materials have been synthesized using a co-precipitation method, and the thermal stability of these materials has been studied by annealing them at 1400 and 1500 °C. (Nd was used as surrogate for Am.) The long-range and local structures of the materials were characterized via powder X-ray diffraction, scanning electron microscopy, wavelength dispersive spectroscopy, and X-ray absorption spectroscopy at the Zr K- and Ymore » K-edges. These results were compared with the previous characterization of Nd-YSZ materials synthesized using a ceramic method. Moreover, the results indicated that the ordering in the local metal–oxygen polyhedral remains relatively unaffected by the synthetic method, but there was increased long-range disorder in the materials prepared by the co-precipitation method. Further, it was found that the materials produced by the co-precipitation method were unexpectedly unstable when annealed at high temperature. This study highlights the importance of determining the effect of synthetic method on material properties and demonstrates how the co-precipitation route could be used to produce inert matrix fuels.« less

Y0.08Sr0.88TiO3-CeO2 composite as a diffusion barrier layer for stainless-steel supported solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Kim, Kun Joong; Kim, Sun Jae; Choi, Gyeong Man

2016-03-01

A new diffusion barrier layer (DBL) is proposed for solid oxide fuel cells (SOFCs) supported on stainless-steel where DBL prevents inter-diffusion of atoms between anode and stainless steel (STS) support during fabrication and operation of STS-supported SOFCs. Half cells consisting of dense yttria-stabilized zirconia (YSZ) electrolyte, porous Ni-YSZ anode layer, and ferritic STS support, with or without Y0.08Sr0.88TiO3-CeO2 (YST-CeO2) composite DBL, are prepared by tape casting and co-firing at 1250 and 1350 °C, respectively, in reducing (H2) atmosphere. The porous YST-CeO2 layer (t ∼ 60 μm) blocks inter-diffusion of Fe and Ni, and captures the evaporated Cr during cell fabrication (1350 °C). The cell with DBL and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode achieved a maximum power density of ∼220 mW cm-2 which is stable at 700 °C. In order to further improve the power performance, Ni coarsening in anode during co-firing must be prevented or alternative anode which is resistive to coarsening is suggested. This study demonstrates that the new YST-CeO2 layer is a promising as a DBL for stainless-steel-supported SOFCs fabricated with co-firing process.

Effect of particle in-flight behavior on the composition of thermal barrier coatings

NASA Astrophysics Data System (ADS)

Zhao, L.; Bai, Y.; Tang, J. J.; Liu, K.; Ding, C. H.; Yang, J. F.; Han, Z. H.

2013-12-01

In this work, 6 to 11 mol% YO1.5-stabilized zirconia (YSZ) coatings were deposited by supersonic and conventional atmospheric plasma spraying. During spraying, the surface temperature and velocity of in-flight particles were monitored by Spray Watch 2i on-line system. The phase composition of as-sprayed coatings was analyzed by X-ray diffractometry (XRD). Lattice parameters, tetragonality and the content of YO1.5 (mol%) of as-sprayed coatings were calculated according to the position of (0 0 4) and (4 0 0) diffraction peaks. It was found that the as-sprayed coatings were composed of metastable non-transformable tetragonal phase (t‧). However, the amount of YO1.5 (mol%) in the as-sprayed coatings decreased with the increase of melting index of in-flight particles due to the partial evaporation of YO1.5 during spraying.

Optical methods and systems for detecting a constituent in a gas containing oxygen in harsh environments

DOEpatents

Carpenter, Michael A [Scotia, NY; Sirinakis, George [Bronx, NY

2011-01-04

A method for detecting a gas phase constituent such as carbon monoxide, nitrogen dioxide, hydrogen, or hydrocarbons in a gas comprising oxygen such as air, includes providing a sensing material or film having a metal embedded in a catalytically active matrix such as gold embedded in a yttria stabilized zirconia (YSZ) matrix. The method may include annealing the sensing material at about 900.degree. C., exposing the sensing material and gas to a temperature above 400.degree. C., projecting light onto the sensing material, and detecting a change in the absorption spectrum of the sensing material due to the exposure of the sensing material to the gas in air at the temperature which causes a chemical reaction in the sensing material compared to the absorption spectrum of the sensing material in the absence of the gas. Systems employing such a method are also disclosed.

Reactivating the Ni-YSZ electrode in solid oxide cells and stacks by infiltration

NASA Astrophysics Data System (ADS)

Skafte, Theis Løye; Hjelm, Johan; Blennow, Peter; Graves, Christopher

2018-02-01

The solid oxide cell (SOC) could play a vital role in energy storage when the share of intermittent electricity production is high. However, large-scale commercialization of the technology is still hindered by the limited lifetime. Here, we address this issue by examining the potential for repairing various failure and degradation mechanisms occurring in the fuel electrode, thereby extending the potential lifetime of a SOC system. We successfully infiltrated the nickel and yttria-stabilized zirconia cermet electrode in commercial cells with Gd-doped ceria after operation. By this method we fully reactivated the fuel electrode after simulated reactant starvation and after carbon formation. Furthermore, by infiltrating after 900 h of operation, the degradation of the fuel electrode was reduced by a factor of two over the course of 2300 h. Lastly, the scalability of the concept is demonstrated by reactivating an 8-cell stack based on a commercial design.

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.

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1990-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Wear and Reactivity Studies of Melt infiltrated Ceramic Matrix Composite

NASA Technical Reports Server (NTRS)

Jarmon, David C.; Ojard, Greg; Brewer, David N.

2013-01-01

As interest grows in the use of ceramic matrix composites (CMCs) for critical gas turbine engine components, the effects of the CMCs interaction with the adjoining structure needs to be understood. A series of CMC/material couples were wear tested in a custom elevated temperature test rig and tested as diffusion couples, to identify interactions. Specifically, melt infiltrated silicon carbide/silicon carbide (MI SiC/SiC) CMC was tested in combination with a nickel-based super alloy, Waspaloy, a thermal barrier coating, Yttria Stabilized Zirconia (YSZ), and a monolithic ceramic, silicon nitride (Si3N4). To make the tests more representative of actual hardware, the surface of the CMC was kept in the as-received state (not machined) with the full surface features/roughness present. Test results include: scanning electron microscope characterization of the surfaces, micro-structural characterization, and microprobe analysis.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Fabrication of composite films containing zirconia and cationic polyelectrolytes.

PubMed

Pang, Xin; Zhitomirsky, Igor

2004-03-30

Composite films were prepared by electrophoretic deposition of poly(ethylenimine) or poly(allylamine hydrochloride) combined with cathodic precipitation of zirconia. Films of up to several micrometers thick were obtained on Ni, Pt, stainless-steel, graphite, and carbon-felt substrates. When the concentration of polyelectrolytes in solutions and the deposition time were varied, the amount of the deposited material and its composition can be varied. The electrochemical intercalation of yttria-stabilized zirconia particles into the composite films has been demonstrated. Obtained results pave the way for the electrodeposition of other polymer-ceramic composites. The deposits were studied by thermogravimetric analysis, X-ray diffraction analysis, scanning electron microscopy, and atomic force microscopy. The mechanisms of deposition are discussed.

Thermal barrier coating

DOEpatents

Bowker, Jeffrey Charles; Sabol, Stephen M.; Goedjen, John G.

2001-01-01

A thermal barrier coating for hot gas path components of a combustion turbine based on a zirconia-scandia system. A layer of zirconium scandate having the hexagonal Zr.sub.3 Sc.sub.4 O.sub.12 structure is formed directly on a superalloy substrate or on a bond coat formed on the substrate.

Health Sensing Functions in Thermal Barrier Coatings Incorporating Rare-Earth-Doped Luminescent Sublayers

NASA Technical Reports Server (NTRS)

Eldridge, J. I.; Singh, J.; Wolfe, D. E.

2004-01-01

Great effort has been directed towards developing techniques to monitor the health of thermal barrier coatings (TBCs) that would detect the approach of safety-threatening conditions. An unconventional approach is presented here where health sensing functionality is integrated into the TBC itself by the incorporation of rare-earth-doped luminescent sublayers to monitor erosion as well as whether the TBC is maintaining the underlying substrate at a sufficiently low temperature. Erosion indication is demonstrated in electron-beam physical vapor deposited (EB-PVD) TBCs consisting of 7wt% yttria-stabilized zirconia (7YSZ) with europium-doped and terbium-doped sublayers. Multiple ingot deposition produced sharp boundaries between the doped sublayers without interrupting the columnar growth of the TBC. The TBC-coated specimens were subjected to alumina particle jet erosion, and the erosion depth was then indicated under ultraviolet illumination that excited easily visible luminescence characteristic of sublayer that was exposed by erosion. In addition, temperature measurements from a bottom-lying europium-doped sublayer in a TBC produced by multiple ingot EB-PVD were accomplished by measuring the temperature-dependent decay time from the 606 nm wavelength emission excited in that sublayer with a 532 nm wavelength laser that was selected for its close match to one of the europium excitation wavelengths as well as being at a wavelength where the TBC is relatively transparent. It is proposed the low dopant levels and absence of interruption of the TBC columnar growth allow the addition of the erosion and temperature sensing functions with minimal effects on TBC performance.

Improving bioactivity of inert bioceramics by a novel Mg-incorporated solution treatment

NASA Astrophysics Data System (ADS)

Dehestani, Mahdi; Zemlyanov, Dmitry; Adolfsson, Erik; Stanciu, Lia A.

2017-12-01

Zirconia/alumina ceramics possess outstanding mechanical properties for dental and orthopedic applications, but due to their poor surface bioactivities they exhibit a weak bone-bonding ability. This work proposes an effective 30-min solution treatment which could successfully induce formation of bone-like apatite on the surface of 3Y-TZP and a ternary composite composed of yttria-stabilized zirconia, ceria-stabilized zirconia, and alumina (35 vol% 3Y-TZP + 35 vol% 12Ce-TZP + 30 vol% Al2O3) after 3 weeks immersion in simulated body fluid (SBF). XRD was used for phase identification in the ceramic materials. The influence of solution treatment on the surface chemistry and its role on apatite formation were investigated via SEM, EDS and XPS. In vitro apatite-forming ability for the solution-treated and untreated samples of the composite and individual substrates of 3Y-TZP, 12Ce-TZP, and Al2O3 was evaluated by immersion in SBF. Apatite crystals were formed only on 3Y-TZP and composite substrates, implying that it is mainly the 3Y-TZP constituent that contributes to the bioactivity of the composite. Further, it was found from the XPS analysis that the zirconia material with higher phase stability (12Ce-TZP) produced less Zrsbnd OH functional groups on its surface after solution treatment which accounts for its weaker bioactivity compared to 3Y-TZP.

Deposition of crystalline hydroxyapatite nano-particle on zirconia ceramic: a potential solution for the poor bonding characteristic of zirconia ceramics to resin cement.

PubMed

Azari, Abbas; Nikzad, Sakineh; Yazdani, Arash; Atri, Faezeh; Fazel Anvari-Yazdi, Abbas

2017-07-01

The poor bonding strength of zirconia to different dental substrates is one of the challenging issues in restorative dentistry. Hydroxyapatite is an excellent biocompatible material with fine bonding properties. In this study, it was hypothesized that hydroxyapatite coating on zirconia would improve its bond strength. Forty-five zirconia blocks were prepared and randomly divided into three groups: hydroxyapatite coating, sandblasting, and no preparation (control). The blocks were bonded to cement and the micro-shear bond strength was measured following load application. The bond strength values were analyzed with the Kruskal-Wallis test in 3 groups and paired comparisons were made using the Mann-Whitney U test. The failure patterns of the specimens were studied by a stereomicroscope and a scanning electron microscope and then analyzed by the chi-square test (significance level = 0.05). Deposition of hydroxyapatite on the zirconia surface significantly improved its bond strength to the resin cement in comparison with the control specimens (p < 0.0001). Also, the bond strength was similar to the sandblasted group (p = 0.34). The sandblasted and control group only showed adhesive failure, but the hydroxyapatite coated group had mixed failures, indicating the better quality of bonding (p < 0.0001). As a final point, hydroxyapatite coating on the zirconia surface improved the bond strength quality and values.

Effect of colouring green stage zirconia on the adhesion of veneering ceramics with different thermal expansion coefficients.

PubMed

Aktas, Guliz; Sahin, Erdal; Vallittu, Pekka; Ozcan, Mutlu; Lassila, Lippo

2013-12-01

This study evaluated the adhesion of zirconia core ceramics with their corresponding veneering ceramics, having different thermal expansion coefficients (TECs), when zirconia ceramics were coloured at green stage. Zirconia blocks (N=240; 6 mm×7 mm×7 mm) were manufactured from two materials namely, ICE Zirconia (Group 1) and Prettau Zirconia (Group 2). In their green stage, they were randomly divided into two groups. Half of the specimens were coloured with colouring liquid (shade A2). Three different veneering ceramics with different TEC (ICE Ceramic, GC Initial Zr and IPS e.max Ceram) were fired on both coloured and non-coloured zirconia cores. Specimens of high noble alloys (Esteticor Plus) veneered with ceramic (VM 13) (n=16) acted as the control group. Core-veneer interface of the specimens were subjected to shear force in the Universal Testing Machine (0.5 mm⋅min(-1)). Neither the zirconia core material (P=0.318) nor colouring (P=0.188) significantly affected the results (three-way analysis of variance, Tukey's test). But the results were significantly affected by the veneering ceramic (P=0.000). Control group exhibited significantly higher mean bond strength values (45.7±8) MPa than all other tested groups ((27.1±4.1)-(39.7±4.7) and (27.4±5.6)-(35.9±4.7) MPa with and without colouring, respectively) (P<0.001). While in zirconia-veneer test groups, predominantly mixed type of failures were observed with the veneering ceramic covering <1/3 of the substrate surface, in the metal-ceramic group, veneering ceramic was left adhered >1/3 of the metal surface. Colouring zirconia did not impair adhesion of veneering ceramic, but veneering ceramic had a significant influence on the core-veneer adhesion. Metal-ceramic adhesion was more reliable than all zirconia-veneer ceramics tested.

The effect of different surface treatments on the bond strength of a gingiva-colored indirect composite veneering material to three implant framework materials.

PubMed

Koizuka, Mai; Komine, Futoshi; Blatz, Markus B; Fushiki, Ryosuke; Taguchi, Kohei; Matsumura, Hideo

2013-09-01

To evaluate and compare the shear-bond strength of a gingiva-colored indirect composite material to three different implant framework materials (zirconia ceramics, gold alloy, and titanium), and to investigate the effect of surface pretreatment by air-particle abrasion and four priming agents. A gingiva-colored indirect composite (Ceramage) was bonded to three framework materials (n = 80): commercially pure titanium (CP- Ti ), ADA (American Dental Association)-type 4 casting gold alloy (Type IV), and zirconia ceramics (Zirconia) with or without airborne-particle abrasion. Before bonding, the surface of the specimens was treated using no (control) or one of four priming agents: Alloy Primer (ALP), Estenia Opaque Primer (EOP), Metal Link Primer (MLP), and V-Primer (VPR). Shear-bond strength was determined after 24-h wet storage. Data were analyzed using Steel-Dwass for multiple comparisons, and Mann-Whitney U-test (P = 0.05). For both CP- Ti and Zirconia substrates, three groups, ALP, EOP, and MLP, showed significantly higher bond strengths (P < 0.05) than the other groups with or without airborne-particle abrasion. For Type IV substrates, significantly higher bond strengths were obtained in ALP and MLP groups (P < 0.01) compared with the other groups with airborne-particle abrasion. Application of priming agents containing specific phosphoric ester groups significantly enhances the bond strength of a gingiva-colored composite material to commercially pure titanium and zirconia frameworks. Combined use of a thione monomer with a phosphoric monomer enhances the bond strengths to airborne-particle abraded type IV gold alloy. © 2012 John Wiley & Sons A/S.

Thermoelectric Properties of Silicon Germanium: An Investigation of the Reduction of Lattice Thermal Conductivity and Enhancement of Power Factor

NASA Astrophysics Data System (ADS)

Lahwal, Ali Sadek

Thermoelectric materials are of technological interest owing to their ability of direct thermal-to-electrical energy conversion. In thermoelectricity, thermal gradients can be used to generate an electrical power output. Recent efforts in thermoelectrics are focused on developing higher efficient power generation materials. In this dissertation, the overall goal is to investigate both the n-type and p-type of the state of the art thermoelectric material, silicon germanium (SiGe), for high temperature power generation. Further improvement of thermoelectric performance of Si-Ge alloys hinges upon how to significantly reduce the as yet large lattice thermal conductivity, and optimizing the thermoelectric power factor PF. Our methods, in this thesis, will be into two different approaches as follow: The first approach is manipulating the lattice thermal conductivity of n and p-type SiGe alloys via direct nanoparticle inclusion into the n-type SiGe matrix and, in a different process, using a core shell method for the p-type SiGe. This approach is in line with the process of in-situ nanocomposites. 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 of heat-carrying phonons. To this end, a promising choice of nano-particle to include by direct mixing into a SiGe matrix would be Yttria Stabilized Zirconia ( YSZ). In this work we report the preparation and thermoelectric study of n-type SiGe + YSZ nanocomposites prepared by direct mechanical mixing followed by Spark Plasma Sintering (SPS) processing. Specifically, we experimentally investigated the reduction of lattice thermal conductivity (kappaL) in the temperature range (30--800K) of n-type Si 80Ge20P2 alloys with the incorporation of YSZ nanoparticles (20 ˜ 40 nm diameter) into the Si-Ge matrix. These samples synthesized by SPS were found to have densities > 95% of the theoretical density. At room temperature, we observed approximately a 50% reduction in the lattice thermal conductivity as result of adding 10 volume % YSZ to the Si80Ge 20P2 host matrix. A phenomenological Callaway model was used to corroborate both the temperature dependence and the reduction of kappaL over the measured temperature range (30--800K) of both Si80Ge 20P2 and Si80 Ge20P2 + YSZ samples. The observed kappaL is discussed and interpreted in terms of various phonon scattering mechanisms including alloy disorder, the Umklapp process, and boundary scattering. Specifically, a contribution from the phonon scattering by YSZ nanoparticles was further included to account for the kappaL of Si80Ge20P 2 +YSZ samples. In addition, a core shell treatment was applied onto p-type SiGe. Ball milled Si80Ge 20B1.7 alloys were coated with YSZ with different thicknesses and characterized upon their thermoelectric properties. The results show that YSZ coatings are capable of greatly reducing the thermal conductivity especially the lattice thermal conductivity. These coatings are applied directly onto mechanical alloyed (MA), p-type SiGe. The only concern about the YSZ core shelling is that these coatings turned out to be too thick degrading the electrical conductivity of the material. Our second approach, in a parallel work, is to enhance the thermoelectric power factor as well as the dimensionless figure of merit ZT of: (i) single element spark plasma sintered (SE SPS) SiGe alloys. (ii) ball milled (BM) SiGe , via sodium boron hydrate (NaBH4) alkali-metal-salt treatment. Sodium boron hydrate alkali-metal-salt thermally decomposes (decompose temperature 600 ˜ 700 K) to elemental solid sodium, solid boron, and hydrogen gas, as binary phases, e.g., Na-B or Na-H, or as a ternary phase, Na- B-H. Upon SPS at 1020 K, it is inferred that Na dopes SiGe while forming Na 2B29 phase, leading to a reduction in the electrical resistivity without much degrading the Seebeck coefficient, consequently enhancement of the power factor. Both Hall and Seebeck coefficient showed that all the samples are p-type. Data analysis shows that the reduction of the electrical resistivity can be attributed to the increased carrier concentration. While the reduction of the thermal conductivity, in the ball milled samples, is mainly due to the enhanced phonon scattering at the increased grain boundaries in addition to contribution of scattering by the Na2B29 phases, consequently resulting in a very significant 80% improvement of the ZT figure of merit. (Abstract shortened by UMI.).

Semiconductor to Metal Transition Characteristics of VO2/NiO Epitaxial Heterostructures Integrated with Si(100)

NASA Astrophysics Data System (ADS)

Molaei, Roya

The novel functionalities of Vanadium dioxide (VO2), such as, several orders of magnitude transition in resistivity and IR transmittance, provide the exciting opportunity for the development of next generation memory, sensor, and field-effect based devices. A critical issue in the development of practical devices based on metal oxides is the integration of high quality epitaxial oxide thin films with the existing silicon technology which is based on silicon (100) substrates. However, silicon is not suitable for epitaxial growth of oxides owing to its tendency to readily form an amorphous oxide layer or silicide at the film-substrate interface. The oxide films deposited directly on silicon exhibit poor crystallinity and are not suitable for device applications. To overcome this challenge, appropriate substrate templates must be developed for the growth of oxide thin films on silicon substrates. The primary objective of this dissertation was to develop an integration methodology of VO2 with Si (100) substrates so they could be used in "smart" sensor type of devices along with other multifunctional devices on the same silicon chip. This was achieved by using a NiO/c- YSZ template layer deposited in situ. It will be shown that if the deposition conditions are controlled properly. This approach was used to integrate VO 2 thin films with Si (100) substrates using pulsed laser deposition (PLD) technique. The deposition methodology of integrating VO2 thin films on silicon using various other template layers will also be discussed. Detailed epitaxial relationship of NiO/c-YSZ/Si(100) heterostructures as a template to growth of VO2 as well as were studied. We also were able to create a p-n junction within a single NiO epilayer through subsequent nanosecond laser annealing, as well as established a structure-property correlation in NiO/c-YSZ/Si(100) thin film epitaxial heterostructures with especial emphasis on the stoichiometry and crystallographic characteristics. NiO/c-YSZ/Si(100) heterostructures were used as template to grow fully relaxed VO2 thin films. The detailed x-ray diffraction, transmission electron microscopy (TEM), electrical characterization results for the deposited films will be presented. In the framework on domain matching epitaxy, epitaxial growth of VO2 (tetragonal crystal structure at growth temperature) on NiO has been explained. Our detailed phi-scan X-ray diffraction measurements corroborate our understanding of the epitaxial growth and in-plane atomic arrangements at the interface. It was observed that the transition characteristics (sharpness, over which electrical property changes are completed, amplitude, transition temperature, and hysteresis) are a strong function of microstructure, strain, and stoichiometry. We have shown that by the choosing the right template layer, strain in the VO2 thin films can be fully relaxed and near-bulk VO2 transition temperatures can be achieved. Finally, I will present my research work on modification of semiconductor-to-metal transition characteristics and effect on room temperature magnetic properties of VO2 thin films upon laser annealing. While the microstructure (epitaxy, crystalline quality etc.) and phase were preserved, we envisage these changes to occur as a result of introduction of oxygen vacancies upon laser treatment.

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.

The Thermochemical Degradation of Hot Section Materials for Gas Turbine Engines in Alternative-Fuel Combustion Environments

NASA Astrophysics Data System (ADS)

Montalbano, Timothy

Gas turbine engines remain an integral part of providing the world's propulsion and power generation needs. The continued use of gas turbines requires increased temperature operation to reach higher efficiencies and the implementation of alternative fuels for a lower net-carbon footprint. This necessitates evaluation of the material coatings used to shield the hot section components of gas turbines in these new extreme environments in order to understand how material degradation mechanisms change. Recently, the US Navy has sought to reduce its use of fossil fuels by implementing a blended hydroprocessed renewable diesel (HRD) derived from algae in its fleet. To evaluate the material degradation in this alternative environment, metal alloys are exposed in a simulated combustion environment using this blended fuel or the traditional diesel-like fuel. Evaluation of the metal alloys showed the development of thick, porous scales with a large depletion of aluminum for the blend fuel test. A mechanism linking an increased solubility of the scale to the blend fuel test environment will be discussed. For power generation applications, Integrated Gasification Combined Cycle (IGCC) power plants can provide electricity with 45% efficiency and full carbon capture by using a synthetic gas (syngas) derived from coal, biomass, or another carbon feedstock. However, the combustion of syngas is known to cause high water vapor content levels in the exhaust stream with unknown material consequences. To evaluate the effect of increased humidity, air-plasma sprayed (APS), yttria-stabilized zirconia (YSZ) is thermally aged in an environment with and without humidity. An enhanced destabilization of the parent phase by humid aging is revealed by x-ray diffraction (XRD) and Raman spectroscopy. Microstructural analysis by transmission electron microscopy (TEM) and scanning-TEM (STEM) indicate an enhanced coarsening of the domain structure of the YSZ in the humid environment. The enhanced destabilization and coarsening in the humid aging environment is explained mechanistically by water-derived species being incorporated into the YSZ structure and altering the anion sublattice. The characterization of the metal alloy and ceramic coatings exposed in these alternative environments allows for a deeper understanding of the mechanisms behind the material evolution in these environments.

Application of infiltrated LSCM-GDC oxide anode in direct carbon/coal fuel cells.

PubMed

Yue, Xiangling; Arenillas, Ana; Irvine, John T S

2016-08-15

Hybrid direct carbon/coal fuel cells (HDCFCs) utilise an anode based upon a molten carbonate salt with an oxide conducting solid electrolyte for direct carbon/coal conversion. They can be fuelled by a wide range of carbon sources, and offer higher potential chemical to electrical energy conversion efficiency and have the potential to decrease CO2 emissions compared to coal-fired power plants. In this study, the application of (La, Sr)(Cr, Mn)O3 (LSCM) and (Gd, Ce)O2 (GDC) oxide anodes was explored in a HDCFC system running with two different carbon fuels, an organic xerogel and a raw bituminous coal. The electrochemical performance of the HDCFC based on a 1-2 mm thick 8 mol% yttria stabilised zirconia (YSZ) electrolyte and the GDC-LSCM anode fabricated by wet impregnation procedures was characterized and discussed. The infiltrated oxide anode showed a significantly higher performance than the conventional Ni-YSZ anode, without suffering from impurity formation under HDCFC operation conditions. Total polarisation resistance (Rp) reached 0.8-0.9 Ω cm(2) from DCFC with an oxide anode on xerogel and bituminous coal at 750 °C, with open circuit voltage (OCV) values in the range 1.1-1.2 V on both carbon forms. These indicated the potential application of LSCM-GDC oxide anode in HDCFCs. The chemical compatibility of LSCM/GDC with carbon/carbonate investigation revealed the emergence of an A2BO4 type oxide in place of an ABO3 perovskite structure in the LSCM in a reducing environment, due to Li attack as a result of intimate contact between the LSCM and Li2CO3, with GDC being stable under identical conditions. Such reaction between LSCM and Li2CO3 was not observed on a LSCM-YSZ pellet treated with Li-K carbonate in 5% H2/Ar at 700 °C, nor on a GDC-LSCM anode after HDCFC operation. The HDCFC durability tests of GDC-LSCM oxide on a xerogel and on raw bituminous coal were performed under potentiostatic operation at 0.7 V at 750 °C. The degradation mechanisms were addressed, especially on raw coal.

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.

A Mössbauer spectral study of degradation in La 0.58Sr 0.4Fe 0.5Co 0.5O 3–x after long-term operation in solid oxide electrolysis cells

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

Mahmoud, Abdelfattah; Daroukh, Mahmoud Al; Lipinska-Chwalek, Marta

Here, degradation processes of oxygen electrodes in solid oxide electrolysis cells (SOECs) were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Mössbauer spectroscopy. La 0.58Sr 0.4Fe 0.5Co 0.5O 3–x (LSCF) anodes (oxygen electrode) were analyzed after different long-term operations durations of 1774, 6100 and 9000 h. The results were compared with a cell in the initial state. Besides the LSCF anode, the SOECs were composed of a Ce 0.8Gd 0.2O 1.9 barrier layer between the anode and electrolyte, yttria-stabilized zirconia (YSZ) as electrolyte and Ni-YSZ as cathode (hydrogen electrode). Mössbauer spectra of the iron-containingmore » anode were acquired in order to determine the alteration of the iron oxidation state and its local environment during operation. Mössbauer spectroscopy yields indirect information about the degradation mechanism, especially in combination with SEM, TEM, and XRD. XRD and TEM revealed the appearance of Co 3O 4 during the SOEC operation and SEM analyses confirmed the formation of SrZrO 3 at the electrode/electrolyte interface. The spectral analysis confirmed the reduction of iron from Fe(IV) to Fe(III) in LSCF after long-term operation. The fraction of Fe(IV) in the electrode decreased with time and 18, 15, 13 and 11% were obtained for 0, 1774, 6100, and 9000 h of operation, respectively.« less

A Mössbauer spectral study of degradation in La 0.58Sr 0.4Fe 0.5Co 0.5O 3–x after long-term operation in solid oxide electrolysis cells

DOE PAGES

Mahmoud, Abdelfattah; Daroukh, Mahmoud Al; Lipinska-Chwalek, Marta; ...

2017-10-21

Here, degradation processes of oxygen electrodes in solid oxide electrolysis cells (SOECs) were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Mössbauer spectroscopy. La 0.58Sr 0.4Fe 0.5Co 0.5O 3–x (LSCF) anodes (oxygen electrode) were analyzed after different long-term operations durations of 1774, 6100 and 9000 h. The results were compared with a cell in the initial state. Besides the LSCF anode, the SOECs were composed of a Ce 0.8Gd 0.2O 1.9 barrier layer between the anode and electrolyte, yttria-stabilized zirconia (YSZ) as electrolyte and Ni-YSZ as cathode (hydrogen electrode). Mössbauer spectra of the iron-containingmore » anode were acquired in order to determine the alteration of the iron oxidation state and its local environment during operation. Mössbauer spectroscopy yields indirect information about the degradation mechanism, especially in combination with SEM, TEM, and XRD. XRD and TEM revealed the appearance of Co 3O 4 during the SOEC operation and SEM analyses confirmed the formation of SrZrO 3 at the electrode/electrolyte interface. The spectral analysis confirmed the reduction of iron from Fe(IV) to Fe(III) in LSCF after long-term operation. The fraction of Fe(IV) in the electrode decreased with time and 18, 15, 13 and 11% were obtained for 0, 1774, 6100, and 9000 h of operation, respectively.« less

Degradation of TBC Systems in Environments Relevant to Advanced Gas Turbines for IGCC Systems

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

Gleeson, Brian

2014-09-30

Air plasma sprayed (APS) thermal barrier coatings (TBCs) are used to provide thermal insulation for the hottest components in gas turbines. Zirconia stabilized with 7wt% yttria (7YSZ) is the most common ceramic top coat used for turbine blades. The 7YSZ coating can be degraded from the buildup of fly-ash deposits created in the power-generation process. Fly ash from an integrated gasification combined cycle (IGCC) system can result from coal-based syngas. TBCs are also exposed to harsh gas environments containing CO 2, SO 2, and steam. Degradation from the combined effects of fly ash and harsh gas atmospheres has the potentialmore » to severely limit TBC lifetimes. The main objective of this study was to use lab-scale testing to systematically elucidate the interplay between prototypical deposit chemistries (i.e., ash and its constituents, K 2SO 4, and FeS) and environmental oxidants (i.e., O 2, H 2O and CO 2) on the degradation behavior of advanced TBC systems. Several mechanisms of early TBC failure were identified, as were the specific fly-ash constituents responsible for degradation. The reactivity of MCrAlY bondcoats used in TBC systems was also investigated. The specific roles of oxide and sulfate components were assessed, together with the complex interplay between gas composition, deposit chemistry and alloy reactivity. Bondcoat composition design strategies to mitigate corrosion were established, particularly with regard to controlling phase constitution and the amount of reactive elements the bondcoat contains in order to achieve optimal corrosion resistance.« less

Electric-Loading Enhanced Kinetics in Oxide Ceramics: Pore Migration, Sintering and Grain Growth: Final Report

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

Chen, I-Wei

Solid oxide fuel cells and solid oxide electrolysis cells rely on solid electrolytes in which a large ionic current dominates. This project was initiated to investigate microstructural changes in such devices under electrochemical forces, because nominally insignificant processes may couple to the large ionic current to yield non-equilibrium phenomena that alter the microstructure. Our studies had focused on yttria-stabilized cubic zirconia (YSZ) widely used in these devices. The experiments have revealed enhanced grain growth at higher temperatures, pore and gas bubble migration at all temperatures, and the latter also lead to enhanced sintering of highly porous ceramics into fully densemore » ceramics at unprecedentedly low temperatures. These results have shed light on kinetic processes that fall completely outside the realm of classical ceramic processing. Other fast-oxygen oxide ceramics closely related to, and often used in conjunction with zirconia ceramics, have also be investigated, as are closely related scientific problems in zirconia ceramics. These include crystal structures, defects, diffusion kinetics, oxygen potentials, low temperature sintering, flash sintering, and coarsening theory, and all have resulted in greater clarity in scientific understanding. The knowledge is leveraged to provide new insight to electrode kinetics and near-electrode mixed conductivity and to new materials. In the following areas, our research has resulted in completely new knowledge that defines the state-of-the-art of the field. (a) Electrical current driven non-equilibrium phenomena, (b) Enhanced grain growth under electrochemically reducing conditions, (c) Development of oxygen potential polarization in electrically loaded electrolyte, (d) Low temperature sintering and grain growth, and (e) Structure, defects and cation kinetics of fluorite-structured oxides. Our research has also contributed to synthesis of new energy-relevant electrochemical materials and new understanding of flash sintering, which is a rapid sintering process initiated by a large electrical loading.« less

Use of La 0.75Sr 0.25Cr 0.5Mn 0.5O 3 materials in composite anodes for direct ethanol solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ye, Xiao-Feng; Wang, S. R.; Wang, Z. R.; Hu, Q.; Sun, X. F.; Wen, T. L.; Wen, Z. Y.

The perovskite system La 1- xSr xCr 1- yM yO 3- δ (M, Mn, Fe and V) has recently attracted much attention as a candidate material for the fabrication of solid oxide fuel cells (SOFCs) due to its stability in both H 2 and CH 4 atmospheres at temperatures up to 1000 °C. In this paper, we report the synthesis of La 0.75Sr 0.25Cr 0.5Mn 0.5O 3 (LSCM) by solid-state reaction and its employment as an alternative anode material for anode-supported SOFCs. Because LSCM shows a greatly decreased electronic conductivity in a reducing atmosphere compared to that in air, we have fabricated Cu-LSCM-ScSZ (scandia-stabilized zirconia) composite anodes by tape-casting and a wet-impregnation method. Additionally, a composite structure (support anode, functional anode and electrolyte) structure with a layer of Cu-LSCM-YSZ (yttria-stabilized zirconia) on the supported anode surface has been manufactured by tape-casting and screen-printing. Single cells with these two kinds of anodes have been fabricated, and their performance characteristics using hydrogen and ethanol have been measured. In the operation period, no obvious carbon deposition was observed when these cells were operated on ethanol. These results demonstrate the stability of LSCM in an ethanol atmosphere and its potential utilization in anode-supported SOFCs.

Method for fabrication of high temperature superconductors

DOEpatents

Balachandran, Uthamalingam; Ma, Beihai; Miller, Dean

2006-03-14

A layered article of manufacture and a method of manufacturing same is disclosed. A substrate has a biaxially textured MgO crystalline layer having the c-axes thereof inclined with respect to the plane of the substrate deposited thereon. A layer of one or more of YSZ or Y₂O₃ and then a layer of CeO₂ is deposited on the MgO. A crystalline superconductor layer with the c-axes thereof normal to the plane of the substrate is deposited on the CeO₂ layer. Deposition of the MgO layer on the substrate is by the inclined substrate deposition method developed at Argonne National Laboratory. Preferably, the MgO has the c-axes thereof inclined with respect to the normal to the substrate in the range of from about 10.degree. to about 40.degree. and YBCO superconductors are used.

Method for fabrication of high temperature superconductors

DOEpatents

Balachandran, Uthamalingam [Hinsdale, IL; Ma, Beihai [Naperville, IL; Miller, Dean [Darien, IL

2009-07-14

A layered article of manufacture and a method of manufacturing same is disclosed. A substrate has a biaxially textured MgO crystalline layer having the c-axes thereof inclined with respect to the plane of the substrate deposited thereon. A layer of one or more of YSZ or Y.sub.2O.sub.3 and then a layer of CeO.sub.2 is deposited on the MgO. A crystalline superconductor layer with the c-axes thereof normal to the plane of the substrate is deposited on the CeO.sub.2 layer. Deposition of the MgO layer on the substrate is by the inclined substrate deposition method developed at Argonne National Laboratory. Preferably, the MgO has the c-axes thereof inclined with respect to the normal to the substrate in the range of from about 10.degree. to about 40.degree. and YBCO superconductors are used.

Effect of the co-spun anode functional layer on the performance of the direct-methane microtubular solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Meng, Xiuxia; Gong, Xun; Yin, Yimei; Yang, Naitao; Tan, Xiaoyao; Ma, Zi-Feng

2014-02-01

NiO-YSZ/porous YSZ (NiO-YSZ/p-YSZ) dual-layer hollow fibers have been fabricated by a co-spinning-sintering method, on which a dense YSZ films has been formed by a dip-coating and sintering process. A LSM-YSZ ink has been dip-coated on the dense YSZ films as cathode, while the Cu-CeO2 carbon-resistant catalyst has been impregnated in the p-YSZ layer to form double-anode supported micro tubular fuel cells (MT-SOFCs). The thickness of the Ni-YSZ layer, so called anode functional layer (AFL), is controlled from 74 μm to 13 μm by varying the spinning rates of the NiO-YSZ dopes. The maximum power density of an MT-SOFC, which is fabricated based on a thin co-spun AFL, reaches 566 mW cm-2 operated at 850 °C fed with dry methane, and is stably operated for 85 h without power declination.

Effects of silane- and MDP-based primers application orders on zirconia-resin adhesion-A ToF-SIMS study.

PubMed

Chuang, Shu-Fen; Kang, Li-Li; Liu, Yi-Chuan; Lin, Jui-Che; Wang, Ching-Cheng; Chen, Hui-Min; Tai, Cheng-Kun

2017-08-01

To evaluate the 3-methacryloyloxypropyltrimethoxysilane (MPS)- and 10-methacryloyloxydecyl-dihydrogen-phosphate (MDP)-base primers, in their single or sequential applications, with regard to modifying zirconia surfaces and improving resin-zirconia adhesion. Zirconia disks received different treatments: without primer (Zr), MPS-base primer (S), MDP-base primer (M), MPS/MDP mixture (SMmix), MPS followed by MDP (SM), and MDP followed by MPS (MS). The compositions and chemical interactions of the coatings to zirconia were analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and reconstructed 3D ion images. Surface wettability of these coatings to water and resin adhesive was assessed. The shear bond strength (SBS) between resin and the treated zirconia was also examined before and after thermocycling. Groups S and MS presented substantial OH - ions in the coatings and zirconia substrate. PO 2 - and PO 3 - fragments existed in all MDP-treatment groups with various proportions and distributions, while groups M and SM showed higher proportions of PO 3 - and the zirconium phosphate related ions. In 3D ion images, PO 3 - in groups M and SM was denser and segregated to the interface, but was dispersed or overlaid above PO 2 - in SMmix and MS. All the primers increased the surface wettability to water and resin, with M and SM presenting superhydrophilic surfaces. All MDP-treatment groups showed improved SBS before thermocycling, while M and SM retained higher SBS after this. The MDP-base primer shows a relevant function in facilitating POZr bonding and enhancing resin-zirconia bonding. The co-treated MPS impairs the chemical activity of MDP, especially if it is the final coat. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Projection parameters for zirconia-alumina-ceria coatings made by flame spraying from results of numerical simulation

NASA Astrophysics Data System (ADS)

Rodríguez, L.; Ferrer, M.; Vargas, F.; Peña, G.

2017-12-01

A numerical simulation was performed with the software Jets et Poudres, the results let choose the parameters to deposit zirconia-alumina-ceria coatings of different composition on substrates of red clay, by thermal spraying with the oxyacetylene flame to obtain homogeneous coatings with good adhesion to the substrate. The effect of the projection distance (7, 10 and 12cm) between the substrate and the torch, the fusion percentage of particles and the K-Sommerfeld number was determined. This number is dimensionless and is affected by the projection distance and by the chemical composition of the particles. For a projection distance of 9cm, the fusion percentage of the particles varies between 83.8% and 100%, and the K-Sommerfeld number between 47.3 and 50 for the different compounds. This makes possible to obtain uniform coatings with good wettability, therefore, good adhesion to the substrate, while for the distance of 7cm the fusion percentage varies between 22% and 38%, due to the short time of the particles in the flame which causes low adhesion, when the projection distance is 12cm the particles do not have sufficient kinetic energy to reach the substrate and therefore the coating is not deposited.

Gadolinium doped ceria interlayers for Solid Oxide Fuel Cells cathodes: Enhanced reactivity with sintering aids (Li, Cu, Zn), and improved densification by infiltration

NASA Astrophysics Data System (ADS)

Nicollet, Clement; Waxin, Jenny; Dupeyron, Thomas; Flura, Aurélien; Heintz, Jean-Marc; Ouweltjes, Jan Pieter; Piccardo, Paolo; Rougier, Aline; Grenier, Jean-Claude; Bassat, Jean-Marc

2017-12-01

This paper reports the study of the densification of 20% Gd doped ceria (Ce0.8Gd0.2O1.9 (GDC)) interlayers in SOFC cathodes through two different routes: the well-known addition of sintering elements, and an innovative densification process by infiltration. First, Li, Cu, and Zn nitrates were added to GDC powders. The effect of these additives on the densification was studied by dilatometry on pellets, and show a large decrease of the sintering temperature from 1330 °C (pure GDC), down to 1080 °C, 950 °C, and 930 °C for Zn, Cu, and Li addition, respectively. However, this promising result does not apply to screen-printed layers, which are more porous than pellets and in which the shrinkage is constrained by the substrate. The second approach consists in preparing a pre-sintered GDC layer, which is subsequently infiltrated with Ce and Gd nitrates and sintered at 1250 °C to increase its density. Such an approach results in highly dense GDC interlayers. Using La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) as electrode, the influence of the interlayers on the cathode performance was studied. The addition of sintering aids dramatically increases the cell resistances, most likely because the additives increase the reactivity between GDC and either Yttria Stabilized Zirconia (YSZ) or LSCF, thus losing the expected benefit related to the decrease of sintering temperatures. The interlayers prepared by infiltration do not induce additional resistances in the cell, which results in power densities of single cells 40-50% higher than those of cells prepared with commercial GDC interlayers, making this approach a valuable alternative to sintering aids.

Dependencies of microstructure and stress on the thickness of GdBa2Cu3O7 − δ thin films fabricated by RF sputtering

PubMed Central

2013-01-01

GdBa2Cu3O7 − δ (GdBCO) films with different thicknesses from 200 to 2,100 nm are deposited on CeO2/yttria-stabilized zirconia (YSZ)/CeO2-buffered Ni-W substrates by radio-frequency magnetron sputtering. Both the X-ray diffraction and scanning electron microscopy analyses reveal that the a-axis grains appear at the upper layers of the films when the thickness reaches to 1,030 nm. The X-ray photoelectron spectroscopy measurement implies that the oxygen content is insufficient in upper layers beyond 1,030 nm for a thicker film. The Williamson-Hall method is used to observe the variation of film stress with increasing thickness of our films. It is found that the highest residual stresses exist in the thinnest film, while the lowest residual stresses exist in the 1,030-nm-thick film. With further increasing film thickness, the film residual stresses increase again. However, the critical current (Ic) of the GdBCO film first shows a nearly linear increase and then shows a more slowly enhancing to a final stagnation as film thickness increases from 200 to 1,030 nm and then to 2,100 nm. It is concluded that the roughness and stress are not the main reasons which cause the slow or no increase in Ic. Also, the thickness dependency of GdBa2Cu3O7 − δ films on the Ic is attributed to three main factors: a-axis grains, gaps between a-axis grains, and oxygen deficiency for the upper layers of a thick film. PMID:23816137

Effect of colouring green stage zirconia on the adhesion of veneering ceramics with different thermal expansion coefficients

PubMed Central

Aktas, Guliz; Sahin, Erdal; Vallittu, Pekka; Özcan, Mutlu; Lassila, Lippo

2013-01-01

This study evaluated the adhesion of zirconia core ceramics with their corresponding veneering ceramics, having different thermal expansion coefficients (TECs), when zirconia ceramics were coloured at green stage. Zirconia blocks (N=240; 6 mm×7 mm×7 mm) were manufactured from two materials namely, ICE Zirconia (Group 1) and Prettau Zirconia (Group 2). In their green stage, they were randomly divided into two groups. Half of the specimens were coloured with colouring liquid (shade A2). Three different veneering ceramics with different TEC (ICE Ceramic, GC Initial Zr and IPS e.max Ceram) were fired on both coloured and non-coloured zirconia cores. Specimens of high noble alloys (Esteticor Plus) veneered with ceramic (VM 13) (n=16) acted as the control group. Core–veneer interface of the specimens were subjected to shear force in the Universal Testing Machine (0.5 mm⋅min−1). Neither the zirconia core material (P=0.318) nor colouring (P=0.188) significantly affected the results (three-way analysis of variance, Tukey's test). But the results were significantly affected by the veneering ceramic (P=0.000). Control group exhibited significantly higher mean bond strength values (45.7±8) MPa than all other tested groups ((27.1±4.1)−(39.7±4.7) and (27.4±5.6)−(35.9±4.7) MPa with and without colouring, respectively) (P<0.001). While in zirconia–veneer test groups, predominantly mixed type of failures were observed with the veneering ceramic covering <1/3 of the substrate surface, in the metal–ceramic group, veneering ceramic was left adhered >1/3 of the metal surface. Colouring zirconia did not impair adhesion of veneering ceramic, but veneering ceramic had a significant influence on the core–veneer adhesion. Metal–ceramic adhesion was more reliable than all zirconia–veneer ceramics tested. PMID:24158142

Phase Transformation and Lattice Parameter Changes of Non-trivalent Rare Earth-Doped YSZ as a Function of Temperature

NASA Astrophysics Data System (ADS)

Jiang, Shengli; Huang, Xiao; He, Zhang; Buyers, Andrew

2018-01-01

To examine the effect of doping/co-doping on high-temperature phase compositions of YSZ, stand-alone YSZ and CeO2 and Nb2O5 co-doped YSZ samples were prepared using mechanical alloy and high-temperature sintering. XRD analysis was performed on these samples from room temperature to 1100 °C. The results show that the structure for the co-doped samples tends to be thermally stable when the test temperature is higher than a critical value. Monoclinic phase was dominant in Nb2O5 co-doped YSZ at temperatures lower than 600 °C, while for the YSZ and CeO2 co-doped YSZ, cubic/tetragonal phase was dominant in the whole test temperature range. The lattice parameters for all the samples increase with increasing test temperature generally. The lattice parameters for the two non-trivalent rare earth oxides co-doped YSZ show that the lattice parameter a for the cubic phase of the Ce4+ co-doped YSZ is consistently greater than that of 7YSZ which is related to the presence of larger radius of Ce4+ in the matrix. The lattice parameters a, b, c for the monoclinic phase of Ce4+ co-doped YSZ are much closer to each other than that of the Nb5+ co-doped YSZ, indicating the former has better tendency to form cubic/tetragonal phase, which is desired for vast engineering applications.

Phase Transformation and Lattice Parameter Changes of Non-trivalent Rare Earth-Doped YSZ as a Function of Temperature

NASA Astrophysics Data System (ADS)

Jiang, Shengli; Huang, Xiao; He, Zhang; Buyers, Andrew

2018-05-01

To examine the effect of doping/co-doping on high-temperature phase compositions of YSZ, stand-alone YSZ and CeO2 and Nb2O5 co-doped YSZ samples were prepared using mechanical alloy and high-temperature sintering. XRD analysis was performed on these samples from room temperature to 1100 °C. The results show that the structure for the co-doped samples tends to be thermally stable when the test temperature is higher than a critical value. Monoclinic phase was dominant in Nb2O5 co-doped YSZ at temperatures lower than 600 °C, while for the YSZ and CeO2 co-doped YSZ, cubic/tetragonal phase was dominant in the whole test temperature range. The lattice parameters for all the samples increase with increasing test temperature generally. The lattice parameters for the two non-trivalent rare earth oxides co-doped YSZ show that the lattice parameter a for the cubic phase of the Ce4+ co-doped YSZ is consistently greater than that of 7YSZ which is related to the presence of larger radius of Ce4+ in the matrix. The lattice parameters a, b, c for the monoclinic phase of Ce4+ co-doped YSZ are much closer to each other than that of the Nb5+ co-doped YSZ, indicating the former has better tendency to form cubic/tetragonal phase, which is desired for vast engineering applications.

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density (i sub o) values being greater than 60mA sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent (compared to H2) for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed tha basis for the lithium oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Image contrast enhancement of Ni/YSZ anode during the slice-and-view process in FIB-SEM.

PubMed

Liu, Shu-Sheng; Takayama, Akiko; Matsumura, Syo; Koyama, Michihisa

2016-03-01

Focused ion beam-scanning electron microscopy (FIB-SEM) is a widely used and easily operational equipment for three-dimensional reconstruction with flexible analysis volume. It has been using successfully and increasingly in the field of solid oxide fuel cell. However, the phase contrast of the SEM images is indistinct in many cases, which will bring difficulties to the image processing. Herein, the phase contrast of a conventional Ni/yttria stabilized zirconia anode is tuned in an FIB-SEM with In-Lens secondary electron (SE) and backscattered electron detectors. Two accessories, tungsten probe and carbon nozzle, are inserted during the observation. The former has no influence on the contrast. When the carbon nozzle is inserted, best and distinct contrast can be obtained by In-Lens SE detector. This method is novel for contrast enhancement. Phase segmentation of the image can be automatically performed. The related mechanism for different images is discussed. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

Properties and rapid sintering of a nanostructured tetragonal zirconia composites

NASA Astrophysics Data System (ADS)

Shon, In-Jin; Yoon, Jin-Kook; Hong, Kyung-Tae

2017-09-01

4YSZ is generally used as oxygen sensors, fuel cells, thermal barrier and hip and knee joint replacements as a result of these excellent properties with its high biocompatibility, low density, good resistance against corrosion, high ionic conductivity, hard phase and melting point. However, 4YTZ with coarse grain has low resistance to wear and abrasion because of low hardness and low fracture toughness at room temperature. The fracture toughness and hardness of a 4YTZ can be improved by forming nanostructured composites and addition of a second hard phase. In this study, nanostuctured 4YTZ-graphene composites with nearly full density were achieved using high-frequency induction heated sintering for one min at a pressure of 80 MPa. The rapid consolidation and addition of graphene to 4YTZ retained the nano-scale structure of the ceramic by inhibiting grain growth. The grain size of 4YTZ was reduced remarkably by the addition of graphene and the addition of graphene to 4YTZ greatly improved the fracture toughness without decrease of hardness.

Cycling Performance of a Columnar-Structured Complex Perovskite in a Temperature Gradient Test

NASA Astrophysics Data System (ADS)

Schlegel, N.; Sebold, D.; Sohn, Y. J.; Mauer, G.; Vaßen, R.

2015-10-01

To increase the efficiency of turbines for the power generation and the aircraft industry, advanced thermal barrier coatings (TBCs) are required. They need to be long-term stable at temperatures higher than 1200 °C. Nowadays, yttria partially stabilized zirconia (YSZ) is applied as standard TBC material. But its long-term application at temperatures higher than 1200 °C leads to detrimental phase changes and sintering effects. Therefore, new materials have to be investigated, for example, complex perovskites. They provide high melting points, high thermal expansion coefficients and thermal conductivities of approx. 2.0 W/(m K). In this work, the complex perovskite La(Al1/4Mg1/2Ta1/4)O3 (LAMT) was investigated. It was deposited by the suspension plasma spraying (SPS) process, resulting in a columnar microstructure of the coating. The coatings were tested in thermal cycling gradient tests and they show excellent results, even though some phase decomposition was found.

Three dimensional characterization of nickel coarsening in solid oxide cells via ex-situ ptychographic nano-tomography

NASA Astrophysics Data System (ADS)

De Angelis, Salvatore; Jørgensen, Peter Stanley; Tsai, Esther Hsiao Rho; Holler, Mirko; Kreka, Kosova; Bowen, Jacob R.

2018-04-01

Nickel coarsening is considered a significant cause of solid oxide cell (SOC) performance degradation. Therefore, understanding the morphological changes in the nickel-yttria stabilized zirconia (Ni-YSZ) fuel electrode is crucial for the wide spread usage of SOC technology. This paper reports a study of the initial 3D microstructure evolution of a SOC analyzed in the pristine state and after 3 and 8 h of annealing at 850 °C, in dry hydrogen. The analysis of the evolution of the same location of the electrode shows a substantial change of the nickel and pore network during the first 3 h of treatment, while only negligible changes are observed after 8 h. The nickel coarsening results in loss of connectivity in the nickel network, reduced nickel specific surface area and decreased total triple phase boundary density. For the condition of this experiment, nickel coarsening is shown to be predominantly curvature driven, and changes in the electrode microstructure parameters are discussed in terms of local microstructural evolution.

Development and testing of an electrochemical methane sensor

DOE PAGES

Sekhar, Praveen K.; Kysar, Jesse; Brosha, Eric Lanich; ...

2016-01-12

In this article, the development of an electrochemical methane sensor is presented. The mixed potential based sensor is based on tin doped indium oxide (ITO) and platinum electrodes and yttria-stabilized zirconia (YSZ) electrolyte. The sensor was fabricated using the inexpensive tape-cast method. The sensor responded to methane with a response time of 15 s. The staircase response to methane indicated a 44 mV sensor response to 100 ppm of methane. The sensor response indicated a log-linear relationship with the methane concentration. Upon 500 h of sensor testing, a 5% reduction in methane sensitivity was observed. The cross-sensitivity study on themore » sensor indicated minimal interference to NO, NO 2, and CO 2. To improve the sensitivity to methane, a signal conditioning method referred to as the pulsed discharge technique (PDT) was applied. Finally, a fourfold increase in methane sensitivity was observed when the sensor was subjected to PDT. Future studies include the miniaturization of the sensor with integrated heater design.« less

Development and testing of an electrochemical methane sensor

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

Sekhar, Praveen K.; Kysar, Jesse; Brosha, Eric Lanich

In this article, the development of an electrochemical methane sensor is presented. The mixed potential based sensor is based on tin doped indium oxide (ITO) and platinum electrodes and yttria-stabilized zirconia (YSZ) electrolyte. The sensor was fabricated using the inexpensive tape-cast method. The sensor responded to methane with a response time of 15 s. The staircase response to methane indicated a 44 mV sensor response to 100 ppm of methane. The sensor response indicated a log-linear relationship with the methane concentration. Upon 500 h of sensor testing, a 5% reduction in methane sensitivity was observed. The cross-sensitivity study on themore » sensor indicated minimal interference to NO, NO 2, and CO 2. To improve the sensitivity to methane, a signal conditioning method referred to as the pulsed discharge technique (PDT) was applied. Finally, a fourfold increase in methane sensitivity was observed when the sensor was subjected to PDT. Future studies include the miniaturization of the sensor with integrated heater design.« less

Nanocomposite thin films for high temperature optical gas sensing of hydrogen

DOEpatents

Ohodnicki, Jr., Paul R.; Brown, Thomas D.

2013-04-02

The disclosure relates to a plasmon resonance-based method for H.sub.2 sensing in a gas stream at temperatures greater than about 500.degree. C. utilizing a hydrogen sensing material. The hydrogen sensing material is comprised of gold nanoparticles having an average nanoparticle diameter of less than about 100 nanometers dispersed in an inert matrix having a bandgap greater than or equal to 5 eV, and an oxygen ion conductivity less than approximately 10.sup.-7 S/cm at a temperature of 700.degree. C. Exemplary inert matrix materials include SiO.sub.2, Al.sub.2O.sub.3, and Si.sub.3N.sub.4 as well as modifications to modify the effective refractive indices through combinations and/or doping of such materials. At high temperatures, blue shift of the plasmon resonance optical absorption peak indicates the presence of H.sub.2. The method disclosed offers significant advantage over active and reducible matrix materials typically utilized, such as yttria-stabilized zirconia (YSZ) or TiO.sub.2.

Nanocomposite thin films for optical gas sensing

DOEpatents

Ohodnicki, Paul R; Brown, Thomas D

2014-06-03

The disclosure relates to a plasmon resonance-based method for gas sensing in a gas stream utilizing a gas sensing material. In an embodiment the gas stream has a temperature greater than about 500.degree. C. The gas sensing material is comprised of gold nanoparticles having an average nanoparticle diameter of less than about 100 nanometers dispersed in an inert matrix having a bandgap greater than or equal to 5 eV, and an oxygen ion conductivity less than approximately 10.sup.-7 S/cm at a temperature of 700.degree. C. Exemplary inert matrix materials include SiO.sub.2, Al.sub.2O.sub.3, and Si.sub.3N.sub.4 as well as modifications to modify the effective refractive indices through combinations and/or doping of such materials. Changes in the chemical composition of the gas stream are detected by changes in the plasmon resonance peak. The method disclosed offers significant advantage over active and reducible matrix materials typically utilized, such as yttria-stabilized zirconia (YSZ) or TiO.sub.2.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-12-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density (i sub o) values being greater than 60mA sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent (compared to H2) for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed tha basis for the lithium oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Physical and electrochemical properties of alkaline earth doped, rare earth vanadates

NASA Astrophysics Data System (ADS)

Adijanto, Lawrence; Balaji Padmanabhan, Venu; Holmes, Kevin J.; Gorte, Raymond J.; Vohs, John M.

2012-06-01

The effect of partial substitution of alkaline earth (AE) ions, Sr2+ and Ca2+, for the rare earth (RE) ions, La3+, Ce3+, Pr3+, and Sm3+, on the physical properties of REVO4 compounds were investigated. The use of the Pechini method to synthesize the vanadates allowed for high levels of AE substitution to be obtained. Coulometric titration was used to measure redox isotherms for these materials and showed that the addition of the AE ions increased both reducibility and electronic conductivity under typical solid oxide fuel cell (SOFC) anode conditions, through the formation of compounds with mixed vanadium valence. In spite of their high electronic conductivity, REVO4-yttira stabilized zirconia (YSZ) composite anodes exhibited only modest performance when used in SOFCs operating with H2 fuel at 973 K due to their low catalytic activity. High performance was obtained, however, after the addition of a small amount of catalytically active Pd to the anode.

Highly Oriented Growth of Piezoelectric Thin Films on Silicon Using Two-Dimensional Nanosheets as Growth Template Layer.

PubMed

Nguyen, Minh D; Yuan, Huiyu; Houwman, Evert P; Dekkers, Matthijn; Koster, Gertjan; Ten Elshof, Johan E; Rijnders, Guus

2016-11-16

Ca 2 Nb 3 O 10 (CNOns) and Ti 0.87 O 2 (TiOns) metal oxide nanosheets (ns) are used as a buffer layer for epitaxial growth of piezoelectric capacitor stacks on Si and Pt/Ti/SiO 2 /Si (Pt/Si) substrates. Highly (001)- and (110)-oriented Pb(Zr 0.52 Ti 0.48 )O 3 (PZT) films are achieved by utilizing CNOns and TiOns, respectively. The piezoelectric capacitors are characterized by polarization and piezoelectric hysteresis loops and by fatigue measurements. The devices fabricated with SrRuO 3 top and bottom electrodes directly on nanosheets/Si have ferroelectric and piezoelectric properties well comparable with devices that use more conventional oxide buffer layers (stacks) such as YSZ, CeO 2 /YSZ, or SrTiO 3 on Si. The devices grown on nanosheets/Pt/Si with Pt top electrodes show significantly improved polarization fatigue properties over those of similar devices grown directly on Pt/Si. The differences in properties are ascribed to differences in the crystalline structures and the density of the films. These results show a route toward the fabrication of single crystal piezoelectric thin films and devices with high quality, long-lifetime piezoelectric capacitor structures on nonperovskite and even noncrystalline substrates such as glass or polished metal surfaces.

Structural properties of zirconia - in-situ high temperature XRD characterization

NASA Astrophysics Data System (ADS)

Kurpaska, Lukasz

2018-07-01

In this work, the effect of high temperature on structural properties of pure zirconium have been investigated. In-situ X-ray diffraction analysis of the oxide layer formed at temperature window 25-600 °C on pure zirconium were performed. Conducted experiment aimed at investigation of the zirconia phases developed on surface of the metallic substrate. Based on the conducted studies, possible stress state (during heating, continuous oxidation and cooling), cell parameters and HWHM factor were analyzed. A tetragonal and monoclinic phases peak shifts and intensities change were observed, suggesting that different phases react in different way upon temperature effect.

Effect of SDC-impregnated LSM cathodes on the performance of anode-supported YSZ films for SOFCs

NASA Astrophysics Data System (ADS)

Chen, Kongfa; Lü, Zhe; Ai, Na; Chen, Xiangjun; Hu, Jinyan; Huang, Xiqiang; Su, Wenhui

Sm 0.2Ce 0.8O 1.9 (SDC)-impregnated La 0.7Sr 0.3MnO 3 (LSM) composite cathodes were fabricated on anode-supported yttria-stabilized zirconia (YSZ) thin films. Electrochemical performances of the solid oxide fuel cells (SOFCs) were investigated in the present study. Four single cells, i.e., Cell-1, Cell-2, Cell-3 and Cell-4 were obtained after the fabrication of four different cathodes, i.e., pure LSM and SDC/LSM composites in the weight ratios of 25/75, 36/64 and 42/58, respectively. Impedance spectra under open-circuit conditions showed that the cathode performance was gradually improved with the increasing SDC loading. Similarly, the maximum power densities (MPD) of the four cells were increased with the SDC amount below 700 °C. Whereas, the cell performance of Cell-4 was lower than that of Cell-3 at 800 °C, arising from the increased concentration polarization at high current densities. This was caused by the lowered porosity with the impregnation cycle. This disadvantage could be suppressed by lowering the operating temperature or by increasing the oxygen concentration at the cathode side. The ratio of electrode polarization loss in the total voltage drop versus current density showed that the cell performance was primarily determined by the electrode polarization. The contribution of the ohmic resistance was increased when the operating temperature was lowered. When a 100 ml min -1 oxygen flow was introduced to the cathode side, Cell-3 produced MPDs of 1905, 1587 and 1179 mW cm -2 at 800, 750 and 700 °C, respectively. The high cell outputs demonstrated the merits of the novel and effective SDC-impregnated LSM cathodes.

Gadolinia doped hafnia (Gd2O3- HfO 2) thermal barrier coatings for gas turbine applications

NASA Astrophysics Data System (ADS)

Gullapalli, Satya Kiran

Thermal efficiency of the gas turbines is influenced by the operating temperature of the hot gas path components. The material used for the hot gas path components can only withstand temperature up to a certain limit. Thermal barrier coatings (TBC) provide the additional thermal protection for these components and help the gas turbine achieve higher firing temperatures. Traditionally available yttria stabilized zirconia (YSZ) TBCs have a limitation up to 1200 C due to their phase transformation. The present work focuses on gadolinia based hafnia (GSH) TBCs to study their potential to replace the YSZ coatings. Different compositions of gadolinia doped hafnia coatings have been deposited using electron beam physical vapor deposition (EB-PVD) technique and characterized using x-ray diffraction (XRD) and scanning electron microscope (SEM). The crystal structure analysis performed using XRD confirmed the stabilization of the high temperature cubic phase of hafnia. Cross sectional analysis confirmed the presence of columnar structure in the coatings which is a signature of the EB-PVD coatings. Mechanical properties of the coatings were investigated using nanoindentation and nano impact testing at both room temperature and high temperature. Indentation tests indicate a reduction in hardness with an increase in temperature and gadolinia content in hafnia. Impact testing reveals the fracture resistance of the coatings as a function of stabilizer content and heat treatment. Thermal measurements and impedance testing was performed on the bulk material to study the effect of gadolinia content. Thermal cycling was performed to study the spallation behavior of the as deposited and aged samples. Finite element models were developed to study the interfacial stress development in the coatings subjected to thermal cycling.

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.

Study on AN Intermediate Temperature Planar Sofc

NASA Astrophysics Data System (ADS)

Wang, Shaorong; Cao, Jiadi; Chen, Wenxia; Lu, Zhiyi; Wang, Daqian; Wen, Ting-Lian

An ITSOFC consisted of Ni/YSZ anode supported YSZ composite thin film and La0.6Sr0.4CoO3 (LSCO) cathode combined with a Ce0.8Sm0.2O1.9 (CSO) interlayer was studied. Tape cast method was applied to prepare green sheets of Ni/YSZ anode supported YSZ composite thin film. After isostatic pressing and cosintering, the YSZ film on the Ni/YSZ anode was gas-tight dense, and 15-30μm thick. The area of the composite film was over 100 cm2. A CSO interlayer was sintered on to the YSZ electrolyte film to protect LSCO cathode from reaction with YSZ at high temperatures. The LSCO cathode layer was screen printed onto the CSO interlayer and sintered at 1200°C for 3h to form a single cell. The obtained single cell was operated with H2 as fuel and O2 as oxidant. The cell performance and impedance were measured and discussed relating with the component contributions.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2012-10-09

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2008-04-01

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

Preparation and substrate reactions of superconducting Y-Ba-Cu-O films

NASA Astrophysics Data System (ADS)

Gurvitch, M.; Fiory, A. T.

1987-09-01

Multiple metal-target dc magnetron sputter deposition of a metallic YBa2Cu3 alloy in pure Ar followed by ex situ oxygen annealing was used to prepare superconducting films on various substrates. This work particularly examines film-substrate reactions which are degrading to superconductivity. Better superconductors were obtained using predeposited buffer layers, notably on cubic zirconia and MgO substrates covered with Ag and Nb. Best films have Tc = 80 K, metallic resistivities with a resistance ratio of about 2, and a critical current density of greater than about 10 kA/sq cm at 4.2 K.

Assessment of Cyclic Lifetime of NiCoCrAlY/ZrO2-Based EB-PVD TBC Systems via Reactive Element Enrichment in the Mixed Zone of the TGO Scale

NASA Astrophysics Data System (ADS)

Fritscher, Klaus; Braue, Wolfgang; Schulz, Uwe

2013-05-01

The chemical composition of the alumina-zirconia mixed zone (MZ) of an electron beam physical vapor deposited thermal barrier coating (EB-PVD TBC) system is affected by service conditions and by the interdiffusion of elements from the substrate alloy below and the zirconia top coat. Three NiCoCrAlY bond-coated Ni-base substrates with YPSZ or CeSZ EB-PVD TBCs were subjected to a cyclic furnace oxidation test (FCT) at 1373 K (1100 °C) in order to provide experimental evidence of a link between chemistry of the MZ, the substrate alloy, the ceramic top coat, and the time in the FCT. Energy dispersive spectroscopy of the MZ revealed preferred accumulation of Cr, Zr, Y, and Ce. The concentration of the reactive elements (RE = Ce + Y + Zr) was related to the respective average lifetimes of the TBC systems at 1373 K (1100 °C). The RE content in the MZ turned out to be a life-limiting parameter for YPSZ and CeSZ TBC systems which can be utilized to predict their relative lifetimes on the individual substrates. Conversely, the TBC failure mechanisms of YPSZ and CeSZ TBC systems are dissimilar.

Optimizing thickness of ceramic coatings on plastic components for orthopedic applications: A finite element analysis.

PubMed

Marchiori, G; Lopomo, N; Boi, M; Berni, M; Bianchi, M; Gambardella, A; Visani, A; Russo, A; Marcacci, M

2016-01-01

Realizing hard ceramic coatings on the plastic component of a joint prosthesis can be strategic for the mechanical preservation of the whole implant and to extend its lifetime. Recently, thanks to the Plasma Pulsed Deposition (PPD) method, zirconia coatings on ultra-high molecular weight polyethylene (UHMWPE) substrates resulted in a feasible outcome. Focusing on both the highly specific requirements defined by the biomedical application and the effective possibilities given by the deposition method in the perspectives of technological transfer, it is mandatory to optimize the coating in terms of load bearing capacity. The main goal of this study was to identify through Finite Element Analysis (FEA) the optimal coating thickness that would be able to minimize UHMWPE strain, possible insurgence of cracks within the coating and stresses at coating-substrate interface. Simulations of nanoindentation and microindentation tests were specifically carried out. FEA findings demonstrated that, in general, thickening the zirconia coating strongly reduced the strains in the UHMWPE substrate, although the 1 μm thickness value was identified as critical for the presence of high stresses within the coating and at the interface with the substrate. Therefore, the optimal thickness resulted to be highly dependent on the specific loading condition and final applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of noble metal substrates and buffer layers for BiSrCaCuO thin films

NASA Astrophysics Data System (ADS)

Matthiesen, M. M.; Rubin, L. M.; Williams, K. E.; Rudman, D. A.

Noble metal buffer layers and substrates for Bi2Sr2CaCu2O8 (BSCCO) films were investigated using bulk ceramic processing and thin-film techniques. Highly oriented, superconducting BSCCO films were fabricated on polycrystalline Ag substrates and on Ag/MgO and Ag/YSZ structures. Such films could not be produced on Au or Pt substrates under any annealing conditions. In addition, superconducting BSCCO films could not be produced on Ag/Al2O3, Ag/SiO2/Si, or Ag/(Haynes 230 alloy) structures using high annealing temperatures (870 C). However, oriented although poorly connected, superconducting BSCCO films were fabricated on Ag/Al2O3 structures by using lower annealing temperatures (820 C). Once lower processing temperatures are optimized, Ag may be usable as a buffer layer for BSCCO films.

Stress-induced magnetization for epitaxial spinel ferrite films through interface engineering

NASA Astrophysics Data System (ADS)

Wakiya, Naoki; Shinozaki, Kazuo; Mizutani, Nobuyasu

2004-08-01

This study found "stress-induced magnetization" for epitaxial ferrite films with spinel structure. We grew (111)- and (001)-epitaxial Ni0.17Zn0.23Fe2.60O4(NZF) films on CeO2/Y0.15Zr0.85O1.93(YSZ )/Si(001) and oxide single-crystal substrates, respectively. There is a window of lattice mismatch (between 0 and 6.5%) to achieve bulk saturation magnetization (Ms). An NZF film grown on CeO2/YSZ //Si(001) showed tensile stress, but that stress was relaxed by introducing a ZnCo2O4(ZC ) buffer layer. NZF films grown on SrTiO3(ST )(001) and (La,Sr)(Al,Ta)O3(LSAT)(001) had compressive stress, which was enhanced by introducing a ZC buffer layer. In both cases, bulk Ms was achieved by introducing the ZC buffer layer. This similarity suggests that magnetization can be controlled by the stress.

Computational investigation of intense short-wavelength laser interaction with rare gas clusters

NASA Astrophysics Data System (ADS)

Bigaouette, Nicolas

Current Very High Temperature Reactor designs incorporate TRi-structural ISOtropic (TRISO) particle fuel, which consists of a spherical fissile fuel kernel surrounded by layers of pyrolytic carbon and silicon carbide. An internal sol-gel process forms the fuel kernel by dropping a cold precursor solution into a column of hot trichloroethylene (TCE). The temperature difference drives the liquid precursor solution to precipitate the metal solution into gel spheres before reaching the bottom of a production column. Over time, gelation byproducts inhibit complete gelation and the TCE must be purified or discarded. The resulting mixed-waste stream is expensive to dispose of or recycle, and changing the forming fluid to a non-hazardous alternative could greatly improve the economics of kernel production. Selection criteria for a replacement forming fluid narrowed a list of ~10,800 chemicals to yield ten potential replacements. The physical properties of the alternatives were measured as a function of temperature between 25 °C and 80 °C. Calculated terminal velocities and heat transfer rates provided an overall column height approximation. 1-bromotetradecane, 1-chlorooctadecane, and 1-iodododecane were selected for further testing, and surrogate yttria-stabilized zirconia (YSZ) kernels were produced using these selected fluids. The kernels were characterized for density, geometry, composition, and crystallinity and compared to a control group of kernels produced in silicone oil. Production in 1-bromotetradecane showed positive results, producing dense (93.8 %TD) and spherical (1.03 aspect ratio) kernels, but proper gelation did not occur in the other alternative forming fluids. With many of the YSZ kernels not properly gelling within the length of the column, this project further investigated the heat transfer properties of the forming fluids and precursor solution. A sensitivity study revealed that the heat transfer properties of the precursor solution have the strongest impact on gelation time. A COMSOL heat transfer model estimated an effective thermal diffusivity range for the YSZ precursor solution as 1.13x10 -8 m2/s to 3.35x10-8 m 2/s, which is an order of magnitude smaller than the value used in previous studies. 1-bromotetradecane is recommended for further investigation with the production of uranium-based kernels.

Deposition of Crystalline Hydroxyapatite Nanoparticles on Y-TZP Ceramic: A Potential Solution to Enhance Bonding Characteristics of Y-TZP Ceramics.

PubMed

Azari, Abbas; Nikzad Jamnani, Sakineh; Yazdani, Arash; Atri, Faezeh; Rasaie, Vania; Fazel Anvari Yazdi, Abbas

2017-03-01

Many advantages have been attributed to dental zirconia ceramics in terms of mechanical and physical properties; however, the bonding ability of this material to dental structure and/or veneering ceramics has always been a matter of concern. On the other hand, hydroxyapatite (HA) shows excellent biocompatibility and good bonding ability to tooth structure, with mechanically unstable and brittle characteristics, that make it clinically unacceptable for use in high stress bearing areas. The main purpose of this study was to introduce two simple yet practical methods to deposit the crystalline HA nanoparticles on zirconia ceramics. zirconia blocks were treated with HA via two different deposition methods namely thermal coating and air abrasion. Specimens were analyzed by scanning electron microscopy, energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). In both groups, the deposition techniques used were successfully accomplished, while the substrate showed no structural change. However, thermal coating group showed a uniform deposition of crystalline HA but in air abrasion method, there were dispersed thin islands of HA. Thermal coating method has the potential to significantly alter the surface characteristics of zirconia. The simple yet practical nature of the proposed method may be able to shift the bonding paradigm of dental zirconia ceramics. This latter subject needs to be addressed in future investigations.

Analysis of the Microstructure and Thermal Shock Resistance of Laser Glazed Nanostructured Zirconia TBCs

NASA Astrophysics Data System (ADS)

Chen, Hui; Hao, Yunfei; Wang, Hongying; Tang, Weijie

2010-03-01

Nanostructured zirconia thermal barrier coatings (TBCs) have been prepared by atmospheric plasma spraying using the reconstituted nanosized yttria partially stabilized zirconia powder. Field emission scanning electron microscope was applied to examine the microstructure of the resulting TBCs. The results showed that the TBCs exhibited a unique, complex structure including nonmelted or partially melted nanosized particles and columnar grains. A CO2 continuous wave laser beam has been applied to laser glaze the nanostructured zirconia TBCs. The effect of laser energy density on the microstructure and thermal shock resistance of the as-glazed coatings has been systematically investigated. SEM observation indicated that the microstructure of the as-glazed coatings was very different from the microstructure of the as-sprayed nanostructured TBCs. It changed from single columnar grain to a combination of columnar grains in the fracture surface and equiaxed grains on the surface with increasing laser energy density. Thermal shock resistance tests have showed that laser glazing can double the lifetime of TBCs. The failure of the as-glazed coatings was mainly due to the thermal stress caused by the thermal expansion coefficient mismatch between the ceramic coat and metallic substrate.

Architectured Nanomembranes

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

Sturgeon, Matthew R.; Hu, Michael Z.

2017-07-01

This paper has reviewed the frontier field of “architectured membranes” that contains anisotropic oriented porous nanostructures of inorganic materials. Three example types of architectured membranes were discussed with some relevant results from our own research: (1) anodized thin-layer titania membranes on porous anodized aluminum oxide (AAO) substrates of different pore sizes, (2) porous glass membranes on alumina substrate, and (3) guest-host membranes based on infiltration of yttrium-stabilized zirconia inside the pore channels of AAO matrices.

Synthesis and surface characterization of alumina-silica-zirconia nanocomposite ceramic fibres on aluminium at room temperature

NASA Astrophysics Data System (ADS)

Mubarak Ali, M.; Raj, V.

2010-04-01

Alumina-silica-zirconia nanocomposite (ASZNC) ceramic fibres were synthesized by conventional anodization route. Scanning Electron Microscopy (SEM), Atomic Force microscopy (AFM), X-Ray Diffraction (XRD) and Energy Dispersive X-Ray spectroscopy (EDAX) were used to characterize the morphology and crystalloid structure of ASZNC fibres. Current density (DC) is one of the important parameters to get the alumina-silica-zirconia nanocomposite (ASZNC) ceramic fibres by this route. Annealing of the films exhibited a drastic change in the properties due to improved crystallinity. The root mean square roughness of the sample observed from atomic force microscopic analysis is about 71.5 nm which is comparable to the average grain size of the coatings which is about 72 nm obtained from X-Ray diffraction. The results indicate that, the ASZNC fibres are arranged well in the nanostructure. The thickness of the coating increased with the anodizing time, but the coatings turned rougher and more porous. At the initial stage the growth of ceramic coating increases inwards to the metal substrate and outwards to the coating surface simultaneously. Subsequently, it mainly grows towards the metal substrate and the density of the ceramic coating increases gradually, which results in the decrease of the total thickness as anodizing time increases. This new approach of preparing ASZNC ceramic fibres may be important in applications ranging from gas sensors to various engineering materials.

Method of depositing a protective layer over a biaxially textured alloy substrate and composition therefrom

DOEpatents

Goyal, Amit; Kroeger, Donald M.; Paranthaman, Mariappan; Lee, Dominic F.; Feenstra, Roeland; Norton, David P.

2002-01-01

A laminate article consists of a substrate and a biaxially textured protective layer over the substrate. The substrate can be biaxially textured and also have reduced magnetism over the magnetism of Ni. The substrate can be selected from the group consisting of nickel, copper, iron, aluminum, silver and alloys containing any of the foregoing. The protective layer can be selected from the group consisting of gold, silver, platinum, palladium, and nickel and alloys containing any of the foregoing. The protective layer is also non-oxidizable under conditions employed to deposit a desired, subsequent oxide buffer layer. Layers of YBCO, CeO.sub.2, YSZ, LaAlO.sub.3, SrTiO.sub.3, Y.sub.2 O.sub.3, RE.sub.2 O.sub.3, SrRuO.sub.3, LaNiO.sub.3 and La.sub.2 ZrO.sub.3 can be deposited over the protective layer. A method of forming the laminate article is also disclosed.

Development of porcelain enamel passive thermal control coatings

NASA Technical Reports Server (NTRS)

Levin, H.; Lent, W. E.; Buettner, D. H.

1973-01-01

A white porcelain enamel coating was developed for application to high temperature metallic alloy substrates on spacecraft. The coating consists of an optically opacifying zirconia pigment, a lithia-zirconia-silica frit, and an inorganic pigment dispersant. The coating is fired at 1000 to 1150 C to form the enamel. The coating has a solar absorptance of 0.22 and a total normal emittance of 0.82 for a 0.017 cm thick coating. The coating exhibits excellent adhesion, cleanability, and integrity and is thermal shock resistant to 900 C. Capability to coat large panels has been demonstrated by successful coating of 30 cm x 30 cm Hastelloy X alloy panels. Preliminary development of low temperature enamels for application to aluminum and titanium alloy substrates was initiated. It was determined that both leaded and leadless frits were feasible when applied with appropriate mill fluxes. Indications were that opacification could be achieved at firing temperatures below 540 C for extended periods of time.

Potentiometric NO2 Sensors Based on Thin Stabilized Zirconia Electrolytes and Asymmetric (La0.8Sr0.2)0.95MnO3 Electrodes

PubMed Central

Zou, Jie; Zheng, Yangong; Li, Junliang; Zhan, Zhongliang; Jian, Jiawen

2015-01-01

Here we report on a new architecture for potentiometric NO2 sensors that features thin 8YSZ electrolytes sandwiched between two porous (La0.8Sr0.2)0.95MnO3 (LSM95) layers—one thick and the other thin—fabricated by the tape casting and co-firing techniques. Measurements of their sensing characteristics show that reducing the porosity of the supporting LSM95 reference electrodes can increase the response voltages. In the meanwhile, thin LSM95 layers perform better than Pt as the sensing electrode since the former can provide higher response voltages and better linear relationship between the sensitivities and the NO2 concentrations over 40–1000 ppm. The best linear coefficient can be as high as 0.99 with a sensitivity value of 52 mV/decade as obtained at 500 °C. Analysis of the sensing mechanism suggests that the gas phase reactions within the porous LSM95 layers are critically important in determining the response voltages. PMID:26205270

Developing Cost-Effective Dense Continuous SDC Barrier Layers for SOFCs

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

Nguyen, Hoang Viet P.; Hardy, John S.; Coyle, Christopher A.

Significantly improved performance during electrochemical testing of a cell with a dense continuous pulsed laser deposited (PLD) samarium doped ceria (SDC) layer spurred investigations into the fabrication of dense continuous SDC barrier layers by means of cost-effective deposition using screen printing which is amenable to industrial production of SOFCs. Many approaches to improve the SDC density have been explored including the use of powder with reduced particle sizes, inks with increased solids loading, and doping with sintering aids (1). In terms of sintering aids, dopants like Mo or binary systems of Mo+Cu or Fe+Co greatly enhance SDC sinterability. In fact,more » adding dopants to a screen printed, prefired, porous SDC layer made it possible to achieve a dense continuous barrier layer atop the YSZ electrolyte without sintering above 1200°C. Although the objective of fabricating a dense continuous layer was achieved, additional studies have been initiated to improve the cell performance. Underlying issues with constrained sintering and dopant-enhanced ceria-zirconia solid solubility are also addressed in this paper.« less

Thermodynamic Properties of Liquid Silver-Antimony-Tin Alloys Determined from Electrochemical and Calorimetric Measurements

NASA Astrophysics Data System (ADS)

Łapsa, Joanna; Onderka, Bogusław

2016-08-01

The thermodynamic properties of liquid Ag-Sb-Sn alloys were obtained through use of the drop solution calorimetric method and electromotive force (emf) measurements of galvanic cells with a yttria stabilized zirconia (YSZ) solid electrolyte. The experiments were carried out along Ag0.25Sb0.75, Ag0.5Sb0.5 and Ag0.75Sb0.25 sections of the ternary system in the temperature range from 973 K to 1223 K. From the measured emf, the tin activity in liquid solutions of Ag-Sb-Sn was determined for the first time. The partial and integral enthalpy of mixing were determined from calorimetric measurements at two temperatures. These measurements were performed along two cross-sections: Sb0.5Sn0.5 at 912 K and 1075 K, and Ag0.75Sb0.25 at 1075 K. Both experimental data sets were used to find ternary interaction parameters by applying the Redlich-Kister-Muggianu model of the substitutional solution. Consequently, the set of parameters describing the thermodynamic properties of the liquid phase was derived.

Temperature measurements during high flux ion beam irradiations

DOE PAGES

Crespillo, Miguel L.; Graham, Joseph T.; Zhang, Yanwen; ...

2016-02-16

A systematic study of the ion beam heating effect was performed in a temperature range of –170 to 900 °C using a 10 MeV Au 3+ ion beam and a Yttria stabilized Zirconia (YSZ) sample at a flux of 5.5 × 10 12 cm –2 s –1. Different geometric configurations of beam, sample, thermocouple positioning, and sample holder were compared to understand the heat/charge transport mechanisms responsible for the observed temperature increase. The beam heating exhibited a strong dependence on the background (initial) sample temperature with the largest temperature increases occurring at cryogenic temperatures and decreasing with increasing temperature. Comparisonmore » with numerical calculations suggests that the observed heating effect is, in reality, a predominantly electronic effect and the true temperature rise is small. Furthermore, a simple model was developed to explain this electronic effect in terms of an electrostatic potential that forms during ion irradiation. Such an artificial beam heating effect is potentially problematic in thermostated ion irradiation and ion beamanalysis apparatus, as the operation of temperature feedback systems can be significantly distorted by this effect.« less

Japan's Sunshine Project

NASA Astrophysics Data System (ADS)

1992-07-01

A summary report is given on the results of hydrogen energy research and development achieved during 1991 under the Sunshine Project. In hydrogen manufacturing, regenerative cells that can also generate power as fuel cells were discussed by using solid macromolecular electrolytic films for the case where no electrolysis is carried out with water electrolysis. Yttria stabilized zirconia (YSZ), an oxide solid electrolyte was used for the basic research on high-temperature steam electrolysis. Compositions of hydrogen storage alloys and their deterioration mechanisms were investigated to develop hydrogen transportation and storage technologies. High-density hydrides were searched, and fluidization due to paraffin was discussed. Electrode materials and forming technologies were discussed to develop a hydrogen to power conversion system using hydrogen storage alloys as reversible electrodes. Hydrogen-oxygen combustion was studied in terms of reactive theories, and so was the control of ignition and combustion using ultraviolet ray ignition plasma. Studies were made on hydrogen brittlement in welds on materials in hydrogen utilization and its preventive measures. Surveys were given on technical movements and development problems in high-efficiency, pollution-free hydrogen combustion turbines.

Standard Gibbs energy of formation of Mo 3Te 4 by emf measurements

NASA Astrophysics Data System (ADS)

Mallika, C.; Sreedharan, O. M.

1990-03-01

The emf of the galvanic cells Pt, Mo, MoO 2¦8 YSZ¦'FeO', Fe, Pt (I) and Pt, Fe,'FeO' ¦8 YSZ¦MoO 2, Mo 3Te 4, MoTe 2(α), C, Pt (II) were measured over the temperature ranges 837 to 1151 K and 775 to 1196 K, respectively, using 8 mass% yttria-stabilized zirconia (8 YSZ) as the solid electrolyte. From the emf values, the partial molar Gibbs energy of solution of molybdenum in Mo 3Te 4/MoTe 2(α), Δ ḠMo was found to be Δ ḠMo ± 1.19 ( kJ/mol) = -025.08 + 0.00420T(K) . Using the literature data for the Gibbs energy of formation of MoTe 2(α). the expression ΔG° f( Mo3Te4, s) ± 5.97 (kj/mol) = -253.58 + 0.09214 T( K) was derived for the range 775 to 1196 K. A third-law analysis yielded a value of -209 ± 10 kJ/mol for ΔH° f.298o of Mo 3Te 4(s).

FIB/SEM and SEM/EDS microstructural analysis of metal-ceramic and zirconia-ceramic interfaces.

PubMed

Massimi, F; Merlati, G; Sebastiani, M; Battaini, P; Menghini, P; Bemporad, E

2012-01-10

Recently introduced FIB/SEM analysis in microscopy seems to provide a high-resolution characterization of the samples by 3D (FIB) cross-sectioning and (SEM) high resolution imaging. The aim of this study was to apply the FIB/SEM and SEM/EDS analysis to the interfaces of a metal-ceramic vs. two zirconia-ceramic systems. Plate samples of three different prosthetic systems were prepared in the dental lab following the manufacturers' instructions, where metal-ceramic was the result of a ceramic veneering (porcelain-fused-to-metal) and the two zirconia-ceramic systems were produced by the dedicated CAD-CAM procedures of the zirconia cores (both with final sintering) and then veneered by layered or heat pressed ceramics. In a FIB/SEM equipment (also called DualBeam), a thin layer of platinum (1 μm) was deposited on samples surface crossing the interfaces, in order to protect them during milling. Then, increasingly deeper trenches were milled by a focused ion beam, first using a relatively higher and later using a lower ion current (from 9 nA to 0.28 nA, 30KV). Finally, FEG-SEM (5KV) micrographs (1000-50,000X) were acquired. In a SEM the analysis of the morphology and internal microstructure was performed by 13KV secondary and backscattered electrons signals (in all the samples). The compositional maps were then performed by EDS probe only in the metal-ceramic system (20kV). Despite the presence of many voids in all the ceramic layers, it was possible to identify: (1) the grain structures of the metallic and zirconia substrates, (2) the thin oxide layer at the metal-ceramic interface and its interactions with the first ceramic layer (wash technique), (3) the roughness of the two different zirconia cores and their interactions with the ceramic interface, where the presence of zirconia grains in the ceramic layer was reported in two system possibly due to sandblasting before ceramic firing.

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

PubMed

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

2017-09-27

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

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

PubMed Central

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

2017-01-01

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

The hydration structure at yttria-stabilized cubic zirconia (110)-water interface with sub-Ångström resolution

DOE PAGES

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

2016-06-15

The interfacial hydration structure of yttria-stabilized cubic zirconia (110) surface in contact with water was determined with ~0.5 Å resolution by high-resolution X-ray reflectivity measurement. The terminal layer shows a reduced electron density compared to the following substrate lattice layers, which indicates there are additional defects generated by metal depletion as well as intrinsic oxygen vacancies, both of which are apparently filled by water species. Above this top surface layer, two additional adsorbed layers are observed forming a characteristic interfacial hydration structure. The first adsorbed layer shows abnormally high density as pure water and likely includes metal species, whereas themore » second layer consists of pure water. The observed interfacial hydration structure seems responsible for local equilibration of the defective surface in water and eventually regulating the long-term degradation processes. As a result, the multitude of water interactions with the zirconia surface results in the complex but highly ordered interfacial structure constituting the reaction front.« 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.

Paramagnetic Defects in Electron-Irradiated Yttria-Stabilized Zirconia: Effect of Yttria Content

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

Costantini, Jean-Marc; Beuneu, Francois; Morrison-Smith, Sarah

2011-01-01

We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are stronglymore » enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 1 eV with subsequent defect re-arrangement.« less

The effect of CMAS interaction on thermal cycle lifetime of YSZ based thermal barrier coatings

NASA Astrophysics Data System (ADS)

Bal, Emre; Karabaş, Muhammet; Yılmaz Taptık, İ.

2018-06-01

The purpose of this research is to produce CMAS resistant YSZ based TBCs and compare thermal cycle performance of the TBCs before and after CMAS interaction. Plasma sprayed YSZ (Y), YSZ + Alumina (YA), YSZ + Titania (YT), and YSZ + Alumina + Titania (YTA) coatings have been exposed to CMAS at 1250 °C for 18 h. Thermal cycling tests were carried out with a propane + oxygen flame at 1250 ± 50 °C. Thermal cycle lifetime of YSZ, YA, YT, YTA, and CMAS contaminated Y, YA, YT, YTA coatings are 450, 416, 426, 438, 122, 211, 141, 298 respectively. After CMAS interaction, while the life span of other coatings has fallen to their life span’s quarter, the life span of YTA coating has decreased slightly. Damages in the coatings after thermal cycle tests have been studied by using SEM to observe the microstructure and x-ray diffraction techniques to analyze the phase composition. Also to see areal distribution of the CMAS through the coating, EDS mapping has been carried out.

Magneto-optical waveguides made of cobalt ferrite nanoparticles embedded in silica/zirconia organic-inorganic matrix

NASA Astrophysics Data System (ADS)

Choueikani, Fadi; Royer, François; Jamon, Damien; Siblini, Ali; Rousseau, Jean Jacques; Neveu, Sophie; Charara, Jamal

2009-02-01

This paper describes a way to develop magneto-optical waveguides via sol-gel process. They are made of cobalt ferrite nanoparticles embedded in a silica/zirconia matrix. Thin films are coated on glass substrate using the dip-coating technique. Annealing and UV treatment are applied to finalize sample preparation. Therefore, planar waveguides combining magneto-optical properties with a low refractive index (≈1,5) are obtained. M-lines and free space ellipsometry measurements show a specific Faraday rotation of 250°/cm and a modal birefringence of 1×10-4 at 820 nm. Thus, the mode conversion efficiency can reach a maximum value around 56%.

An in vitro comparison of shear bond strength of zirconia to enamel using different surface treatments.

PubMed

Zandparsa, Roya; Talua, Nayrouz A; Finkelman, Matthew D; Schaus, Scott E

2014-02-01

The purpose of this in vitro study was to compare the shear bond strength of an airborne-particle abraded zirconia, an acid-etched zirconia (Piranha solution), an Alloy Primer treated zirconia, and a silaned zirconia to enamel, all bonded with a phosphate-methacrylate resin luting agent. Seventy extracted intact human molars were collected, cleaned, and mounted in autopolymerizing acrylic resin, with the experimental surface of the teeth exposed. The specimens were randomly divided into seven groups of zirconia specimens (4 mm diameter, 2 mm thick). Group 1: Airborne-particle abrasion; group 2: Airborne-particle abrasion and Z-PRIME Plus; group 3: Airborne-particle abrasion and alloy primer; group 4: Piranha solution 7:1; group 5: Piranha solution 7:1 and Z-PRIME Plus; group 6: Piranha solution 7:1 and Alloy primer; group 7: CoJet and silane. All specimens were luted with a phosphate-methacrylate resin luting agent (Panavia F2.0) and stored in distilled water for 1 day, then thermocycled (5°C and 55°C) for 500 cycles and tested for shear bond strength (SBS), measured in MPa, with a universal testing machine at a 0.55 mm/min crosshead speed. All specimens were inspected under a scanning electron microscope to determine mode of failure. The mean values and standard deviations of all specimens were calculated for each group. A one-way ANOVA was performed, and multiple pairwise comparisons were then completed with post hoc Tukey test (alpha = 0.05). The airborne-particle abrasion and Z-PRIME Plus group resulted in a significantly higher SBS than the other groups (21.11 ± 6.32 MPa) (p < 0.001). The CoJet and silane group (15.99 ± 8.92 MPa) and airborne-particle abrasion and alloy primer group (11.07 ± 4.34 MPa) showed high shear bond strength but not statistically significant from the airborne-particle abrasion group (14.23 ± 5.68 MPa). Failure mode was predominately mixed in groups 1, 2, 3, and 7 with islands of retained resin on the zirconia and enamel surfaces; however, groups 4, 5, and 6 showed mostly adhesive failures, which left the zirconia surface free of the adhesive materials. No cohesive failures of the substrates (ceramic, resin, or enamel) were observed. Airborne-particle abrasion followed by the application of a zirconia primer produced the highest bond strength to enamel. Therefore, it can be recommended as a promising surface treatment method to achieve a durable bond to densely sintered zirconia ceramics. © 2013 by the American College of Prosthodontists.

Surface-texture evolution of different chemical-vapor-deposited zinc sulfide flats polished with various magnetorheological fluids

DOE PAGES

Salzman, S.; Romanofsky, H. J.; Jacobs, S. D.; ...

2015-08-19

The macro-structure of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) substrates is characterizedby cone-like structures that start growing at the early stages of deposition. As deposition progresses,these cones grow larger and reach centimeter size in height and millimeter size in width. It is challengingto polish out these features from the top layer, particularly for the magnetorheological finishing (MRF)process. A conventional MR fluid tends to leave submillimeter surface artifacts on the finished surface,which is a direct result of the cone-like structure. Here we describe the MRF process of polishing four CVD ZnS substrates, manufactured by four differentvendors, with conventional MR fluid at pHmore » 10 and zirconia-coated-CI (carbonyl iron) MR fluids at pH 4, 5,and 6. We report on the surface–texture evolution of the substrates as they were MRF polished with thedifferent fluids. We show that performances of the zirconia-coated-CI MR fluid at pH 4 are significantlyhigher than that of the same fluid at pH levels of 5 and 6 and moderately higher than that of a conventionalMR fluid at pH 10. An improvement in surface–texture variability from part to part was also observedwith the pH 4 MR fluid.« less

Lost Mold Rapid Infiltration Forming of Mesoscale Ceramics: Part 1, Fabrication

PubMed Central

Antolino, Nicholas E.; Hayes, Gregory; Kirkpatrick, Rebecca; Muhlstein, Christopher L.; Frecker, Mary I.; Mockensturm, Eric M.; Adair, James H.

2009-01-01

Free-standing mesoscale (340 μm × 30 μm × 20 μm) bend bars with an aspect ratio over 15:1 and an edge resolution as fine as a single grain diameter (∼400 nm) have been fabricated in large numbers on refractory ceramic substrates by combining a novel powder processing approach with photoresist molds and an innovative lost-mold thermal process. The colloid and interfacial chemistry of the nanoscale zirconia particulates has been modeled and used to prepare highly concentrated suspensions. Engineering solutions to challenges in mold fabrication and casting have yielded free-standing, crack-free parts. Molds are fabricated using high-aspect-ratio photoresist on ceramic substrates. Green parts are formed using a rapid infiltration method that exploits the shear thinning behavior of the highly concentrated ceramic suspension in combination with gelcasting. The mold is thermally decomposed and the parts are sintered in place on the ceramic substrate. Chemically aided attrition milling disperses and concentrates the as-received 3Y-TZP powder to produce a dense, fine-grained sintered microstructure. Initial three-point bend strength data are comparable to that of conventional zirconia; however, geometric irregularities (e.g., trapezoidal cross sections) are present in this first generation and are discussed with respect to the distribution of bend strength. PMID:19809595

Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

NASA Astrophysics Data System (ADS)

Luo, Yu; Shi, Yixiang; Li, Wenying; Cai, Ningsheng

2018-03-01

CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

Silicone Disclosing Material used after Ceramic Surface Treatment Reduces Bond Strength.

PubMed

Fraga, Sara; Oliveira, Sara Cioccari; Pereira, Gabriel Kalil Rocha; Beekman, Pieter; Rippe, Marília Pivetta; Kleverlaan, Cornelis J

To evaluate the effect of a silicone disclosing procedure performed at different timepoints on the shear bond strength (SBS) of cements (self-adhesive composite cement, self-etch composite cement, resin-reinforced glass-ionomer cement) to different substrates (zirconia, lithium disilicate, bovine dentin). The substrate/cement combinations were assigned to two groups (n = 15) according to the timepoint, at which the vinyl polyether silicone disclosing agent was applied: after (experimental groups, EXP) or before (control groups, CTRL) specific micromechanical treatments of the substrate surface. To increase standardization, the cements were applied into rubber rings (2.2 mm diameter x 1.0 mm thickness) positioned on the substrate surface. After luting procedures, all specimens were stored in 37°C distilled water for 24 h, then subjected to SBS testing using a wire loop of 0.2 mm diameter at a crosshead speed of 1 mm/min until failure. Failure analysis was performed for all tested specimens. SBS data were submitted to Weibull analysis. The silicone disclosing procedure performed after micromechanical surface treatment reduced the characteristic shear bond strength to zirconia and lithium disilicate when compared to CTRL. However, for dentin specimens, there was no significant difference between CTRL and EXP for any of the cements investigated. Failure analysis showed a predominance of interfacial failures. The silicone disclosing procedure performed after the micromechanical treatment of ceramic surfaces negatively affected the cement bond strength. Therefore, after using it to check the fit of a prosthesis, clinicians should carefully clean the ceramic surface.

Oxygen disorder, a way to accommodate large epitaxial strains in oxides

DOE PAGES

Zhang, Yu Yang; Mishra, Rohan; Pennycook, Timothy J.; ...

2015-09-22

Density-functional calculations (total-energy comparisons) and checks for negative-frequency phonon modes are employed as a stability indicator to show that, in rutile- and fluorite-structure oxides, e.g., zirconia strained by a strontium titanate substrate, oxygen-sublattice disorder can be the energetically preferred way to accommodate strain.

Effects of Impurity Content on the Sintering Characteristics of Plasma-Sprayed Zirconia

NASA Astrophysics Data System (ADS)

Paul, S.; Cipitria, A.; Golosnoy, I. O.; Xie, L.; Dorfman, M. R.; Clyne, T. W.

2007-12-01

Yttria-stabilized zirconia powders, containing different levels of SiO2 and Al2O3, have been plasma sprayed onto metallic substrates. The coatings were detached from their substrates and a dilatometer was used to monitor the dimensional changes they exhibited during prolonged heat treatments. It was found that specimens containing higher levels of silica and alumina exhibited higher rates of linear contraction, in both in-plane and through-thickness directions. The in-plane stiffness and the through-thickness thermal conductivity were also measured after different heat treatments and these were found to increase at a greater rate for specimens with higher impurity (silica and alumina) levels. Changes in the pore architecture during heat treatments were studied using Mercury Intrusion Porosimetry (MIP). Fine scale porosity (< ˜50 nm) was found to be sharply reduced even by relatively short heat treatments. This is correlated with improvements in inter-splat bonding and partial healing of intra-splat microcracks, which are responsible for the observed changes in stiffness and conductivity, as well as the dimensional changes.

Monolithic integrated high-T.sub.c superconductor-semiconductor structure

NASA Technical Reports Server (NTRS)

Barfknecht, Andrew T. (Inventor); Garcia, Graham A. (Inventor); Russell, Stephen D. (Inventor); Burns, Michael J. (Inventor); de la Houssaye, Paul R. (Inventor); Clayton, Stanley R. (Inventor)

2000-01-01

A method for the fabrication of active semiconductor and high-temperature superconducting device of the same substrate to form a monolithically integrated semiconductor-superconductor (MISS) structure is disclosed. A common insulating substrate, preferably sapphire or yttria-stabilized zirconia, is used for deposition of semiconductor and high-temperature superconductor substructures. Both substructures are capable of operation at a common temperature of at least 77 K. The separate semiconductor and superconductive regions may be electrically interconnected by normal metals, refractory metal silicides, or superconductors. Circuits and devices formed in the resulting MISS structures display operating characteristics which are equivalent to those of circuits and devices prepared on separate substrates.

Ferroelectricity in epitaxial Y-doped HfO2 thin film integrated on Si substrate

NASA Astrophysics Data System (ADS)

Lee, K.; Lee, T. Y.; Yang, S. M.; Lee, D. H.; Park, J.; Chae, S. C.

2018-05-01

We report on the ferroelectricity of a Y-doped HfO2 thin film epitaxially grown on Si substrate, with an yttria-stabilized zirconia buffer layer pre-deposited on the substrate. Piezoresponse force microscopy results show the ferroelectric domain pattern, implying the existence of ferroelectricity in the epitaxial HfO2 film. The epitaxially stabilized HfO2 film in the form of a metal-ferroelectric-insulator-semiconductor structure exhibits ferroelectric hysteresis with a clear ferroelectric switching current in polarization-voltage measurements. The HfO2 thin film also demonstrates ferroelectric retention comparable to that of current perovskite-based metal-ferroelectric-insulator-semiconductor structures.

[Effects of different surface modifications on micro-structure and adhesion of zirconia ceramic: an in vitro study].

PubMed

Siwen, Li; Shishi, Li; Yanhong, Wang; Hongmei, Ma

2017-02-01

This study evaluated the effect of different mechanical-chemical surface treatments on the characteristics, microstructure, and composition of zirconia ceramics and on the zirconia-dentin adhesion. The sintered commercial zirconia blocks (IPS e.max ZirCAD) were sectioned into 126 beams (6 mm×6 mm×5 mm) and randomly assigned to seven experimental groups (n=18). The zirconia block specimens were further treated as follows: (A) untreated, as control; (B) sandblasted with 50 μm Al2O3; (C) sandblasted with 50 μm Al2O3+30 μm silica powder; (D) sandblasted with 50 μm Al2O3+30% silica-sol coating; (E) sandblasted with 110 μm Al2O3; (F) sandblasted with 110 μm Al2O3+30 μm silica powder; and (G) sandblasted with 110 μm Al2O3+30% silica-sol coating. The surface roughness (Ra) of zirconia ceramics using X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX) after seven surface treatments was analyzed. Seventy specimens of dentin surfaces were prepared. A dual-cure resin cement was applied into zirconia surfaces with its corresponding adhesive components to dentin. Shear bond strength (SBS) of each sample was measured using a universal testing machine. The data were analyzed by ANOVA using SPSS 17.0 software. Ra of zirconia were significantly different compared with the control group (P<0.05). The crystalline transformation from tetragonal phase to monoclinic phase was observed after surface modification. Monoclinic volume content of the heat-treated group was highest than that in other groups. The content of element Si in the heat-treated group was higher than that in other treatment groups accompanied by a decrease in elements Zr, Y, and Hf after being treated by two silica-coating methods. Air abrasion significantly increased the micro-cracks in the ceramic surface and caused the grain boundaries to disappear. A serious shrinkage of the thin silica film can be observed after sintering procedure. This process induced cracks and the film to strip away slightly from the surfaces of Y-TZP substrate. The SBS values from large to small were F and G groups, C and D groups, B and E groups (P<0.05), and control group (P<0.05). Alumina sandblasting, silica powder abrasion, and silica-sol coating affect the surface morphology, structure, and composition of the tooth. This effect can also achieve the improved micro-mechanical interlocking or chemical bonding and finally increase the bond strength between zirconia and tooth. Alumina sandblasting followed by silica coating is an effective technique to increase the bonding strength between the zirconia ceramic and dentin.
.

Preparation of thin ceramic films via an aqueous solution route

DOEpatents

Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

1989-01-01

A new chemical method of forming thin ceramic films has been developed. An aqueous solution of metal nitrates or other soluble metal salts and a low molecular weight amino acid is coated onto a substrate and pyrolyzed. The amino acid serves to prevent precipitation of individual solution components, forming a very viscous, glass-like material as excess water is evaporated. Using metal nitrates and glycine, the method has been demonstrated for zirconia with various levels of yttria stabilization, for lanthanum-strontium chromites, and for yttrium-barium-copper oxide superconductors on various substrates.

Degradation Of Environmental Barrier Coatings (EBC) Due To Chemical and Thermal Expansion Incompatibility

NASA Technical Reports Server (NTRS)

Lee, Kang N.; King, Deboran (Technical Monitor)

2001-01-01

Current environmental barrier coatings (EBCs) consist of multiple layers, with each layer having unique properties to meet the various requirements for successful EBCs. As a result, chemical and thermal expansion compatibility between layers becomes an important issue to maintaining durability. Key constituents in current EBCs are mullite (3Al2O3-2SiO2), BSAS (BaO(1-x)-SrO(x)-Al2O3-2SiO2), and YSZ (ZrO2-8 wt.% Y2O3). The mullite-BSAS combination appears benign although significant diffusion occurs. Mullite-YSZ and BSAS-YSZ combinations do not react up to 1500 C. Thermally grown SiO2- BSAS and mullite-BSAS-YSZ combinations are most detrimental, forming low melting glasses. Thermal expansion mismatch between YSZ and mullite or BSAS causes severe cracking and delamination.

Formation of (111) orientation-controlled ferroelectric orthorhombic HfO{sub 2} thin films from solid phase via annealing

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

Mimura, Takanori; Katayama, Kiliha; Shimizu, Takao

2016-08-01

0.07YO{sub 1.5}-0.93HfO{sub 2} (YHO7) films were prepared on various substrates by pulse laser deposition at room temperature and subsequent heat treatment to enable a solid phase reaction. (111)-oriented 10 wt. % Sn-doped In{sub 2}O{sub 3}(ITO)//(111) yttria-stabilized zirconia, (111)Pt/TiO{sub x}/SiO{sub 2}/(001)Si substrates, and (111)ITO/(111)Pt/TiO{sub x}/SiO{sub 2}/(001)Si substrates were employed for film growth. In this study, X-ray diffraction measurements including θ–2θ measurements, reciprocal space mappings, and pole figure measurements were used to study the films. The film on (111)ITO//(111)yttria-stabilized zirconia was an (111)-orientated epitaxial film with ferroelectric orthorhombic phase; the film on (111)ITO/(111)Pt/TiO{sub x}/SiO{sub 2}/(001)Si was an (111)-oriented uniaxial textured film with ferroelectricmore » orthorhombic phase; and no preferred orientation was observed for the film on the (111)Pt/TiO{sub x}/SiO{sub 2}/(001)Si substrate, which does not contain ITO. Polarization–hysteresis measurements confirmed that the films on ITO covered substrates had saturated ferroelectric hysteresis loops. A remanent polarization (P{sub r}) of 9.6 and 10.8 μC/cm{sup 2} and coercive fields (E{sub c}) of 1.9 and 2.0 MV/cm were obtained for the (111)-oriented epitaxial and uniaxial textured YHO7 films, respectively. These results demonstrate that the (111)-oriented ITO bottom electrodes play a key role in controlling the orientation and ferroelectricity of the phase formation of the solid films deposited at room temperature.« less

Post-thermocycling shear bond strength of a gingiva-colored indirect composite layering material to three implant framework materials.

PubMed

Komine, Futoshi; Koizuka, Mai; Fushiki, Ryosuke; Taguchi, Kohei; Kamio, Shingo; Matsumura, Hideo

2013-09-01

To evaluate shear bond strength of a gingiva-colored indirect composite to three implant framework materials, before and after thermocycling, and verify the effect of surface pre-treatment for each framework. Commercially pure titanium (CP-Ti), American Dental Association (ADA) type 4 casting gold alloy (Type IV) and zirconia ceramics (Zirconia) were assessed. For each substrate, 96 disks were divided into six groups and primed with one of the following primers: Alloy Primer (ALP), Clearfil Photo Bond (CPB), Clearfil Photo Bond with Clearfil Porcelain Bond Activator (CPB+Activator), Estenia Opaque Primer (EOP), Metal Link (MLP) and V-Primer (VPR). The specimens were then bonded to a gingiva-colored indirect composite (Ceramage Concentrate GUM-D). Shear bond strengths were measured at 0 and 20 000 thermocycles and data were analyzed with the Steel-Dwass test and Mann-Whitney U-test. Shear bond strengths were significantly lower after thermocycling, with the exception of Type IV specimens primed with CPB (p = 0.092) or MLP (p = 0.112). For CP-Ti and Zirconia specimens, priming with CPB or CPB+Activator produced significantly higher bond strengths at 0 and 20 000 thermocycles, as compared with the other groups. For Type IV specimens, priming with ALP or MLP produced higher bond strengths at 0 and 20 000 thermocycles. Shear bond strength of a gingiva-colored indirect composite to CP-Ti, gold alloy and zirconia ceramics was generally lower after thermocycling. Application of a hydrophobic phosphate monomer and polymerization initiator was effective in maintaining bond strength of CP-Ti and zirconia ceramics. Combined use of a thione monomer and phosphoric monomer enhanced the durable bond strength of gold alloy.

Electrical behavior of aluminosilicate glass-ceramic sealants and their interaction with metallic solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Goel, Ashutosh; Tulyaganov, Dilshat U.; Kharton, Vladislav V.; Yaremchenko, Aleksey A.; Ferreira, José M. F.

A series of alkaline-earth aluminosilicate glass-ceramics (GCs) were appraised with respect to their suitability as sealants for solid oxide fuel cells (SOFCs). The parent composition with general formula Ca 0.9MgAl 0.1La 0.1Si 1.9O 6 was modified with Cr 2O 3 and BaO. The addition of BaO led to a substantial decrease in the total electrical conductivity of the GCs, thus improving their insulating properties. BaO-containing GCs exhibited higher coefficient of thermal expansion (CTE) in comparison to BaO-free GCs. An extensive segregation of oxides of Ti and Mn, components of the Crofer22 APU interconnect alloy, along with negligible formation of BaCrO 4 was observed at the interface between GC/interconnects diffusion couples. Thermal shock resistance and gas-tightness of GC sealants in contact with yttria-stabilized zirconia electrolyte (8YSZ) was evaluated in air and water. Good matching of CTE and strong, but not reactive, adhesion to the solid electrolyte and interconnect, in conjunction with a high level of electrical resistivity, are all advantageous for potential SOFC applications.

Electrochemical performance of solid oxide fuel cells having electrolytes made by suspension and solution precursor plasma spraying

NASA Astrophysics Data System (ADS)

Marr, M.; Kuhn, J.; Metcalfe, C.; Harris, J.; Kesler, O.

2014-01-01

Yttria-stabilized zirconia (YSZ) electrolytes were deposited by suspension plasma spraying (SPS) and solution precursor plasma spraying (SPPS). The electrolytes were evaluated for permeability, microstructure, and electrochemical performance. With SPS, three different suspensions were tested to explore the influence of powder size distribution and liquid properties. Electrolytes made from suspensions of a powder with d50 = 2.6 μm were more gas-tight than those made from suspensions of a powder with d50 = 0.6 μm. A peak open circuit voltage of 1.00 V was measured at 750 °C with a cell with an electrolyte made from a suspension of d50 = 2.6 μm powder. The use of a flammable suspension liquid was beneficial for improving electrolyte conductivity when using lower energy plasmas, but the choice of liquid was less important when using higher energy plasmas. With SPPS, peak electrolyte conductivities were comparable to the peak conductivities of the SPS electrolytes. However, leak rates through the SPPS electrolytes were higher than those through the electrolytes made from suspensions of d50 = 2.6 μm powder. The electrochemical test data on SPPS electrolytes are the first reported in the literature.

Growth and Surface Modification of LaFeO3 Thin Films Induced By Reductive Annealing

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

Flynn, Brendan T.; Zhang, Hongliang; Shutthanandan, V.

2015-03-01

The electronic and ionic conductivity of perovskite oxides has enabled their use in diverse applications such as automotive exhaust catalysts, solid oxide fuel cell cathodes, and visible light photocatalysts. The redox chemistry at the surface of perovskite oxides is largely dependent on the oxidation state of the metal cations as well as the oxide surface stoichiometry. In this study, LaFeO3 (LFO) thin films grown on yttria-stabilized zirconia (YSZ) was characterized using both bulk and surface sensitive techniques. A combination of in situ reflection high energy electron diffraction (RHEED), x-ray diffraction (XRD), transmission electron microscopy (TEM) and Rutherford backscattering spectrometry (RBS)more » demonstrated that the film is highly oriented and stoichiometric. The film was annealed in an ultra-high vacuum chamber to simulate reducing conditions and studied by angle-resolved x-ray photoelectron spectroscopy (XPS). Iron was found to exist as Fe(0), Fe(II), and Fe(III) depending on the annealing conditions and the depth within the film. A decrease in the concentration of surface oxygen species was correlated with iron reduction. These results should help guide and enhance the design of perovskite materials for catalysts.« less

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

Dissolved oxygen control and monitoring implementation in the liquid lead bismuth eutectic loop: HELIOS

NASA Astrophysics Data System (ADS)

Nam, Hyo On; Lim, Jun; Han, Dong Yoon; Hwang, Il Soon

2008-06-01

A 12 m tall LBE coolant loop, named as HELIOS, has been developed by thermal-hydraulic scaling of the PEACER-300MWe. Thermo-hydraulic experiment and materials test are the principal purposes of HELIOS operation. In this study, an yttria stabilized zirconia (YSZ) based oxygen sensor that was hermetically sealed for long-term applications using the electromagnetically swaged metal-ceramic joining method, have been developed for high temperature oxygen control application over a long period of time. The rugged electrode design has been calibrated to absolute metal-oxide equilibrium by using a first principle of detecting pure metal-oxide transition using electrochemical impedance spectroscopy (EIS). During the materials tests in HELIOS, dissolved oxygen concentration was administered at the intended condition of 10 -6 wt% by direct gas bubbling with Ar + 4%H 2, Ar + 5%O 2 and/or pure Ar while corrosion tests were conducted for up to 1000 h with inspection after each 333 h. During the total 1000 h corrosion test, oxygen concentration was measured by oxygen sensor. The result confirmed that the direct gas bubbling method is a viable and practical option for controlling oxygen concentration in large loops including HELIOS.

XRD investigation of the Effect of MgO Additives on ZTA-TiO2 Ceramic Composites

NASA Astrophysics Data System (ADS)

Azhar, Ahmad Zahirani Ahmad; Manshor, Hanisah; Ali, Afifah Mohd

2018-01-01

Alumina (Al2O3) based ceramics possess good mechanical properties and suitable for the application of cutting inserts. However, this monolithic ceramics suffer from lack of toughness. Hence, there are some modification were made such as the addition of yttria stabilized zirconia (YSZ) to the Al2O3 helps in increasing the toughness of the Al2O3 ceramics. Some additives such as MgO and TiO2 were used to further improve the mechanical properties of ZTA. In this study, high purity raw materials which consist of ZTA-TiO2 were mixed with different amount of MgO (0.0 - 1.0 wt %). The mixture of materials was going through wet mixing, compaction and pressureless sintering at 1600°C for one hour. The samples were characterized for phase analysis, microstructure, shrinkage rate, bulk density, Vickers hardness and fracture toughness. Based on the XRD analysis results, the secondary phase (MgAl2O4) was detected in the sample with 0.5 wt% of MgO onwards which leads to grains refinement, thus improve the density and hardness of ZTA-TiO2-MgO ceramics composites.

Glass/Ceramic Composites for Sealing Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Choi, Sung R.

2007-01-01

A family of glass/ceramic composite materials has been investigated for use as sealants in planar solid oxide fuel cells. These materials are modified versions of a barium calcium aluminosilicate glass developed previously for the same purpose. The composition of the glass in mole percentages is 35BaO + 15CaO + 5Al2O3 + 10B2O3 + 35SiO2. The glass seal was found to be susceptible to cracking during thermal cycling of the fuel cells. The goal in formulating the glass/ ceramic composite materials was to (1) retain the physical and chemical advantages that led to the prior selection of the barium calcium aluminosilicate glass as the sealant while (2) increasing strength and fracture toughness so as to reduce the tendency toward cracking. Each of the composite formulations consists of the glass plus either of two ceramic reinforcements in a proportion between 0 and 30 mole percent. One of the ceramic reinforcements consists of alumina platelets; the other one consists of particles of yttria-stabilized zirconia wherein the yttria content is 3 mole percent (3YSZ). In preparation for experiments, panels of the glass/ceramic composites were hot-pressed and machined into test bars.

Smart Nanocomposite Coatings with Chameleon Surface Adaptation in Tribological Applications

NASA Astrophysics Data System (ADS)

Voevodin, A. A.; Zabinski, J. S.

Smart nanocomposite tribological coatings were designed to respond to changing environmental conditions by self-adjustment of their surface properties to maintain good tribological performance in any environment. These coatings have been dubbed "chameleon" because of their ability to change their surface chemistry and structure to avoid wear. The first "chameleon" coatings were made of WC, WS2, and DLC; these coatings provided superior mechanical toughness and performance in dry/humid environmental cycling. In order to address temperature variation, the second generation of "chameleon" coatings were made of yttria stabilized zirconia (YSZ) in a gold matrix with encapsulated nano-sized reservoirs of MoS2 and DLC. High temperature lubrication with low melting point glassy ceramic phases was also explored. All coatings were produced using a combination of laser ablation and magnetron sputtering. They were thoroughly characterized by various analytical, mechanical, and tribological methods. Coating toughness was remarkably enhanced by activation of a grain boundary sliding mechanism. Friction and wear endurance measurements were performed in controlled humidity air, dry nitrogen, and vacuum environments, as well as at 500-600 °C in air. Unique friction and wear performance in environmental cycling was demonstrated.

Method for making a monolithic integrated high-T.sub.c superconductor-semiconductor structure

NASA Technical Reports Server (NTRS)

Burns, Michael J. (Inventor); de la Houssaye, Paul R. (Inventor); Russell, Stephen D. (Inventor); Garcia, Graham A. (Inventor); Barfknecht, Andrew T. (Inventor); Clayton, Stanley R. (Inventor)

2000-01-01

A method for the fabrication of active semiconductor and high-temperature perconducting devices on the same substrate to form a monolithically integrated semiconductor-superconductor (MISS) structure is disclosed. A common insulating substrate, preferably sapphire or yttria-stabilized zirconia, is used for deposition of semiconductor and high-temperature superconductor substructures. Both substructures are capable of operation at a common temperature of at least 77 K. The separate semiconductor and superconductive regions may be electrically interconnected by normal metals, refractory metal silicides, or superconductors. Circuits and devices formed in the resulting MISS structures display operating characteristics which are equivalent to those of circuits and devices prepared on separate substrates.

Ceramic electrolyte coating methods

DOEpatents

Seabaugh, Matthew M.; Swartz, Scott L.; Dawson, William J.; McCormick, Buddy E.

2004-10-12

Processes for preparing aqueous suspensions of a nanoscale ceramic electrolyte material such as yttrium-stabilized zirconia. The invention also includes a process for preparing an aqueous coating slurry of a nanoscale ceramic electrolyte material. The invention further includes a process for depositing an aqueous spray coating slurry including a ceramic electrolyte material on pre-sintered, partially sintered, and unsintered ceramic substrates and products made by this process.

Fracture-resistant monolithic dental crowns.

PubMed

Zhang, Yu; Mai, Zhisong; Barani, Amir; Bush, Mark; Lawn, Brian

2016-03-01

To quantify the splitting resistance of monolithic zirconia, lithium disilicate and nanoparticle-composite dental crowns. Fracture experiments were conducted on anatomically-correct monolithic crown structures cemented to standard dental composite dies, by axial loading of a hard sphere placed between the cusps. The structures were observed in situ during fracture testing, and critical loads to split the structures were measured. Extended finite element modeling (XFEM), with provision for step-by-step extension of embedded cracks, was employed to simulate full failure evolution. Experimental measurements and XFEM predictions were self-consistent within data scatter. In conjunction with a fracture mechanics equation for critical splitting load, the data were used to predict load-sustaining capacity for crowns on actual dentin substrates and for loading with a sphere of different size. Stages of crack propagation within the crown and support substrate were quantified. Zirconia crowns showed the highest fracture loads, lithium disilicate intermediate, and dental nanocomposite lowest. Dental nanocomposite crowns have comparable fracture resistance to natural enamel. The results confirm that monolithic crowns are able to sustain high bite forces. The analysis indicates what material and geometrical properties are important in optimizing crown performance and longevity. Copyright © 2015 Academy of Dental Materials. All rights reserved.

FRACTURE-RESISTANT MONOLITHIC DENTAL CROWNS

PubMed Central

Zhang, Yu; Mai, Zhisong; Barani, Amir; Bush, Mark; Lawn, Brian

2016-01-01

Objective To quantify the splitting resistance of monolithic zirconia, lithium disilicate and nanoparticle-composite dental crowns. Methods Fracture experiments were conducted on anatomically-correct monolithic crown structures cemented to standard dental composite dies, by axial loading of a hard sphere placed between the cusps. The structures were observed in situ during fracture testing, and critical loads to split the structures were measured. Extended finite element modeling (XFEM), with provision for step-by-step extension of embedded cracks, was employed to simulate full failure evolution. Results Experimental measurements and XFEM predictions were self consistent within data scatter. In conjunction with a fracture mechanics equation for critical splitting load, the data were used to predict load-sustaining capacity for crowns on actual dentin substrates and for loading with a sphere of different size. Stages of crack propagation within the crown and support substrate were quantified. Zirconia crowns showed the highest fracture loads, lithium disilicate intermediate, and dental nanocomposite lowest. Dental nanocomposite crowns have comparable fracture resistance to natural enamel. Significance The results confirm that monolithic crowns are able to sustain high bite forces. The analysis indicates what material and geometrical properties are important in optimizing crown performance and longevity. PMID:26792623

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 commercialization of Si-based ceramic components in gas turbines is on the horizon, a major emphasis is placed on EBCs for two reasons. First, they are absolute necessity for the protection of Si-based ceramics from water vapor. Second, they can enable a major enhancement in the performance of gas turbines by creating temperature gradients with the incorporation of a low thermal conductivity layer. Thorough understanding of current state-of-the-art EBCs will provide the foundation upon which development of future EBCs will be based. Phase stability and thermal conductivity of EPM EBCs are published elsewhere. This paper will discuss the chemical/environmental durability and silica volatility of EPM EBCs and their impact on the coating's upper temperature limit.

Formation of high heat resistant coatings by using gas tunnel type plasma spraying.

PubMed

Kobayashi, A; Ando, Y; Kurokawa, K

2012-06-01

Zirconia sprayed coatings are widely used as thermal barrier coatings (TBC) for high temperature protection of metallic structures. However, their use in diesel engine combustion chamber components has the long run durability problems, such as the spallation at the interface between the coating and substrate due to the interface oxidation. Although zirconia coatings have been used in many applications, the interface spallation problem is still waiting to be solved under the critical conditions such as high temperature and high corrosion environment. The gas tunnel type plasma spraying developed by the author can make high quality ceramic coatings such as Al2O3 and ZrO2 coating compared to other plasma spraying method. A high hardness ceramic coating such as Al2O3 coating by the gas tunnel type plasma spraying, were investigated in the previous study. The Vickers hardness of the zirconia (ZrO2) coating increased with decreasing spraying distance, and a higher Vickers hardness of about Hv = 1200 could be obtained at a shorter spraying distance of L = 30 mm. ZrO2 coating formed has a high hardness layer at the surface side, which shows the graded functionality of hardness. In this study, ZrO2 composite coatings (TBCs) with Al2O3 were deposited on SS304 substrates by gas tunnel type plasma spraying. The performance such as the mechanical properties, thermal behavior and high temperature oxidation resistance of the functionally graded TBCs was investigated and discussed. The resultant coating samples with different spraying powders and thickness are compared in their corrosion resistance with coating thickness as variables. Corrosion potential was measured and analyzed corresponding to the microstructure of the coatings. High Heat Resistant Coatings, Gas Tunnel Type Plasma Spraying, Hardness,

Multilayer Article Characterized by Low Coefficient of Thermal Expansion Outer Layer

NASA Technical Reports Server (NTRS)

Lee, Kang N. (Inventor)

2004-01-01

A multilayer article comprises a substrate comprising a ceramic or a silicon-containing metal alloy. The ceramic is a Si-containing ceramic or an oxide ceramic with or without silicon. An outer layer overlies the substrate and at least one intermediate layer is located between the outer layer and thc substrate. An optional bond layer is disposed between thc 1 least one intermediate layer and thc substrate. The at least one intermediate layer may comprise an optional chemical barrier layer adjacent the outer layer, a mullite-containing layer and an optional chemical barrier layer adjacent to the bond layer or substrate. The outer layer comprises a compound having a low coefficient of thermal expansion selected from one of the following systems: rare earth (RE) silicates; at least one of hafnia and hafnia-containing composite oxides; zirconia-containing composite oxides and combinations thereof.

Glass-(nAg, nCu) biocide coatings on ceramic oxide substrates.

PubMed

Esteban-Tejeda, Leticia; Malpartida, Francisco; Díaz, Luis Antonio; Torrecillas, Ramón; Rojo, Fernando; Moya, José Serafín

2012-01-01

The present work was focused on obtaining biocide coatings constituted by a glassy soda-lime matrix containing silver or copper nanoparticles on ceramic (alumina and zirconia based) substrates. Both glassy coatings showed a high biocide activity against Gram-, Gram+ bacteria and yeast, reducing cell numbers more than three logarithms. Silver nanoparticles had a significantly higher biocide activity than copper nanoparticles, since the lixiviation levels required to reduce cell numbers more than 3 logarithms was of almost 1-2 µg/cm(2) in the case of silver nanoparticles, and 10-15 µg/cm(2) for the copper nanoparticles.

Analysis of an Interface Crack for a Functionally Graded Strip Sandwiched between Two Homogeneous Layers of Finite Thickness

NASA Technical Reports Server (NTRS)

Shbeeh, N. I.; Binienda, W. K.

1999-01-01

The interface crack problem for a composite layer that consists of a homogeneous substrate, coating and a non-homogeneous interface was formulated for singular integral equations with Cauchy kernels and integrated using the Lobatto-Chebyshev collocation technique. Mixed-mode Stress Intensity Factors and Strain Energy Release Rates were calculated. The Stress Intensity Factors were compared for accuracy with relevant results previously published. The parametric studies were conducted for the various thickness of each layer and for various non-homogeneity ratios. Particular application to the Zirconia thermal barrier on steel substrate is demonstrated.

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.