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

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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.

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.

Spin coating of electrolytes

DOEpatents

Stetter, Joseph R.; Maclay, G. Jordan

1989-01-01

Methods for spin coating electrolytic materials onto substrates are disclosed. More particularly, methods for depositing solid coatings of ion-conducting material onto planar substrates and onto electrodes are disclosed. These spin coating methods are employed to fabricate electrochemical sensors for use in measuring, detecting and quantifying gases and liquids.

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.

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.

Solid oxide fuel cell electrolytes produced via very low pressure suspension plasma spray and electrophoretic deposition

NASA Astrophysics Data System (ADS)

Fleetwood, James D.

Solid oxide fuel cells (SOFCs) are a promising element of comprehensive energy policies due to their direct mechanism for converting the oxidization of fuel, such as hydrogen, into electrical energy. Both very low pressure plasma spray and electrophoretic deposition allow working with high melting temperature SOFC suspension based feedstock on complex surfaces, such as in non-planar SOFC designs. Dense, thin electrolytes of ideal composition for SOFCs can be fabricated with each of these processes, while compositional control is achieved with dissolved dopant compounds that are incorporated into the coating during deposition. In the work reported, sub-micron 8 mole % Y2O3-ZrO2 (YSZ) and gadolinia-doped ceria (GDC), powders, including those in suspension with scandium-nitrate dopants, were deposited on NiO-YSZ anodes, via very low pressure suspension plasma spray (VLPSPS) at Sandia National Laboratories' Thermal Spray Research Laboratory and electrophoretic deposition (EPD) at Purdue University. Plasma spray was carried out in a chamber held at 320 - 1300 Pa, with the plasma composed of argon, hydrogen, and helium. EPD was characterized utilizing constant current deposition at 10 mm electrode separation, with deposits sintered from 1300 -- 1500 °C for 2 hours. The role of suspension constituents in EPD was analyzed based on a parametric study of powder loading, powder specific surface area, polyvinyl butyral (PVB) content, polyethyleneimine (PEI) content, and acetic acid content. Increasing PVB content and reduction of particle specific surface area were found to eliminate the formation of cracks when drying. PEI and acetic acid content were used to control suspension stability and the adhesion of deposits. Additionally, EPD was used to fabricate YSZ/GDC bilayer electrolyte systems. The resultant YSZ electrolytes were 2-27 microns thick and up to 97% dense. Electrolyte performance as part of a SOFC system with screen printed LSCF cathodes was evaluated with peak

Effect of fabrication parameters on coating properties of tubular solid oxide fuel cell electrolyte prepared by vacuum slurry coating

NASA Astrophysics Data System (ADS)

Son, Hui-Jeong; Song, Rak-Hyun; Lim, Tak-Hyoung; Lee, Seung-Bok; Kim, Sung-Hyun; Shin, Dong-Ryul

The process of vacuum slurry coating for the fabrication of a dense and thin electrolyte film on a porous anode tube is investigated for application in solid oxide fuel cells. 8 mol% yttria stabilized zirconia is coated on an anode tube by vacuum slurry-coating process as a function of pre-sintering temperature of the anode tube, vacuum pressure, slurry concentration, number of coats, and immersion time. A dense electrolyte layer is formed on the anode tube after final sintering at 1400 °C. With decrease in the pre-sintering temperature of the anode tube, the grain size of the coated electrolyte layer increases and the number of surface pores in the coating layer decreases. This is attributed to a reduced difference in the respective shrinkage of the anode tube and the electrolyte layer. The thickness of the coated electrolyte layer increases with the content of solid powder in the slurry, the number of dip-coats, and the immersion time. Although vacuum pressure has no great influence on the electrolyte thickness, higher vacuum produces a denser coating layer, as confirmed by low gas permeability and a reduced number of defects in the coating layer. A single cell with the vacuum slurry coated electrolyte shows a good performance of 620 mW cm -2 (0.7 V) at 750 °C. These experimental results indicate that the vacuum slurry-coating process is an effective method to fabricate a dense thin film on a porous anode support.

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.

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.

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.

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.

Improved Oxidation Life of Segmented Plasma Sprayed 8YSZ Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Smialek, James L.

2004-03-01

Unconventional plasma sprayed thermal barrier coating (TBC) systems were produced and evaluated by interrupted or cyclic furnace oxidation life testing. First, approximately 250 µm thick 8YSZ coatings were directly sprayed onto grit blasted surfaces of PWA 1484, without a bond coat, to take advantage of the excellent oxidation resistance of this superalloy. For nominal sulfur (S) contents of 1 ppmw, total coating separation took place at relatively short times (200 h at 1100°C). Reductions in the S content, by melt desulfurization commercially (0.3 ppmw) or by hydrogen (H2) annealing in the laboratory (0.01 ppmw), improved scale adhesion and extended life appreciably, by factors of 5-10. However, edge-initiated failure persisted, producing massive delamination as one sheet of coating. Secondly, surfaces of melt desulfurized PWA 1484 were machined with a grid of grooves or ribs (˜250 µm wide and high), resulting in a segmented TBC surface macrostructure, for the purpose of subverting this failure mechanism. In this case, failure occurred only as independent, single-segment events. For grooved samples, 1100 °C segment life was extended to ˜1000h for 5 mm wide segments, with no failure observed out to 2000 h for segments ≤2.5 mm wide. Ribbed samples were even more durable, and segments ≤6 mm remained intact for 2000 h. Larger segments failed by buckling at times inversely related to the segment width and decreased by oxidation effects at higher temperatures. This critical buckling size was consistent with that predicted for elastic buckling of a TBC plate subject to thermal expansion mismatch stresses. Thus, low S substrates demonstrate appreciable coating lives without a bond coat, while rib segmenting extends life considerably.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Electrodeposition of Dense Chromium Coatings from Molten Salt Electrolytes

DTIC Science & Technology

1991-04-01

AD-A235 978 . JUN 03 391 ELECTRODEPOSITION OF DENSE CHROMIUM COATINGS FROM MOLTEN SALT ELECTROLYTES Final Technical Report J t ]Vgca or by ~ 4 OTC... molten salts , pulsed currents, electrodeposition. 2. The results, on the electrodeposition of dense chromium coatings from molten salt electrolytes... salts dissolved in molten salts using the cell Cl2/C/!Cr 2 + in LiCI-KCI//Cr metal The chromium ions are introduced by anodizing a piece of chromium and

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-04-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-05-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Formation of a Spinel Coating on AZ31 Magnesium Alloy by Plasma Electrolytic Oxidation

NASA Astrophysics Data System (ADS)

Sieber, Maximilian; Simchen, Frank; Scharf, Ingolf; Lampke, Thomas

2016-03-01

Plasma electrolytic oxidation (PEO) is a common means for the surface modification of light metals. However, PEO of magnesium substrates in dilute electrolytes generally leads to the formation of coatings consisting of unfavorable MgO magnesium oxide. By incorporation of electrolyte components, the phase constitution of the oxide coatings can be modified. Coatings consisting exclusively of MgAl2O4 magnesium-aluminum spinel are produced by PEO in an electrolyte containing hydroxide, aluminate, and phosphate anions. The hardness of the coatings is 3.5 GPa on Martens scale on average. Compared to the bare substrate, the coatings reduce the corrosion current density in dilute sodium chloride solution by approx. one order of magnitude and slightly shift the corrosion potential toward more noble values.

Coated powder for electrolyte matrix for carbonate fuel cell

DOEpatents

Iacovangelo, Charles D.; Browall, Kenneth W.

1985-01-01

A plurality of electrolyte carbonate-coated ceramic particle which does not differ significantly in size from that of the ceramic particle and wherein no significant portion of the ceramic particle is exposed is fabricated into a porous tape comprised of said coated-ceramic particles bonded together by the coating for use in a molten carbonate fuel cell.

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.

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

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

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

2015-07-11

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

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

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.

Electrochemical Formation of Multilayer SnO2-Sb x O y Coating in Complex Electrolyte

NASA Astrophysics Data System (ADS)

Maizelis, Antonina; Bairachniy, Boris

2017-02-01

The multilayer antimony-doped tin dioxide coating was obtained by cathodic deposition of multilayer metal-hydroxide coating with near 100-nm thickness layers on the alloy underlayer accompanied by the anodic oxidation of this coating. The potential regions of deposition of tin, antimony, tin-antimony alloy, and mixture of this metals and their hydroxides in the pyrophosphate-tartrate electrolyte were revealed by the cyclic voltammetric method. The possibility of oxidation of cathodic deposit consisting of tin and Sn(II) hydroxide compounds to the hydrated tin dioxide in the same electrolyte was demonstrated. The operations of alloy underlayer deposition and oxidation of multilayer metal-hydroxide coating were proposed to carry out in the diluted pyrophosphate-tartrate electrolyte, similar to the main electrolyte. The accelerated tests showed higher service life of the titanium electrode with multilayer antimony-doped tin dioxide coating compared to both electrode with single-layer electrodeposited coating and the electrode with the coating obtained using prolonged heat treatment step.

Electrochemical Formation of Multilayer SnO2-Sb x O y Coating in Complex Electrolyte.

PubMed

Maizelis, Antonina; Bairachniy, Boris

2017-12-01

The multilayer antimony-doped tin dioxide coating was obtained by cathodic deposition of multilayer metal-hydroxide coating with near 100-nm thickness layers on the alloy underlayer accompanied by the anodic oxidation of this coating. The potential regions of deposition of tin, antimony, tin-antimony alloy, and mixture of this metals and their hydroxides in the pyrophosphate-tartrate electrolyte were revealed by the cyclic voltammetric method. The possibility of oxidation of cathodic deposit consisting of tin and Sn(II) hydroxide compounds to the hydrated tin dioxide in the same electrolyte was demonstrated.The operations of alloy underlayer deposition and oxidation of multilayer metal-hydroxide coating were proposed to carry out in the diluted pyrophosphate-tartrate electrolyte, similar to the main electrolyte.The accelerated tests showed higher service life of the titanium electrode with multilayer antimony-doped tin dioxide coating compared to both electrode with single-layer electrodeposited coating and the electrode with the coating obtained using prolonged heat treatment step.

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

NASA Astrophysics Data System (ADS)

Zhao, Yan; Gao, Yang

2017-12-01

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

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

The influence of pore formers on the microstructure of plasma-sprayed NiO-YSZ anodes

NASA Astrophysics Data System (ADS)

Poon, Michael; Kesler, Olivera

2012-07-01

Four types of pore formers: high-density polyethylene (HDPE), polyether-ether-ketone (PEEK), mesocarbon-microbead (MCMB) carbon powder, and baking flour, are processed and characterized, then incorporated with NiO-YSZ nano-agglomerate powder to produce plasma sprayed SOFC anode coatings. Scanning electron microscopy (SEM) of the coating microstructure, gas permeability measurements, and porosity determinations by image analysis are used to evaluate the effectiveness of each potential pore former powder. Under the spray conditions studied, the flour and MCMB pore former powders are effective as plasma sprayed pore formers, increasing the permeability of the coatings by factors of four and two, respectively, compared to a similarly sprayed NiO-YSZ coating without pore formers. The HDPE powder is unable to survive the plasma spray process and does not contribute to the final coating porosity. The PEEK pore former, though ineffective with the current powder characteristics and spray parameters, exhibits the highest relative deposition efficiency and the most favorable thermal characteristics.

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.

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

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

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

2013-09-01

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

Zirconia based ceramic coating on a metal with plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Akatsu, T.; Kato, T.; Shinoda, Y.; Wakai, F.

2011-10-01

We challenge to fabricate a thermal barrier coating (TBC) made of ZrO2 based ceramics on a Ni based single crystal superalloy with plasma electrolytic oxidation (PEO) by incorporating metal species from electrolyte into the coating. The PEO process is carried out on the superalloy galvanized with aluminium for 15min in Na4O7P4 solution for an oxygen barrier coating (OBC) and is followed by PEO in K2[Zr(CO3)2(OH)2] solution for TBC. We obtained the following results; (1) Monoclinic-, tetragonal-, cubic-ZrO2 crystals were detected in TBC. (2) High porosity with large pores was observed near the interface between OBC and TBC. The fine grain structure with a grain size of about 300nm was typically observed. (3) The adhesion strength between PEO coatings and substrate was evaluated to be 26.8±6.6MPa. At the adhesion strength test, PEO coatings fractured around the interface between OBC and TBC. The effect of coating structure on adhesion strength is explained through the change in spark discharge during PEO process.

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.

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte

NASA Astrophysics Data System (ADS)

Chen, Wei; Rakhi, R. B.; Alshareef, H. N.

2013-05-01

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles).We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles). Electronic supplementary information (ESI) available: Experimental section, supporting figures including SEM, TEM, XPS, BET, CV and CD curves and a summary table of capacitance. See DOI: 10.1039/c3nr00773a

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.

Characterization of Micro-arc Oxidation Coatings on 6N01 Aluminum Alloy Under Different Electrolyte Temperature Control Modes

NASA Astrophysics Data System (ADS)

Wang, Xuefei; Zhu, Zongtao; Li, Yuanxing; Chen, Hui

2018-03-01

The micro-arc oxidation coatings of 6N01 aluminum alloy produced under different control modes of the electrolyte temperature are discussed in detail. Compared to those coated by a thermostatically controlled treatment, the coatings had different surface characterizations when they were coated without controlling the electrolyte temperature, particularly after treatment involving boiling electrolytes. Scanning electron microscopy and confocal laser scanning microscopy were used to observe the morphology of the coatings. Energy-dispersive spectrometry and x-ray diffractometer were used to characterize their elemental and crystalline phase compositions. The results indicate that the treatment without a controlled electrolyte temperature ultimately led to a thicker and rougher film with a respectably thick inner barrier film, a lower content of γ-Al2O3 and better corrosion resistance.

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-05-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-04-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

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.

Transmission electron microscopy of coatings formed by plasma electrolytic oxidation of titanium.

PubMed

Matykina, E; Arrabal, R; Skeldon, P; Thompson, G E

2009-05-01

Transmission electron microscopy and supporting film analyses are used to investigate the changes in composition, morphology and structure of coatings formed on titanium during DC plasma electrolytic oxidation in a calcium- and phosphorus-containing electrolyte. The coatings are of potential interest as bioactive surfaces. The initial barrier film, of mixed amorphous and nanocrystalline structure, formed below the sparking voltage of 180 V, incorporates small amounts of phosphorus and calcium species, with phosphorus confined to the outer approximately 63% of the coating thickness. On commencement of sparking, calcium- and phosphorus-rich amorphous material forms at the coating surface, with local heating promoting crystallization in underlying and adjacent anodic titania. The amorphous material thickens with increased treatment time, comprising almost the whole of the approximately 5.7-microm-thick coating formed at 340 V. At this stage, the coating is approximately 4.4 times thicker than the oxidized titanium, with a near-surface composition of about 12 at.% Ti, 58 at.% O, 19 at.% P and 11 at.% Ca. Further, the amount of titanium consumed in forming the coating is similar to that calculated from the anodizing charge, although there may be non-Faradaic contributions to the coating growth.

Electrophoretic deposition of bi-layered LSM/LSM-YSZ cathodes for solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Itagaki, Yoshiteru; Watanabe, Shinji; Yamaji, Tsuyoshi; Asamoto, Makiko; Yahiro, Hidenori; Sadaoka, Yoshihiko

2012-09-01

Bi-layered cathodes with the LSM/LSM-YSZ structure for solid oxide fuel cells were successfully formed on the carbon-sputtered surface of a YSZ sheet by electrophoretic deposition (EPD). The thicknesses of the first layer of LSM-YSZ (LY) and the second layer of La0.8Sr0.2MnO3 (LSM) could be controlled by adjusting the deposition time in the EPD process. The cathodic properties of the bi-layered structures were superior to those of the mono-layered structures, and were dependent on the thickness of each layer. Decreasing the thickness of the first layer and increasing that of the second layer tended to reduce both polarization and ohmic resistances. The optimal thickness of the first layer at the operating temperature of 600 °C was 4 μm, suggesting that an effective three-phase boundary was extended from the interface between the electrolyte and cathode film to around 4 μm thickness.

Investigating catalyst coated membrane equilibration time for polymer electrolyte membrane fuel cell manufacturing

NASA Astrophysics Data System (ADS)

Cote, Philippe

Mercedes-Benz Canada Inc., Fuel Cell Division, manufactures polymer electrolyte membrane fuel cell stacks for use in vehicles. The manufacturing line is being optimized for efficiency and quality control, in order to uphold the high standards of Mercedes-Benz Inc. vehicles. In an operating polymer electrolyte membrane fuel cell, the catalyst coated membrane facilitates the electrochemical reaction that generates electricity. This research examines the equilibration of catalyst coated membrane rolls to controlled temperature and humidity conditions, before they are used in the manufacturing of polymer electrolyte membrane fuel cells. Equilibration involves allowing the water content in the catalyst coated membrane to stabilize at the controlled conditions, in order to reduce mechanical stress in the material for better manufacturability. Initial equilibration measurements were conducted on discrete catalyst coated membrane samples using novel electronic conductivity measurements of the catalyst layer, and compared to ionic conductivity measurements of the membrane. Electronic conductivity measurements are easier to implement in the manufacturing environment than the more complex ionic conductivity measurements. When testing discrete catalyst coated membrane samples in an environmental chamber, the equilibration trends for the measured ionic and electronic conductivity signals were similar enough to permit us to adapt the electronic conductivity measurements for catalyst coated membrane in roll form. Equilibration measurements of catalyst coated membrane rolls were optimized to achieve a robust and repeatable procedure which could be used in the manufacturing environment at Mercedes-Benz Canada Inc., Fuel Cell Division.

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte.

PubMed

Chen, Wei; Rakhi, R B; Alshareef, H N

2013-05-21

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50,000 cycles).

Plasma Electrolytic Oxidation Coatings on Pure Ti Substrate: Effects of Na3PO4 Concentration on Morphology and Corrosion Behavior of Coatings in Ringer's Physiological Solution

NASA Astrophysics Data System (ADS)

Roknian, Masoud; Fattah-alhosseini, Arash; Gashti, Seyed Omid

2018-03-01

Plasma electrolytic oxidation has been used as a relatively new method for applying ceramic coatings having different features. In the present study, commercially pure titanium is used as substrate, and effects of trisodium phosphate electrolyte concentration on the microstructure, as well as corrosion behavior of the coating in Ringer's physiological solution are investigated. The morphology and phase compositions of coatings were analyzed by using scanning electron microscopy (SEM) and x-ray diffraction patterns. The study on the corrosion behavior of samples in a Ringer's physiological solution was carried out using open-circuit potential potentiodynamic polarization and electrochemical impedance spectroscopy. The results of electrochemical analysis proved that higher concentration of phosphate electrolyte leads to increase in the corrosion resistance of applied coatings. Accordingly, obtained results revealed that the optimum electrolyte concentration for the best corrosion behavior was 20 g L-1. Furthermore, SEM images and reduction in the dielectric breakdown potential indicated that increase in the electrolyte concentration leads to morphological improvement and smoothening of the surface.

In situ Van der Pauw measurements of the Ni/YSZ anode during exposure to syngas with phosphine contaminant

NASA Astrophysics Data System (ADS)

Demircan, Oktay; Xu, Chunchuan; Zondlo, John; Finklea, Harry O.

Solid oxide fuel cells (SOFCs) represent an option to provide a bridging technology for energy conversion (coal syngas) as well as a long-term technology (hydrogen from biomass). Whether the fuel is coal syngas or hydrogen from biomass, the effect of impurities on the performance of the anode is a vital question. The anode resistivity during SOFC operation with phosphine-contaminated syngas was studied using the in situ Van der Pauw method. Commercial anode-supported solid oxide fuel cells (Ni/YSZ composite anodes, YSZ electrolytes) were exposed to a synthetic coal syngas mixture (H 2, H 2O, CO, and CO 2) at a constant current and their performance evaluated periodically with electrochemical methods (cyclic voltammetry, impedance spectroscopy, and polarization curves). In one test, after 170 h of phosphine exposure, a significant degradation of cell performance (loss of cell voltage, increase of series resistance and increase of polarization resistance) was evident. The rate of voltage loss was 1.4 mV h -1. The resistivity measurements on Ni/YSZ anode by the in situ Van der Pauw method showed that there were no significant changes in anode resistivity both under clean syngas and syngas with 10 ppm PH 3. XRD analysis suggested that Ni 5P 2 and P 2O 5 are two compounds accumulated on the anode. XPS studies provided support for the presence of two phosphorus phases with different oxidation states on the external anode surface. Phosphorus, in a positive oxidation state, was observed in the anode active layer. Based on these observations, the effect of 10 ppm phosphine impurity (or its reaction products with coal syngas) is assigned to the loss of performance of the Ni/YSZ active layer next to the electrolyte, and not to any changes in the thick Ni/YSZ support 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

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.

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.

Preparation and Characterization of Plasma Electrolytic Oxidation Coating on 5005 Aluminum Alloy with Red Mud as an Electrolyte Additive

NASA Astrophysics Data System (ADS)

Liu, Shifeng; Zeng, Jianmin; Wang, Youbin

2017-10-01

A coating with red mud as an electrolyte additive was applied to 5005 aluminum alloy using plasma electrolytic oxidation (PEO). The phase composition of the coating was investigated using X-ray diffraction. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) was used to determine the microstructure and composition profiles of the coating. The coating/substrate adhesion was determined by scratch testing. The corrosion behaviors of the substrate and coating were evaluated using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). The results indicated that the PEO coating with red mud consisted mainly of α-Al2O3 and γ-Al2O3, with small amounts of Fe2O3, CaCO3, and CaTiO3. The surface of the coating was the color of the red mud. The coating had a uniform thickness of about 80 μm and consisted of two main layers: a 6- μm porous outer layer and a 74- μm dense inner layer, which showed typical metallurgical adhesion (coating/substrate adhesion strength of 59 N). The coating hardness was about 1142 HV, much higher than that of the substrate (60 HV). The corrosion potential E corr and corrosion current density i corr of the coating were estimated to be -0.743 V and 3.85 × 10-6 A cm-2 from the PDP curve in 3.5 wt pct NaCl solution, and the maximum impedance and phase angle of the coating were 11 000 Ω and -67 deg, respectively, based on EIS. PEO coating with red mud improved the surface properties and corrosion resistance of 5005 aluminum alloy. This study also shows a potential method for reusing red mud.

Thermal barrier coatings

DOEpatents

Alvin, Mary Anne [Pittsburg, PA

2010-06-22

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

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.

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.

The black and white coatings on Ti-6Al-4V alloy or pure titanium by plasma electrolytic oxidation in concentrated silicate electrolyte

NASA Astrophysics Data System (ADS)

Han, Jun-xiang; Cheng, Yu-lin; Tu, Wen-bin; Zhan, Ting-Yan; Cheng, Ying-liang

2018-01-01

Black TiO2 has triggered scientific interest due to its unique properties such as enhanced solar-driven photocatalytic activity. In this paper, plasma electrolytic oxidation (PEO) treatment of Ti-6Al-4V alloy has been carried out in concentrated sodium silicate electrolyte. Silica-based black and white TiO2 coatings respectively have been obtained by controlling the oxidation time. The black coating, which was formed with a short treatment time, shows good corrosion resistance and the black appearance can be attributed to the presence of Ti2+ and Ti3+ in the coating. The lower valence titanium ions are absent in the white coatings and they also contain relatively higher Na content compared to the black coatings. The white coatings have great surface roughnesses and super hydrophilicity. The bonding strengths of the black and white coatings on the Ti-6Al-4V alloy are ∼14.4 and 4.3 MPa, respectively. The vanadium contributes little to the black appearance of the coating on Ti6Al4V alloy, since the same phenomena occur for the PEO of a pure titanium substrate.

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.

Corrosion evaluation of zirconium doped oxide coatings on aluminum formed by plasma electrolytic oxidation.

PubMed

Bajat, Jelena; Mišković-Stanković, Vesna; Vasilić, Rastko; Stojadinović, Stevan

2014-01-01

The plasma electrolytic oxidation (PEO) of aluminum in sodium tungstate (Na(2)WO(4) · (2)H(2)O) and Na(2)WO(4) · (2)H(2)O doped with Zr was analyzed in order to obtain oxide coatings with improved corrosion resistance. The influence of current density in PEO process and anodization time was investigated, as well as the influence of Zr, with the aim to find out how they affect the chemical content, morphology, surface roughness, and corrosion stability of oxide coatings. It was shown that the presence of Zr increases the corrosion stability of oxide coatings for all investigated PEO times. Evolution of EIS spectra during the exposure to 3% NaCl, as a strong corrosive agent, indicated the highest corrosion stability for PEO coating formed on aluminum at 70 mA/cm(2) for 2 min in a zirconium containing electrolyte.

Phase analysis of plasma-sprayed zirconia-yttria coatings

NASA Technical Reports Server (NTRS)

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

1983-01-01

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

Surface analysis of Fe-Co-Mo electrolytic coatings

NASA Astrophysics Data System (ADS)

Yar-Mukhamedova, G. Sh; Sakhnenko, N. D.; Ved', M. V.; Yermolenko, I. Yu; Zyubanova, S. I.

2017-06-01

Coatings Fe-Co-Mo with a composition of 47 at.% iron, 28 at.% Cobalt and 25 at.% Molybdenum were deposited from citrate electrolyte using pulse electrolysis mode. Scanning electron and atomic force microscopy have established the surface morphology and topography. It was identified the parts with a globular structure which have an average size of 0.2-0.5μm and singly located sharp grains. Within the same scan area sites with developed surface were detected the topography of which is identical to the crystal structure of cobalt with the crystallites size of 0.2-1.75μm. The parameters Ra and Rq for parts with different morphology as well as average characteristics of coatings demonstrated the low roughness of the surface. It is found that the coercive force of Fe-Co-Mo films is 7-10 Oe, which allow us to classify the Fe-Co-Mo coatings as soft magnetic materials.

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.

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

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.

Infrared Radiative Properties of Yttria-Stabilized Zirconia Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

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.

3D Microstructure Effects in Ni-YSZ Anodes: Influence of TPB Lengths on the Electrochemical Performance.

PubMed

Pecho, Omar M; Mai, Andreas; Münch, Beat; Hocker, Thomas; Flatt, Robert J; Holzer, Lorenz

2015-10-21

3D microstructure-performance relationships in Ni-YSZ anodes for electrolyte-supported cells are investigated in terms of the correlation between the triple phase boundary (TPB) length and polarization resistance ( R pol ). Three different Ni-YSZ anodes of varying microstructure are subjected to eight reduction-oxidation (redox) cycles at 950 °C. In general the TPB lengths correlate with anode performance . However, the quantitative results also show that there is no simplistic relationship between TPB and R pol . The degradation mechanism strongly depends on the initial microstructure. Finer microstructures exhibit lower degradation rates of TPB and R pol . In fine microstructures, TPB loss is found to be due to Ni coarsening, while in coarse microstructures reduction of active TPB results mainly from loss of YSZ percolation. The latter is attributed to weak bottlenecks associated with lower sintering activity of the coarse YSZ. The coarse anode suffers from complete loss of YSZ connectivity and associated drop of TPB active by 93%. Surprisingly, this severe microstructure degradation did not lead to electrochemical failure. Mechanistic scenarios are discussed for different anode microstructures. These scenarios are based on a model for coupled charge transfer and transport, which allows using TPB and effective properties as input. The mechanistic scenarios describe the microstructure influence on current distributions, which explains the observed complex relationship between TPB lengths and anode performances. The observed loss of YSZ percolation in the coarse anode is not detrimental because the electrochemical activity is concentrated in a narrow active layer. The anode performance can be predicted reliably if the volume-averaged properties (TPB active , effective ionic conductivity) are corrected for the so-called short-range effect, which is particularly important in cases with a narrow active layer.

3D Microstructure Effects in Ni-YSZ Anodes: Influence of TPB Lengths on the Electrochemical Performance

PubMed Central

Pecho, Omar M.; Mai, Andreas; Münch, Beat; Hocker, Thomas; Flatt, Robert J.; Holzer, Lorenz

2015-01-01

3D microstructure-performance relationships in Ni-YSZ anodes for electrolyte-supported cells are investigated in terms of the correlation between the triple phase boundary (TPB) length and polarization resistance (Rpol). Three different Ni-YSZ anodes of varying microstructure are subjected to eight reduction-oxidation (redox) cycles at 950 °C. In general the TPB lengths correlate with anode performance. However, the quantitative results also show that there is no simplistic relationship between TPB and Rpol. The degradation mechanism strongly depends on the initial microstructure. Finer microstructures exhibit lower degradation rates of TPB and Rpol. In fine microstructures, TPB loss is found to be due to Ni coarsening, while in coarse microstructures reduction of active TPB results mainly from loss of YSZ percolation. The latter is attributed to weak bottlenecks associated with lower sintering activity of the coarse YSZ. The coarse anode suffers from complete loss of YSZ connectivity and associated drop of TPBactive by 93%. Surprisingly, this severe microstructure degradation did not lead to electrochemical failure. Mechanistic scenarios are discussed for different anode microstructures. These scenarios are based on a model for coupled charge transfer and transport, which allows using TPB and effective properties as input. The mechanistic scenarios describe the microstructure influence on current distributions, which explains the observed complex relationship between TPB lengths and anode performances. The observed loss of YSZ percolation in the coarse anode is not detrimental because the electrochemical activity is concentrated in a narrow active layer. The anode performance can be predicted reliably if the volume-averaged properties (TPBactive, effective ionic conductivity) are corrected for the so-called short-range effect, which is particularly important in cases with a narrow active layer. PMID:28793624

Plasma electrolytic oxidation treatment mode influence on corrosion properties of coatings obtained on Zr-1Nb alloy in silicate-phosphate electrolyte

NASA Astrophysics Data System (ADS)

Farrakhov, R. G.; Mukaeva, V. R.; Fatkullin, A. R.; Gorbatkov, M. V.; Tarasov, P. V.; Lazarev, D. M.; Babu, N. Ramesh; Parfenov, E. V.

2018-01-01

This research is aimed at improvement of corrosion properties for Zr-1Nb alloy via plasma electrolytic oxidation (PEO). The coatings obtained in DC, pulsed unipolar and pulsed bipolar modes were assessed using SEM, XRD, PDP and EIS techniques. It was shown that pulsed unipolar mode provides the PEO coatings having promising combination of the coating thickness, surface roughness, porosity, corrosion potential and current density, and charge transfer resistance, all contributing to corrosion protection of the zirconium alloy for advanced fuel cladding applications.

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.

A study on microstructure and corrosion resistance of ZrO2-containing PEO coatings formed on AZ31 Mg alloy in phosphate-based electrolyte

NASA Astrophysics Data System (ADS)

Zhuang, J. J.; Guo, Y. Q.; Xiang, N.; Xiong, Y.; Hu, Q.; Song, R. G.

2015-12-01

ZrO2-containing ceramic coatings formed on the AZ31 Mg alloy were fabricated in an alkaline electrolyte containing sodium phosphate and potassium fluorozirconate (K2ZrF6) by plasma electrolytic oxidation (PEO). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) techniques were used to study the phase structure and composition of the coatings. It is indicated that the coatings formed in the K2ZrF6-containing electrolyte were composed of MgO, MgF2 and t-ZrO2. Morphological investigation carried out by scanning electron microscopy (SEM) and stereoscopic microscopy, revealed that the uniformity of coatings increased and roughness of coatings decreased after the addition of K2ZrF6. Electrochemical investigation was achieved by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) test. The results showed that the PEO coating formed in K2ZrF6-containing electrolyte exhibited an improved corrosion resistance than that of the coating formed in K2ZrF6-free electrolyte. In addition, the polarization and EIS tests results both showed that the suitable concentration (2.5 g/l) of K2ZrF6 is of significant ability to improve the corrosion resistance of coatings. However, 5 g/l and 10 g/l K2ZrF6 has a negative effect on improving the corrosion resistance of PEO coatings compared with the coating formed in 2.5 g/l K2ZrF6-containing electrolyte.

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.

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.

Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries.

PubMed

Gomez-Ballesteros, Jose L; Balbuena, Perla B

2017-07-20

Surface modification of Si anodes in Li-ion batteries by deposition of a thin alucone coating has demonstrated an effective way to help maintain a stable anode/electrolyte interface and good battery performance. In this work, we investigate the interactions and reactivity of the film with electrolyte components using ab initio molecular dynamics simulations. Adsorption of solvent molecules (ethylene carbonate, EC) and salt (LiPF 6 ) and reduction by two mechanisms depending on the Li content of the film (yielding open EC adsorbed on the film or C 2 H 4 + CO 3 2- ) take place near the film/electrolyte and film/anode interfaces. Reaction products incorporate into the structure of the film and create a new kind of solid-electrolyte interphase layer.

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

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.

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

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.

Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries

DOE PAGES

Gomez-Ballesteros, Jose L.; Balbuena, Perla B.

2017-07-07

Surface modification of Si anodes in Li-ion batteries by deposition of a thin alucone coating has demonstrated an effective way to help maintain a stable anode/electrolyte interface and good battery performance. In this paper, we investigate the interactions and reactivity of the film with electrolyte components using ab initio molecular dynamics simulations. Adsorption of solvent molecules (ethylene carbonate, EC) and salt (LiPF 6), and reduction by two mechanisms depending on the Li content of the film (yielding open EC adsorbed on the film or C 2H 4 + CO 3 2-) take place near the film/electrolyte and film/anode interfaces. Finally,more » reactions products incorporate to the structure of the film and create a new kind of solid-electrolyte interphase layer.« less

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.

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.

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.

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

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.

Preparation of ceramic coating on Ti substrate by Plasma electrolytic oxidation in different electrolytes and evaluation of its corrosion resistance

NASA Astrophysics Data System (ADS)

Shokouhfar, M.; Dehghanian, C.; Baradaran, A.

2011-01-01

Ceramic oxide coatings (titania) were produced on Ti by micro-arc oxidation in different aluminate and carbonate based electrolytes. This process was conducted under constant pulsed DC voltage condition. The effect of KOH and NaF in aluminate based solution was also studied. The surface morphology, growth and phase composition of coatings were investigated using scanning electron microscope and X-ray diffraction. Corrosion behavior of the coatings was also examined by potentiodynamic polarization and electrochemical impedance spectroscopy. It was found that the sparking initiation voltage (spark voltage) had a significant effect on the form and properties of coatings. Coatings obtained from potassium aluminate based solution had a lower spark voltage, higher surface homogeneity and a better corrosion resistance than the carbonate based solution. Addition of NaF instead of KOH had improper effects on the homogeneity and adhesion of coatings which in turn caused a poor corrosion protection behavior of the oxide layer. AC impedance curves showed two time constants which is an indication of the coatings with an outer porous layer and an inner compact layer.

Evaluation of coated metallic bipolar plates for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Yoon, Wonseok; Huang, Xinyu; Fazzino, Paul; Reifsnider, Kenneth L.; Akkaoui, Michael A.

Metallic bipolar plates for polymer electrolyte membrane (PEM) fuel cells typically require coatings for corrosion protection. Other requirements for the corrosion protective coatings include low electrical contact resistance, good mechanical robustness, low material and fabrication cost. The authors have evaluated a number of protective coatings deposited on stainless steel substrates by electroplating and physical vapor deposition (PVD) methods. The coatings are screened with an electrochemical polarization test for corrosion resistance; then the contact resistance test was performed on selected coatings. The coating investigated include Gold with various thicknesses (2 nm, 10 nm, and 1 μm), Titanium, Zirconium, Zirconium Nitride (ZrN), Zirconium Niobium (ZrNb), and Zirconium Nitride with a Gold top layer (ZrNAu). The substrates include three types of stainless steel: 304, 310, and 316. The results show that Zr-coated samples satisfy the DOE target for corrosion resistance at both anode and cathode sides in typical PEM fuel cell environments in the short-term, but they do not meet the DOE contact resistance goal. Very thin gold coating (2 nm) can significantly decrease the electrical contact resistance, however a relatively thick gold coating (>10 nm) with our deposition method is necessary for adequate corrosion resistance, particularly for the cathode side of the bipolar plate.

Formation of Ca/P ceramic coatings by Plasma Electrolytic Oxidation (PEO) on Ti6Al4V ELI alloy

NASA Astrophysics Data System (ADS)

Rodriguez-Jaimes, Y.; Naranjo, D. I.; Blanco, S.; García-Vergara, S. J.

2017-12-01

The formation of PEO ceramic coatings on Ti6Al4V ELI alloy was investigated using a phosphate/calcium containing electrolyte at 300 and 400V at 310K for different times. The Plasma Electrolytic Oxidation (PEO) coated specimens were then heat treated at 873 and 1073K for 2 hours. Scanning electron microscopy, Energy Dispersive X-Ray Spectroscopy (EDS) and X-ray diffraction analysis were used to study the composition and the morphology of the ceramic coatings. The corrosion behaviour of the coatings was studied by Electrochemical Impedance Spectroscopy (EIS) in Simulated Body Fluid (SBF). The PEO-treated specimens primarily revealed a porous structure with thickness between 4 and 12μm, according to the voltage and process time used. The coatings are mainly composed of hydroxyapatite; however, as the voltage and anodizing time increase, the Ca/P ratio decreases. Generally, the corrosion resistance of the alloy was improved by the PEO-treated coatings, although the specimens treated at 1073K showed the presence of cracks that reduced the protective effect of the coatings.

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.

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

PubMed

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

2017-03-09

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

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

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Composite Solid Electrolyte For Lithium Cells

NASA Technical Reports Server (NTRS)

Peled, Emmanuel; Nagasubramanian, Ganesan; Halpert, Gerald; Attia, Alan I.

1994-01-01

Composite solid electrolyte material consists of very small particles, each coated with thin layer of Lil, bonded together with polymer electrolyte or other organic binder. Material offers significant advantages over other solid electrolytes in lithium cells and batteries. Features include high ionic conductivity and strength. Composite solid electrolyte expected to exhibit flexibility of polymeric electrolytes. Polymer in composite solid electrolyte serves two purposes: used as binder alone, conduction taking place only in AI2O3 particles coated with solid Lil; or used as both binder and polymeric electrolyte, providing ionic conductivity between solid particles that it binds together.

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

Electrochemical testing of suspension plasma sprayed solid oxide fuel cell electrolytes

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

Electrochemical performance of metal-supported plasma sprayed (PS) solid oxide fuel cells (SOFCs) was tested for three nominal electrolyte thicknesses and three electrolyte fabrication conditions to determine the effects of electrolyte thickness and microstructure on open circuit voltage (OCV) and series resistance (R s). The measured OCV values were approximately 90% of the Nernst voltages, and electrolyte area specific resistances below 0.1 Ω cm 2 were obtained at 750 °C for electrolyte thicknesses below 20 μm. Least-squares fitting was used to estimate the contributions to R s of the YSZ bulk material, its microstructure, and the contact resistance between the current collectors and the cells. It was found that the 96% dense electrolyte layers produced from high plasma gas flow rate conditions had the lowest permeation rates, the highest OCV values, and the smallest electrolyte-related voltage losses. Optimal electrolyte thicknesses were determined for each electrolyte microstructure that would result in the lowest combination of OCV loss and voltage loss due to series resistance for operating voltages of 0.8 V and 0.7 V.

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.

Adjustment of the ratio of Ca/P in the ceramic coating on Mg alloy by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Yao, Zhongping; Li, Liangliang; Jiang, Zhaohua

2009-04-01

The ceramic coatings containing Ca and P were prepared on AZ91D Mg alloy by plasma electrolytic oxidation technique in NaOH system and Na 2SiO 3 system, respectively. The phase composition, morphology and the element distribution of the coatings was studied by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. The corrosion resistance of the coatings was examined by polarizing curve methods in a 0.9% NaCl solution. In NaOH system, there were a large number of micro-holes distributing evenly on the surface of the coating, and the coating was mainly composed of Mg, Al, P and Ca. In Na 2SiO 3 system, the micro-holes in the coatings were reduced greatly in number and the distribution of the micro-holes was uneven, and the coating was mainly composed of Mg, Al, Si, P and Ca. The ratio of Ca/P in the coating can be controlled by the adjustment of the technique parameters to a certain extent. The adjustment of the concentration of Ca 2+ in the electrolyte was an effective method to change the ratio of Ca/P in the coating in both systems; the reaction time and the working voltage for the adjustment of the ratio of Ca/P in the coating was more suitable for the NaSi 2O 3 system than the NaOH system. The polarizing curve tests showed the coatings improved the corrosion resistance of the AZ91D Mg alloy in 0.9% NaCl solution by nearly two orders of magnitude.

Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes.

PubMed

Gómez-Marín, Ana M; Hernández-Ortíz, Juan P

2014-09-24

A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott-Schottky or Gouy-Chapman-Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

An investigation of the typical corrosion parameters used to test polymer electrolyte fuel cell bipolar plate coatings, with titanium nitride coated stainless steel as a case study

NASA Astrophysics Data System (ADS)

Orsi, A.; Kongstein, O. E.; Hamilton, P. J.; Oedegaard, A.; Svenum, I. H.; Cooke, K.

2015-07-01

Stainless steel bipolar plates (BPP) for polymer electrolyte membrane fuel cells (PEMFCs) have good manufacturability, durability and low costs, but inadequate corrosion resistance and elevated interfacial contact resistance (ICR) in the fuel cell environment. Thin film coatings of titanium nitride (TiN) of 1 μm in thickness, were deposited by means of physical vapour deposition (PVD) process on to stainless steel (SS) 316L substrates and were evaluated, in a series of tests, for their level of corrosion protection and ICR. In the ex-situ corrosion tests, variables such as applied potential, experimental duration and pH of the sulphate electrolyte at 80 °C were altered. The ICR values were found to increase after exposure to greater applied potentials and electrolytes of a higher pH. In terms of experimental duration, the ICR increased most rapidly at the beginning of each experiment. It was also found that the oxidation of TiN was accelerated after exposure to electrolytes of a higher pH. When coated BPPs were incorporated into an accelerated fuel cell test, the degradation of the fuel cell cathode resembled the plates that were tested at the highest anodic potential (1.4 VSHE).

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.

Bridging Redox Species-Coated Graphene Oxide Sheets to Electrode for Extending Battery Life Using Nanocomposite Electrolyte.

PubMed

Huang, Yi Fu; Ruan, Wen Hong; Lin, Dong Ling; Zhang, Ming Qiu

2017-01-11

Substituting conventional electrolyte for redox electrolyte has provided a new intriguing method for extending battery life. The efficiency of utilizing the contained redox species (RS) in the redox electrolyte can benefit from increasing the specific surface area of battery electrodes from the electrode side of the electrode-electrolyte interface, but is not limited to that. Herein, a new strategy using nanocomposite electrolyte is proposed to enlarge the interface with the aid of nanoinclusions from the electrolyte side. To do this, graphene oxide (GO) sheets are first dispersed in the electrolyte solution of tungstosilicic salt/lithium sulfate/poly(vinyl alcohol) (SiWLi/Li 2 SO 4 /PVA), and then the sheets are bridged to electrode, after casting and evaporating the solution on the electrode surface. By applying in situ conductive atomic force microscopy and Raman spectra, it is confirmed that the GO sheets doped with RS of SiWLi/Li 2 SO 4 can be bridged and electrically reduced as an extended electrode-electrolyte interface. As a result, the RS-coated GO sheets bridged to LiTi 2 (PO 4 ) 3 //LiMn 2 O 4 battery electrodes are found to deliver extra energy capacity (∼30 mAh/g) with excellent electrochemical cycling stability, which successfully extends the battery life by over 50%.

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.

The formation of tungsten doped Al2O3/ZnO coatings on aluminum by plasma electrolytic oxidation and their application in photocatalysis

NASA Astrophysics Data System (ADS)

Stojadinović, Stevan; Vasilić, Rastko; Radić, Nenad; Tadić, Nenad; Stefanov, Plamen; Grbić, Boško

2016-07-01

Tungsten doped Al2O3/ZnO coatings are formed by plasma electrolytic oxidation of aluminum substrate in supporting electrolyte (0.1 M boric acid + 0.05 M borax + 2 g/L ZnO) with addition of different concentrations of Na2WO4·2H2O. The morphology, crystal structure, chemical composition, and light absorption characteristics of formed surface coatings are investigated. The X-ray diffraction and X-ray photoelectron spectroscopy results indicate that formed surface coatings consist of alpha and gamma phase of Al2O3, ZnO, metallic tungsten and WO3. Obtained results showed that incorporated tungsten does not have any influence on the absorption spectra of Al2O3/ZnO coatings, which showed invariable band edge at about 385 nm. The photocatalytic activity of undoped and tungsten doped Al2O3/ZnO coatings is estimated by the photodegradation of methyl orange. The photocatalytic activity of tungsten doped Al2O3/ZnO coatings is higher thanof undoped Al2O3/ZnO coatings; the best photocatalytic activity is ascribed to coatings formed in supporting electrolyte with addition of 0.3 g/L Na2WO4·2H2O. Tungsten in Al2O3/ZnO coatings acts as a charge trap, thus reducing the recombination rate of photogenerated electron-hole pairs. The results of PL measurements are in agreement with photocatalytic activity. Declining PL intensity corresponds to increasing photocatalytic activity of the coatings, indicating slower recombination of electron-hole pairs.

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

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.

Plasma Electrolytic Oxidation (PEO) Coatings on an A356 Alloy for Improved Corrosion and Wear Resistance

NASA Astrophysics Data System (ADS)

Peng, Zhijing

Plasma electrolytic oxidizing (PEO) is an advanced technique that has been used to deposit thick and hard ceramic coatings on aluminium (Al) alloys. This work was however to use the PEO process to produce thin ceramic oxide coatings on an A356 Al alloy for improving corrosion and wear resistance of the alloy. Effects of current density and treatment time on surface morphologies and thickness of the PEO coatings were investigated. The improvement of galvanic corrosion properties of the coated A356 alloy vs. steel and carbon fibre were evaluated in E85 fuel or NaCl environments. Tribological properties of the coatings were studied with comparison to the uncoated A356 substrate and other commercially-used engine bore materials. The research results indicated that the PEO coatings could have excellent tribological and corrosion properties for aluminium engine applications.

Low temperature solid oxide electrolytes (LT-SOE): A review

NASA Astrophysics Data System (ADS)

Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

2017-01-01

Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

Corrosion behaviors and effects of corrosion products of plasma electrolytic oxidation coated AZ31 magnesium alloy under the salt spray corrosion test

NASA Astrophysics Data System (ADS)

Wang, Yan; Huang, Zhiquan; Yan, Qin; Liu, Chen; Liu, Peng; Zhang, Yi; Guo, Changhong; Jiang, Guirong; Shen, Dejiu

2016-08-01

The effects of corrosion products on corrosion behaviors of AZ31 magnesium alloy with a plasma electrolytic oxidation (PEO) coating were investigated under the salt spray corrosion test (SSCT). The surface morphology, cross-sectional microstructure, chemical and phase compositions of the PEO coating were determined using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction analysis (XRD), respectively. Further, the corrosion process of the samples under the SSCT was examined in a non-aqueous electrolyte (methanol) using electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit. The results show that the inner layer of the coating was destroyed firstly and the corrosion products have significant effects on the corrosion behaviors of the coating. The results above are discussed and an electrochemical corrosion model is proposed in the paper.

Effects of pH Value of the Electrolyte and Glycine Additive on Formation and Properties of Electrodeposited Zn-Fe Coatings

PubMed Central

2013-01-01

Environmentally friendly and cyanide-free sulfate bath under continuous current and the corrosion behavior of electrodeposits of zinc-iron alloys were studied by means of electrochemical tests in a solution of 3.5% NaCl in presence and absence of glycine. The effects of pH on the quality of Zn-Fe coatings were investigated in order to improve uniformity and corrosion protection performance of the coating films. The deposit morphology was analyzed using scanning electron microscopy (SEM), and X-ray diffraction (XRD) was used to determine the preferred crystallographic orientations of the deposits. It was found that the uniformity and corrosion resistance of Zn-Fe coating films were strongly associated with pH of the coating electrolyte. To obtain the effect of pH on the film quality and corrosion performances of the films, the corrosion test was performed with potentiodynamic anodic polarization method. It was also observed that uniformity and corrosion resistivity of the coating films were decreased towards pH = 5 and then improved with increasing pH value of the electrolyte. The presence of glycine in the plating bath decreases the corrosion resistance of Zn-Fe coatings. PMID:23844388

In vivo performance of two different hydroxyapatite coatings on titanium prepared by discharging in electrolytes.

PubMed

Yamamoto, Hiroki; Shibata, Yo; Tachikawa, Tetsuhiko; Miyazaki, Takashi

2006-07-01

This study reports a discharging method for bone-like carbonated HA (cHA)-coating (Ca/P 1.71) and stoichiometric HA (sHA)-coating (Ca/P 1.67) with micrometer order thicknesses on titanium plates, using modified body fluid and acidic calcium phosphate solutions, respectively. In vivo histological performance of the HA coatings prepared by discharging in electrolytes was evaluated. Bone-contact indexes of HA coatings were measured microscopically. Additionally, bone-coating interface was analyzed by scanning electron microscopy and the use of an electron probe microanalyzer. Results demonstrated that there was no significant difference in contact index between HA coatings. However, the cHA coating was practically replaced by immature bone, and the titanium metal substrate was directly connected to the bone structure whereas the sHA coating layer remained and was partially detached from the titanium metal substrate. Since detached coating particles are pathogens, and can cause peri-implantitis, the cHA coating was more favorable than the sHA coating even if contact index was equivalent to that of the sHA coating. It is thought that coating thickness and chemical composition of coatings are important for biological stability of implants. In conclusion, since bone-like thin cHA coating showed high osteoconductivity and bone replacement, bone-like HA is superior to sHA coating for use in dental implants.

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�

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.

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.

Influence of the electrolyte's pH on the properties of electrochemically deposited hydroxyapatite coating on additively manufactured Ti64 alloy.

PubMed

Vladescu, Alina; Vranceanu, Diana M; Kulesza, Slawek; Ivanov, Alexey N; Bramowicz, Mirosław; Fedonnikov, Alexander S; Braic, Mariana; Norkin, Igor A; Koptyug, Andrey; Kurtukova, Maria O; Dinu, Mihaela; Pana, Iulian; Surmeneva, Maria A; Surmenev, Roman A; Cotrut, Cosmin M

2017-12-01

Properties of the hydroxyapatite obtained by electrochemical assisted deposition (ED) are dependent on several factors including deposition temperature, electrolyte pH and concentrations, applied potential. All of these factors directly influence the morphology, stoichiometry, crystallinity, electrochemical behaviour, and particularly the coating thickness. Coating structure together with surface micro- and nano-scale topography significantly influence early stages of the implant bio-integration. The aim of this study is to analyse the effect of pH modification on the morphology, corrosion behaviour and in vitro bioactivity and in vivo biocompatibility of hydroxyapatite prepared by ED on the additively manufactured Ti64 samples. The coatings prepared in the electrolytes with pH = 6 have predominantly needle like morphology with the dimensions in the nanometric scale (~30 nm). Samples coated at pH = 6 demonstrated higher protection efficiency against the corrosive attack as compared to the ones coated at pH = 5 (~93% against 89%). The in vitro bioactivity results indicated that both coatings have a greater capacity of biomineralization, compared to the uncoated Ti64. Somehow, the coating deposited at pH = 6 exhibited good corrosion behaviour and high biomineralization ability. In vivo subcutaneous implantation of the coated samples into the white rats for up to 21 days with following histological studies showed no serious inflammatory process.

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.

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.

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.

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.

Characterization of coatings formed on AZX magnesium alloys by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Anawati, Anawati; Gumelar, Muhammad Dikdik

2018-05-01

Plasma Electrolytic Oxidation (PEO) is an electrochemical anodization process which involves the application of a high voltage to create intense plasma on a metal surface to form a ceramic type of oxide. The resulted coating exhibits high wear resistance and good corrosion barrier which are suitable to enhance the performance of biodegradable Mg alloys. In this work, the role of alloying element Ca in modifying the characteristics of PEO layer formed on AZ61 series magnesium alloys was investigated. PEO treatment was conducted on AZ61, AZX611, and AZX612 alloys in 0.5 M Na3PO4 solution at a constant current of 200 A/m2 at 25°C for 8 min. The resulted coatings were characterized by field emission-scanning electron microscope (FESEM), X-ray diffraction spectroscopy (XRD), and X-ray fluorescence spectroscopy (XRF), as well as hardness test. The presence of alloying element Ca in the AZ61 alloys accelerated the PEO coatings formation without altering the coating properties significantly. The coating formed on AZX specimen was slightly thicker ( 14-17 µm) than that of formed onthe AZ specimens ( 13 µm). Longer exposure time to plasma discharge was the reason for faster thickening of the coating layer on AZX specimen. XRD detected a similar crystalline oxide phase of Mg3(PO4)2 in the oxide formed on all of the specimens. Zn was highly incorporated in the coatings with a concentration in the range 24-30 wt%, as analyzed by XRF. Zn compound might exist in amorphous phases. The microhardness test on the coatings revealed similar average hardness 124 HVon all of the specimens.

High Current Plasma Electrolytic Oxidation Coating Processes for Wear and Corrosion Prevention of Al 2024

NASA Astrophysics Data System (ADS)

Wang, Rui

Plasma electrolytic oxidation (PEO) treatments have been used in the aerospace and automotive industries because the coating formed on light metals or alloys has great hardness, high wear, corrosion, and oxidation resistance, and a low friction coefficient that improves lifetime length and provide a higher surface quality. However, the PEO treatments that are presently used for industrial applications require a long period of time to confirm the quality of the coating. For this reason, the present study seeks to increase the current density of PEO treatments to improve their efficiency and explore the performance of the obtained coatings. It was found that for high current density (0.18A/cm2) PEO treatments, smaller ratio, such as 50% and 70%, is beneficial to obtaining a better performance coating. When compared with the coating of a "normal" (current density: 0.09A/cm2) PEO treatment, it had better wear resistance; however, for corrosion resistance, it had a lower performance than the coatings obtained by the "normal" current density PEO treatment which was attributed to the negative influence of porosity increase.

Composition of highly concentrated silicate electrolytes and ultrasound influencing the plasma electrolytic oxidation of magnesium

NASA Astrophysics Data System (ADS)

Simchen, F.; Rymer, L.-M.; Sieber, M.; Lampke, T.

2017-03-01

Magnesium and its alloys are increasingly in use as lightweight construction materials. However, their inappropriate corrosion and wear resistance often prevent their direct practical use. The plasma electrolytic oxidation (PEO) is a promising, environmentally friendly method to improve the surface characteristics of magnesium materials by the formation of oxide coatings. These PEO layers contain components of the applied electrolyte and can be shifted in their composition by increasing the concentration of the electrolyte constituents. Therefore, in contrast to the use of conventional low concentrated electrolytes, the process results in more stable protective coatings, in which electrolyte species are the dominating constitutes. In the present work, the influence of the composition of highly concentrated alkaline silicate electrolytes with additives of phosphate and glycerol on the quality of PEO layers on the magnesium alloy AZ31 was examined. The effect of ultrasound coupled into the electrolyte bath was also considered. The process was monitored by recording the electrical process variables with a transient recorder and by observation of the discharge phenomena on the sample surface with a camera. The study was conducted on the basis of a design of experiments. The effects of the process parameter variation are considered with regard to the coatings thickness, hardness and corrosion resistance. Information about the statistical significance of the effects of the parameters on the considered properties is obtained by an analysis of variance (ANOVA).

In-situ grown MgO-ZnO ceramic coating with high thermal emittance on Mg alloy by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Li, Hang; Lu, Songtao; Qin, Wei; Wu, Xiaohong

2017-07-01

Intense solar radiation and internal heat generation determine the equilibrium temperature of an in-orbit spacecraft. Thermal control coatings with low solar absorptance and high thermal emittance effectively maintain the thermal equilibrium within safe operating limits for exposed, miniaturized and highly integrated components. A novel ceramic coating with high thermal emittance and good adhesion was directly prepared on the Mg substrate using an economical process of controlled plasma electrolytic oxidation (PEO) in the electrolyte containing ZnSO4. XRD and XPS results showed that this coating was mainly composed of the MgO phase as well as an unusual ZnO crystalline phase. The adhesive strength between the coating and substrate determined by a pull-off test revealed an excellent adhesion. Thermal and optical properties test revealed that the coating exhibited a high infrared emittance of 0.88 (2-16 μm) and low solar absorptance of 0.35 (200-2500 nm). The result indicated that the formation of ZnO during the PEO process played an important role in the improvement of the coating emittance. The process developed provides a simple surface method for improving the thermal emittance of Mg alloy, which presents a promising application prospect in the thermal management of the spacecraft.

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.

Sodium Aluminate Concentration Effects on Microstructure and Corrosion Behavior of the Plasma Electrolytic Oxidation Coatings on Pure Titanium

NASA Astrophysics Data System (ADS)

Molaei, Maryam; Fattah-Alhosseini, Arash; Gashti, Seyed Omid

2018-01-01

Sodium aluminate (NaAlO2) concentration was varied in order to understand the influence of the chemical composition of electrolyte on the spark characteristics, microstructure, and corrosion behavior of plasma electrolytic oxidation (PEO) coatings. For this purpose, PEO coatings were formed on the pure titanium substrate surface using solutions of four diverse sodium aluminate concentrations (6, 8, 10, and 12 g/L). The PEO process was carried out at constant time and voltage (180 seconds and 420 V). Studying the microstructures of samples by scanning electron microscope (SEM) and their corrosion behavior in 3.5 wt pct NaCl solutions indicated that the increase in NaAlO2 concentration (up to 10 g/L) led to an increase in uniformity and compactness, thus decreasing the size of micro-pores and increment of corrosion resistance. However, at a certain level of NaAlO2 concentration (12 g/L), large and severe sparks were created on the surface of the sample during the process, worsening the corrosion resistance and microstructure of coating.

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

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

Plasma sprayed coatings for containment of Cu-Mg-Si metallic phase change material

DOE PAGES

Withey, Elizabeth Ann; Kruizenga, Alan Michael; Andraka, Charles E.; ...

2016-01-01

In this study, the performance of Y 2O 3-stabilized ZrO 2 (YSZ), Y 2O 3, and Al 2O 3 plasma sprayed coatings are investigated for their ability to prevent attack of Haynes 230 by a near-eutectic Cu-Mg-Si metallic phase change material (PCM) in a closed environment at 820 °C. Areas where coatings failed were identified with optical and scanning electron microscopy, while chemical interactions were clarified through elemental mapping using electron microprobe analysis. Despite its susceptibility to reduction by Mg, the Al 2O 3 coating performed well while the YSZ and Y 2O 3 coating showed clear areas of attack.more » These results are attributed to the evolution of gaseous Mg at 820 °C leading to the formation of MgO and MgAl 2O 4.« less

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

Effect upon biocompatibility and biocorrosion properties of plasma electrolytic oxidation in trisodium phosphate electrolytes.

PubMed

Kim, Yu-Kyoung; Park, Il-Song; Lee, Kwang-Bok; Bae, Tae-Sung; Jang, Yong-Seok; Oh, Young-Min; Lee, Min-Ho

2016-03-01

Surface modification to improve the corrosion resistance and biocompatibility of the Mg-Al-Zn-Ca alloy was conducted via plasma electrolytic oxidation (PEO) in an electrolyte that included phosphate. Calcium phosphate can be easily induced on the surface of a PEO coating that includes phosphate in a physiological environment because Ca(2+) ions in body fluids can be combined with PO4 (3-). Cytotoxicity of the PEO coating formed in electrolytes with various amounts of Na3PO4 was identified. In particular, the effects that PEO films have upon oxidative stress and differentiation of osteoblast activity were studied. As the concentration of Na3PO4 in the electrolyte increased, the oxide layer was found to become thicker, which increased corrosion resistance. However, the PEO coating formed in electrolytes with over 0.2 M of added Na3PO4 exhibited more microcracks and larger pores than those formed in smaller Na3PO4 concentrations owing to a large spark discharge. A nonuniform oxide film that included more phosphate caused more cytotoxicity and oxidative stress, and overabundant phosphate content in the oxide layer interrupted the differentiation of osteoblasts. The corrosion resistance of the magnesium alloy and the thickness of the oxide layer were increased by the addition of Na3PO4 in the electrolyte for PEO treatment. However, excessive phosphate content in the oxide layer led to oxidative stress, which resulted in reduced cell viability and activity.

Evolution processes of the corrosion behavior and structural characteristics of plasma electrolytic oxidation coatings on AZ31 magnesium alloy

NASA Astrophysics Data System (ADS)

Chen, Dong; Wang, Ruiqiang; Huang, Zhiquan; Wu, Yekang; Zhang, Yi; Wu, Guorui; Li, Dalong; Guo, Changhong; Jiang, Guirong; Yu, Shengxue; Shen, Dejiu; Nash, Philip

2018-03-01

Evolution processes of the corrosion behavior and structural characteristics of the plasma electrolytic oxidation (PEO) coated AZ31 magnesium alloy were investigated by using scanning electron microscope (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), potentio-dynamic polarization curves and electrochemical impedance spectroscopy (EIS) measurements. Detached coating samples were fabricated by an electrochemical method and more details of the internal micro-structure of coatings were clearly observed on the fractured cross-section morphologies of the samples compared to general polished cross-section morphologies. Evolution mechanisms of the coating corrosion behavior in relation to the evolution of micro-structural characteristics were discussed in detail.

Effects of Current Density on Microstructure and Corrosion Property of Coating on AZ31 Mg Alloy Processed via Plasma Electrolytic Oxidation

NASA Astrophysics Data System (ADS)

Lee, Kang Min; Einkhah, Feryar; Sani, Mohammad Ali Faghihi; Ko, Young Gun; Shin, Dong Hyuk

The effects of the current density on the micro structure and the corrosion property of the coating on AZ31 Mg alloy processed by the plasma electrolytic oxidation (PEO) were investigated. The present coatings were produced in an acid electrolyte containing K2ZrF6 with three different current densities, i.e., 100, 150, and 200 mA/cm2. From the microstructural observations, as the applied current density was increased, the diameter of micro-pores formed by the plasma discharges with high temperature increased. The coatings on AZ31 Mg alloy were mainly composed of MgO, ZrO2, MgF2, and Mg2Zr5O12 phases. The results of potentiodynamic polarization clearly showed that the PEO-treated AZ31 Mg alloy applied at 100 mA/cm2 of current density exhibited better corrosion properties than the others.

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.

Long-term evaluation of solid oxide fuel cell candidate materials in a 3-cell generic short stack fixture, Part II: sealing glass stability, microstructure and interfacial reactions.

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

Chou, Y. S.; Stevenson, Jeffry W.; Choi, Jung-Pyung

2014-03-15

A generic solid oxide fuel cell stack test fixture was developed to evaluate candidate materials and processing methods under realistic conditions. Part I of the work addressed the stack fixture, seal system and cell performance of a 3-cell short stack tested at 800oC for 6000h. Commercial NiO-YSZ anode-supported thin YSZ electrolyte cells with LSM cathodes were used for assessment and were tested in constant current mode with dilute (~50% H2) fuel versus air. Part II of the work examined the sealing glass stability, microstructure development, interfacial reactions, and volatility issues. Part III of the work investigated the stability of Ce-(Mn,Co)more » spinel coating, AISI441 metallic interconnect, alumina coating, and cell degradation. After 6000h of testing, the refractory sealing glass YSO77 (Ba-Sr-Y-B-Si) showed desirable chemical compatibility with YSZ electrolyte in that no discernable interfacial reaction was identified, consistent with thermodynamic calculations. In addition, no glass penetration into the thin electrolyte was observed. At the aluminized AISI441 interface, the protective alumina coating appeared to be corroded by the sealing glass. Air side interactions appeared to be more severe than fuel side interactions. Metal species such as Cr, Mn, and Fe were detected in the glass, but were limited to the vicinity of the interface. No alkaline earth chromates were found at the air side. Volatility was also studied in a similar glass and weight loss in a wet reducing environment was determined. Using the steady-state volatility data, the life time (40,000h) weight loss of refractory sealing glass YSO77 was estimated to be less than 0.1 wt%.« less

High-compactness coating grown by plasma electrolytic oxidation on AZ31 magnesium alloy in the solution of silicate-borax

NASA Astrophysics Data System (ADS)

Shen, M. J.; Wang, X. J.; Zhang, M. F.

2012-10-01

A ceramic coating was formed on the surface of AZ31 magnesium alloy by plasma electrolytic oxidation (PEO) in the silicate solution with and without borax doped. The composition, morphology, elements and roughness as well as mechanical property of the coating were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and reciprocal-sliding tribometer. The results show that the PEO coating is mainly composed of magnesia. When using borax dope, boron element is permeating into the coating and the boron containing phase exist in the form of amorphous. In addition, the microhardness and compactness of the PEO coating are improved significantly due to doped borax.

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.

Effect of KOH to Na2SiO3 Ratio on Microstructure and Hardness of Plasma Electrolytic Oxidation Coatings on AA 6061 Alloy

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Jang, Yong-Joo; Jung, Jae Pil

2017-10-01

In this study, plasma electrolytic oxidation (PEO) process has been employed to fabricate alumina coatings on AA 6061 aluminum alloy from an electrolyte containing water glass (Na2SiO3) and alkali (KOH). The effect of deposition time and the alkali to water glass (KOH: Na2SiO3) composition ratio on the coating morphology and properties are studied. The different phases of the oxide layer and microstructure are investigated by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. The results indicate that initially γ-Al2O3 forms in the coating, and as the processing time is increased from 5 to 60 minutes, α-Al2O3 phase becomes prominent. Further, higher the content of Na2SiO3, higher is the hardness and coating growth rate due to the formation of stable α-Al2O3 and Al-Si-O phase. It has been reported that the optimum properties of the PEO coatings can be obtained at a ratio of KOH: Na2SiO3 ≈ 15:10 followed by 10:10.

Plasma electrolytic oxidation of Titanium Aluminides

NASA Astrophysics Data System (ADS)

Morgenstern, R.; Sieber, M.; Grund, T.; Lampke, T.; Wielage, B.

2016-03-01

Due to their outstanding specific mechanical and high-temperature properties, titanium aluminides exhibit a high potential for lightweight components exposed to high temperatures. However, their application is limited through their low wear resistance and the increasing high-temperature oxidation starting from about 750 °C. By the use of oxide ceramic coatings, these constraints can be set aside and the possible applications of titanium aluminides can be extended. The plasma electrolytic oxidation (PEO) represents a process for the generation of oxide ceramic conversion coatings with high thickness. The current work aims at the clarification of different electrolyte components’ influences on the oxide layer evolution on alloy TNM-B1 (Ti43.5Al4Nb1Mo0.1B) and the creation of compact and wear resistant coatings. Model experiments were applied using a ramp-wise increase of the anodic potential in order to show the influence of electrolyte components on the discharge initiation and the early stage of the oxide layer growth. The production of PEO layers with technically relevant thicknesses close to 100 μm was conducted in alkaline electrolytes with varying amounts of Na2SiO3·5H2O and K4P2O7 under symmetrically pulsed current conditions. Coating properties were evaluated with regard to morphology, chemical composition, hardness and wear resistance. The addition of phosphates and silicates leads to an increasing substrate passivation and the growth of compact oxide layers with higher thicknesses. Optimal electrolyte compositions for maximum coating hardness and thickness were identified by statistical analysis. Under these conditions, a homogeneous inner layer with low porosity can be achieved. The frictional wear behavior of the compact coating layer is superior to a hard anodized layer on aluminum.

Bioactivity and biocompatibility of hydroxyapatite-based bioceramic coatings on zirconium by plasma electrolytic oxidation.

PubMed

Aktuğ, Salim Levent; Durdu, Salih; Yalçın, Emine; Çavuşoğlu, Kültigin; Usta, Metin

2017-02-01

In the present work, hydroxyapatite (HAP)-based plasma electrolytic oxide (PEO) coatings were produced on zirconium at different current densities in a solution containing calcium acetate and β-calcium glycerophosphate by a single step. The phase structure, surface morphology, functional groups, thickness and roughness of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), eddy current method and surface profilometer, respectively. The phases of cubic-zirconia, calcium zirconate and HAP were detected by XRD. The amount of HAP and calcium zirconate increased with increasing current density. The surface of the coatings was very porous and rough. Moreover, bioactivity and biocompatibility of the coatings were analyzed in vitro immersion simulated body fluid (SBF) and MTT (3-(4,5-dimethyl thiazol-2yl)-2,5-diphenyl tetrazolium bromide) assay, hemolysis assay and bacterial formation. The apatite-forming ability of the coatings was evaluated after immersion in SBF up to 28days. After immersion, the bioactivity of HAP-based coatings on zirconium was greater than the ones of uncoated zirconium and zirconium oxide-based surface. The bioactivity of PEO surface on zirconium was significantly improved under SBF conditions. The bacterial adhesion of the coatings decreased with increasing current density. The bacterial adhesion of the coating produced at 0.370A/cm 2 was minimum compared to uncoated zirconium coated at 0.260 and 0.292A/cm 2 . The hemocompatibility of HAP-based surfaces was improved by PEO. The cell attachment and proliferation of the PEO coatings were better than the one of uncoated zirconium according to MTT assay results. Copyright © 2016 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Mohan, Prabhakar

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

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.

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.

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.

Multi-layer thin-film electrolytes for metal supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Haydn, Markus; Ortner, Kai; Franco, Thomas; Uhlenbruck, Sven; Menzler, Norbert H.; Stöver, Detlev; Bräuer, Günter; Venskutonis, Andreas; Sigl, Lorenz S.; Buchkremer, Hans-Peter; Vaßen, Robert

2014-06-01

A key to the development of metal-supported solid oxide fuel cells (MSCs) is the manufacturing of gas-tight thin-film electrolytes, which separate the cathode from the anode. This paper focuses the electrolyte manufacturing on the basis of 8YSZ (8 mol.-% Y2O3 stabilized ZrO2). The electrolyte layers are applied by a physical vapor deposition (PVD) gas flow sputtering (GFS) process. The gas-tightness of the electrolyte is significantly improved when sequential oxidic and metallic thin-film multi-layers are deposited, which interrupt the columnar grain structure of single-layer electrolytes. Such electrolytes with two or eight oxide/metal layers and a total thickness of about 4 μm obtain leakage rates of less than 3 × 10-4 hPa dm3 s-1 cm-2 (Δp: 100 hPa) at room temperature and therefore fulfill the gas tightness requirements. They are also highly tolerant with respect to surface flaws and particulate impurities which can be present on the graded anode underground. MSC cell tests with double-layer and multilayer electrolytes feature high power densities more than 1.4 W cm-2 at 850 °C and underline the high potential of MSC cells.

Surface characteristic of chemically converted graphene coated low carbon steel by electro spray coating method for polymer electrolyte membrane fuel cell bipolar plate.

PubMed

Kim, Jungsoo; Kim, Yang Do; Nam, Dae Geun

2013-05-01

Graphene was coated on low carbon steel (SS400) by electro spray coating method to improve its properties of corrosion resistance and contact resistance. Exfoliated graphite was made of the graphite by chemical treatment (Chemically Converted Graphene, CCG). CCG is distributed using dispersing agent, and low carbon steel was coated with diffuse graphene solution by electro spray coating method. The structure of the CCG was analyzed using XRD and the coating layer of surface was analyzed using SEM. Analysis showed that multi-layered graphite structure was destroyed and it was transformed in to fine layers graphene structure. And the result of SEM analysis on the surface and the cross section, graphene layer was uniformly formed with 3-5 microm thickness on the surface of substrate. Corrosion resistance test was applied in the corrosive solution which is similar to the polymer electrolyte membrane fuel cell (PEMFC) stack inside. And interfacial contact resistance (ICR) test was measured to simulate the internal operating conditions of PEMFC stack. As a result of measuring corrosion resistance and contact resistance, it could be confirmed that low carbon steel coated with CCG was revealed to be more effective in terms of its applicability as PEMFC bipolar plate.

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.

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.

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

Corrosion behavior and cytocompatibility of fluoride-incorporated plasma electrolytic oxidation coating on biodegradable AZ31 alloy

PubMed Central

Tian, Peng; Peng, Feng; Wang, Donghui; Liu, Xuanyong

2017-01-01

Fluoride-incorporated plasma electrolytic oxidation (PEO) coating was fabricated on biodegradable AZ31 alloy. The surface morphologies and phases were investigated by scanning electron microscopy and X-ray diffraction. The effect of fluoride incorporation in coatings on corrosion behaviour was investigated in simulated body fluid and in vitro cytocompatibility of the coatings was also studied by evaluating cytotoxicity, adhesion, proliferation and live–dead stain of osteoblast cells (MC3T3-E1). Furthermore, the corrosion morphologies in vivo were examined. The results showed that the fluoride could be incorporated into the coating to form MgF2 phase. In vitro and in vivo degradation tests revealed that the corrosion resistance of the coating could be improved by the incorporation of fluoride, which may attribute to the chemical stability of MgF2 phase. Moreover, good cytocompatibility of fluoride-incorporated coating was confirmed with no obvious cytotoxicity, enhanced cell adhesion and proliferation. However, when the fluoride content was high, a slight inhibition of cell growth was observed. The results indicate that although fluoride incorporation can enhance the corrosion resistance of the coatings, thus resulting a more suitable environment for cells, the high content of fluoride in the coating also kill cells ascribed to the high released of fluorine. If the content of fluoride is well controlled, the PEO coating with MgF2 phase is a promising surface modification of Mg alloys. PMID:28149524

Corrosion behavior and cytocompatibility of fluoride-incorporated plasma electrolytic oxidation coating on biodegradable AZ31 alloy.

PubMed

Tian, Peng; Peng, Feng; Wang, Donghui; Liu, Xuanyong

2017-02-01

Fluoride-incorporated plasma electrolytic oxidation (PEO) coating was fabricated on biodegradable AZ31 alloy. The surface morphologies and phases were investigated by scanning electron microscopy and X-ray diffraction. The effect of fluoride incorporation in coatings on corrosion behaviour was investigated in simulated body fluid and in vitro cytocompatibility of the coatings was also studied by evaluating cytotoxicity, adhesion, proliferation and live-dead stain of osteoblast cells (MC3T3-E1). Furthermore, the corrosion morphologies in vivo were examined. The results showed that the fluoride could be incorporated into the coating to form MgF 2 phase. In vitro and in vivo degradation tests revealed that the corrosion resistance of the coating could be improved by the incorporation of fluoride, which may attribute to the chemical stability of MgF 2 phase. Moreover, good cytocompatibility of fluoride-incorporated coating was confirmed with no obvious cytotoxicity, enhanced cell adhesion and proliferation. However, when the fluoride content was high, a slight inhibition of cell growth was observed. The results indicate that although fluoride incorporation can enhance the corrosion resistance of the coatings, thus resulting a more suitable environment for cells, the high content of fluoride in the coating also kill cells ascribed to the high released of fluorine. If the content of fluoride is well controlled, the PEO coating with MgF 2 phase is a promising surface modification of Mg alloys.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

PubMed

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-17

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes

NASA Astrophysics Data System (ADS)

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-01

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g-1 at a current density of 2 A g-1, when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg-1 and 41 Wh kg-1, respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

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.

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.

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.

Effect of the voltage pulse frequency on the structure of TiO2 coatings grown by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Torres-Cerón, D. A.; Gordillo-Delgado, F.; Moya-Betancourt, S. N.

2017-12-01

Plasma Electrolytic Oxidation (PEO) is used to synthetize titanium dioxide (TiO2) ceramic coatings with the appropriate selection of an electrolyte. The dimension of the micro-cavities and the particle size at the surface can be controlled through the pulse frequency of the voltage that is applied between the electrodes. The change of surface morphology can increase the surface area-to-volume ratio. In this work, PEO of an ASME SB-265 titanium substrate (20×20×1mm) was made in a water solution containing 8g/L Na3PO4 and 0.4g/L NaOH. Hence, the coatings were fabricated using voltage pulses of 340V for 10 minutes with a 10% duty cycle and frequencies of 1000, 1500 and 2000Hz. According to the X-ray diffractograms of the obtained samples, the sintering process at 500°C during 1 hour generated Anatase titanium dioxide porous coatings. The grain size decreased approximately from 29nm for 1000 and 1500Hz pulse frequencies until 21nm for 2000Hz. On the other hand, from the micrographs of scanning electron microscopy was possible to see the uniform formation of the micro-cavities with the largest diameter, 900nm, for the lowest frequency value used in PEO.

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

Lithium-ion batteries having conformal solid electrolyte layers

DOEpatents

Kim, Gi-Heon; Jung, Yoon Seok

2014-05-27

Hybrid solid-liquid electrolyte lithium-ion battery devices are disclosed. Certain devices comprise anodes and cathodes conformally coated with an electron insulating and lithium ion conductive solid electrolyte layer.

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.

Corrosion Behavior of PEO Coatings Formed on AZ31 Alloy in Phosphate-Based Electrolytes with Calcium Acetate Additive

NASA Astrophysics Data System (ADS)

Ziyaei, E.; Atapour, M.; Edris, H.; Hakimizad, A.

2017-07-01

The PEO coating started on magnesium AZ31 using a unipolar DC power source. The coating was generated in the electrolyte based on Na3PO4·12H2O and KOH with calcium acetate as additive. The x-ray diffraction method showed some phases containing calcium and phosphate, which was created in the presence of additive. Also, the EDS tests of the sample's surfaces proved the existence of calcium on the surface. Based on the electrochemical tests results, the most corrosion resistance belongs to the sample with calcium acetate additive. In fact, the results of the EIS tests showed the coating with calcium acetate has the highest resistance but the lowest capacitance. However, this state belongs to the surface morphology, the lower porosity, and surface chemical composition.

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

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.

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

Design and manufacture of solid ZrO2 electrolyte

NASA Technical Reports Server (NTRS)

1988-01-01

The following project assignment was given to the students: 'design and build a suitable YSZ solid electrolyte cell. Describe advantages of the design and fabrication method. Finally, to the limits of available resources, fabricate the design. Explain why it would be superior to other designs.' Clemson University students definitely benefitted from this experience with USRA/NASA. The challenge that this project gave the students was both exciting and attention-getting. Students spent far more time per credit hour on this project than on their other course. This project advanced the art of making efficient oxygen generators as well. Clemson students are now well on the way to designing a solid electrolyte with a large active surface area and comparatively small volume. Previous devices have had to endure the limitation of using only simple shapes such as tubes. The results of this project have demonstrated that better configurations are not only possible but practical.

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

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.

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.

Advanced thermal barrier coatings for operation in high hydrogen content fueled gas turbines.

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

Sampath, Sanjay

2015-04-02

roughness and resulted in improved TBC lifetimes. Processing based approaches of identifying optimal processing regimes deploying advanced in-situ coating property measurements and in-flight diagnostic tools were used to develop process maps for bond coats. Having established a framework for the bond coat processing using the HVOF process, effort were channeled towards fabrication of APS and VPS bond coats with the same material composition. Comparative evaluation of the three deposition processes with regard to their microstrcuture , surface profiles and TBC performance were carried out and provided valuable insights into factors that require concurrent consideration for the development of bond coats for advanced TBC systems. Over the course of this program several advancements were made on the development of durable thermal barrier coatings. Process optimization techniques were utilized to identify processing regimes for both conventional YSZ as well as other TBC compositions such as Gadolinium Zirconate and other Co-doped materials. Measurement of critical properties for these formed the initial stages of the program to identify potential challenges in their implementation as part of a TBC system. High temperature thermal conductivity measurements as well as sintering behavior of both YSZ and GDZ coatings were evaluated as part of initial efforts to undersand the influence of processing on coating properties. By effectively linking fundamental coating properties of fracture toughness and elastic modulus to the cyclic performance of coatings, a durability strategy for APS YSZ coatings was developed. In order to meet the goals of fabricating a multimaterial TBC system further research was carried out on the development of a gradient thermal conductivity model and the evaluation of sintering behavior of multimaterial coatings. Layer optimization for desired properties in the multimaterial TBC was achieved by an iterative feedback approach utilizing process maps and in

Influence of albumin and inorganic ions on electrochemical corrosion behavior of plasma electrolytic oxidation coated magnesium for surgical implants

NASA Astrophysics Data System (ADS)

Wan, Peng; Lin, Xiao; Tan, LiLi; Li, Lugee; Li, WeiRong; Yang, Ke

2013-10-01

Magnesium and its alloys are of great interest for biodegradable metallic devices. However, the degradation behavior and mechanisms of magnesium treated with coating in physiological environment in the presence of organic compound such as albumin have not been elucidated. In this study, the plasma electrolytic oxidation coated magnesium immersed in four different simulated body fluids: NaCl, PBS and with the addition of albumin to investigate the influence of protein and inorganic ions on degradation behavior by electrochemical methods. The results of electrochemical tests showed that aggressive corrosion took place in 0.9 wt.% NaCl solution; whereas albumin can act as an inhibitor, its adsorption impeded further dissolution of the coating. The mechanism was attributed to the synergistic effect of protein adsorption and precipitation of insoluble salts.

Electrolytic Manganese Dioxide Coatings on High Aspect Ratio Micro-Pillar Arrays for 3D Thin Film Lithium Ion Batteries.

PubMed

Zargouni, Yafa; Deheryan, Stella; Radisic, Alex; Alouani, Khaled; Vereecken, Philippe M

2017-05-27

In this work, we present the electrochemical deposition of manganese dioxide (MnO₂) thin films on carbon-coated TiN/Si micro-pillars. The carbon buffer layer, grown by plasma enhanced chemical vapor deposition (PECVD), is used as a protective coating for the underlying TiN current collector from oxidation, during the film deposition, while improving the electrical conductivity of the stack. A conformal electrolytic MnO₂ (EMD) coating is successfully achieved on high aspect ratio C/TiN/Si pillar arrays by tailoring the deposition process. Lithiation/Delithiation cycling tests have been performed. Reversible insertion and extraction of Li⁺ through EMD structure are observed. The fabricated stack is thus considered as a good candidate not only for 3D micorbatteries but also for other energy storage applications.

Electrolytic Manganese Dioxide Coatings on High Aspect Ratio Micro-Pillar Arrays for 3D Thin Film Lithium Ion Batteries

PubMed Central

Zargouni, Yafa; Deheryan, Stella; Radisic, Alex; Alouani, Khaled; Vereecken, Philippe M.

2017-01-01

In this work, we present the electrochemical deposition of manganese dioxide (MnO2) thin films on carbon-coated TiN/Si micro-pillars. The carbon buffer layer, grown by plasma enhanced chemical vapor deposition (PECVD), is used as a protective coating for the underlying TiN current collector from oxidation, during the film deposition, while improving the electrical conductivity of the stack. A conformal electrolytic MnO2 (EMD) coating is successfully achieved on high aspect ratio C/TiN/Si pillar arrays by tailoring the deposition process. Lithiation/Delithiation cycling tests have been performed. Reversible insertion and extraction of Li+ through EMD structure are observed. The fabricated stack is thus considered as a good candidate not only for 3D micorbatteries but also for other energy storage applications. PMID:28555017

Effect of Borates and Silicates on Wearing Properties of Mao Coatings

NASA Astrophysics Data System (ADS)

Zhang, Yu; Zhao, Yan-Wei; Xiang, Nan; Song, Ren-Guo

In the present study, microarc oxidation (MAO) coatings were formed on ZL101A aluminum alloy in an electrolytic bath containing 3g/L KOH + 2g/L Na2WO4+ 4g/L KF. The morphology and wearing behavior were investigated. In both electrolytes, the additives were borates (Na2B4O718g/L) and silicates (Na2SiO3 18g/L), respectively. It was found that the coating formed in borates-containing electrolyte was of compact and smooth structure than that of the one formed in silicates-containing electrolyte at the optimum treatment time. It was found that all the coatings were composed of á-Al2O3 and ã-Al2O3. The microhardness and wear tests proved that the coating formed in borates-containing electrolyte was having better mechanical properties than those of the coating formed in silicates-containing electrolyte.

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.

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.

Polymer Coatings Reduce Electro-osmosis

NASA Technical Reports Server (NTRS)

Herren, Blair J.; Snyder, Robert; Shafer, Steven G.; Harris, J. Milton; Van Alstine, James M.

1989-01-01

Poly(ethylene glycol) film controls electrostatic potential. Electro-osmosis in quartz or glass chambers reduced or reversed by coating inside surface of chambers with monomacromolecular layers of poly(ethylene glycol). Stable over long times. Electrostatic potential across surface of untreated glass or plastic chamber used in electro-phoresis is negative and attracts cations in aqueous electrolyte. Cations solvated, entrains flow of electrolyte migrating toward cathode. Electro-osmotic flow interferes with desired electrophoresis of particles suspended in electrolyte. Polymer coats nontoxic, transparent, and neutral, advantageous for use in electrophoresis.

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

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.

Ultra-High Temperature Thermal Barrier Coatings

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

Jordan, Eric; Gell, Maurice; Wang, Jiwen

In this project, HiFunda LLC worked with the University of Connecticut (UConn) to demonstrate an attractive option for thermal barrier coatings (TBCs), namely yttrium aluminum garnet (YAG), which was well known to have proven thermal stability and excellent high-temperature mechanical properties. YAG and other higher temperature TBCs have not been used to date because they exhibit inadequate durability, resulting from (a) poor erosion resistance and (b) greater thermal expansion mismatch strains compared to 7YSZ. UConn had previously demonstrated that the solution precursor plasma spray (SPPS) process could produce a durable 7YSZ TBC resulting from a highly strain tolerant microstructure, consistingmore » of through-coating-thickness vertical cracks. HiFunda/UConn reasoned at the start of Phase I that such a strain-tolerant microstructure could produce durable, higher temperature TBCs. The Phase I work demonstrated the feasibility of that concept and of SPPS YAG TBCs. The Phase II work demonstrated that SPPS YAG coating possessed the necessary range of properties to be a viable high temperature TBC, including cyclic durability and reduced elevated temperature thermal conductivity. The SPPS YAG TBCs were shown to have the potential to be used at temperatures 200°C higher than APS YSZ, based on thermal stability, sinter resistance, and CMAS resistance. The overall technical objectives of this Phase 2A project were to further improve the commercial viability of SPPS by improving their performance capabilities and manufacturing economics. The improved performance capability was to be achieved through: (1) further reductions in thermal conductivity, which allows higher gas temperatures and/or thinner coatings to achieve similar gas temperatures; and (2) improved resistance to calcium magnesium alumnoslicate (CMAS) attack of the TBCs, which can yield improved lifetimes. The improved thermal conductivity and CMAs resistance was to be accomplished through compositional

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.

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

Photoluminescence properties of Eu3+ doped HfO2 coatings formed by plasma electrolytic oxidation of hafnium

NASA Astrophysics Data System (ADS)

Stojadinović, Stevan; Tadić, Nenad; Ćirić, Aleksandar; Vasilić, Rastko

2018-03-01

Plasma electrolytic oxidation was used for synthesis of Eu3+ doped monoclinic HfO2 coatings on hafnium substrate. Results of photoluminescence (PL) measurements show the existence of two distinct regions: one that is related to the blue emission originating from oxygen vacancy defects in HfO2 and the other one characterized with a series of sharp orange-red emission peaks related to f-f transitions of Eu3+ from excited level 5D0 to lower levels 7FJ (J = 0, 1, 2, 3, and 4). PL peaks appearing in excitation spectra of obtained coatings are attributed either to charge transfer state of Eu3+ or to direct excitation of the Eu3+ ground state 7F0 into higher levels of the 4f-manifold. PL of formed coatings increases with PEO time due to an increase of oxygen vacancy defects and the content of Eu3+. Acquired experimental data suggest that hypersensitive electrical dipole transition is much more intense than the magnetic dipole transition, indicating that Eu3+ ions occupy a non-inversion symmetry sites.

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

MAO-derived hydroxyapatite/TiO2 nanostructured multi-layer coatings on titanium substrate

NASA Astrophysics Data System (ADS)

Abbasi, S.; Golestani-Fard, F.; Rezaie, H. R.; Mirhosseini, S. M. M.

2012-11-01

In this study, titanium substrates which previously oxidized through Micro arc oxidation method, was coated by Hydroxyapatite (HAp) coating once more by means of the same method. Morphology, topography and chemical properties as well as phase composition and thickness of layers were studied to reveal the effect of the electrolyte concentration on coating features. According to results, the obtained coatings are consisted of HAp and titania as the major phases along with minor amounts of calcium titanate and α-tri calcium phosphate. Ca and P are present on surface of obtained layers as well as predictable Ti and O based on the XPS results. Thickness profile of coatings figured out that by increasing the electrolyte concentration, especially by addition of more Calcium Acetate (CA) to electrolyte, the thickness of HAp layer would rise, consequently. However, the influence of coating time on thickness of obtained coatings would be more considerable than electrolyte concentration. High specific area coatings with nest morphology were obtained in Electrolyte containing 5 g/L β-Glycero Phosphate (β-GP) and 5 g/L CA. Increasing coating duration time in this kind of coatings would cause deduction of the nesting in their structure.

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.

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.

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.

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.

Characterization of ceria electrolyte in solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Milliken, Christopher Edward

The goal of this research effort is to characterize cation doped cerium dioxide for use as an electrolyte material in solid oxide fuel cell applications. A variety of analytical techniques including thermogravimetric analysis, controlled atmosphere dilatometry, and AC/DC electronic measurements on single cells and stacks have been coupled with thermodynamic calculations to evaluate the suitability of several doping schemes. The results of this analysis indicate that doping CeOsb2 with 20% SmOsb{1.5} or codoping with 19% GdOsb{1.5} + 1% PrOsb{1.83} provides the best combination of stability and performance. Under dual atmosphere fuel cell conditions, these dopants do not provide sufficient stabilization energy to prevent the reduction of ceria. A significant oxygen leakage current can be expected, particularly near open circuit conditions. Incorporation of 10% SrO provides similar short-term advantages to the lanthanide doped system but this electrolyte material undergoes an irreversible degradation mechanism that results in cell failure within 1500 hours of test. Under fuel cell conditions, the maximum efficiency of such systems in stacks will be below 40% at 200 mW/cmsp2 when operated on humidified hydrogen fuels. This compares to an expected efficiency of 45-50% at a similar power density for nonmixed conducting electrolyte (e.g., YSZ).

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.

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

Hydroxyapatite coatings containing Zn and Si on Ti-6Al-4Valloy by plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Hwang, In-Jo; Choe, Han-Cheol

2018-02-01

In this study, hydroxyapatite coatings containing Zn and Si on Ti-6Al-4Valloy by plasma electrolytic oxidation were researched using various experimental instruments. The pore size is depended on the electrolyte concentration and the particle size and number of pore increase on surface part and pore part. In the case of Zn/Si sample, pore size was larger than that of Zn samples. The maximum size of pores decreased and minimum size of pores increased up to 10Zn/Si and Zn and Si affect the formation of pore shapes. As Zn ion concentration increases, the size of the particle tends to increase, the number of particles on the surface part is reduced, whereas the size of the particles and the number of particles on pore part increased. Zn is mainly detected at pore part, and Si is mainly detected at surface part. The crystallite size of anatase increased as the Zn ion concentration, whereas, in the case of Si ion added, crystallite size of anatase decreased.

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; Lim, James

2008-01-01

Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

Surface Charge at the Oxide/Electrolyte Interface: Toward Optimization of Electrolyte Composition for Treatment of Aluminum and Magnesium by Plasma Electrolytic Oxidation.

PubMed

Nominé, Alexandre; Martin, Julien; Noël, Cédric; Henrion, Gérard; Belmonte, Thierry; Bardin, Ilya V; Lukeš, Petr

2016-02-09

Controlling microdischarges in plasma electrolytic oxidation is of great importance in order to optimize coating quality. The present study highlights the relationship between the polarity at which breakdown occurs and the electrolyte pH as compared with the isoelectric point (IEP). It is found that working at a pH higher than the IEP of the grown oxide prevents the buildup of detrimental cathodic discharges. The addition of phosphates results in a shift in the IEP to a lower value and therefore promotes anodic discharges at the expense of cathodic ones.

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.

Lithium sulfide compositions for battery electrolyte and battery electrode coatings

DOEpatents

Liang, Chengdu; Liu, Zengcai; Fu, Wujun; Lin, Zhan; Dudney, Nancy J; Howe, Jane Y; Rondinone, Adam J

2014-10-28

Method of forming lithium-containing electrolytes are provided using wet chemical synthesis. In some examples, the lithium containing electrolytes are composed of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7. The solid electrolyte may be a core shell material. In one embodiment, the core shell material includes a core of lithium sulfide (Li.sub.2S), a first shell of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7, and a second shell including one of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7 and carbon. The lithium containing electrolytes may be incorporated into wet cell batteries or solid state batteries.

Enhanced mechanical properties and increased corrosion resistance of a biodegradable magnesium alloy by plasma electrolytic oxidation (PEO).

PubMed

White, Leon; Koo, Youngmi; Neralla, Sudheer; Sankar, Jagannathan; Yun, Yeoheung

2016-06-01

We report the enhanced mechanical properties of AZ31 magnesium alloys by plasma electrolytic oxidation (PEO) coating in NaOH, Na 2 SiO 3 , KF and NaH 2 PO 4 ·2H 2 O containing electrolytes. Mechanical properties including wear resistance, surface hardness and elastic modulus were increased for PEO-coated AZ31 Mg alloys (PEO-AZ31). DC polarization in Hank's solution indicating that the corrosion resistance significantly increased for PEO-coating in KF-contained electrolyte. Based on these results, the PEO coating method shows promising potential for use in biodegradable implant applications where tunable corrosion and mechanical properties are needed.

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.

Porous Architecture of SPS Thick YSZ Coatings Structured at the Nanometer Scale (~50 nm)

NASA Astrophysics Data System (ADS)

Bacciochini, Antoine; Montavon, Ghislain; Ilavsky, Jan; Denoirjean, Alain; Fauchais, Pierre

2010-01-01

Suspension plasma spraying (SPS) is a fairly recent technology that is able to process sub-micrometer-sized or nanometer-sized feedstock particles and permits the deposition of coatings thinner (from 20 to 100 μm) than those resulting from conventional atmospheric plasma spraying (APS). SPS consists of mechanically injecting within the plasma flow a liquid suspension of particles of average diameter varying between 0.02 and 1 μm. Due to the large volume fraction of the internal interfaces and reduced size of stacking defects, thick nanometer- or sub-micrometer-sized coatings exhibit better properties than conventional micrometer-sized ones (e.g., higher coefficients of thermal expansion, lower thermal diffusivity, higher hardness and toughness, better wear resistance, among other coating characteristics and functional properties). They could hence offer pertinent solutions to numerous emerging applications, particularly for energy production, energy saving, etc. Coatings structured at the nanometer scale exhibit nanometer-sized voids. Depending upon the selection of operating parameters, among which plasma power parameters (operating mode, enthalpy, spray distance, etc.), suspension properties (particle size distribution, powder mass percentage, viscosity, etc.), and substrate characteristics (topology, temperature, etc.), different coating architectures can be manufactured, from dense to porous layers, from connected to non-connected network. Nevertheless, the discrimination of porosity in different classes of criteria such as size, shape, orientation, specific surface area, etc., is essential to describe the coating architecture. Moreover, the primary steps of the coating manufacturing process affect significantly the coating porous architecture. These steps need to be further understood. Different types of imaging experiments were performed to understand, describe and quantify the pore level of thick finely structured ceramics coatings.

Synthesis and characterization of nanocomposite polymer blend electrolyte thin films by spin-coating method

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

Chapi, Sharanappa; Niranjana, M.; Devendrappa, H., E-mail: dehu2010@gmail.com

2016-05-23

Solid Polymer blend electrolytes based on Polyethylene oxide (PEO) and poly vinyl pyrrolidone (PVP) complexed with zinc oxide nanoparticles (ZnO NPs; Synthesized by Co-precipitation method) thin films have prepared at a different weight percent using the spin-coating method. The complexation of the NPs with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR). The variation in film morphology was examined by polarized optical micrographs (POMs). The thermal behavior of blends was investigated under non-isothermal conditions by differential thermal analyses (DTA). A single glass transition temperature for each blend was observed, which supports the existence ofmore » compatibility of such system. The obtained results represent that the ternary based thin films are prominent materials for battery and optoelectronic device applications.« less

Formation of ZrO{sub 2} in coating on Mg–3 wt.%Al–1 wt.%Zn alloy via plasma electrolytic oxidation: Phase and structure of zirconia

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

Lee, Kang Min; Kim, Yeon Sung; Yang, Hae Woong

2015-01-15

An investigation of the coating structure formed on Mg–3 wt.%Al–1 wt.%Zn alloy sample subjected to plasma electrolytic oxidation was examined by field-emission transmission electron microscopy. The plasma electrolytic oxidation process was conducted in a phosphoric acid electrolyte containing K{sub 2}ZrF{sub 6} for 600 s. Microstructural observations showed that the coating consisting of MgO, MgF{sub 2}, and ZrO{sub 2} phases was divided into three distinctive parts, the barrier, intermediate, and outer layers. Nanocrystalline MgO and MgF{sub 2} compounds were observed mainly in the barrier layer of ~ 1 μm thick near to the substrate. From the intermediate to outer layers, variousmore » ZrO{sub 2} polymorphs appeared due to the effects of the plasma arcing temperature on the phase transition of ZrO{sub 2} compounds during the plasma electrolytic oxidation process. In the outer layer, MgO compound grew in the form of a dendrite-like structure surrounded by cubic ZrO{sub 2}. - Highlights: • The barrier layer containing MgO and MgF{sub 2} was observed near to the Mg substrate. • In the intermediate layer, m-, t-, and o-ZrO{sub 2} compounds were additionally detected. • The outer layer contained MgO with the dendrite-like structure surrounded by c-ZrO{sub 2}. • The grain sizes of compounds in oxide layer increased from barrier to outer layer.« less

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Controlling Solid-Electrolyte-Interphase Layer by Coating P-Type Semiconductor NiOx on Li4Ti5O12 for High-Energy-Density Lithium-Ion Batteries.

PubMed

Jo, Mi Ru; Lee, Gi-Hyeok; Kang, Yong-Mook

2015-12-23

Li4Ti5O12 is a promising anode material for rechargeable lithium batteries due to its well-known zero strain and superb kinetic properties. However, Li4Ti5O12 shows low energy density above 1 V vs Li(+)/Li. In order to improve the energy density of Li4Ti5O12, its low-voltage intercalation behavior beyond Li7Ti5O12 has been demonstrated. In this approach, the extended voltage window is accompanied by the decomposition of liquid electrolyte below 1 V, which would lead to an excessive formation of solid electrolyte interphase (SEI) films. We demonstrate an effective method to improve electrochemical performance of Li4Ti5O12 in a wide working voltage range by coating Li4Ti5O12 powder with p-type semiconductor NiOx. Ex situ XRD, XPS, and FTIR results show that the NiOx coating suppresses electrochemical reduction reactions of the organic SEI components to Li2CO3, thereby promoting reversibility of the charge/discharge process. The NiOx coating layer offers a stable SEI film for enhanced rate capability and cyclability.

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, Terje A.

1985-01-01

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, T.A.

1984-10-19

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

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

Lu, Dongping; Tao, Jinhui; Yan, Pengfei

2017-02-10

Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, inmore » which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.« less

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.

Investigation of the effects of process sequence on the contact resistance characteristics of coated metallic bipolar plates for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Turan, Cabir; Cora, Ömer Necati; Koç, Muammer

2013-12-01

In this study, results of an investigation on the effects of manufacturing and coating process sequence on the contact resistance (ICR) of metallic bipolar plates (BPP) for polymer electrolyte membrane fuel cells (PEMFCs) are presented. Firstly, uncoated stainless steel 316L blanks were formed into BPP through hydroforming and stamping processes. Then, these formed BPP samples were coated with three different PVD coatings (CrN, TiN and ZrN) at three different thicknesses (0.1, 0.5 and 1 μm). Secondly, blanks of the same alloy were coated first with the same coatings, thickness and technique; then, they were formed into BPPs of the same shape and dimensions using the manufacturing methods as in the first group. Finally, these two groups of BPP samples were tested for their ICR to reveal the effect of process sequence. ICR tests were also conducted on the BPP plates both before and after exposure to corrosion to disclose the effect of corrosion on ICR. Coated-then-formed BPP samples exhibited similar or even better ICR performance than formed-then-coated BPP samples. Thus, manufacturing of coated blanks can be concluded to be more favorable and worth further investigation in quest of making cost effective BPPs for mass production of PEMFC.

Thermal barrier coating resistant to sintering

DOEpatents

Subramanian, Ramesh; Sabol, Stephen M.

2001-01-01

A device (10) having a ceramic thermal barrier coating layer (16) characterized by a microstructure having gaps (18) with a sintering inhibiting material (22) disposed on the columns (20) within the gaps (18). The sintering resistant material (22) is stable over the range of operating temperatures of the device (10) and is not soluble with the underlying ceramic layer (16). For a YSZ ceramic layer (16) the sintering resistant layer (22) may preferably be aluminum oxide or yttrium aluminum oxide, deposited as a continuous layer or as nodules.

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

Hard Chrome-Coated and Fullerene-Doped Metal Surfaces in Orthopedic Bearings.

PubMed

Sonntag, Robert; Feige, Katja; Dos Santos, Claudia Beatriz; Kretzer, Jan Philippe

2017-12-20

Metal-on-metal bearings for total hip replacements have been introduced as an alternative to polyethylene in young and more active patients. These have, however, been shown to be prone to implant malpositioning and have been limited by some specific design features. In that context, coatings present an option to increase wear resistance by keeping the high fracture strength of the metal substrate. A custom-made electroplating setup was designed for the coating of CoCr substrates using (a) an industrial standard chromium electrolyte; (b) a custom-made hexavalent chromium (Cr 6+ ) electrolyte with a reduced chromium trioxide (CrO₃) content, both without solid additives and (c) with the addition of fullerene (C 60 ) nanoparticles; and (d) a trivalent chromium (Cr 3+ ) electrolyte with C 60 addition. All coatings showed an increase in microhardness compared with the metal substrate. Trivalent coatings were thinner (10 µm) than the hexavalent coatings (23-40 µm) and resulted in increased roughness and crack density. Wear was found to be reduced for the hexavalent chromium coatings by 70-84% compared with the CoCr-CoCr reference bearing while the trivalent chromium coating even increased wear by more than 300%. The addition of fullerenes to the electrolyte did not show any further tribological effect.

Hard Chrome-Coated and Fullerene-Doped Metal Surfaces in Orthopedic Bearings

PubMed Central

Feige, Katja; dos Santos, Claudia Beatriz; Kretzer, Jan Philippe

2017-01-01

Metal-on-metal bearings for total hip replacements have been introduced as an alternative to polyethylene in young and more active patients. These have, however, been shown to be prone to implant malpositioning and have been limited by some specific design features. In that context, coatings present an option to increase wear resistance by keeping the high fracture strength of the metal substrate. A custom-made electroplating setup was designed for the coating of CoCr substrates using (a) an industrial standard chromium electrolyte; (b) a custom-made hexavalent chromium (Cr6+) electrolyte with a reduced chromium trioxide (CrO3) content, both without solid additives and (c) with the addition of fullerene (C60) nanoparticles; and (d) a trivalent chromium (Cr3+) electrolyte with C60 addition. All coatings showed an increase in microhardness compared with the metal substrate. Trivalent coatings were thinner (10 µm) than the hexavalent coatings (23–40 µm) and resulted in increased roughness and crack density. Wear was found to be reduced for the hexavalent chromium coatings by 70–84% compared with the CoCr–CoCr reference bearing while the trivalent chromium coating even increased wear by more than 300%. The addition of fullerenes to the electrolyte did not show any further tribological effect. PMID:29261128

Influence of Electrode Design and Contacting Layers on Performance of Electrolyte Supported SOFC/SOEC Single Cells.

PubMed

Kusnezoff, Mihails; Trofimenko, Nikolai; Müller, Martin; Michaelis, Alexander

2016-11-08

The solid oxide cell is a basis for highly efficient and reversible electrochemical energy conversion. A single cell based on a planar electrolyte substrate as support (ESC) is often utilized for SOFC/SOEC stack manufacturing and fulfills necessary requirements for application in small, medium and large scale fuel cell and electrolysis systems. Thickness of the electrolyte substrate, and its ionic conductivity limits the power density of the ESC. To improve the performance of this cell type in SOFC/SOEC mode, alternative fuel electrodes, on the basis of Ni/CGO as well as electrolytes with reduced thickness, have been applied. Furthermore, different interlayers on the air side have been tested to avoid the electrode delamination and to reduce the cell degradation in electrolysis mode. Finally, the influence of the contacting layer on cell performance, especially for cells with an ultrathin electrolyte and thin electrode layers, has been investigated. It has been found that Ni/CGO outperform traditional Ni/8YSZ electrodes and the introduction of a ScSZ interlayer substantially reduces the degradation rate of ESC in electrolysis mode. Furthermore, it was demonstrated that, for thin electrodes, the application of contacting layers with good conductivity and adhesion to current collectors improves performance significantly.

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.

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.

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.

In vitro studying corrosion behavior of porous titanium coating in dynamic electrolyte.

PubMed

Chen, Xuedan; Fu, Qingshan; Jin, Yongzhong; Li, Mingtian; Yang, Ruisong; Cui, Xuejun; Gong, Min

2017-01-01

Porous titanium (PT) is considered as a promising biomaterials for orthopedic implants. Besides biocompatibility and mechanical properties, corrosion resistance in physiological environment is the other important factor affecting the long stability of an implant. In order to investigate the corrosion behavior of porous titanium implants in a dynamic physiological environment, a dynamic circle system was designed in this study. Then a titanium-based implant with PT coating was fabricated by plasma spraying. The corrosion resistance of PT samples in flowing 0.9% NaCl solution was evaluated by electrochemical measurements. Commercial pure solid titanium (ST) disc was used as a control. The studies of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) show that the pores in the PT play a negetive part in corrosion resistance and the flowing electrolyte can increase the corrosive rate of all titanium samples. The results suggest that pore design of titanium implants should pay attention to the effect of dynamic process of a physiological environment on the corrosion behavior of implants. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Lithium sulfide compositions for battery electrolyte and battery electrode coatings

DOEpatents

Liang, Chengdu; Liu, Zengcai; Fu, Wunjun; Lin, Zhan; Dudney, Nancy J; Howe, Jane Y; Rondinone, Adam J

2013-12-03

Methods of forming lithium-containing electrolytes are provided using wet chemical synthesis. In some examples, the lithium containing electroytes are composed of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7. The solid electrolyte may be a core shell material. In one embodiment, the core shell material includes a core of lithium sulfide (Li.sub.2S), a first shell of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7, and a second shell including one or .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7 and carbon. The lithium containing electrolytes may be incorporated into wet cell batteries or solid state batteries.

Enhanced fatigue performance of porous coated Ti6Al4V biomedical alloy

NASA Astrophysics Data System (ADS)

Apachitei, I.; Leoni, A.; Riemslag, A. C.; Fratila-Apachitei, L. E.; Duszczyk, J.

2011-05-01

Biofunctional coatings are necessary to improve integration of titanium implants in the host tissue but they may be detrimental for the implant fatigue properties. This study presents an attempt towards enhancement of the in vitro fatigue strength of plasma electrolytic oxidation coated Ti6Al4V alloy by applying shot peening process prior to coating. The electrolytic oxidation was performed in calcium acetate and calcium glycerophosphate electrolytes that allowed formation of porous oxide coatings with high surface free energy and apatite like ability. A deformed surface layer coupled with induced residual compressive stresses seem to affect oxide growth rate and fatigue behavior of the titanium alloy.

General method to predict voltage-dependent ionic conduction in a solid electrolyte coating on electrodes

NASA Astrophysics Data System (ADS)

Pan, Jie; Cheng, Yang-Tse; Qi, Yue

2015-04-01

Understanding the ionic conduction in solid electrolytes in contact with electrodes is vitally important to many applications, such as lithium ion batteries. The problem is complex because both the internal properties of the materials (e.g., electronic structure) and the characteristics of the externally contacting phases (e.g., voltage of the electrode) affect defect formation and transport. In this paper, we developed a method based on density functional theory to study the physics of defects in a solid electrolyte in equilibrium with an external environment. This method was then applied to predict the ionic conduction in lithium fluoride (LiF), in contact with different electrodes which serve as reservoirs with adjustable Li chemical potential (μLi) for defect formation. LiF was chosen because it is a major component in the solid electrolyte interphase (SEI) formed on lithium ion battery electrodes. Seventeen possible native defects with their relevant charge states in LiF were investigated to determine the dominant defect types on various electrodes. The diffusion barrier of dominant defects was calculated by the climbed nudged elastic band method. The ionic conductivity was then obtained from the concentration and mobility of defects using the Nernst-Einstein relationship. Three regions for defect formation were identified as a function of μLi: (1) intrinsic, (2) transitional, and (3) p -type region. In the intrinsic region (high μLi, typical for LiF on the negative electrode), the main defects are Schottky pairs and in the p -type region (low μLi, typical for LiF on the positive electrode) are Li ion vacancies. The ionic conductivity is calculated to be approximately 10-31Scm-1 when LiF is in contact with a negative electrode but it can increase to 10-12Scm-1 on a positive electrode. This insight suggests that divalent cation (e.g., Mg2+) doping is necessary to improve Li ion transport through the engineered LiF coating, especially for LiF on negative

Quantification of the degradation of Ni-YSZ anodes upon redox cycling

NASA Astrophysics Data System (ADS)

Song, Bowen; Ruiz-Trejo, Enrique; Bertei, Antonio; Brandon, Nigel P.

2018-01-01

Ni-YSZ anodes for Solid Oxide Fuel Cells are vulnerable to microstructural damage during redox cycling leading to a decrease in the electrochemical performance. This study quantifies the microstructural changes as a function of redox cycles at 800 °C and associates it to the deterioration of the mechanical properties and polarisation resistance. A physically-based model is used to estimate the triple-phase boundary (TPB) length from impedance spectra, and satisfactorily matches the TPB length quantified by FIB-SEM tomography: within 20 redox cycles, the TPB density decreases from 4.63 μm-2 to 1.06 μm-2. Although the polarisation resistance increases by an order of magnitude after 20 cycles, after each re-reduction the electrode polarisation improves consistently due to the transient generation of Ni nanoparticles around the TPBs. Nonetheless, the long-term degradation overshadows this transient improvement due to the nickel agglomeration. In addition, FIB-SEM tomography reveals fractures along YSZ grain boundaries, Ni-YSZ detachment and increased porosity in the composite that lead to irreversible mechanical damage: the elastic modulus diminishes from 36.4 GPa to 20.2 GPa and the hardness from 0.40 GPa to 0.15 GPa. These results suggest that microstructural, mechanical and electrochemical properties are strongly interdependent in determining the degradation caused by redox cycling.

Electrospun Nanofiber-Coated Membrane Separators for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Lee, Hun

Lithium-ion batteries are widely used as a power source for portable electronic devices and hybrid electric vehicles due to their excellent energy and power densities, long cycle life, and enhanced safety. A separator is considered to be the critical component in lithium-ion rechargeable batteries. The separator is placed between the positive and negative electrodes in order to prevent the physical contact of electrodes while allowing the transportation of ions. In most commercial lithium-ion batteries, polyolefin microporous membranes are commonly used as the separator due to their good chemical stability and high mechanical strength. However, some of their intrinsic natures, such as low electrolyte uptake, poor adhesion property to the electrodes, and low ionic conductivity, can still be improved to achieve higher performance of lithium-ion batteries. In order to improve these intrinsic properties, polyolefin microporous membranes can be coated with nanofibers by using electrospinning technique. Electrospinning is a simple and efficient method to prepare nanofibers which can absorb a significant amount of liquid electrolyte to achieve low internal resistance and battery performance. This research presents the preparation and investigation of composite membrane separators prepared by coating nanofibers onto polyolefin microporous membranes via electrospinning technique. Polyvinylidene fluoride polymers and copolymers were used for the preparation of electrospun nanofiber coatings because they have excellent electrochemical stability, good adhesion property, and high temperature resistance. The nanofiber coatings prepared by electrospinning form an interconnected and randomly orientated structure on the surface of the polyolefin microporous membranes. The size of the nanofibers is on a scale that does not interfere with the micropores in the membrane substrates. The resultant nanofiber-coated membranes have the potential to combine advantages of both the polyolefin

Electrochemical and biological characterization of coatings formed on Ti-15Mo alloy by plasma electrolytic oxidation.

PubMed

Kazek-Kęsik, Alicja; Krok-Borkowicz, Małgorzata; Pamuła, Elżbieta; Simka, Wojciech

2014-10-01

β-Type titanium alloys are considered the future materials for bone implants. To improve the bioactivity of Ti-15Mo, the surface was modified using the plasma electrolytic oxidation (PEO) process. Tricalcium phosphate (TCP, Ca3PO4), wollastonite (CaSiO3) and silica (SiO2) were selected as additives in the anodizing bath to enhance the bioactivity of the coatings formed during the PEO process. Electrochemical analysis of the samples was performed in Ringer's solution at 37°C. The open-circuit potential (EOCP) as a function of time, corrosion potential (ECORR), corrosion current density (jCORR) and polarization resistance (Rp) of the samples were determined. Surface modification improved the corrosion resistance of Ti-15Mo in Ringer's solution. In vitro studies with MG-63 osteoblast-like cells were performed for 1, 3 and 7 days. After 24h, the cells were well adhered on the entire surfaces, and their number increased with increasing culture time. The coatings formed in basic solution with wollastonite exhibited better biological performance compared with the as-ground sample. Copyright © 2014 Elsevier B.V. All rights reserved.

Lead-Free Sn-Ce-O Composite Coating on Cu Produced by Pulse Electrodeposition from an Aqueous Acidic Sulfate Electrolyte

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Das, Karabi; Das, Siddhartha

2017-10-01

Pulse-electrodeposited Sn-Ce-O composite solder coatings were synthesized on a Cu substrate from an aqueous acidic solution containing stannous sulfate (SnSO4·3H2O), sulfuric acid (H2SO4), and Triton X-100 as an additive. The codeposition was achieved by adding nano-cerium oxide powder in varying concentrations from 5 g/L to 20 g/L into the electrolytic bath. Microstructural characterization was carried out using x-ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy. The XRD analysis showed that the deposits consist mainly of tetragonal β (Sn) with reduced cerium oxide species. The composite coatings thus obtained exhibit a smaller grain size, possess higher microhardness, and a lower melting point than the monolithic Sn coating. The electrical resistivity of the developed composites increases, however, but lies within the permissible limits for current lead-free solder applications. Also, an optimum balance of properties in terms of microhardness, adhesion, melting point and resistivity can be obtained with 0.9 wt.% cerium oxide in the Sn matrix, which enables potential applications in solder joints and packaging.

Practical stability limits of magnesium electrolytes

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

Lipson, Albert L.; Han, Sang -Don; Pan, Baofei

2016-08-13

The development of a Mg ion based energy storage system could provide several benefits relative to today's Li-ion batteries, such as improved energy density. The electrolytes for Mg batteries, which are typically designed to efficiently plate and strip Mg, have not yet been proven to work with high voltage cathode materials that are needed to achieve high energy density. One possibility is that these electrolytes are inherently unstable on porous electrodes. To determine if this is indeed the case, the electrochemical properties of a variety of electrolytes were tested using a porous carbon coating on graphite foil and stainless steelmore » electrodes. It was determined that the oxidative stability limit on these porous electrodes is considerably reduced as compared to those found using polished platinum electrodes. Furthermore, the voltage stability was found to be about 3 V vs. Mg metal for the best performing electrolytes. In conclusion, these results imply the need for further research to improve the stability of Mg electrolytes to enable high voltage Mg batteries.« less

Effective Infiltration of Gel Polymer Electrolyte into Silicon-Coated Vertically Aligned Carbon Nanofibers as Anodes for Solid-State Lithium-Ion Batteries.

PubMed

Pandey, Gaind P; Klankowski, Steven A; Li, Yonghui; Sun, Xiuzhi Susan; Wu, Judy; Rojeski, Ronald A; Li, Jun

2015-09-23

This study demonstrates the full infiltration of gel polymer electrolyte into silicon-coated vertically aligned carbon nanofibers (Si-VACNFs), a high-capacity 3D nanostructured anode, and the electrochemical characterization of its properties as an effective electrolyte/separator for future all-solid-state lithium-ion batteries. Two fabrication methods have been employed to form a stable interface between the gel polymer electrolyte and the Si-VACNF anode. In the first method, the drop-casted gel polymer electrolyte is able to fully infiltrate into the open space between the vertically aligned core-shell nanofibers and encapsulate/stabilize each individual nanofiber in the polymer matrix. The 3D nanostructured Si-VACNF anode shows a very high capacity of 3450 mAh g(-1) at C/10.5 (or 0.36 A g(-1)) rate and 1732 mAh g(-1) at 1C (or 3.8 A g(-1)) rate. In the second method, a preformed gel electrolyte film is sandwiched between an Si-VACNF electrode and a Li foil to form a half-cell. Most of the vertical core-shell nanofibers of the Si-VACNF anode are able to penetrate into the gel polymer film while retaining their structural integrity. The slightly lower capacity of 2800 mAh g(-1) at C/11 rate and ∼1070 mAh g(-1) at C/1.5 (or 2.6 A g(-1)) rate have been obtained, with almost no capacity fade for up to 100 cycles. Electrochemical impedance spectroscopy does not show noticeable changes after 110 cycles, further revealing the stable interface between the gel polymer electrolyte and the Si-VACNFs anode. These results show that the infiltrated flexible gel polymer electrolyte can effectively accommodate the stress/strain of the Si shell due to the large volume expansion/contraction during the charge-discharge processes, which is particularly useful for developing future flexible solid-state lithium-ion batteries incorporating Si-anodes.

Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes

PubMed Central

2018-01-01

Electrodeposition is a widely practiced method for creating metal, colloidal, and polymer coatings on conductive substrates. In the Newtonian liquid electrolytes typically used, the process is fundamentally unstable. The underlying instabilities have been linked to failure of microcircuits, dendrite formation on battery electrodes, and overlimiting conductance in ion-selective membranes. We report that viscoelastic electrolytes composed of semidilute solutions of very high–molecular weight neutral polymers suppress these instabilities by multiple mechanisms. The voltage window ΔV in which a liquid electrolyte can operate free of electroconvective instabilities is shown to be markedly extended in viscoelastic electrolytes and is a power-law function, ΔV : η1/4, of electrolyte viscosity, η. This power-law relation is replicated in the resistance to ion transport at liquid/solid interfaces. We discuss consequences of our observations and show that viscoelastic electrolytes enable stable electrodeposition of many metals, with the most profound effects observed for reactive metals, such as sodium and lithium. This finding is of contemporary interest for high-energy electrochemical energy storage. PMID:29582017

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.

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.

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.

Precision and accuracy of luminescence lifetime-based phosphor thermometry: A case study of Eu(III):YSZ

NASA Astrophysics Data System (ADS)

Heeg, B.; Jenkins, T. P.

2013-09-01

Laser induced phosphor thermometry as a reliable technique requires an analysis of factors controlling or contributing to the precision and accuracy of a measurement. In this paper, we discuss several critical design parameters in the development of luminescence lifetime-based phosphor thermometry instrumentation for use at elevated temperatures such as encountered in hot sections of gas turbine engines. As precision is predominantly governed by signal and background photon shot noise and detector noise, a brief summary is presented of how these noise contributions may affect the measurement. Accuracy, on the other hand, is governed by a range of effects including, but not limited to, detector response characteristics, laser-induced effects, the photo-physics of the sensor materials, and also the method of data reduction. The various possible outcomes of measurement precision and accuracy are discussed with luminescence lifetime measurements on Eu(III):YSZ sensor coatings.

Zinc phosphate conversion coatings

DOEpatents

Sugama, Toshifumi

1997-01-01

Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate .alpha.-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal.

Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method

DOEpatents

Bates, John B.

1994-01-01

A battery structure including a cathode, a lithium metal anode and an electrolyte disposed between the lithium anode and the cathode utilizes a thin-film layer of lithium phosphorus oxynitride overlying so as to coat the lithium anode and thereby separate the lithium anode from the electrolyte. If desired, a preliminary layer of lithium nitride may be coated upon the lithium anode before the lithium phosphorous oxynitride is, in turn, coated upon the lithium anode so that the separation of the anode and the electrolyte is further enhanced. By coating the lithium anode with this material lay-up, the life of the battery is lengthened and the performance of the battery is enhanced.

Comparative study of polymer and liquid electrolytes in quantum dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Poudyal, Uma; Wang, Wenyong

We present the study of CdS/CdSe quantum dot sensitized solar cells (QDSSCs) in which Zn2SnO4\\ nanowires on the conductive glass are used as photoanode. The CdS/CdSe quantum dots (QDs) are deposited in the Zn2SnO4 photoanode by the Successive Ionic Layer Adsorption and Reaction (SILAR) method. CdS is first deposited on the nanowires after which it is further coated with 5 cycles of CdSe QDs. Finally, ZnS is coated on the QDs as a passivation layer. The QD sensitized photoanode are then used to assemble a solar device with the polymer and liquid electrolytes. The Incident Photon to Current Efficiency (IPCE) spectra are obtained for the CdS/CdSe coated nanowires. Further, a stability test of these devices is performed, using the polymer and liquid electrolytes, which provides insight to determine the better working electrolyte in the CdS/CdSe QDSSCs. Department of Energy.

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.

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.

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.

Evaluation of a single cell and candidate materials with high water content hydrogen in a generic solid oxide fuel cell stack test fixture, Part II: materials and interface characterization

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

Chou, Y. S.; Stevenson, Jeffry W.; Choi, Jung-Pyung

2013-01-01

A generic solid oxide fuel cell (SOFC) test fixture was developed to evaluate candidate materials under realistic conditions. A commerical 50 mm x 50 mm NiO-YSZ anode supported thin YSZ electrolyte cell with lanthanum strontium manganite (LSM) cathode was tested to evaluate the stability of candidate materials. The cell was tested in two stages at 800oC: stage I of low (~3% H2O) humidity and stage II of high (~30% H2O) humidity hydrogen fuel at constant voltage or constant current mode. Part I of the work was published earlier with information of the generic test fixture design, materials, cell performance, andmore » optical post-mortem analysis. In part II, detailed microstructure and interfacial characterizations are reported regarding the SOFC candidate materials: (Mn,Co)-spinel conductive coating, alumina coating for sealing area, ferritic stainless steel interconnect, refractory sealing glass, and their interactions with each other. Overall, the (Mn,Co)-spinel coating was very effective in minimizing Cr migration. No Cr was identified in the cathode after 1720h at 800oC. Aluminization of metallic interconnect also proved to be chemically compatible with alkaline-earth silicate sealing glass. The details of interfacial reaction and microstructure development are discussed.« less

Mechanical properties of PEO-coatings on the surface of magnesium alloy MA8 modified by TiN nanoparticles

NASA Astrophysics Data System (ADS)

Imshinetsky, Igor M.; Mashtalyar, Dmitriy V.; Sunebryukhov, Sergey L.; Gnedenkov, Sergey V.

2017-09-01

The methods to form protective coatings by the plasma electrolytic oxidation method (PEO) in the electrolytic system containing nanosized particles of titanium nitride has been develoted. Tribological and morfological studies of the composite coatings have been carried out. It has been established that the microhardness of the coating with nanoparticles concentration of 3 g/l increases by 2 folds, while the wear resistance - by 2.2 fold, as compared to respective values for the PEO-coating formed in the electrolyte without nanoparticles.

Zinc phosphate conversion coatings

DOEpatents

Sugama, T.

1997-02-18

Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate {alpha}-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal. 33 figs.

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.

A prefilter for mitigating PH 3 contamination of a Ni-YSZ anode

NASA Astrophysics Data System (ADS)

Xu, Chunchuan; Zondlo, John W.; Sabolsky, Edward M.

Ni-YSZ is used as the anode of a solid oxide fuel cell (SOFC) because it has excellent electrochemical performance for operation with coal-derived syngas. However, trace impurities, PH 3 H 2S AsH 3, and Sb in coal-syngas can cause SOFC degradation. Described here is a means of removing PH 3 impurity from syngas by using a Ni-based prefilter. In one test, a thin Ni-based filter was set upstream of a Ni-YSZ anode-supported SOFC. The SOFC was exposed to syngas with PH 3 under a constant current load at 800 °C. The filter decreased 20 ppm PH 3 in the feed to a level which did not degrade the SOFC for over 400 h until the filter became saturated. In another test, both H 2S and PH 3 were co-fed to the cell with Ni-based and Fe/Ni-based filters. The interaction between these two impurities did not significantly impact the filter performance with respect to PH 3 removal for both filter formulations. The cell performance was evaluated by current-voltage measurements and impedance spectroscopy. Post-mortem analyses of the cell and filter were performed by means of XRD, SEM/EDS and XPS. With proper filter design, the Ni-YSZ SOFC can operate on contaminated coal-syngas without degradation over a prescribed period of time.

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

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.

Characteristics and in vitro response of thin hydroxyapatite–titania films produced by plasma electrolytic oxidation of Ti alloys in electrolytes with particle additions

PubMed Central

Yeung, W. K.; Sukhorukova, I. V.; Shtansky, D. V.; Levashov, E. A.; Zhitnyak, I. Y.; Gloushankova, N. A.; Kiryukhantsev-Korneev, P. V.; Petrzhik, M. I.; Matthews, A.

2016-01-01

The enhancement of the biological properties of Ti by surface doping with hydroxyapatite (HA) is of great significance, especially for orthodontic applications. This study addressed the effects of HA particle size in the electrolyte suspension on the characteristics and biological properties of thin titania-based coatings produced on Ti–6Al–4V alloy by plasma electrolytic oxidation (PEO). Detailed morphological investigation of the coatings formed by a single-stage PEO process with two-step control of the electrical parameters was performed using the Minkowski functionals approach. The surface chemistry was studied by glow discharge optical emission spectroscopy and Fourier transform infrared spectroscopy, whereas mechanical properties were evaluated using scratch tests. The biological assessment included in vitro evaluation of the coating bioactivity in simulated body fluid (SBF) as well as studies of spreading, proliferation and osteoblastic differentiation of MC3T3-E1 cells. The results demonstrated that both HA micro- and nanoparticles were successfully incorporated in the coatings but had different effects on their surface morphology and elemental distributions. The micro-particles formed an irregular surface morphology featuring interpenetrated networks of fine pores and coating material, whereas the nanoparticles penetrated deeper into the coating matrix which retained major morphological features of the porous TiO2 coating. All coatings suffered cohesive failure in scratch tests, but no adhesive failure was observed; moreover doping with HA increased the coating scratch resistance. In vitro tests in SBF revealed enhanced bioactivity of both HA-doped PEO coatings; furthermore, the cell proliferation/morphometric tests showed their good biocompatibility. Fluorescence microscopy revealed a well-organised actin cytoskeleton and focal adhesions in MC3T3-E1 cells cultivated on these substrates. The cell alkaline phosphatase activity in the presence of

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.

A rocking chair type all-solid-state lithium ion battery adopting Li2O-ZrO2 coated LiNi0.8Co0.15Al0.05O2 and a sulfide based electrolyte

NASA Astrophysics Data System (ADS)

Ito, Seitaro; Fujiki, Satoshi; Yamada, Takanobu; Aihara, Yuichi; Park, Youngsin; Kim, Tae Young; Baek, Seung-Wook; Lee, Jae-Myung; Doo, Seokgwang; Machida, Nobuya

2014-02-01

An all-solid-state lithium-ion battery (ASSB) using non-flammable solid electrolytes is a candidate for a next-generation battery. Although the excellent cycle performance and its high energy density are suggested in the literature, a practical size battery has not been appeared yet. In this paper, we have adopted a sulfide based electrolyte, Li2S-P2S5 (80:20 mol%) to a rocking chair type lithium ion battery. The electrochemical cell consists of a Li2O-ZrO2 coated LiNi0.8Co0.15Al0.05O2 (NCA) cathode, an artificial graphite anode and the sulfide based electrolyte without any organic and inorganic liquids. The cathode charge transfer resistance is significantly reduced by the Li2O-ZrO2 coating. The total cell resistance of the Li2O-ZrO2 (LZO) coated NCA adopted cell is approximately one quarter of non-treated one. A standard type single cell with the nominal capacity of 100 mAh at 25 °C is fabricated by wet printing process, and its capacity retention is approximately 80% at 100 cycles. Also, a 1 Ah class battery was constructed by stacking the single cells, and demonstrated.

Thermal barrier coatings (TBC's) for high heat flux thrust chambers

NASA Astrophysics Data System (ADS)

Bradley, Christopher M.

-section components has become critical, but at the same time the service conditions have put our best alloy systems to their limits. As a result, implementation of cooling holes and thermal barrier coatings are new advances in hot-section technologies now looked at for modifications to reach higher temperature applications. Current thermal barrier coatings used in today's turbine applications is known as 8%yttria-stabilized zirconia (YSZ) and there are no coatings for current thrust chambers. Current research is looking at the applicability of 8%yttria-stabilized hafnia (YSH) for turbine applications and the implementation of 8%YSZ onto thrust chambers. This study intends to determine if the use of thermal barrier coatings are applicable for high heat flux thrust chambers using industrial YSZ will be advantageous for improvements in efficiency, thrust and longer service life by allowing the thrust chambers to be used more than once.

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

Influence of sealing post-treatments on the corrosion resistance of PEO coated AZ91 magnesium alloy

NASA Astrophysics Data System (ADS)

Mingo, B.; Arrabal, R.; Mohedano, M.; Llamazares, Y.; Matykina, E.; Yerokhin, A.; Pardo, A.

2018-03-01

The effect of three different post-treatments carried out on Plasma Electrolytic Oxidation (PEO) coated magnesium alloys are evaluated in terms of characterisation and corrosion resistance. Special interest is given to the role of a common additive (NaF) to the coating properties. The post-treatments are based on immersion sealing processes in aqueous solutions of inorganic salts (cerium and stannate based salts) and alcoholic solution of an organic acid (octodecylphosphate acid, ODP). Sealing mechanisms for each post-treatment are proposed. Cerium and stannate sealings are based on filling of the pores with the products of dissolution/precipitation reactions, while the ODP acid sealing is based on the formation of a thin layer of ODP over the coating through specific interactions between the polar part of the organic acid and the coating surface. All coatings are evaluated by salt fog test and analysed by electrochemical impedance spectroscopy. All sealings show a slight increase in the corrosion resistance of the coatings formed in the NaF-free electrolyte, but their positive influence is boosted in case of the coatings obtained in the NaF-containing electrolyte. This is related to the chemical and morphological changes at the coating surface induced by the presence of NaF in the electrolyte.

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.

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).

A study of the physical, chemical and biological properties of TiO2 coatings produced by micro-arc oxidation in a Ca-P-based electrolyte.

PubMed

dos Santos, Amanda; Araujo, Joyce R; Landi, Sandra M; Kuznetsov, Alexei; Granjeiro, José M; de Sena, Lidia Ágata; Achete, Carlos Alberto

2014-07-01

In this work, a porous and homogeneous titanium dioxide layer was grown on commercially pure titanium substrate using a micro-arc oxidation (MAO) process and Ca-P-based electrolyte. The structure and morphology of the TiO2 coatings were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, and profilometry. The chemical properties were studied using electron dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy. The wettability of the coating was evaluated using contact angle measurements. During the MAO process, Ca and P ions were incorporated into the oxide layer. The TiO2 coating was composed of a mixture of crystalline and amorphous structures. The crystalline part of the sample consisted of a major anatase phase and a minor rutile phase. A cross-sectional image of the coating-substrate interface reveals the presence of voids elongated along the interface. An osteoblast culture was performed to verify the cytocompatibility of the anodized surface. The results of the cytotoxicity tests show satisfactory cell viability of the titanium dioxide films produced in this study.

Characterization of Microstructure and Thermal Properties of YSZ Coatings Obtained by Axial Suspension Plasma Spraying (ASPS)

NASA Astrophysics Data System (ADS)

Ganvir, Ashish; Curry, Nicholas; Björklund, Stefan; Markocsan, Nicolaie; Nylén, Per

2015-10-01

The paper aims at demonstrating various microstructures which can be obtained using the suspension spraying technique and their respective significance in enhancing the thermal insulation property of a thermal barrier coating. Three different types of coating microstructures are discussed which were produced by the Axial Suspension Plasma Spraying. Detailed characterization of coatings was then performed. Optical and scanning electron microscopy were utilized for microstructure evaluations; x-ray diffraction for phase analysis; water impregnation, image analysis, and mercury intrusion porosimetry for porosity analysis, and laser flash analysis for thermal diffusivity measurements were used. The results showed that Axial Suspension Plasma Spraying can generate vertically cracked, porous, and feathery columnar-type microstructures. Pore size distribution was found in micron, submicron, and nanometer range. Higher overall porosity, the lower density of vertical cracks or inter-column spacing, and higher inter-pass porosity favored thermal insulation property of the coating. Significant increase in thermal diffusivity and conductivity was found at higher temperature, which is believed to be due to the pore rearrangement (sintering and pore coarsening). Thermal conductivity values for these coatings were also compared with electron beam physical vapor deposition (EBPVD) thermal barrier coatings from the literature and found to be much lower.

Titanium surface modification by microarc oxidation in electrolyte based on wollastonite and hydroxyapatite

NASA Astrophysics Data System (ADS)

Sharkeev, Yu. P.; Sedelnikova, M. B.; Komarova, E. G.; Khlusov, I. A.

2015-11-01

An investigation of titanium surface modification by microarc oxidation in the electrolyte based on wollastonite and hydroxyapatite was presented. The dependences of the coating properties on the microarc oxidation parameters were found. A variation of the process parameters allowed producing wollastonite-calcium phosphate coatings with aplate-like structure, thickness 25-30 µm, roughness 2.5-5.0 µm, and adhesion strength 57 MPa. The optimum microarc oxidation parameters such as the electrical voltage of 150 V, process duration of 5-10 min, and pulse duration of 100-300 µs were revealed. The wollastonite addition to the electrolyte based on the aqueous solution of phosphoric acid and hydroxyapatite allowed us to form wollastonite-calcium phosphate coatings on the titanium surface by the microarc oxidation method with enhanced strength properties and an increased ability to osseointegration.

Suspension plasma spraying of La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes: Influence of carbon black pore former on performance and degradation

NASA Astrophysics Data System (ADS)

Fan, E. S. C.; Kuhn, J.; Kesler, O.

2016-06-01

Suspension plasma spray deposition is utilized to fabricate solid oxide fuel cell cathodes with minimal material decomposition. Adding carbon black as a pore former to the feedstock suspension results in smoother and more porous coatings, but over the range of carbon black concentrations studied, has little impact on the overall symmetrical cell performance. The cathode made with a suspension containing 25 wt% carbon has the highest deposition efficiency and a polarization resistance of 0.062 Ωcm2 at 744 °C. This cathode is tested for 500 h, and it is observed that adding an SDC interlayer between the YSZ electrolyte and the cathode(s) and/or coating the metal substrate with lanthanum chromite decrease the rate of performance degradation.

Influence of process parameters on plasma electrolytic surface treatment of tantalum for biomedical applications

NASA Astrophysics Data System (ADS)

Sowa, Maciej; Woszczak, Maja; Kazek-Kęsik, Alicja; Dercz, Grzegorz; Korotin, Danila M.; Zhidkov, Ivan S.; Kurmaev, Ernst Z.; Cholakh, Seif O.; Basiaga, Marcin; Simka, Wojciech

2017-06-01

This work aims to quantify the effect of anodization voltage and electrolyte composition used during DC plasma electrolytic oxidation (PEO), operated as a 2-step process, on the surface properties of the resulting oxide coatings on tantalum. The first step consisted of galvanostatic anodization (150 mA cm-2) of the tantalum workpiece up to several limiting voltages (200, 300, 400 and 500 V). After attaining the limiting voltage, the process was switched to voltage control, which resulted in a gradual decrease of the anodic current density. The anodic treatment was realized in a 0.5 M Ca(H2PO2)2 solution, which was then modified by the addition of 1.15 M Ca(HCOO)2 as well as 1.15 M and 1.5 M Mg(CH3COO)2. The increasing voltage of anodization led to the formation of thicker coatings, with larger pores and enriched with electrolytes species to a higher extent. The solutions containing HCOO- and CH3COO- ions caused the formation of coatings which were slightly hydrophobic (high contact angle). In the case of the samples anodized up to 500 V, scattered crystalline deposits were observed. Bioactive phases, such as hydroxyapatite, were detected in the treated oxide coatings by XRD and XPS.

Gas diffusion layers coated with a microporous layer containing hydrophilic carbon nanotubes for performance enhancement of polymer electrolyte fuel cells under both low and high humidity conditions

NASA Astrophysics Data System (ADS)

Kitahara, Tatsumi; Nakajima, Hironori; Okamura, Kosuke

2015-06-01

Gas diffusion layers (GDLs) coated with a hydrophobic microporous layer (MPL) composed of carbon black and polytetrafluoroethylene (PTFE) have been commonly used to improve the water management characteristics of polymer electrolyte fuel cells (PEFCs). However, the hydrophobic MPL coated GDL designed to prevent dehydration of the membrane under low humidity conditions is generally inferior at reducing flooding under high humidity conditions. It is therefore important to develop a robust MPL coated GDL that can enhance the PEFC performance regardless of the humidity conditions. In the present study, a GDL coated with an MPL containing hydrophilic carbon nanotubes (CNTs) was developed. The less hydrophobic pores incorporating CNTs are effective at conserving the membrane humidity under low humidity conditions. The MPL with CNTs is also effective at expelling excess water from the catalyst layer while maintaining oxygen flow pathways from the GDL substrate, allowing the mean flow pore diameter to be decreased to 2 μm without reducing the ability of the MPL to prevent flooding under high humidity conditions. An MPL coated GDL with a CNT content of 4 mass% exhibits significantly higher performance under both low and high humidity conditions than a hydrophobic MPL coated GDL.

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.

Method for producing electricity from a fuel cell having solid-oxide ionic electrolyte

DOEpatents

Mason, David M.

1984-01-01

Stabilized quadrivalent cation oxide electrolytes are employed in fuel cells at elevated temperatures with a carbon and/or hydrogen containing fuel anode and an oxygen cathode. The fuel cell is operated at elevated temperatures with conductive metallic coatings as electrodes and desirably having the electrolyte surface blackened. Of particular interest as the quadrivalent oxide is zirconia.

Microhardness and wear resistance of PEO-coated 5754 aluminum alloy

NASA Astrophysics Data System (ADS)

Vyaliy, I. E.; Egorkin, V. S.; Sinebryukhov, S. L.; Minaev, A. N.; Gnedenkov, S. V.

2017-09-01

We present results of the study aimed at assessing the effect of duty cycle (D) during plasma electrolytic oxidation (PEO) on protective properties of the coatings produced on 5754 aluminum alloy. It is shown that increasing the duty cycle of a microsecond current pulses leads to increased hardness and reduced abrasive wear of the PEO-layers, improving mechanical properties. The obtained data allowed confirming, that increasing the amount of energy consumed for coating growth leads to the formation of thicker PEO-layers with improved tribological properties. The effect of duty cycle during plasma electrolytic oxidation on protective properties of the produced coatings was assessed.

An environmentally compliant cerium-based conversion coating for aluminum protection

NASA Astrophysics Data System (ADS)

Lin, Xuan

Chromate conversion coatings have been extensively used in the aircraft industry for the corrosion protection of aluminum alloys. Unfortunately, hexavalent chromium, which is a primary component in the chromating process, is a confirmed carcinogen. Because of rising remediation and disposal costs caused by increasingly strict regulations, the replacement of the traditional chromate conversion process is becoming a top priority in the metal finishing industry. This research focused on the electrodeposition of cerium-based coatings on 7075-T6 aluminum alloy in an electrolyte containing a cerium salt, an oxidizing agent and an organic solvent. The cerium-rich deposits were characterized by phase composition, oxidation state, coating thickness, surface morphology, deposition mechanism and polarization behavior. Chemical and electrochemical tests were utilized to compare the corrosion resistance between cerium-based coatings and chromate conversion coatings. To characterize and simulate the deposition process, a variety of approaches were utilized to study the oxidation states of cerium in various soluble and precipitated forms as a function of hydrogen peroxide and electrolyte pH. The pH ranges where the oxidation and reduction reactions dominate were determined. Further studies were performed to optimize the corrosion performance of cerium-based coatings and to understand the effects of electrolyte constituents and deposition parameters. The optimum levels for these variables were identified. A patent disclosure on the cerium-based coating process was made to the University of Missouri-Rolla and has now been officially filed with the U.S. Patent Office.

Investigation of absorptance and emissivity of thermal control coatings on Mg–Li alloys and OES analysis during PEO process

PubMed Central

Yao, Zhongping; Xia, Qixing; Ju, Pengfei; Wang, Jiankang; Su, Peibo; Li, Dongqi; Jiang, Zhaohua

2016-01-01

Thermal control ceramic coatings on Mg–Li alloys have been successfully prepared in silicate electrolyte system by plasma electrolytic oxidation (PEO) method. The PEO coatings are mainly composed of crystallized Mg2SiO4 and MgO, which have typical porous structure with some bulges on the surface; OES analysis shows that the plasma temperature, which is influenced by the technique parameters, determines the formation of the coatings with different crystalline phases and morphologies, combined with “quick cooling effect” by the electrolyte; and the electron concentration is constant, which is related to the electric spark breakdown, determined by the nature of the coating and the interface of coating/electrolyte. Technique parameters influence the coating thickness, roughness and surface morphology, but do not change the coating composition in the specific PEO regime, and therefore the absorptance (αS) and emissivity (ε) of the coatings can be adjusted by the technique parameters through changing thickness and roughness in a certain degree. The coating prepared at 10 A/dm2, 50 Hz, 30 min and 14 g/L Na2SiO3 has the minimum value of αS (0.35) and the maximum value of ε (0.82), with the balance temperature of 320 K. PMID:27383569

Aluminium Electroplating on Steel from a Fused Bromide Electrolyte

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

Prabhat Tripathy; Laura Wurth; Eric Dufek

A quaternary bromide bath (LiBr-KBr-CsBr-AlBr3) was used to electro-coat aluminium on steel substrates. The electrolyte was prepared by the addition of AlBr3 into the eutectic LiBr-KBr-CsBr melt. A smooth, thick, adherent and shiny aluminium coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminium coverage. Both salt immersion and open circuit potential measurement suggest that the coatings did display good corrosion-resistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminium coating inmore » preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminium coating on both ferrous and non-ferrous metals, including complex surfaces/geometries.« 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

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.

Systematic Investigation on the Influence of Spray Parameters on the Mechanical Properties of Atmospheric Plasma-Sprayed YSZ Coatings

NASA Astrophysics Data System (ADS)

Mutter, Markus; Mauer, Georg; Mücke, Robert; Guillon, Olivier; Vaßen, Robert

2018-04-01

In the atmospheric plasma spray (APS) process, micro-sized ceramic powder is injected into a thermal plasma where it is rapidly heated and propelled toward the substrate. The coating formation is characterized by the subsequent impingement of a large number of more or less molten particles forming the so-called splats and eventually the coating. In this study, a systematic investigation on the influence of selected spray parameters on the coating microstructure and the coating properties was conducted. The investigation thereby comprised the coating porosity, the elastic modulus, and the residual stress evolution within the coating. The melting status of the particles at the impingement on the substrate in combination with the substrate surface condition is crucial for the coating formation. Single splats were collected on mirror-polished substrates for selected spray conditions and evaluated by identifying different types of splats (ideal, distorted, weakly bonded, and partially molten) and their relative fractions. In a previous study, these splat types were evaluated in terms of their effect on the above-mentioned coating properties. The particle melting status, which serves as a measure for the particle spreading behavior, was determined by in-flight particle temperature measurements and correlated to the coating properties. It was found that the gun power and the spray distance have a strong effect on the investigated coating properties, whereas the feed rate and the cooling show minor influence.

Rational coating of Li7P3S11 solid electrolyte on MoS2 electrode for all-solid-state lithium ion batteries

NASA Astrophysics Data System (ADS)

Xu, R. C.; Wang, X. L.; Zhang, S. Z.; Xia, Y.; Xia, X. H.; Wu, J. B.; Tu, J. P.

2018-01-01

Large interfacial resistance between electrode and electrolyte limits the development of high-performance all-solid-state batteries. Herein we report a uniform coating of Li7P3S11 solid electrolyte on MoS2 to form a MoS2/Li7P3S11 composite electrode for all-solid-state lithium ion batteries. The as-synthesized Li7P3S11 processes a high ionic of 2.0 mS cm-1 at room temperature. Due to homogeneous union and reduced interfacial resistance, the assembled all-solid-state batteries with the MoS2/Li7P3S11 composite electrode exhibit higher reversible capacity of 547.1 mAh g-1 at 0.1 C and better cycling stability than the counterpart based on untreated MoS2. Our study provides a new reference for design/fabrication of advanced electrode materials for high-performance all-solid-state batteries.

Effects of CH3OH Addition on Plasma Electrolytic Oxidation of AZ31 Magnesium Alloys

NASA Astrophysics Data System (ADS)

He, Yongyi; Chen, Li; Yan, Zongcheng; Zhang, Yalei

2015-09-01

Plasma electrolytic oxidation (PEO) films on AZ31 magnesium alloys were prepared in alkaline silicate electrolytes (base electrolyte) with the addition of different volume concentrations of CH3OH, which was used to adjust the thickness of the vapor sheath. The compositions, morphologies, and thicknesses of ceramic layers formed with different CH3OH concentrations were determined via X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), and scanning electron microscopy (SEM). Corrosion behavior of the oxide films was evaluated in 3.5 wt.% NaCl solution using potentiodynamic polarization tests. PEO coatings mainly comprised Mg, MgO, and Mg2SiO4. The addition of CH3OH in base electrolytes affected the thickness, pores diameter, and Mg2SiO4 content in the films. The films formed in the electrolyte containing 12% CH3OH exhibited the highest thickness. The coatings formed in the electrolyte containing different concentrations of CH3OH exhibited similar corrosion resistance. The energy consumption of PEO markedly decreased upon the addition of CH3OH to the electrolytes. The result is helpful for energy saving in the PEO process. supported by National Natural Science Foundation of China (No. 21376088), the Project of Production, Education and Research, Guangdong Province and Ministry of Education (Nos. 2012B09100063, 2012A090300015), and Guangzhou Science and Technology Plan Projects of China (No. 2014Y2-00042)

Study of Scanning Micro-arc Oxidation and Coating Development

NASA Astrophysics Data System (ADS)

Xia, Lingqin; Han, Jianmin; Domblesky, Joseph P.; Yang, Zhiyong; Li, Weijing

2017-11-01

Micro-arc oxidation (MAO) continues to be the focus of numerous investigations, whereas relatively few studies have considered scanning micro-arc oxidation (SMAO). In the present work, an experimental study was performed using stationary and moving electrodes to investigate coating development in SMAO and discern the effect of key process parameters. Examination of oxide deposits made on A356 aluminum show that coating thickness and growth rate are inversely related to inter-electrode spacing and travel speed. An evaluation of SMAO deposits made by stationary and moving nozzles revealed that coating thickness profiles follow a Gaussian distribution due to the electrolyte flow field in the impingement zone. Hardness surveys and scanning electron microscope analysis of SMAO coatings revealed that micro-hardness distributions and cross-sectional morphology are similar to MAO for a stationary nozzle but that a denser outer layer develops when a moving nozzle is used. This is attributed to a high density of discharge occurring in micropores of the oxide film and remelting which results from the moving electrolyte column. Analysis of voltage-current characteristic curves shows that the resistance of the electrolyte column is essentially linear over the range considered and results indicate that it can be modeled as a variable length resistor. While further testing is needed, results confirm that SMAO is suitable for coating large, planar parts and for repairing worn surfaces.

Advances in the electrodeposition of aluminum from ionic liquid based electrolytes

NASA Astrophysics Data System (ADS)

Leadbetter, Kirt C.

Aluminum plating is of considerable technical and economic interest because it provides an eco-friendly substitute for cadmium coatings used on many military systems. However, cadmium has been determined to be a significant environmental safety and occupational health (ESOH) hazard because of its toxicity and carcinogenic nature. Furthermore, the cost of treating and disposing of generated wastes, which often contain cyanide, is costly and is becoming prohibitive in the face of increasingly stringent regulatory standards. The non-toxic alternative aluminum is equivalent or superior in performance to cadmium. In addition, it could serve to provide an alternative to hexavalent chromium coatings used on military systems for similar reasons to that of cadmium. Aluminum is a beneficial alternative in that it demonstrates self-healing corrosion resistance in the form of a tightly-bound, impervious oxide layer. A successfully plated layer would be serviceable over a wider temperature range, 925 °F for aluminum compared to 450 oF for cadmium. In addition, an aluminum layer can be anodized to make it non-conducting and colorable. In consideration of the plating process, aluminum cannot be deposited from aqueous solutions because of its reduction potential. Therefore, nonaqueous electrolytes are required for deposition. Currently, aluminum can be electrodeposited in nonaqueous processes that use hazardous chemicals such as toluene and pyrophoric aluminum alkyls. Electrodeposition from ionic liquids provides the potential for a safer method that could be easily scaled up for industrial application. The plating process could be performed at a lower temperature and higher current density than other commercially available aluminum electrodeposition processes; thus a reduced process cost could be possible. The current ionic liquid based electrolytes are more expensive; however production on a larger scale and a long electrolyte lifetime are associated with a reduction in price

Molecular Dynamics Simulation of the Structure and Ion Transport in the Ce1 - x Gd x O2 - δ|YSZ Heterosystem

NASA Astrophysics Data System (ADS)

Galin, M. Z.; Ivanov-Schitz, A. K.; Mazo, G. N.

2018-01-01

Molecular dynamics simulation has been used to develop a realistic atomistic model of two-layer Ce1 - x Gd x O2 - δ|YSZ heterosystem. It is shown that Ce1 - x Gd x O2 - δ and YSZ layers (about 15 and 16 Å thick, respectively) retain their crystal structure on the whole. The main structural distortions are found to occur near the Ce1 - x Gd x O2 - δ|YSZ geometric interface, within a narrow interfacial region of few angstroms thick. Both the generalized diffusion characteristics of the system as a whole and the oxygen diffusion coefficients in the layers are calculated, and the diffusion activation energies are determined.

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.

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.

Electrolytic plating apparatus for discrete microsized particles

DOEpatents

Mayer, Anton

1976-11-30

Method and apparatus are disclosed for electrolytically producing very uniform coatings of a desired material on discrete microsized particles. Agglomeration or bridging of the particles during the deposition process is prevented by imparting a sufficiently random motion to the particles that they are not in contact with a powered cathode for a time sufficient for such to occur.

Electrochemical corrosion behaviour of nickel chromium-chromium carbide coating by HVOF process

NASA Astrophysics Data System (ADS)

Amudha, A.; Nagaraja, H. S.; Shashikala, H. D.

2018-04-01

To overcome the corrosion problem in marine industry, coatings are one of the most economical solutions. In this paper, the corrosion behaviour of 25(NiCr)-75Cr3C2 cermet coating on low carbon steel substrate by HVOF process is studied. Different phases such as Cr7C3 and Cr3C2, along with Ni and chromium oxide(Cr3O2) constituents present in the coating were revealed by X-Ray Diffraction (XRD) analysis. The morphology of the coating obtained by scanning electron microscope (SEM) gave confirmation for the XRD analysis. Electrochemical corrosion techniques such as Linear Polarization Resistance (LPR) and Electrochemical Impedance Spectroscopy (EIS) were used to study the corrosion behaviour of the cermet in 3.5wt% NaCl electrolyte solution. The corrosion current density of the coated sample and substrate were found to be 6.878µA/cm-2 and 21.091µA/cm-2 respectively. The Nyquist Impedance spectra were used to derive an equivalent circuit to analyze the interaction between the coating and electrolyte. The Bode Impedance plots obtained by EIS for the coating showed a typical passive material capacitive behaviour, indicated by medium to low frequency with phase angle approaching -60o, suggesting that a stable film is formed on the tested material in the electrolyte used.

Nickel electroplating on copper pre-activated Al alloy in the electrolyte containing PEG1000 as an additive

NASA Astrophysics Data System (ADS)

Guan, Jie; Wang, Jinwei; Zhang, Dawei

2018-06-01

Ni coatings are prepared on Cu-pretreated anodic Al alloy by electroplating technique in environment-friendly electrolytes with PEG1000 as an additive. Some defects like pores, cracks and even uncovered areas are observed for the sample of the Cu-pretreated anodic Al alloy, and these defects seem to be remedied with the following Ni electroplating as observed from their SEM images; while the covering effect of Ni onto the Cu layer is rather limited as judged by their corrosion current data of polarization test. After adding PEG1000 in the Ni electroplating electrolyte, the obtained coating surfaces are seen smoother and thicker; and most of the tiny particles are seen closely packed together with some bigger particles on them. The diffusion of nickel particles into copper layer are confirmed by the line and mapping mode of EDS element analysis for the Ni-Cu composite coating. Their much lower corrosion current density ( I corr) and higher micro-hardness support the fact that the addition of PEG1000 in Ni plating electrolyte has a function of promoting the refinement of Ni particles and the formation of more compacter, thicker and smoother Ni-Cu composite coating.

Influences of urea and sodium nitrite on surface coating of plasma electrolytic oxidation

NASA Astrophysics Data System (ADS)

Yeh, Shang-Chun; Tsai, Dah-Shyang; Guan, Sheng-Yong; Chou, Chen-Chia

2015-11-01

Urea and sodium nitrite are generally viewed as nitridation additives in the electrolyte for plasma electrolytic oxidation (PEO) of aluminum alloys. We study the influences of these two convenient chemicals in presence of sodium aluminate and find very different effects on film growth. Urea addition enhances the nitrogen content of PEO layer, diminishes the layer thickness, increases the porosity, interferes with the α-alumina formation, and promotes precipitation in the electrolyte. Hence, the electrolytic urea content ought to be maintained less than 45 g dm-3. On the other hand, sodium nitrite behaves like an oxidation additive, more than a nitridation additive. NaNO2 addition effectively introduces nitrogen in the PEO layer at low concentration, yet the nitrogen content of oxide layer decreases with increasing NaNO2 concentration. The effects of NaNO2, such as increasing layer thickness, reducing porosity, promoting α-alumina formation are attributed to oxidation enhancement, not because of nitridation.

Coated particles for lithium battery cathodes

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

Singh, Mohit; Eitouni, Hany Basam; Pratt, Russell Clayton

Particles of cathodic materials are coated with polymer to prevent direct contact between the particles and the surrounding electrolyte. The polymers are held in place either by a) growing the polymers from initiators covalently bound to the particle, b) attachment of the already-formed polymers by covalently linking to functional groups attached to the particle, or c) electrostatic interactions resulting from incorporation of cationic or anionic groups in the polymer chain. Carbon or ceramic coatings may first be formed on the surfaces of the particles before the particles are coated with polymer. The polymer coating is both electronically and ionically conductive.

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.

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.

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.

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

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

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

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

Artificial Solid Electrolyte Interphase to Address the Electrochemical Degradation of Silicon Electrodes

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

Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-01-01

Electrochemical degradation on Si anodes prevents them from being successfully used in lithium-ion full cells. Unlike the case of graphite anodes, natural solid electrolyte interphase (SEI) films generated from carbonate electrolyte do not self-passivate on Si and causes continuous electrolyte decomposition. In this work we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphor oxynitride (Lipon), that conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, significant effect is observed in suppressing the electrolyte decomposition, while Lipon of thinner than 40more » nm has little effect. Ionic and electronic conductivity measurement reveals that the artificial SEI is effective when it is a pure ionic conductor, and the electrolyte decomposition is not suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40~50 nm. This work provides guidance for designing artificial SEI for high capacity lithium-ion battery electrodes using solid electrolyte materials.« less

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.

Carbon Disulfide Cosolvent Electrolytes for High-Performance Lithium Sulfur Batteries.

PubMed

Gu, Sui; Wen, Zhaoyin; Qian, Rong; Jin, Jun; Wang, Qingsong; Wu, Meifen; Zhuo, Shangjun

2016-12-21

Development of lithium sulfur (Li-S) batteries with high Coulombic efficiency and long cycle stability remains challenging due to the dissolution and shuttle of polysulfides in electrolyte. Here, a novel additive, carbon disulfide (CS 2 ), to the organic electrolyte is reported to improve the cycling performance of Li-S batteries. The cells with the CS 2 -additive electrolyte exhibit high Coulombic efficiency and long cycle stability, showing average Coulombic efficiency >99% and a capacity retention of 88% over the entire 300 cycles. The function of the CS 2 additive is 2-fold: (1) it inhibits the migration of long-chain polysulfides to the anode by forming complexes with polysulfides and (2) it passivates electrode surfaces by inducing the protective coatings on both the anode and the cathode.

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."

Self-Passivating Lithium/Solid Electrolyte/Iodine Cells

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar; Whitcare, Jay; Narayanan, Sekharipuram; West, William

2006-01-01

Robust lithium/solid electrolyte/iodine electrochemical cells that offer significant advantages over commercial lithium/ iodine cells have been developed. At room temperature, these cells can be discharged at current densities 10 to 30 times those of commercial lithium/iodine cells. Moreover, from room temperature up to 80 C, the maximum discharge-current densities of these cells exceed those of all other solid-electrolyte-based cells. A cell of this type includes a metallic lithium anode in contact with a commercial flexible solid electrolyte film that, in turn, is in contact with an iodine/ graphite cathode. The solid electrolyte (the chemical composition of which has not been reported) offers the high ionic conductivity needed for high cell performance. However, the solid electrolyte exhibits an undesirable chemical reactivity to lithium that, if not mitigated, would render the solid electrolyte unsuitable for use in a lithium cell. In this cell, such mitigation is affected by the formation of a thin passivating layer of lithium iodide at the anode/electrolyte interface. Test cells of this type were fabricated from iodine/graphite cathode pellets, free-standing solid-electrolyte films, and lithium-foil anodes. The cathode mixtures were made by grinding together blends of nominally 10 weight percent graphite and 90 weight percent iodine. The cathode mixtures were then pressed into pellets at 36 kpsi (248 MPa) and inserted into coin-shaped stainless-steel cell cases that were coated with graphite paste to minimize corrosion. The solid-electrolyte film material was stamped to form circular pieces to fit in the coin cell cases, inserted in the cases, and pressed against the cathode pellets with polyethylene gaskets. Lithium-foil anodes were placed directly onto the electrolyte films. The layers described thus far were pressed and held together by stainless- steel shims, wave springs, and coin cell caps. The assembled cells were then crimped to form hermetic seals

ELECTROLYTIC CLADDING OF ZIRCONIUM ON URANIUM

DOEpatents

Wick, J.J.

1959-09-22

A method is presented for coating uranium with zircoalum by rendering the uranium surface smooth and oxidefree, immersing it in a molten electrolytic bath in NaCI, K/sub 2/ZrF/sub 6/, KF, and ZrO/sub 2/, and before the article reaches temperature equilibrium with the bath, applying an electrolyzing current of 60 amperes per square dectmeter at approximately 3 volts to form a layer of zirconium metal on the uranium.

Surface-protected LiCoO2 with ultrathin solid oxide electrolyte film for high-voltage lithium ion batteries and lithium polymer batteries

NASA Astrophysics Data System (ADS)

Yang, Qi; Huang, Jie; Li, Yejing; Wang, Yi; Qiu, Jiliang; Zhang, Jienan; Yu, Huigen; Yu, Xiqian; Li, Hong; Chen, Liquan

2018-06-01

Surface modification of LiCoO2 with the ultrathin film of solid state electrolyte of Li1.4Al0.4Ti1.6(PO4)3 (LATP) has been realized by a new and facile solution-based method. The coated LiCoO2 reveals enhanced structural and electrochemical stability at high voltage (4.5 V vs Li+/Li) in half-cell with liquid electrolyte. Transmission electron microscopy (TEM) images show that a dense LATP coating layer is covered on the surface of LiCoO2 uniformly with thickness of less than 20 nm. The LATP coating layer is proven to be able to prevent the direct contact between the cathode and the electrolyte effectively and thus to suppress the side reactions of liquid electrolyte with LiCoO2 surface at high charging voltage. As a result, dissolution of Co3+ has been largely suppressed over prolonged cycling as indicated by the X-ray photoelectron spectroscopy (XPS) measurements. Due to this surface passivating feature, the electrochemical performance of 0.5 wt% LATP modified LiCoO2 has also been evaluated in an all solid lithium battery with poly(ethylene oxide)-based polymer electrolyte. The cell exhibits 93% discharge capacity retention of the initial discharge capacity after 50 cycles at the charging cut-off voltage of 4.2 V, suggesting that the LATP coating layer is effective to suppress the oxidation of PEO at high voltage.

Thermal Diffusivity Measurement for Thermal Spray Coating Attached to Substrate Using Laser Flash Method

NASA Astrophysics Data System (ADS)

Akoshima, Megumi; Tanaka, Takashi; Endo, Satoshi; Baba, Tetsuya; Harada, Yoshio; Kojima, Yoshitaka; Kawasaki, Akira; Ono, Fumio

2011-11-01

Ceramic-based thermal barrier coatings are used as heat and wear shields of gas turbine blades. There is a strong need to evaluate the thermal conductivity of coating for thermal design and use. The thermal conductivity of a bulk material is obtained as the product of thermal diffusivity, specific heat capacity, and density above room temperature in many cases. Thermal diffusivity and thermal conductivity are unique for a given material because they are sensitive to the structure of the material. Therefore, it is important to measure them in each sample. However it is difficult to measure the thermal diffusivity and thermal conductivity of coatings because coatings are attached to substrates. In order to evaluate the thermal diffusivity of a coating attached to the substrate, we have examined the laser flash method with the multilayer model on the basis of the response function method. We carried out laser flash measurements in layered samples composed of a CoNiCrAlY bond coating and a 8YSZ top coating by thermal spraying on a Ni-based superalloy substrate. It was found that the procedure using laser flash method with the multilayer model is useful for the thermal diffusivity evaluation of a coating attached to a substrate.

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.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Quality Improvement of Chrome-Diamond Coatings on Flowing Chrome Plating

NASA Astrophysics Data System (ADS)

Belyaev, V. N.; Koslyuk, A. Yu; Lobunets, A. V.; Andreyev, A. S.

2016-04-01

The research results of the process of flowing chrome plating of internal surfaces of long-length cylindrical articles with the usage of electrolyte with ultra-dispersed diamonds when continuous article rotation, while chromium-plating, are presented. During experiments the following varying technological parameters: electrolyte temperature and article frequency rotation were chosen, and experimental samples were obtained. Estimation of porosity, micro-hardness, thickness of chrome coatings and uniformity were performed as well as the precipitation structure by the method of scanning electron microscopy. The results showed that the use of ultra-dispersed diamonds and realization of the scheme with rotation of detail-cathode when flowing chromium-plating allows one to increase servicing characteristics of the coating due to the decrease of grains size of chrome coating and porosity, and due to the increase of micro-hardness, so confirming the efficiency of using the suggested scheme of coating application and the given type of ultra-dispersed fillers when chromium-plating.

Low Conductive Thermal Barrier Coatings Produced by Ion Beam Assisted EB-PVD with Controlled Porosity, Microstructure Refinement and Alloying Additions for High Temperature Applications

NASA Technical Reports Server (NTRS)

Wolfe, Douglas E.; Singh, Jogender

2005-01-01

Various advanced Hafnia-based thermal barrier coatings (TBC) were applied on nickel-based superalloy coupons by electron beam physical vapor deposition. In addition, microstructural modifications to the coating material were made in an effort to reduce the thermal conductivity of the coating materials. Various processing parameters and coating system modifications were made in order to deposit the alloyed TBC with the desired microstructure and thus coating performance, some of which include applying coatings at substrate temperatures of 1150 C on both PtAl and CoNiCrAlY bond coated samples, as well as using 8YSZ as a bond layer. In addition, various characterization techniques including thermal cyclic tests, scanning electron microscopy, x-ray diffraction, thermal conductivity, and reflectivity measurements were performed. Although the coating microstructure was never fully optimized due to funding being cut short, significant reductions in thermal conductivity were accomplished through both chemistry changes (composition) and microstructural modifications.

Mussel-Inspired Coating and Adhesion for Rechargeable Batteries: A Review.

PubMed

Jeong, You Kyeong; Park, Sung Hyeon; Choi, Jang Wook

2018-03-07

A significant effort is currently being invested to improve the electrochemical performance of classical lithium-ion batteries (LIBs) or to accelerate the advent of new chemistry-based post-LIBs. Regardless of the governing chemistry associated with charge storage, stable electrode-electrolyte interface and wet-adhesion among the electrode particles are universally desired for rechargeable batteries adopting liquid electrolytes. In this regard, recent studies have witnessed the usefulness of mussel-inspired polydopamine or catechol functional group in modifying the key battery components, such as active material, separator, and binder. In particular, the uniform conformal coating capability of polydopamine protects active materials from unwanted side reactions with electrolytes and increases the wettability of separators with electrolytes, both of which significantly contribute to the improvement of key battery properties. The wet-adhesion originating from catechol functional groups also largely increases the cycle lives of emerging high-capacity electrodes accompanied by huge volume expansion. This review summarizes the representative examples of mussel-inspired approaches in rechargeable batteries and offers central design principles of relevant coating and adhesion processes.

Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

PubMed

Li, Juchuan; Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-07-09

Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials.

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

Strong Flux Pinning of Nano-Sized Ysz Particles in Ybco Films Prepared by Mod Method

NASA Astrophysics Data System (ADS)

Ye, S.; Suo, H. L.; Liu, M.; Tang, X.; Wu, Z. P.; Zhao, Y.; Zhou, M. L.

The YBCO films with doped YSZ nanoparticles have been prepared successfully by metal organic doepositon method using trifluoroacetates (TFA-MOD) through dissolving Zr organic salt into the YBCO precursor solution. The doped films have well in-plane and out-plane textures detected by both XRD Φ-scan and ω-scan. The YSZ nanoparticles with the size of about 5 ~ 15 nm were observed on the surface of the YBCO films using both FE-SEM and TEM. By comparing the superconducting properties, it was found that the doped YBCO films had lower Tc than that of undoped YBCO films. However, as increasing the applied magnetic field, Jc of the doped YBCO films were much better than that of undoped one. The Jc was as higher as 2.5 times than that of undoped YBCO film at 77 K and 1 T applied field.

Study on Microstructure and Electrochemical Corrosion Behavior of PEO Coatings Formed on Aluminum Alloy

NASA Astrophysics Data System (ADS)

Xiang, N.; Song, R. G.; Li, H.; Wang, C.; Mao, Q. Z.; Xiong, Y.

2015-12-01

Plasma electrolytic oxidation (PEO) treated 6063 aluminum alloy was applied in a silicate- and borate-based alkaline solution. The microstructure and electrochemical corrosion behavior were studied by scanning electron microscopy, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization techniques. The results showed that the silicate-based PEO coating was of a denser structure compared with that of borate-based PEO coating. In addition, the silicate-based PEO coating was composed of more phased (Al9Si) than borate-based PEO coating. The results of corrosion test indicated that the silicate-based PEO coating provided a superior protection to 6063 aluminum alloy substrate, while borate-based PEO coating with a porous structure showed an inferior conservancy against corrosive electrolyte. Furthermore, the EIS tests proved that both coatings were capable to resist the aggressive erosion in 0.5 M NaCl solution after 72 h of immersion. However, the borate-based PEO coating could not provide sufficient protection to the substrate after 72-h immersion in 1 M NaCl solution.

One-pot synthesis of carbon-coated nanosized LiTi2(PO4)3 as anode materials for aqueous lithium ion batteries

NASA Astrophysics Data System (ADS)

Liu, Zhantao; Qin, Xusong; Xu, Hui; Chen, Guohua

2015-10-01

In this study, a one-pot sintering process incorporating sol-gel preparation route and in-situ carbon coating was proposed for the synthesis of carbon-coated nanosized LiTi2(PO4)3. Experimental results show that the prepared LiTi2(PO4)3 particles are of high crystallinity and well-coated by turbostratic carbon. Attributed to nanosized particles and enhanced conductivity provided by turbostratic carbon coating, the carbon-coated LiTi2(PO4)3 showed high rate performance and good cycling life in aqueous electrolyte. Particularly, the carbon-coated LiTi2(PO4)3 exhibited initial specific capacities of 103 and 89 mAh g-1, and retained 80.6% and 97% of the initial capacities after 120 cycles at 1C and 10C in aqueous electrolyte, respectively. The high rate performance and good cycling life of carbon-coated LiTi2(PO4)3 in aqueous electrolyte reveal its potential as negative electrode in aqueous lithium-ion batteries for electric vehicles and industrial-scale energy storage systems.

Effects of different electrolytes for micro-arc oxidation on the bond strength between titanium and porcelain.

PubMed

Yuan, Xiaohui; Tan, Fei; Xu, Haitao; Zhang, Shaojun; Qu, Fuzhen; Liu, Jie

2017-07-01

The aim of this study is to investigate the effects of different electrolytes on the titanium-porcelain bond strength after micro-arc oxidation (MAO) treatment. Three electrolytes at the same concentration were used as MAO reaction solutions: Na 2 SiO 3 , KF, and MgSiF 6 . Blasting treatment was chosen as a control. After MAO treatment in each electrolyte, the titanium-porcelain bond strengths were measured by the three-point bending test, as described in ISO 9693. The morphologies and elemental compositions of the MAO coating on the titanium substrate were evaluated by scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). The interface between the titanium and porcelain was also observed by SEM and EDS. The MAO coatings created in different electrolytes exhibited completely different morphologies and compositions. The bond strengths of the Na 2 SiO 3 and MgSiF 6 groups were significantly higher than those of the other groups (p<0.05). Additionally, the titanium-porcelain interfaces were compact in the former two groups, whereas pores and cracks were visible at the interfaces in the other groups. These results indicate that MAO treatment with an appropriate electrolyte could be an effective method to increase the titanium-porcelain bonding strength. According to ISO 9693, titanium-porcelain restorations subjected to MAO treatment with an appropriate electrolyte could be appropriate for clinical use. Copyright © 2016 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Computer-Assisted Optimization of Electrodeposited Hydroxyapatite Coating Parameters on Medical Alloys

NASA Astrophysics Data System (ADS)

Coşkun, M. İbrahim; Karahan, İsmail H.; Yücel, Yasin; Golden, Teresa D.

2016-04-01

CoCrMo bio-metallic alloys were coated with a hydroxyapatite (HA) film by electrodeposition using various electrochemical parameters. Response surface methodology and central composite design were used to optimize deposition parameters such as electrolyte pH, deposition potential, and deposition time. The effects of the coating parameters were evaluated within the limits of solution pH (3.66 to 5.34), deposition potential (-1.13 to -1.97 V), and deposition time (6.36 to 73.64 minutes). A 5-level-3-factor experimental plan was used to determine ideal deposition parameters. Optimum conditions for the deposition parameters of the HA coating with high in vitro corrosion performance were determined as electrolyte pH of 5.00, deposition potential of -1.8 V, and deposition time of 20 minutes.

Safe and Durable High-Temperature Lithium-Sulfur Batteries via Molecular Layer Deposited Coating.

PubMed

Li, Xia; Lushington, Andrew; Sun, Qian; Xiao, Wei; Liu, Jian; Wang, Biqiong; Ye, Yifan; Nie, Kaiqi; Hu, Yongfeng; Xiao, Qunfeng; Li, Ruying; Guo, Jinghua; Sham, Tsun-Kong; Sun, Xueliang

2016-06-08

Lithium-sulfur (Li-S) battery is a promising high energy storage candidate in electric vehicles. However, the commonly employed ether based electrolyte does not enable to realize safe high-temperature Li-S batteries due to the low boiling and flash temperatures. Traditional carbonate based electrolyte obtains safe physical properties at high temperature but does not complete reversible electrochemical reaction for most Li-S batteries. Here we realize safe high temperature Li-S batteries on universal carbon-sulfur electrodes by molecular layer deposited (MLD) alucone coating. Sulfur cathodes with MLD coating complete the reversible electrochemical process in carbonate electrolyte and exhibit a safe and ultrastable cycle life at high temperature, which promise practicable Li-S batteries for electric vehicles and other large-scale energy storage systems.

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.

Printed environmentally friendly supercapacitors with ionic liquid electrolytes on paper

NASA Astrophysics Data System (ADS)

Pettersson, F.; Keskinen, J.; Remonen, T.; von Hertzen, L.; Jansson, E.; Tappura, K.; Zhang, Y.; Wilén, C.-E.; Österbacka, R.

2014-12-01

Environmentally friendly supercapacitors are fabricated using commercial grade aluminum coated paper as a substrate and symmetrical activated carbon electrodes as large area electrodes. Different choline chloride-based eutectic solvents are used as electrolyte. These are inexpensive, environmentally friendly and have a larger operating window compared to that of water electrolytes. As the entire device is printed and the materials used are inexpensive, both small- and large-area power sources can be fabricated to be used in cheap, disposable and recyclable devices. Supercapacitors with different eutectic solvents are measured using cyclic charge-discharge and impedance spectroscopy measurements and compared to one widely used and one "green" imidazolium ionic liquid; EMIM:TFSI and EcoEng 212™, respectively. A mixture of ethylene glycol and choline chloride, Glyceline™, show the highest capacitance and power densities of the electrolytes being tested, including the imidazolium alternatives.

Use of Repeated Fluoropolymer Suspensions to Obtain Composite Electrochemical Coating Based on Zinc

NASA Astrophysics Data System (ADS)

Musikhina, T. A.; Zemtsova, E. A.; Fuks, C. L.

2017-11-01

This article deals with the issues of utilization of the waste products of fluoropolymers, namely, the suspensions of fluoroplasts that have lost their consumer properties. Such waste is recommended to be used as a filler of zinc coatings to provide increased corrosion resistance. Using the method of mathematical planning of the experiment, the authors establish the optimal compositions of galvanizing chloride-ammonium electrolytes to obtain the corrosion-resistant composite electrochemical coatings (CEC) of zinc-fluoropolymer. As a result, coatings with a finely crystalline structure were obtained differing in the distribution pattern on the surface of the samples and depending on the variation in the zinc concentration in the electrolytes. The samples of steel reinforcement with the zinc-fluoropolymer coating were tested on corrosion resistance. The increase of anticorrosive properties in CEC zinc-fluoropolymer and a slight decrease in microhardness were indicated.

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

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

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

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE PAGES

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...

2018-04-24

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Preparation of immobilized coating Fenton-like catalyst for high efficient degradation of phenol.

PubMed

Wang, Jiankang; Yao, Zhongping; Wang, Yajing; Xia, Qixing; Chu, Huiya; Jiang, Zhaohua

2017-05-01

In this study, solid acid amorphous Fe 3 O 4 /SiO 2 ceramic coating decorated with sulfur on Q235 carbon steel as Fenton-like catalyst for phenol degradation was successfully prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte containing Na 2 S 2 O 8 as sulfur source. The surface morphology and phase composition were characterized by SEM, EDS, XRD and XPS analyses. NH 3 -TPD was used to evaluate surface acidity of PEO coating. The results indicated that sulfur decorated amorphous Fe 3 O 4 /SiO 2 ceramic coatings with porous structure and higher acid strength had the similar pore size and the surface became more and more uneven with the increase of Na 2 S 2 O 8 in the silicate electrolyte. The Fenton-like catalytic activity of sulfur decorated PEO coatings was also evaluated. In contrast to negligible catalytic activity of sulfur undecorated PEO coating, catalytic activity of sulfur decorated PEO coating was excellent and PEO coating prepared with 3.0 g Na 2 S 2 O 8 had the highest catalytic activity which could degrade 99% of phenol within 8 min under circumneutral pH. The outstanding performance of sulfur decorated PEO coating was attributed to strong acidic microenvironment and more Fe 2+ on the surface. The strong acid sites played a key factor in determining catalytic activity of catalyst. In conclusion, rapid phenol removal under circumneutral pH and easier separation endowed it potential application in wastewater treatment. In addition, this strategy of preparing immobilized solid acid coating could provide guidance for designing Fenton-like catalyst with excellent catalytic activity and easier separation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation of protective composite coatings with the use of SPTFE suspensions

NASA Astrophysics Data System (ADS)

Nadaraia, K. V.; Mashtalyar, D. V.; Sinebryukhov, S. L.; Gnedenkov, S. V.

2017-09-01

The method of protective composite coatings formation with the use of the plasma electrolytic oxidation (PEO) and subsequent treatment in isopropanol or aqueous suspension of the superdispersed polytetrafluoroethylene (SPTFE) have been developed. Morphological, electrochemical and tribological studies, as well as wetting ability of the protective coatings have been carried out. The obtained results corroborated the increase of the corrosion and wear resistance parameters for the polymer-containing coating in comparison with the base PEO-coating and uncoated material.

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

PubMed

Aydin, Halit; Korte, Carsten; Janek, Jürgen

2013-06-01

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

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

PubMed Central

Aydin, Halit; Korte, Carsten; Janek, Jürgen

2013-01-01

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

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.

Microstructure and corrosion behavior of coated AZ91 alloy by microarc oxidation for biomedical application

NASA Astrophysics Data System (ADS)

Wang, Y. M.; Wang, F. H.; Xu, M. J.; Zhao, B.; Guo, L. X.; Ouyang, J. H.

2009-08-01

Magnesium and its alloy currently are considered as the potential biodegradable implant materials, while the accelerated corrosion rate in intro environment leads to implant failure by losing the mechanical integrity before complete restoration. Dense oxide coatings formed in alkaline silicate electrolyte with and without titania sol addition were fabricated on magnesium alloy using microarc oxidation process. The microstructure, composition and degradation behavior in simulated body fluid (SBF) of the coated specimens were evaluated. It reveals that a small amount of TiO 2 is introduced into the as-deposited coating mainly composed of MgO and Mg 2SiO 4 by the addition of titania sol into based alkaline silicate electrolytic bath. With increasing concentration of titania sol from 0 to 10 vol.%, the coating thickness decreases from 22 to 18 μm. Electrochemical tests show that the Ecorr of Mg substrate positively shifted about 300˜500 mV and icorr lowers more than 100 times after microarc oxidation. However, the TiO 2 modified coatings formed in electrolyte containing 5 and 10 vol.% titania sol indicate an increasing worse corrosion resistance compared with that of the unmodified coating, which is possibly attributed to the increasing amorphous components caused by TiO 2 involvement. The long term immersing test in SBF is consistent with the electrochemical test, with the coated Mg alloy obviously slowing down the biodegradation rate, meanwhile accompanied by the increasing damage trends in the coatings modified by 5 and 10 vol.% titania sol.

A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment

NASA Astrophysics Data System (ADS)

Liu, Zhenmin; Gao, Wei

2006-12-01

A novel Ni based coating - plasma electrolytic oxidation (PEO) pre-treatment followed by electroless nickel (EN) plating - has been developed to produce pore free Ni coatings on AZ91 magnesium alloy. The application of the PEO film between the nickel coating and the substrate acts as an effective barrier and catalytic layer for the subsequent nickel plating. The potentiodynamic tests indicated that the corrosion current density of the PEO + EN plating on AZ91 decreased by almost two orders of magnitudes compared to the traditional EN coating. Salt fog spray testing further proved this improvement. More importantly, the new technique does not use Cr +6 and HF in its pretreatment, therefore is a much environmentally friendlier process.

Atomic Layer Deposition Alumina-Passivated Silicon Nanowires: Probing the Transition from Electrochemical Double-Layer Capacitor to Electrolytic Capacitor.

PubMed

Gaboriau, Dorian; Boniface, Maxime; Valero, Anthony; Aldakov, Dmitry; Brousse, Thierry; Gentile, Pascal; Sadki, Said

2017-04-19

Silicon nanowires were coated by a 1-5 nm thin alumina layer by atomic layer deposition (ALD) in order to replace poorly reproducible and unstable native silicon oxide by a highly conformal passivating alumina layer. The surface coating enabled probing the behavior of symmetric devices using such electrodes in the EMI-TFSI electrolyte, allowing us to attain a large cell voltage up to 6 V in ionic liquid, together with very high cyclability with less than 4% capacitance fade after 10 6 charge/discharge cycles. These results yielded fruitful insights into the transition between an electrochemical double-layer capacitor behavior and an electrolytic capacitor behavior. Ultimately, thin ALD dielectric coatings can be used to obtain hybrid devices exhibiting large cell voltage and excellent cycle life of dielectric capacitors, while retaining energy and power densities close to the ones displayed by supercapacitors.

Electrodeposition and characterization of Ni-Mo-ZrO2 composite coatings

NASA Astrophysics Data System (ADS)

Laszczyńska, A.; Winiarski, J.; Szczygieł, B.; Szczygieł, I.

2016-04-01

Ni-Mo-ZrO2 composite coatings were produced by electrodeposition technique from citrate electrolytes containing dispersed ZrO2 nanopowder. The influence of deposition parameters i.e. concentration of molybdate and ZrO2 nanoparticles in the electrolyte, bath pH and deposition current density on the composition and surface morphology of the coating has been investigated. The structure, microhardness and corrosion properties of Ni-Mo-ZrO2 composites with different molybdenum and ZrO2 content have been also examined. It was found that ZrO2 content in the deposit is increased by rising the nanoparticles concentration in the plating solution up to 20 g dm-3. An increase in molybdate concentration in the electrolyte affects negatively the amount of codeposited ZrO2 nanoparticles. The correlation between the deposition current efficiency and ZrO2 content in the composite coating has been also observed. A decrease in deposition current efficiency leads to deposition of Ni-Mo-ZrO2 composite with low nanoparticles content. This may be explained by formation of higher amounts of gas bubbles on the cathode surface, which prevent the adsorption of ZrO2 nanoparticles on the growing deposit. The XRD analysis revealed that all the studied Ni-Mo-ZrO2 coatings were composed of a single, nanocrystalline phase with FCC structure. It was found that the incorporation of ZrO2 nanoparticles into Ni-Mo alloy matrix affects positively the microhardness and also slightly improves the corrosion properties of Ni-Mo alloy coating.

The properties of electrodeposited Zn-Co coatings

NASA Astrophysics Data System (ADS)

Mahieu, J.; de Wit, K.; de Cooman, B. C.; de Boeck, A.

1999-10-01

The possibility of increasing the corrosion resistance of automotive sheet steel by electrodepositing with Zn-Co alloy coatings was investigated. Process variables during electrodeposition such as current density, electrolyte flow rate, and pH were varied in order to examine their influence on the electroplating process. Cobalt contents varying from 0.2 to 7 wt% were easily obtained. The influence of these process parameters on the characteristics of the coating could be related to the hydroxide suppression mechanism for anomalous codeposition. The structure and the morphology of the coatings were determined using SEM and XRD analysis. Application properties important for coating systems used in the automotive industry, such as friction behavior, adhesion, and corrosion behavior, were investigated on coatings with varying cobalt content. The corrosion resistance of the Zn-Co alloy layers was found to be better than that of pure zinc coatings.

Electrolytic cell stack with molten electrolyte migration control

DOEpatents

Kunz, H. Russell; Guthrie, Robin J.; Katz, Murray

1988-08-02

An electrolytic cell stack includes inactive electrolyte reservoirs at the upper and lower end portions thereof. The reservoirs are separated from the stack of the complete cells by impermeable, electrically conductive separators. Reservoirs at the negative end are initially low in electrolyte and the reservoirs at the positive end are high in electrolyte fill. During stack operation electrolyte migration from the positive to the negative end will be offset by the inactive reservoir capacity. In combination with the inactive reservoirs, a sealing member of high porosity and low electrolyte retention is employed to limit the electrolyte migration rate.

Electrolytic cell stack with molten electrolyte migration control

DOEpatents

Kunz, H.R.; Guthrie, R.J.; Katz, M.

1987-03-17

An electrolytic cell stack includes inactive electrolyte reservoirs at the upper and lower end portions thereof. The reservoirs are separated from the stack of the complete cells by impermeable, electrically conductive separators. Reservoirs at the negative end are initially low in electrolyte and the reservoirs at the positive end are high in electrolyte fill. During stack operation electrolyte migration from the positive to the negative end will be offset by the inactive reservoir capacity. In combination with the inactive reservoirs, a sealing member of high porosity and low electrolyte retention is employed to limit the electrolyte migration rate. 5 figs.

Bright metal coatings from sustainable electrolytes: the effect of molecular additives on electrodeposition of nickel from a deep eutectic solvent.

PubMed

Abbott, Andrew P; Ballantyne, Andrew; Harris, Robert C; Juma, Jamil A; Ryder, Karl S

2017-01-25

Organic and inorganic additives are often added to nickel electroplating solutions to improve surface finish, reduce roughness and promote uniform surface morphology of the coatings. Such additives are usually small molecules and often referred to as brighteners or levellers. However, there have been limited investigations into the effect of such additives on electrodeposition from ionic liquids (ILs) and deep eutectic solvents (DESs). Here we study the effect of four additives on electrolytic nickel plating from an ethyleneglycol based DES; these are nicotinic acid (NA), methylnicotinate (MN), 5,5-dimethylhydantoin (DMH) and boric acid (BA). The additives show limited influence on the bulk Ni(ii) speciation but have significant influence on the electrochemical behaviour of Ni deposition. Small concentrations (ca. 15 mM) of NA and MN show inhibition of Ni(ii) reduction whereas high concentrations of DMH and BA are required for a modest difference in behaviour from the additive free system. NA and MN also show that they significantly alter the nucleation and growth mechanism when compared to the additive free system and those with DMH and BA. Each of the additive systems had the effect of producing brighter and flatter bulk electrodeposits with increased coating hardness but XRD shows that NA and MN direct crystal growth to the [111] orientation whereas DMH and BA direct crystal growth to the [220] orientation.

Formation of protective composite coatings with the use of solution of TFE telomers

NASA Astrophysics Data System (ADS)

Mashtalyar, D. V.; Gnedenkov, S. V.; Sinebryukhov, S. L.; Nadaraia, K. V.; Kiryukhin, D. P.; Kushch, P. P.; Kichigina, G. A.; Buznik, V. M.

2017-09-01

This paper presents the method of fabricate and the results of investigation of electrochemical properties and wettability of the composite coatings obtained on the magnesium alloy by plasma electrolytic oxidation (PEO) and the use of the solution of tetrafluoroethylene (TFE) telomers. The fluoropolymer-containing coatings decrease corrosion current density, increase contact angle in comparison with the base PEO-coating and the bare alloy.

Development of YAG:Dy Thermographic Phosphor Coatings for Turbine Engine Applications

NASA Technical Reports Server (NTRS)

Eldridge, J. I.; Jenkins, T. P.; Allison, S. W.; Wolfe, D. E.; Jordan, E. H.

2012-01-01

The selection and development of thermographic phosphor coatings were pursued to meet the objective of demonstrating luminescence-decay-based temperature measurements up to 1300C on the surface of a vane in an operating demonstrator turbine engine. To meet this objective, YAG:Dy was selected based on the desirable luminescence performance observed for YAG:Dy powder: (1) excellent temperature sensitivity and intensity at operating turbine engine temperatures, (2) an emission peak at the relatively short wavelength of 456 nm, where the interference from background blackbody radiation is fairly low, and (3) its nearly single exponential decay which makes for a simple, reliable temperature calibration. However, implementation of YAG:Dy for surface temperature measurements required application of YAG:Dy as a coating onto the surface of a superalloy component with a preexisting yttria-stabilized zirconia (YSZ) thermal barrier coating (TBC). An inherent dilemma in producing a YAG:Dy coating is that coating processing is constrained to be performed at temperatures below (less than 1200C) what is considered safe for the superalloy component, much lower than temperatures used to produce the high quality crystalline powder. Therefore, YAG:Dy coatings tend to exhibit lower luminescence performance compared to well prepared YAG:Dy powder, and the luminescence performance of the coating will depend on the method of coating deposition. In this presentation, the luminescence performance of YAG:Dy coatings prepared by the different methods of (1) application of a binder-based YAG:Dy-containing paint, (2) solution precursor plasma spray (SPPS), and (3) electron-beam physical vapor deposition (EB-PVD) and the effect of post-deposition heat treatments will be discussed.

Microporous ceramic coated separators with superior wettability for enhancing the electrochemical performance of sodium-ion batteries

NASA Astrophysics Data System (ADS)

Suharto, Yustian; Lee, Yongho; Yu, Ji-Sang; Choi, Wonchang; Kim, Ki Jae

2018-02-01

Finding an alternative to glass fiber (GF) separators is a crucial factor for the fast commercialization of sodium-ion batteries (SIBs), because GF separators are too thick for use in SIBs, thereby decreasing the volumetric and gravimetric energy density. Here we propose a microporous composite separator prepared by introducing a polymeric coating layer of polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP co-polymer) with ZrO2 nanoparticles to a polyethylene (PE) separator. The coated separator efficiently enhances the cell performance of SIBs. The ZrO2 nanoparticles, finely dispersed on the polymeric coating layer, induce the formation of many micropores on the polymeric coating layer, suggesting that micropore formation on the coating layer renders the composite separator more open in structure. An ethylene carbonate/propylene carbonate liquid electrolyte for SIBs is not absorbed by PE separators even after 1 h of electrolyte droplet testing, while the proposed separator with many micropores is completely wetted by the electrolyte. Sodium ion migration across the composite separator is therefore effectively enhanced by the formation of ion transfer pathways, which improve ionic conductivity. As a result, the microporous composite separator affords stable cycle performances and excellent specific capacity retention (95.8%) after 50 cycles, comparable to those offered by a SIB with a GF separator.

Experimental Evaluation of the Synthetic Solid Electrolyte Interface (SSEI) Concept for the Primary Ca-SOCl2 Battery System

DTIC Science & Technology

1988-12-01

coatings based on the Ca(Sr,Y)- Ge-S system can serve as an effective SSEI for Ca anodes in Ca-SOC12 primary cells using 1 M Ca(AlCl4 )2 as the electrolyte...I iy - LFI. CDY 4 EXPERIMENTAL EVALUATION OF THE SYNTHETIC SOLID ELECTROLYTE INTERFACE ( SSEI ) CONCEPT FOR THE PRIMARY Ca-SOC1 2 BA LERY SYSTEM...apply the concept of a synthetic solid electrolyte interface ( SSEI ) to overcome the problem of Ca corro- sion in Ca-SOC 2 primary cells. / To this end

High-temperature electrolysis of CO2-enriched mixtures by using fuel-electrode supported La0.6Sr0.4CoO3/YSZ/Ni-YSZ solid oxide cells

NASA Astrophysics Data System (ADS)

Kim, Si-Won; Bae, Yonggyun; Yoon, Kyung Joong; Lee, Jong-Ho; Lee, Jong-Heun; Hong, Jongsup

2018-02-01

To mitigate CO2 emissions, its reduction by high-temperature electrolysis using solid oxide cells is extensively investigated, for which excessive steam supply is assumed. However, such condition may degrade its feasibility due to massive energy required for generating hot steam, implying the needs for lowering steam demand. In this study, high-temperature electrolysis of CO2-enriched mixtures by using fuel-electrode supported La0.6Sr0.4CoO3/YSZ/Ni-YSZ solid oxide cells is considered to satisfy such needs. The effect of internal and external steam supply on its electrochemical performance and gas productivity is elucidated. It is shown that the steam produced in-situ inside the fuel-electrode by a reverse water gas shift reaction may decrease significantly the electrochemical resistance of dry CO2-fed operations, attributed to self-sustaining positive thermo-electrochemical reaction loop. This mechanism is conspicuous at low current density, whereas it is no longer effective at high current density in which total reactant concentrations for electrolysis is critical. To overcome such limitations, a small amount of external steam supply to the CO2-enriched feed stream may be needed, but this lowers the CO2 conversion and CO/H2 selectivity. Based on these results, it is discussed that there can be minimum steam supply sufficient for guaranteeing both low electrochemical resistance and high gas productivity.

Polarization study on doped lanthanum gallate electrolyte using impedance spectroscopy

NASA Astrophysics Data System (ADS)

Gong, Wenquan; Gopalan, Srikanth; Pal, Uday B.

2004-06-01

Alternating current complex impedance spectroscopy studies were conducted on symmetrical cells of the type [gas, electrode/La1-x Sr x Ga1-y Mg y O3 (LSGM) electrolyte/electrode, gas]. The electrode materials were slurry-coated on both sides of the LSGM electrolyte support. The electrodes selected for this investigation are candidate materials for solid oxide fuel cell (SOFC) electrodes. Cathode materials include La1-x Sr x MnO3 (LSM), La1-x Sr x Co y Fe1-y O3 (LSCF), a two-phase particulate composite consisting of LSM and doped-lanthanum gallate (LSGM), and LSCF + LSGM. Pt metal electrodes were also used for the purpose of comparison. Anode material investigated was the Ni + Ce0.85Gd0.15O2 composite. The study revealed important details pertaining to the charge-transfer reactions that occur in such electrodes. The information obtained can be used to design electrodes for intermediate temperature SOFCs based on LSGM electrolytes.

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.

Impacts of electrode coating irregularities on polymer electrolyte membrane fuel cell lifetime using quasi in-situ infrared thermography and accelerated stress testing

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

Phillips, Adam; Ulsh, Michael; Neyerlin, K. C.

In-line quality control diagnostics for roll-to-roll (R2R) manufacturing techniques will play a key role in the future commercialization of the polymer electrolyte membrane fuel cell (PEMFC) used in automotive applications. These diagnostics monitor the fabrication of the membrane electrode assembly (MEA), which detect and flag any non-uniformity that may potentially harm PEMFC performance and/or lifetime. This will require quantitative thresholds and a clear distinction between harmful defects and harmless coating irregularities. Thus, novel fuel cell hardware with quasi in-situ infrared (IR) thermography capabilities is utilized to understand how bare spots in the cathode electrode impact MEA lifetime. An accelerated stressmore » test (AST) simulates chemical and mechanical degradation modes seen in vehicular operation. The actual open circuit voltage and rate of change of this voltage are used as in-situ indicators for MEA failure, enabling capture of the progression of failure point development. Bare spot coating irregularities located at the center of the electrode were found to have no impact on MEA lifetime when compared to a pristine MEA. However, MEA lifetime was found to be considerably shortened when these same irregularities are located at the cathode inlet and, especially, the anode inlet regions of the fuel cell.« less

Impacts of electrode coating irregularities on polymer electrolyte membrane fuel cell lifetime using quasi in-situ infrared thermography and accelerated stress testing

DOE PAGES

Phillips, Adam; Ulsh, Michael; Neyerlin, K. C.; ...

2018-03-02

In-line quality control diagnostics for roll-to-roll (R2R) manufacturing techniques will play a key role in the future commercialization of the polymer electrolyte membrane fuel cell (PEMFC) used in automotive applications. These diagnostics monitor the fabrication of the membrane electrode assembly (MEA), which detect and flag any non-uniformity that may potentially harm PEMFC performance and/or lifetime. This will require quantitative thresholds and a clear distinction between harmful defects and harmless coating irregularities. Thus, novel fuel cell hardware with quasi in-situ infrared (IR) thermography capabilities is utilized to understand how bare spots in the cathode electrode impact MEA lifetime. An accelerated stressmore » test (AST) simulates chemical and mechanical degradation modes seen in vehicular operation. The actual open circuit voltage and rate of change of this voltage are used as in-situ indicators for MEA failure, enabling capture of the progression of failure point development. Bare spot coating irregularities located at the center of the electrode were found to have no impact on MEA lifetime when compared to a pristine MEA. However, MEA lifetime was found to be considerably shortened when these same irregularities are located at the cathode inlet and, especially, the anode inlet regions of the fuel cell.« less

Coating of tips for electrochemical scanning tunneling microscopy by means of silicon, magnesium, and tungsten oxides

NASA Astrophysics Data System (ADS)

Salerno, Marco

2010-09-01

Different combinations of metal tips and oxide coatings have been tested for possible operation in electrochemical scanning tunneling microscopy. Silicon and magnesium oxides have been thermally evaporated onto gold and platinum-iridium tips, respectively. Two different thickness values have been explored for both materials, namely, 40 and 120 nm for silicon oxide and 20 and 60 nm for magnesium oxide. Alternatively, tungsten oxide has been grown on tungsten tips via electrochemical anodization. In the latter case, to seek optimal results we have varied the pH of the anodizing electrolyte between one and four. The oxide coated tips have been first inspected by means of scanning electron microscopy equipped with microanalysis to determine the morphological results of the coating. Second, the coated tips have been electrically characterized ex situ for stability in time by means of cyclic voltammetry in 1 M aqueous KCl supporting electrolyte, both bare and supplemented with K3[Fe(CN)6] complex at 10 mM concentration in milliQ water as an analyte. Only the tungsten oxide coated tungsten tips have shown stable electrical behavior in the electrolyte. For these tips, the uncoated metal area has been estimated from the electrical current levels, and they have been successfully tested by imaging a gold grating in situ, which provided stable results for several hours. The successful tungsten oxide coating obtained at pH=4 has been assigned to the WO3 form.

Coating of tips for electrochemical scanning tunneling microscopy by means of silicon, magnesium, and tungsten oxides.

PubMed

Salerno, Marco

2010-09-01

Different combinations of metal tips and oxide coatings have been tested for possible operation in electrochemical scanning tunneling microscopy. Silicon and magnesium oxides have been thermally evaporated onto gold and platinum-iridium tips, respectively. Two different thickness values have been explored for both materials, namely, 40 and 120 nm for silicon oxide and 20 and 60 nm for magnesium oxide. Alternatively, tungsten oxide has been grown on tungsten tips via electrochemical anodization. In the latter case, to seek optimal results we have varied the pH of the anodizing electrolyte between one and four. The oxide coated tips have been first inspected by means of scanning electron microscopy equipped with microanalysis to determine the morphological results of the coating. Second, the coated tips have been electrically characterized ex situ for stability in time by means of cyclic voltammetry in 1 M aqueous KCl supporting electrolyte, both bare and supplemented with K(3)[Fe(CN)(6)] complex at 10 mM concentration in milliQ water as an analyte. Only the tungsten oxide coated tungsten tips have shown stable electrical behavior in the electrolyte. For these tips, the uncoated metal area has been estimated from the electrical current levels, and they have been successfully tested by imaging a gold grating in situ, which provided stable results for several hours. The successful tungsten oxide coating obtained at pH=4 has been assigned to the WO(3) form.

Interaction of High Flash Point Electrolytes and PE-Based Separators for Li-Ion Batteries

PubMed Central

Hofmann, Andreas; Kaufmann, Christoph; Müller, Marcus; Hanemann, Thomas

2015-01-01

In this study, promising electrolytes for use in Li-ion batteries are studied in terms of interacting and wetting polyethylene (PE) and particle-coated PE separators. The electrolytes are characterized according to their physicochemical properties, where the flow characteristics and the surface tension are of particular interest for electrolyte–separator interactions. The viscosity of the electrolytes is determined to be in a range of η = 4–400 mPa∙s and surface tension is finely graduated in a range of γL = 23.3–38.1 mN∙m−1. It is verified that the technique of drop shape analysis can only be used in a limited matter to prove the interaction, uptake and penetration of electrolytes by separators. Cell testing of Li|NMC half cells reveals that those cell results cannot be inevitably deduced from physicochemical electrolyte properties as well as contact angle analysis. On the other hand, techniques are more suitable which detect liquid penetration into the interior of the separator. It is expected that the results can help fundamental researchers as well as users of novel electrolytes in current-day Li-ion battery technologies for developing and using novel material combinations. PMID:26343636

Transport, retention, and long-term release behavior of polymer-coated silver nanoparticles in saturated quartz sand: The impact of natural organic matters and electrolyte.

PubMed

Hou, Jun; Zhang, Mingzhi; Wang, Peifang; Wang, Chao; Miao, Lingzhan; Xu, Yi; You, Guoxiang; Lv, Bowen; Yang, Yangyang; Liu, Zhilin

2017-10-01

This study investigated the transport and long-term release of stabilized silver nanoparticles (AgNPs), including polyvinylpyrrolidone-coated AgNPs (PVP-AgNPs) and bare AgNPs (Bare-AgNPs), in the presence of natural organic matters (NOMs; both humic acids (HA) and alginate (Alg)) and an electrolyte (Ca 2+ ) in a sand-packed column. Very low breakthrough rate (C/C 0 ) of AgNPs (below 0.04) occurred in the absence of NOM and the electrolyte. Increasing the concentration of NOM and decreasing the influent NOM solution's ionic strength (IS) reduced the retention of AgNPs. The reduced NP retention at high NOM and low IS was mainly attributed to the increased energy barrier between the AgNPs and the sand grain surface. Notably, the retention of PVP-AgNPs was enhanced at high Alg concentration and low IS, which mainly resulted from the improved hydrophobicity that could increase the interaction between the PVP-AgNPs and the collector. The total release amount of PVP-AgNPs (10.03%, 9.50%, 28.42%, 6.37%) and Bare-AgNPs (3.28%, 2.58%, 10.36%, 1.54%) were gained when exposed to four kinds of NOM solutions, including deionized water, an electrolyte solution (1 mM Ca 2+ ), HA with an electrolyte (1 mM Ca 2+ ), and a Alg (40 mg/L) solution with an electrolyte (1 mM Ca 2+ ). The long-term release of retained silver nanoparticles in the quartz sand was mostly through the form of released Ag NPs. The factors that increased the mobility of AgNPs in quartz sand could improve the release of the AgNPs. The release of AgNPs had no significant change in the presence Ca 2+ but were increased in the presence of HA. The Alg slightly decreased the release of AgNPs by increasing the hydrophobicity of AgNPs. The results of the study indicated that all the tested NOM and Ca 2+ have prominent influence on the transport and long-term release behavior of silver nanoparticles in saturated quartz sand. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Investigation into the role of primer, pre-treatments and coating microstructure in preventing cut edge corrosion of organically coated steels

NASA Astrophysics Data System (ADS)

Khan, Khalil

Investigations were carried out to assess the role of primer, pretreatments and coating microstructure in preventing cutedge corrosion of chrome free organically coated steels. Zinc runoff was monitored from a range of organically coated steels with a large cutedge length exposed over 18 months at Swansea University roof top site. The zinc in the runoff leaches from the zinc-aluminium alloy coating of the substrate. The paint systems' corrosion performance was assessed by monitoring the levels of zinc in the runoff. Consequently the levels of zinc reflected the effectiveness of the applied paint system against corrosion. Runoff was high in initial months with zinc levels reducing with time due to the build up of corrosion products that hindered the progress of corrosion. An accelerated laboratory test using a distilled water electrolyte was developed that predict long-term external weathering runoff from panels of a range of organically coated steels. The corrosion mechanisms of a variety of organically coated Galvalloy steel have been examined using the scanning vibrating electrode technique (SVET) in 0.1%NaCI. The corrosion behaviour of a coating is related to the zinc-aluminium alloy coating structure and combination of pretreatment and primer. The SVET has been used to assess total zinc loss and the corrosion rate for a comparative measure of organically coating system performance. A correlation has been developed from SVET 24hour experiment data to accelerated weathering data and external weather data that can aid more accurately predicting the in service life of the product. Also considered were the effects of electrolyte conductivity on the morphology of corrosion on pure zinc. A mathematical model has been developed to predict corrosion pit population. Altered microstructure of solidifying zinc aluminium alloy melt via ultrasonication was investigated. Ultrasound irradiation significantly altered the final microstructure. The influence of morphed

Novel technique for preparing Ca- and P-containing ceramic coating on Ti-6Al-4V by micro-arc oxidation.

PubMed

Yu, Sirong; Yang, Xizhen; Yang, Long; Liu, Yaohui; Yu, Yingjie

2007-11-01

A novel technique for preparing the Ca- and P-containing ceramic coating on Ti-6Al-4V alloy by micro-arc oxidation (MAO) was developed successfully in this paper. In the new technique, Ti alloy first was micro-arc oxidated in P-containing electrolyte, and then it was micro-arc oxidated in Ca-containing electrolyte. This technique can avoid the undesired chemical reaction between Ca-containing salt and P-containing salt in electrolyte. The surface morphologies, composition, and phases of MAO coatings were studied by means of SEM, EDS, and XRD. The results show that the P- and Ca-containing coating on Ti-6Al-4V alloy contains Ti, TiO(2) (rutile), alpha-Ca(PO(3))(2), CaTiO(3), and AlTi(3). There are many small and uniform pores in the coating. Most of these pores are coterminous. The microhardness of the coating is 720 HV and higher than that of Ti-6Al-4V alloy (220 HV). The coating is more wear-resistant than Ti-6Al-4V alloy under the lubricant of the artificial saliva and not easy to desquamate from the substrate of Ti-6Al-4V alloy.

High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

PubMed

Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

2013-06-21

Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

Robust Pinhole-free Li3N Solid Electrolyte Grown from Molten Lithium

PubMed Central

2017-01-01

Lithium metal is the ultimate anode choice for high energy density rechargeable lithium batteries. However, it suffers from inferior electrochemical performance and safety issues due to its high reactivity and the growth of lithium dendrites. It has long been desired to develop a materials coating on Li metal, which is pinhole-free, mechanically robust without fracture during Li metal deposition and stripping, and chemically stable against Li metal and liquid electrolytes, all while maintaining adequate ionic conductivity. However, such an ideal material coating has yet to be found. Here we report a novel synthesis method by reacting clean molten lithium foil directly with pure nitrogen gas to generate instantaneously a pinhole-free and ionically conductive α-Li3N film directly bonded onto Li metal foil. The film consists of highly textured large Li3N grains (tens of μm) with (001) crystalline planes parallel to the Li metal surface. The bonding between textured grains is strong, resulting in a mechanically robust film which does not crack even when bent to a 0.8 cm curvature radius and is found to maintain pinhole-free coverage during Li metal deposition and stripping. The measured ionic conductivity is up to 5.2 × 10–4 S cm–1, sufficient for maintaining regular current densities for controllable film thicknesses ranging from 2 to 30 μm. This Li3N coating is chemically stable, isolating the reactive metallic lithium from liquid electrolyte, prevents continuous electrolyte consumption during battery cycling, and promotes dendrite-free uniform lithium plating/stripping underneath. We demonstrated Li|Li4Ti5O12 cells with stable and flat potential profiles for 500 cycles without capacity decay or an increase in potential hysteresis. PMID:29392181

Corrosion resistance of the microarc oxidation coatings prepared on magnesium alloy

NASA Astrophysics Data System (ADS)

Lv, Ying; Li, Jun Gang; Wu, Ming Zhong; Ma, Zhen; Zhang, Jing Qiang; Wang, Le Le

2018-06-01

Ceramic coatings were prepared on the surface of AZ91D magnesium alloy by microarc oxidation technology. The effects of different voltages on morphology, phase composition and thickness of the coatings were characterized by SEM and XRD. The corrosion resistance of the coatings was measured by electrochemical workstation. Results indicated that the microarc oxidation coatings prepared in sodium silicate electrolyte exhibited porous surface and mainly comprised MgO, Mg2SiO4 and a small amount of MgAl2O4. The thickness of the oxide coatings increased rapidly with the increase of voltage. The coating prepared at 400V voltage had good electrochemical corrosion resistance in 3.5wt% NaCl solution.

Process for forming a metal compound coating on a substrate

DOEpatents

Sharp, D.J.; Vernon, M.E.; Wright, S.A.

1988-06-29

A method of coating a substrate with a thin layer of a metal compound by forming a dispersion of an electrophoretically active organic colloid and a precursor of the metal compound in an electrolytic cell in which the substrate is an electrode. Upon application of an electric potential, the electrode is coated with a mixture of the organic colloid and the precursor to the metal compound, and the coated substrate is then heated in the presence of an atmosphere or vacuum to decompose the organic colloid and form a coating of either a combination of metal compound and carbon, or optionally forming a porous metal compound coating by heating to a temperature high enough to chemically react the carbon.

High current density cathode for electrorefining in molten electrolyte

DOEpatents

Li, Shelly X.

2010-06-29

A high current density cathode for electrorefining in a molten electrolyte for the continuous production and collection of loose dendritic or powdery deposits. The high current density cathode eliminates the requirement for mechanical scraping and electrochemical stripping of the deposits from the cathode in an anode/cathode module. The high current density cathode comprises a perforated electrical insulated material coating such that the current density is up to 3 A/cm.sup.2.

Electrodeposited MCrAlY Coatings for Gas Turbine Engine Applications

NASA Astrophysics Data System (ADS)

Zhang, Y.

2015-11-01

Electrolytic codeposition is a promising alternative process for fabricating MCrAlY coatings. The coating process involves two steps, i.e., codeposition of CrAlY-based particles and a metal matrix of Ni, Co, or (Ni,Co), followed by a diffusion heat treatment to convert the composite coating to the desired MCrAlY microstructure. Despite the advantages such as low cost and non-line-of-sight, this coating process is less known than electron beam-physical vapor deposition and thermal spray processes for manufacturing high-temperature coatings. This article provides an overview of the electro-codeposited MCrAlY coatings for gas turbine engine applications, highlighting the unique features of this coating process and some important findings in the past 30 years. Challenges and research opportunities for further optimization of this type of MCrAlY coatings are also discussed.

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.

Electrolyte for batteries with regenerative solid electrolyte interface

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

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

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.

Zirconia coating stabilized super-iron alkaline cathodes

NASA Astrophysics Data System (ADS)

Yu, Xingwen; Licht, Stuart

A low-level zirconia coating significantly stabilizes high energy alkaline super-iron cathodes, and improves the energy storage capacity of super-iron batteries. Zirconia coating is derived from ZrCl 4 in an organic medium through the conversion of ZrCl 4 to ZrO 2. In alkaline battery system, ZrO 2 provides an intact shield for the cathode materials and the hydroxide shuttle through the coating sustains alkaline cathode redox chemistry. Most super-iron cathodes are solid-state stable, such as K 2FeO 4 and Cs 2FeO 4, but tend to be passivated in alkaline electrolyte due to the formation of Fe(III) over layer. Zirconia coating effectively enhances the stability of these super-iron cathodes. However, for solid-state unstable super-iron cathode (e.g. BaFeO 4), only a little stabilization effect of zirconia coating is observed.

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.

LOW TEMPERATURE CATHODE SUPPORTED ELECTROLYTES

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

Harlan U. Anderson; Fatih Dogan; Vladimir Petrovsky

2002-03-31

This project has three main goals: Thin Films Studies, Preparation of Graded Porous Substrates and Basic Electrical Characterization and testing of Planar Single Cells. This period has continued to address the problem of making dense 1/2 to 5 {micro}m thick dense layers on porous substrates (the cathode LSM). Our current status is that we are making structures of 2-5 cm{sup 2} in area, which consist of either dense YSZ or CGO infiltrated into a 2-5 {micro}m thick 50% porous layer made of either nanoncrystalline CGO or YSZ powder. This composite structure coats a macroporous cathode or anode; which serves asmore » the structural element of the bi-layer structure. These structures are being tested as SOFC elements. A number of structures have been evaluated both as symmetrical and as button cell configuration. Results of this testing indicates that the cathodes contribute the most to cell losses for temperatures below 750 C. In this investigation different cathode materials were studied using impedance spectroscopy of symmetric cells and IV characteristics of anode supported fuel cells. Cathode materials studied included La{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (LSCF), La{sub 0.7}Sr{sub 0.2}MnO{sub 3} (LSM), Pr{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}O{sub 3} (PSCF), Sm{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF), and Yb{sub .8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF). A new technique for filtering the Fourier transform of impedance data was used to increase the sensitivity of impedance analysis. By creating a filter specifically for impedance spectroscopy the resolution was increased. The filter was tailored to look for specific circuit elements like R//C, Warburg, or constant phase elements. As many as four peaks can be resolved using the filtering technique on symmetric cells. It may be possible to relate the different peaks to material parameters, like the oxygen exchange coefficient. The cathode grouped in order from lowest to highest

Characterization of stainless steel surface processed using electrolytic oxidation and titanium complex ion solution

NASA Astrophysics Data System (ADS)

Kang, Yubin; Choi, Jaeyoung; Park, Jinju; Kim, Woo-Byoung; Lee, Kun-Jae

2017-09-01

This study attempts to improve the physical and chemical adhesion between metals and ceramics by using electrolytic oxidation and a titanium organic/inorganic complex ion solution on the SS-304 plate. Surface analysis confirmed the existence of the Tisbnd Osbnd Mx bonds formed by the bonding between the metal ions and the Ti oxide at the surface of the pre-processed SS plate, and improved chemical adhesion during ceramic coating was expected by confirming the presence of the carboxylic group. The adhesion was evaluated by using the ceramic coating solution in order to assess the improved adhesion of the SS plate under conditions. The results showed that both the adhesion and durability were largely improved in the sample processed with all the pre-processing steps, thus confirming that the physical and chemical adhesion between metals and ceramics can be improved by enhancing the physical roughness via electrolytic oxidation and pre-processing using a Ti complex ion solution.

Mechanical measurements on lithium phosphorous oxynitride coated silicon thin film electrodes for lithium-ion batteries during lithiation and delithiation

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

Al-Obeidi, Ahmed, E-mail: alobeidi@mit.edu; Thompson, Carl V., E-mail: reiner.moenig@kit.edu, E-mail: cthomp@mit.edu; Kramer, Dominik, E-mail: dominik.kramer@kit.edu

2016-08-15

The development of large stresses during lithiation and delithiation drives mechanical and chemical degradation processes (cracking and electrolyte decomposition) in thin film silicon anodes that complicate the study of normal electrochemical and mechanical processes. To reduce these effects, lithium phosphorous oxynitride (LiPON) coatings were applied to silicon thin film electrodes. Applying a LiPON coating has two purposes. First, the coating acts as a stable artificial solid electrolyte interphase. Second, it limits mechanical degradation by retaining the electrode's planar morphology during cycling. The development of stress in LiPON-coated electrodes was monitored using substrate curvature measurements. LiPON-coated electrodes displayed highly reproducible cycle-to-cyclemore » behavior, unlike uncoated electrodes which had poorer coulombic efficiency and exhibited a continual loss in stress magnitude with continued cycling due to film fracture. The improved mechanical stability of the coated silicon electrodes allowed for a better investigation of rate effects and variations of mechanical properties during electrochemical cycling.« less

Wear Resistance Properties Reinforcement Using Nano-Al/Cu Composite Coating in Sliding Bearing Maintenance.

PubMed

Liu, Hongtao; Li, Zhixiong; Wang, Jianmei; Sheng, Chenxing; Liu, Wanli

2018-03-01

Sliding bearing maintenance is crucial for reducing the cost and extending the service life. An efficient and practical solution is to coat a restorative agent onto the worn/damaged bearings. Traditional pure-copper (Cu) coating results in a soft surface and poor abrasion resistance. To address this issue, this paper presents a nano-composite repairing coating method. A series of nano-Al/Cu coatings were prepared on the surface of 45 steel by composite electro-brush plating (EBP). Their micro-hardness was examined by a MHV-2000 Vickers hardness tester, and tribological properties by a UMT-2M Micro-friction tester, 3D profiler and SEM. Then, the influence of processing parameters such as nano-particle concentration and coating thickness on the micro-hardness of nano-Al/Cu coating was analyzed. The experimental analysis results demonstrate that, when the nano-Al particle concentration in electrolyte was 10 g/L, the micro-hardness of the composite coating was 1.1 times as much as that of pure-Cu coating. When the Al nano-particle concentration in electrolyte was 20 g/L, the micro-hardness of the composite coating reached its maximum value (i.e., 231.6 HV). Compared with the pure-Cu coating, the hardness and wear resistance of the nano-composite coating were increased, and the friction coefficient and wear volume were decreased, because of the grain strengthening and dispersion strengthening. The development in this work may provide a feasible and effective nano-composite EBP method for sliding bearing repair.

High-Temperature Oxidation-Resistant and Low Coefficient of Thermal Expansion NiAl-Base Bond Coat Developed for a Turbine Blade Application

NASA Technical Reports Server (NTRS)

2003-01-01

is lower than that of the commercially used coating alloy 16-6. To examine the potential of NiAl-AlN-CoCrAlY as a bond coat, we subjected two samples to cyclic furnace testing. The furnace cycle consisted of 45 min at 1163 C (2125 F ) followed by 15 min of cooling out of the furnace. The current NASA baseline TBC is a NiCrAlY bond coat below the 7YSZ top coat. The average TBC life for this baseline coating on Ren N5 is 188 plus or minus 19 cycles. NiAl-AlN-CoCrAlY specimens coated with the same 7YSZ top coat were still intact even after 1000 cycles. Therefore, the NiAl-AlN-CoCrAlY as a bulk substrate material, exhibits more than 5 times the life of the current state-of-the-art material. The next step is to evaluate this material as a coating on the same superalloy substrate.

Electrolyte creepage barrier for liquid electrolyte fuel cells

DOEpatents

Li, Jian [Alberta, CA; Farooque, Mohammad [Danbury, CT; Yuh, Chao-Yi [New Milford, CT

2008-01-22

A dielectric assembly for electrically insulating a manifold or other component from a liquid electrolyte fuel cell stack wherein the dielectric assembly includes a substantially impermeable dielectric member over which electrolyte is able to flow and a barrier adjacent the dielectric member and having a porosity of less than 50% and greater than 10% so that the barrier is able to measurably absorb and chemically react with the liquid electrolyte flowing on the dielectric member to form solid products which are stable in the liquid electrolyte. In this way, the barrier inhibits flow or creepage of electrolyte from the dielectric member to the manifold or component to be electrically insulated from the fuel cell stack by the dielectric assembly.

Thermal Conductivity and Expansion Coefficient of (Sm1- x Yb x )2Ce2O7 Ceramics for Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Xiaoge, Chen; Hongsong, Zhang; Kun, Sun; Xudan, Dang; Haoming, Zhang; Bo, Ren; An, Tang

2017-12-01

In the current paper, the (Sm1- x Yb x )2Ce2O7 ceramics were prepared via sol-gel and high-temperature solid reaction methods. The phase composition, microstructure, thermal conductivity, and expansion coefficient were investigated. Results indicate that pure (Sm1- x Yb x )2Ce2O7 ceramics with single defect-fluorite structure are synthesized successfully. Owing to the phonon scattering caused by Yb addition, the thermal conductivity of (Sm1- x Yb x )2Ce2O7 ceramics decreases with increasing Yb2O3 content at identical temperatures, which is lower than that of YSZ. Due to the relatively low ionic radius of Yb3+ ions, the addition of Yb2O3 decreases the thermal expansion coefficient of (Sm1- x Yb x )2Ce2O7 ceramics, which is higher than that of 8YSZ. The synthesized (Sm1- x Yb x )2Ce2O7 ceramics can be explored as candidate materials for thermal barrier coatings.

Self-generated concentration and modulus gradient coating design to protect Si nano-wire electrodes during lithiation

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

Kim, Sung-Yup; Ostadhossein, Alireza; van Duin, Adri C. T.

2016-01-01

Surface coatings as artificial solid electrolyte interphases have been actively pursued as an effective way to improve the cycle efficiency of nanostructured Si electrodes for high energy density lithium ion batteries, where the mechanical stability of the surface coatings on Si is as critical as Si itself.

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.

Protective coatings for metal alloys and methods incorporating the same

DOEpatents

Seabaugh, Matthew M.; Ibanez, Sergio; Swartz, Scott L.

2015-06-09

An electrochemical device having one or more solid oxide fuel cells (SOFCs), each of the SOFCs including a cathode, an anode, and an electrolyte layer positioned between the cathode and anode; and at least one additional component comprising a metallic substrate having an electronically conductive, chromium-free perovskite coating deposited directly thereon. The perovskite coating has the formula ABO.sub.3, wherein A is a lanthanide element or Y, and B is a mixture of two or more transition elements, with the A site undoped by any alkaline earth element, and the perovskite coating exhibits limited or no ionic transport of oxygen.

Inorganic-Organic Coating via Molecular Layer Deposition Enables Long Life Sodium Metal Anode.

PubMed

Zhao, Yang; Goncharova, Lyudmila V; Zhang, Qian; Kaghazchi, Payam; Sun, Qian; Lushington, Andrew; Wang, Biqiong; Li, Ruying; Sun, Xueliang

2017-09-13

Metallic Na anode is considered as a promising alternative candidate for Na ion batteries (NIBs) and Na metal batteries (NMBs) due to its high specific capacity, and low potential. However, the unstable solid electrolyte interphase layer caused by serious corrosion and reaction in electrolyte will lead to big challenges, including dendrite growth, low Coulombic efficiency and even safety issues. In this paper, we first demonstrate the inorganic-organic coating via advanced molecular layer deposition (alucone) as a protective layer for metallic Na anode. By protecting Na anode with controllable alucone layer, the dendrites and mossy Na formation have been effectively suppressed and the lifetime has been significantly improved. Moreover, the molecular layer deposition alucone coating shows better performances than the atomic layer deposition Al 2 O 3 coating. The novel design of molecular layer deposition protected Na metal anode may bring in new opportunities to the realization of the next-generation high energy-density NIBs and NMBs.

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).

Self-healing effect of the protective inhibitor-containing coatings on Mg alloys

NASA Astrophysics Data System (ADS)

Gnedenkov, A. S.; Sinebryukhov, S. L.; Mashtalyar, D. V.; Gnedenkov, S. V.

2017-09-01

The method of self-healing coating formation on the surface of magnesium alloys on the base of plasma electrolytic oxidation (PEO) with subsequent impregnation of the obtained layer with inhibitor has been suggested. The protective and electrochemical properties of such coatings have been described. Localised Scanning Electrochemical Methods were used for determining the kinetics and mechanism of the self-healing process. The treatment with the solution containing inhibitor enables us to increase the protective properties of the PEO-coating in 30 times in the corrosion-active environment.

Sound Absorption Characteristics of Aluminum Foams Treated by Plasma Electrolytic Oxidation

PubMed Central

Jin, Wei; Liu, Jiaan; Wang, Zhili; Wang, Yonghua; Cao, Zheng; Liu, Yaohui; Zhu, Xianyong

2015-01-01

Open-celled aluminum foams with different pore sizes were fabricated. A plasma electrolytic oxidation (PEO) treatment was applied on the aluminum foams to create a layer of ceramic coating. The sound absorption coefficients of the foams were measured by an impedance tube and they were calculated by a transfer function method. The experimental results show that the sound absorption coefficient of the foam increases gradually with the decrease of pore size. Additionally, when the porosity of the foam increases, the sound absorption coefficient also increases. The PEO coating surface is rough and porous, which is beneficial for improvement in sound absorption. After PEO treatment, the maximum sound absorption of the foam is improved to some extent. PMID:28793653

A Fe3O4/FeAl2O4 composite coating via plasma electrolytic oxidation on Q235 carbon steel for Fenton-like degradation of phenol.

PubMed

Wang, Jiankang; Yao, Zhongping; Yang, Min; Wang, Yajing; Xia, Qixing; Jiang, Zhaohua

2016-08-01

The Fe3O4/FeAl2O4 composite coatings were successfully fabricated on Q235 carbon steel by plasma electrolytic oxidation technique and used to degrade phenol by Fenton-like system. XRD, SEM, and XPS indicated that Fe3O4 and FeAl2O4 composite coating had a hierarchical porous structure. The effects of various parameters such as pH, phenol concentration, and H2O2 dosage on catalytic activity were investigated. The results indicated that with increasing of pH and phenol content, the phenol degradation efficiency was reduced significantly. However, the degradation rate was improved with the addition of H2O2, but dropped with further increasing of H2O2. Moreover, 100 % removal efficiency with 35 mg/L phenol was obtained within 60 min at 303 K and pH 4.0 with 6.0 mmol/L H2O2 on 6-cm(2) iron oxide coating. The degradation process consisted of induction period and rapid degradation period; both of them followed pseudo-first-order reaction. Hydroxyl radicals were the mainly oxidizing species during phenol degradation by using n-butanol as hydroxyl radical scavenger. Based on Fe leaching and the reaction kinetics, a possible phenol degradation mechanism was proposed. The catalyst exhibited excellent stability.

Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-10-06

First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aidmore » of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.« less

Corrosion resistance of micro-arc oxidation coatings formed on aluminum alloy with addition of Al2O3

NASA Astrophysics Data System (ADS)

Zhang, Y.; Chen, Y.; Du, H. Q.; Zhao, YW

2018-03-01

Micro-arc oxidation (MAO) coatings were formed on the aluminum alloy in silicate-based electrolyte without and with the addition of Al2O3. It is showed that the coating produced in 7 g l‑1 Al2O3-containing electrolyte was of the most superior corrosion resistance. Besides, the corrosion properties of the coatings were studied by means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) test in both 0.5 M and 1 M NaCl solution. The results proved that the coating is capable to protect the substrate from the corrosion of aggressive Cl‑ in 0.5 M NaCl after 384 h immersion. However, it can not offer protection to the aluminum alloy substrate after 384 h immersion in 1 M NaCl solution. The schematic diagrams illustrate the corrosion process and matched well with the corrosion test results.

Stabilization of Silicon Carbide (SiC) micro- and nanoparticle dispersions in the presence of concentrated electrolyte.

PubMed

Vilinska, Annamaria; Ponnurangam, Sathish; Chernyshova, Irina; Somasundaran, Ponisseril; Eroglu, Damla; Martinez, Jose; West, Alan C

2014-06-01

Achieving a stable and robust dispersion of ultrafine particles in concentrated electrolytes is challenging due to the shielding of electrostatic repulsion. Stable dispersion of ultrafine particles in concentrated electrolytes is critical for several applications, including electro-codeposition of ceramic particles in protective metal coatings. We achieved the steric stabilization of SiC micro- and nano-particles in highly concentrated electroplating Watts solutions using their controlled coating with linear and branched polyethyleneimines (PEI) as dispersants. Branched polyethyleneimine of 60,000 MW effectively disperses both microparticles and nanoparticles at a concentration of 1000 ppm. However, lower polymer dosages and smaller polymers fail to disperse, presumably due to insufficient coverage and bridging flocculation. Dispersion stability correlates well with the adsorption density of PEI on microparticles. We discuss the results in the framework of DLVO theory and suggest possible dispersion mechanisms. However, though the dispersion is enhanced with extended adsorption time, the residual PEI in solution adversely affects electroplating. We overcome this drawback by precoating the particles with the polymer and resuspending them in Watts solution. With this novel approach, we obtained robust dispersions. These results offer new possibilities to control dispersion at high electrolyte concentration, as well as bring new insights into the dispersion phenomenon. Copyright © 2014 Elsevier Inc. All rights reserved.

Electrochemical properties of lithium iron phosphate cathode material using polymer electrolyte

NASA Astrophysics Data System (ADS)

Kim, Jae-Kwang; Choi, Jae-Won; Cheruvally, Gouri; Shin, Yong-Jo; Ahn, Jou-Hyeon; Cho, Kwon-Koo; Ahn, Hyo-Jun; Kim, Ki-Won

2007-12-01

Carbon-coated lithium iron phosphate (LiFePO4/C) cathode material was synthesized by mechano-chemical activation method. The performance of LiFePO4/C in lithium battery was tested with an electrospun polymer-based electrolyte. Liquid electrolyte of 1M lithium hexafluorophosphate (LiPF6) in ethylene carbonate/dimethyl carbonate (EC/DMC) (1 : 1vol) was incorporated in electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-HFP)) microfibrous membrane to prepare the polymer electrolyte (PE). The cell based on Li|PE|Li FePO4/C exhibited an initial discharge capacity of 142 mAh g-1 at 0.1 C-rate at room temperature. Good cycling performance even under the high current density of 2 C could be obtained. Impedance spectroscopy was applied to investigate the material behavior during 0.1 C-rate charge-discharge cycling. When the fresh cell and the cell after different cycles were compared, impedance resistance was found to decrease with cycling. Impedance study indicated good cycle life for the cell when tested at room temperature.

Method for providing uranium articles with a corrosion resistant anodized coating

DOEpatents

Waldrop, Forrest B.; Washington, Charles A.

1982-01-01

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75.degree. C. with a current flow of less than about 0.036 A/cm.sup.2 of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

Method for providing uranium articles with a corrosion-resistant anodized coating

DOEpatents

Waldrop, F.B.; Washington, C.A.

1981-01-07

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75/sup 0/C with a current flow of less than about 0.036 A/cm/sup 2/ of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

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

A general strategy toward the rational synthesis of metal tungstate nanostructures using plasma electrolytic oxidation method

NASA Astrophysics Data System (ADS)

Jiang, Yanan; Liu, Baodan; Zhai, Zhaofeng; Liu, Xiaoyuan; Yang, Bing; Liu, Lusheng; Jiang, Xin

2015-11-01

A new method based on conventional plasma electrolytic oxidation (PEO) technology has been developed for the rational synthesis of metal tungstate nanostructures. Using this method, ZnWO4 and NiWO4 nanostructures with controllable morphologies (nanorods, nanosheets and microsheets) and superior crystallinity have been synthesized. It has been found that the morphology diversity of ZnWO4 nanostructures can be selectively tailored through tuning the electrolyte concentration and annealing temperatures, showing obvious advantages in comparison to traditional hydrothermal and sol-gel methods. Precise microscopy analyses on the cross section of the PEO coating and ZnWO4 nanostructures confirmed that the precursors initially precipitated in the PEO coating and its surface during plasma discharge process are responsible for the nucleation and subsequent growth of metal tungstate nanostructures by thermal annealing. The method developed in this work represents a general strategy toward the rational synthesis of metal oxide nanostructures and the formation mechanism of metal tungstate nanostructures fabricated by the PEO method is finally discussed.

Electrode effects on temporal changes in electrolyte pH and redox potential for water treatment

PubMed Central

Ciblak, Ali; Mao, Xuhui; Padilla, Ingrid; Vesper, Dorothy; Alshawabkeh, Iyad; Alshawabkeh, Akram N.

2012-01-01

The performance of electrochemical remediation methods could be optimized by controlling the physicochemical conditions of the electrochemical redox system. The effects of anode type (reactive or inert), current density and electrolyte composition on the temporal changes in pH and redox potential of the electrolyte were evaluated in divided and mixed electrolytes. Two types of electrodes were used: iron as a reactive electrode and mixed metal oxide coated titanium (MMO) as an inert electrode. Electric currents of 15, 30, 45 and 60 mA (37.5 mA L−1, 75 mA L−1, 112.5 mA L−1 and 150 mA L−1) were applied. Solutions of NaCl, Na2SO4 and NaHCO3 were selected to mimic different wastewater or groundwater composition. Iron anodes resulted in highly reducing electrolyte conditions compared to inert anodes. Electrolyte pH was dependent on electrode type, electrolyte composition and current density. The pH of mixed-electrolyte was stable when MMO electrodes were used. When iron electrodes were used, the pH of electrolyte with relatively low current density (37.5 mA L−1) did not show significant changes but the pH increased sharply for relatively high current density (150 mA L−1). Sulfate solution showed more basic and relatively more reducing electrolyte condition compared to bicarbonate and chloride solution. The study shows that a highly reducing environment could be achieved using iron anodes in divided or mixed electrolytes and the pH and redox potential could be optimized by using appropriate current and polarity reversal. PMID:22416866

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode.

PubMed

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-05-23

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

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.

Effects of shielding coatings on the anode shaping process during counter-rotating electrochemical machining

NASA Astrophysics Data System (ADS)

Wang, Dengyong; Zhu, Zengwei; Wang, Ningfeng; Zhu, Di

2016-09-01

Electrochemical machining (ECM) has been widely used in the aerospace, automotive, defense and medical industries for its many advantages over traditional machining methods. However, the machining accuracy in ECM is to a great extent limited by the stray corrosion of the unwanted material removal. Many attempts have been made to improve the ECM accuracy, such as the use of a pulse power, passivating electrolytes and auxiliary electrodes. However, they are sometimes insufficient for the reduction of the stray removal and have their limitations in many cases. To solve the stray corrosion problem in CRECM, insulating and conductive coatings are respectively used. The different implement processes of the two kinds of coatings are introduced. The effects of the two kinds of shielding coatings on the anode shaping process are investigated. Numerical simulations and experiments are conducted for the comparison of the two coatings. The simulation and experimental results show that both the two kinds of coatings are valid for the reduction of stray corrosion on the top surface of the convex structure. However, for insulating coating, the convex sidewall becomes concave when the height of the convex structure is over 1.26 mm. In addition, it is easy to peel off by the high-speed electrolyte. In contrast, the conductive coating has a strong adhesion, and can be well reserved during the whole machining process. The convex structure fabricated by using a conductive iron coating layer presents a favorable sidewall profile. It is concluded that the conductive coating is more effective for the improvement of the machining quality in CRECM. The proposed shielding coatings can also be employed to reduce the stray corrosion in other schemes of ECM.