Search results for: zirconia
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 60

Search results for: zirconia

30 Drop Impact Study on Flexible Superhydrophobic Surface Containing Micro-Nano Hierarchical Structures

Authors: Abinash Tripathy, Girish Muralidharan, Amitava Pramanik, Prosenjit Sen

Abstract:

Superhydrophobic surfaces are abundant in nature. Several surfaces such as wings of butterfly, legs of water strider, feet of gecko and the lotus leaf show extreme water repellence behaviour. Self-cleaning, stain-free fabrics, spill-resistant protective wears, drag reduction in micro-fluidic devices etc. are few applications of superhydrophobic surfaces. In order to design robust superhydrophobic surface, it is important to understand the interaction of water with superhydrophobic surface textures. In this work, we report a simple coating method for creating large-scale flexible superhydrophobic paper surface. The surface consists of multiple layers of silanized zirconia microparticles decorated with zirconia nanoparticles. Water contact angle as high as 159±10 and contact angle hysteresis less than 80 was observed. Drop impact studies on superhydrophobic paper surface were carried out by impinging water droplet and capturing its dynamics through high speed imaging. During the drop impact, the Weber number was varied from 20 to 80 by altering the impact velocity of the drop and the parameters such as contact time, normalized spread diameter were obtained. In contrast to earlier literature reports, we observed contact time to be dependent on impact velocity on superhydrophobic surface. Total contact time was split into two components as spread time and recoil time. The recoil time was found to be dependent on the impact velocity while the spread time on the surface did not show much variation with the impact velocity. Further, normalized spreading parameter was found to increase with increase in impact velocity.

Keywords: contact angle, contact angle hysteresis, contact time, superhydrophobic

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29 Electrical and Structural Properties of Solid Electrolyte Systems

Authors: Yasin Polat, Yılmaz Dağdemir, Mehmet Arı

Abstract:

Samarium (III) oxide and Ytterbium (III) oxide doped Bismuth trioxide solid solutions, the nano ceramic (Bi2O3)1-x-y(Sm2O3)x(Yb2O3)y ternary system were obtained with x=5, 20 mol %, and y=5, 20 mol % dopant concentrations have been synthesized in air atmosphere with solid state reaction. Temperature dependent electrical conductivity of the samples have been investigated by 4-point probe technique by heating and cooling process. Doped-Bi2O3 materials of solid electrolyte systems are good oxygen anions O2-conductors which have collected much attention as potential solid ceramic electrolytes for solid oxide fuel cells (SOFCs) because of their relatively high oxygen ionic conductivity at lower temperatures.(Bi2O3)-based electrolytes have also wide other technological applications in devices with high economical interest such as oxygen sensors, ceramic membranes for oxygen separation, oxygen pumps, catalyzing of some heterogeneous reactions, partial oxidation of the hydrocarbons, and additive material in paints. In recent years, many experimental researches have mostly focused on improving of the Bi-based electrolytes which have high oxide ionic conductivity at low temperatures and better performance as alternatives to traditional stabilized zirconia has taken place. Generally, these systems are much better solid electrolytes than well-known stabilized zirconia, because some of the bismuth trioxide phases exhibit higher ion conductivity than other oxide ionic conductors. Crystal structure of the Nano ceramic (Bi2O3)1-x-y(Sm2O3)x(Yb2O3)y has been determined by X-Ray powder diffractions (XRD) measurements before and after electrical conductivity measurements of the samples. Surface and grain structure properties of the samples were determined by SEM analysis. The samples which synthesized in this study can be used in industrial applications such as electrolytes of the solid oxide fuel cells (SOFC).

Keywords: 4-point probe technique, bismuth trioxide, solid state reaction, solid oxide fuel cell

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28 Li2o Loss of Lithium Niobate Nanocrystals during High-Energy Ball-Milling

Authors: Laura Kocsor, Laszlo Peter, Laszlo Kovacs, Zsolt Kis

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The aim of our research is to prepare rare-earth-doped lithium niobate (LiNbO3) nanocrystals, having only a few dopant ions in the focal point of an exciting laser beam. These samples will be used to achieve individual addressing of the dopant ions by light beams in a confocal microscope setup. One method for the preparation of nanocrystalline materials is to reduce the particle size by mechanical grinding. High-energy ball-milling was used in several works to produce nano lithium niobate. Previously, it was reported that dry high-energy ball-milling of lithium niobate in a shaker mill results in the partial reduction of the material, which leads to a balanced formation of bipolarons and polarons yielding gray color together with oxygen release and Li2O segregation on the open surfaces. In the present work we focus on preparing LiNbO3 nanocrystals by high-energy ball-milling using a Fritsch Pulverisette 7 planetary mill. Every ball-milling process was carried out in zirconia vial with zirconia balls of different sizes (from 3 mm to 0.1 mm), wet grinding with water, and the grinding time being less than an hour. Gradually decreasing the ball size to 0.1 mm, an average particle size of about 10 nm could be obtained determined by dynamic light scattering and verified by scanning electron microscopy. High-energy ball-milling resulted in sample darkening evidenced by optical absorption spectroscopy measurements indicating that the material underwent partial reduction. The unwanted lithium oxide loss decreases the Li/Nb ratio in the crystal, strongly influencing the spectroscopic properties of lithium niobate. Zirconia contamination was found in ground samples proved by energy-dispersive X-ray spectroscopy measurements; however, it cannot be explained based on the hardness properties of the materials involved in the ball-milling process. It can be understood taking into account the presence of lithium hydroxide formed the segregated lithium oxide and water during the ball-milling process, through chemically induced abrasion. The quantity of the segregated Li2O was measured by coulometric titration. During the wet milling process in the planetary mill, it was found that the lithium oxide loss increases linearly in the early phase of the milling process, then a saturation of the Li2O loss can be seen. This change goes along with the disappearance of the relatively large particles until a relatively narrow size distribution is achieved in accord with the dynamic light scattering measurements. With the 3 mm ball size and 1100 rpm rotation rate, the mean particle size achieved is 100 nm, and the total Li2O loss is about 1.2 wt.% of the original LiNbO3. Further investigations have been done to minimize the Li2O segregation during the ball-milling process. Since the Li2O loss was observed to increase with the growing total surface of the particles, the influence of ball-milling parameters on its quantity has also been studied.

Keywords: high-energy ball-milling, lithium niobate, mechanochemical reaction, nanocrystals

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27 Nanomaterials Based Biosensing Chip for Non-Invasive Detection of Oral Cancer

Authors: Suveen Kumar

Abstract:

Oral cancer (OC) is the sixth most death causing cancer in world which includes tumour of lips, floor of the mouth, tongue, palate, cheeks, sinuses, throat, etc. Conventionally, the techniques used for OC detection are toluidine blue staining, biopsy, liquid-based cytology, visual attachments, etc., however these are limited by their highly invasive nature, low sensitivity, time consumption, sophisticated instrument handling, sample processing and high cost. Therefore, we developed biosensing chips for non-invasive detection of OC via CYFRA-21-1 biomarker. CYFRA-21-1 (molecular weight: 40 kDa) is secreted in saliva of OC patients which is a non-invasive biological fluid with a cut-off value of 3.8 ng mL-1, above which the subjects will be suffering from oral cancer. Therefore, in first work, 3-aminopropyl triethoxy silane (APTES) functionalized zirconia (ZrO2) nanoparticles (APTES/nZrO2) were used to successfully detect CYFRA-21-1 in a linear detection range (LDR) of 2-16 ng mL-1 with sensitivity of 2.2 µA mL ng-1. Successively, APTES/nZrO2-RGO was employed to prevent agglomeration of ZrO2 by providing high surface area reduced graphene oxide (RGO) support and much wider LDR (2-22 ng mL-1) was obtained with remarkable limit of detection (LOD) as 0.12 ng mL-1. Further, APTES/nY2O3/ITO platform was used for oral cancer bioseneor development. The developed biosensor (BSA/anti-CYFRA-21-1/APTES/nY2O3/ITO) have wider LDR (0.01-50 ng mL-1) with remarkable limit of detection (LOD) as 0.01 ng mL-1. To improve the sensitivity of the biosensing platform, nanocomposite of yattria stabilized nanostructured zirconia-reduced graphene oxide (nYZR) based biosensor has been developed. The developed biosensing chip having ability to detect CYFRA-21-1 biomolecules in the range of 0.01-50 ng mL-1, LOD of 7.2 pg mL-1 with sensitivity of 200 µA mL ng-1. Further, the applicability of the fabricated biosensing chips were also checked through real sample (saliva) analysis of OC patients and the obtained results showed good correlation with the standard protein detection enzyme linked immunosorbent assay (ELISA) technique.

Keywords: non-invasive, oral cancer, nanomaterials, biosensor, biochip

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26 Experimental Investigation of Performance Anode Side of PEM Fuel Cell with Spin Method Coated with YSZ+SDC

Authors: Gürol Önal, Kevser Dinçer, Salih Yayla

Abstract:

In this study, performance of proton exchange membrane PEM fuel cell was experimentally investigated. Coating on the anode side of the PEM fuel cell was accomplished with the spin method by using YSZ+SDC. A solution having 0,1 gr YttriaStabilized Zirconia (YSZ) + 0,1 Samarium-Doped Ceria (SDC) + 10 mL methanol was prepared. This solution was taken out and filled into a micro-pipette. Then the anode side of PEM fuel cell was coated with YSZ+ SDC by using spin method. In the experimental study, current, voltage and power performances before and after coating were recorded and then compared to each other. It was found that the efficiency of PEM fuel cell increases after the coating with YSZ+SDC.

Keywords: fuel cell, Polymer Electrolyte Membrane (PEM), membrane, spin method

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25 Studies on Plasma Spray Deposited La2O3 - YSZ (Yttria-Stabilized Zirconia) Composite Thermal Barrier Coating

Authors: Prashant Sharma, Jyotsna Dutta Majumdar

Abstract:

The present study concerns development of a composite thermal barrier coating consisting of a mixture of La2O3 and YSZ (with 8 wt.%, 32 wt.% and 50 wt.% 50% La2O3) by plasma spray deposition technique on a CoNiCrAlY based bond coat deposited on Inconel 718 substrate by high velocity oxy-fuel deposition (HVOF) technique. The addition of La2O3 in YSZ causes the formation of pyrochlore (La2Zr2O7) phase in the inter splats boundary along with the presence of LaYO3 phase. The coefficient of thermal expansion is significantly reduced from due to the evolution of different phases and structural defects in the sprayed coating. The activation energy for TGO growth under isothermal and cyclic oxidation was increased in the composite coating as compared to YSZ coating.

Keywords: plasma spraying, oxidation resistance, thermal barrier coating, microstructure, X-ray method

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24 High Thermal Selective Detection of NOₓ Using High Electron Mobility Transistor Based on Gallium Nitride

Authors: Hassane Ouazzani Chahdi, Omar Helli, Bourzgui Nour Eddine, Hassan Maher, Ali Soltani

Abstract:

The real-time knowledge of the NO, NO₂ concentration at high temperature, would allow manufacturers of automobiles to meet the upcoming stringent EURO7 anti-pollution measures for diesel engines. Knowledge of the concentration of each of these species will also enable engines to run leaner (i.e., more fuel efficient) while still meeting the anti-pollution requirements. Our proposed technology is promising in the field of automotive sensors. It consists of nanostructured semiconductors based on gallium nitride and zirconia dioxide. The development of new technologies for selective detection of NO and NO₂ gas species would be a critical enabler of superior depollution. The current response was well correlated to the NO concentration in the range of 0–2000 ppm, 0-2500 ppm NO₂, and 0-300 ppm NH₃ at a temperature of 600.

Keywords: NOₓ sensors, HEMT transistor, anti-pollution, gallium nitride, gas sensor

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23 Physical Properties of Alkali Resistant-Glass Fibers in Continuous Fiber Spinning Conditions

Authors: Ji-Sun Lee, Soong-Keun Hyun, Jin-Ho Kim

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In this study, a glass fiber is fabricated using a continuous spinning process from alkali resistant (AR) glass with 4 wt% zirconia. In order to confirm the melting properties of the marble glass, the raw material is placed into a Pt crucible and melted at 1650 ℃ for 2 h, and then annealed. In order to confirm the transparency of the clear marble glass, the visible transmittance is measured, and the fiber spinning condition is investigated by using high temperature viscosity measurements. A change in the diameter is observed according to the winding speed in the range of 100–900 rpm; it is also verified as a function of the fiberizing temperature in the range of 1200–1260 ℃. The optimum winding speed and spinning temperature are 500 rpm and 1240 ℃, respectively. The properties of the prepared spinning fiber are confirmed using optical microscope, tensile strength, modulus, and alkali-resistant tests.

Keywords: glass composition, fiber diameter, continuous filament fiber, continuous spinning, physical properties

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22 Hot Corrosion Behavior of Calcium Zirconate Modified YSZ Coatings

Authors: Naveed Ejaz, Liaqat Ali, Amer Nusair

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Thermal barrier coatings (TBCs) serve as thermal barriers against the high temperature of the hot regions of the aircraft turbine engines keeping the surface of the turbine blades, vanes and combustion chamber at comparatively lower temperature. The life of these coatings depends on many in-service environmental factors. Among these factors, the behavior of the bond coat as well as the top coat at high temperature aggravated by the corrosive environments having S, V, Na and Cl plays a key role. The incorporation of the 5-15% CaZrO3 in YSZ coatings was studied after hot corrosion in vanadium oxide environment. It was observed that the reactivity of the V gradually switched from Y to Ca making CaV2O4 instead of YVO4; the percentage of CaV2O4 increased with the increase of CaZrO3 in YSZ. It eventually prevented leaching out of the Y from YSZ leaving the YSZ without any harmful phase change. The thermal insulation was found to be improved in case of CaZrO3 incorporated YSZ coatings as compared to only YSZ coating.

Keywords: hot corrosion, thermal barrier coatings, yttria stabilized zirconia, calcium zirconate

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21 Exploring Mechanical Properties of Additive Manufacturing Ceramic Components Across Techniques and Materials

Authors: Venkatesan Sundaramoorthy

Abstract:

The field of ceramics has undergone a remarkable transformation with the advent of additive manufacturing technologies. This comprehensive review explores the mechanical properties of additively manufactured ceramic components, focusing on key materials such as Alumina, Zirconia, and Silicon Carbide. The study delves into various authors' review technology into the various additive manufacturing techniques, including Stereolithography, Powder Bed Fusion, and Binder Jetting, highlighting their advantages and challenges. It provides a detailed analysis of the mechanical properties of these ceramics, offering insights into their hardness, strength, fracture toughness, and thermal conductivity. Factors affecting mechanical properties, such as microstructure and post-processing, are thoroughly examined. Recent advancements and future directions in 3D-printed ceramics are discussed, showcasing the potential for further optimization and innovation. This review underscores the profound implications of additive manufacturing for ceramics in industries such as aerospace, healthcare, and electronics, ushering in a new era of engineering and design possibilities for ceramic components.

Keywords: mechanical properties, additive manufacturing, ceramic materials, PBF

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20 Sonochemically Prepared Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion

Authors: Przemyslaw J. Jodlowski, Roman J. Jedrzejczyk, Damian K. Chlebda, Anna Dziedzicka, Lukasz Kuterasinski, Anna Gancarczyk, Maciej Sitarz

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The aim of this study was to obtain highly active catalysts based on non-noble metal oxides supported on zirconia prepared via a sonochemical method. In this study, the influence of the stabilizers addition during the preparation step was checked. The final catalysts were characterized by using such characterization methods as X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The proposed preparation method allowed to obtain uniformly dispersed metal-oxide nanoparticles at the support’s surface. The catalytic activity of prepared catalyst samples was measured in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was considerably higher than their counterparts prepared by the incipient wetness method.

Keywords: methane catalytic combustion, nanoparticles, non-noble metals, sonochemistry

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19 Synthesis, Structure and Properties of NZP/NASICON Structured Materials

Authors: E. A. Asabina, V. I. Pet'kov, P. A. Mayorov, A. V. Markin, N. N. Smirnova, A. M. Kovalskii, A. A. Usenko

Abstract:

The purpose of this work was to synthesize and investigate phase formation, structure and thermophysical properties of the phosphates M0.5+xM'xZr2–x(PO4)3 (M – Cd, Sr, Pb; M' – Mg, Co, Mn). The compounds were synthesized by sol-gel method. The results showed formation of limited solid solutions of NZP/NASICON type. The crystal structures of triple phosphates of the compositions MMg0.5Zr1.5(PO4)3 were refined by the Rietveld method using XRD data. Heat capacity (8–660 K) of the phosphates Pb0.5+xMgxZr2-x(PO4)3 (x = 0, 0.5) was measured, and reversible polymorphic transitions were found at temperatures, close to the room temperature. The results of Rietveld structure refinement showed the polymorphism caused by disordering of lead cations in the cavities of NZP/NASICON structure. Thermal expansion (298−1073 K) of the phosphates MMg0.5Zr1.5(PO4)3 was studied by XRD method, and the compounds were found to belong to middle and low-expanding materials. Thermal diffusivity (298–573 K) of the ceramic samples of phosphates slightly decreased with temperature increasing. As was demonstrated, the studied phosphates are characterized by the better thermophysical characteristics than widespread fire-resistant materials, such as zirconia and etc.

Keywords: NASICON, NZP, phosphate, structure, synthesis, thermophysical properties

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18 Effect of Leaks in Solid Oxide Electrolysis Cells Tested for Durability under Co-Electrolysis Conditions

Authors: Megha Rao, Søren H. Jensen, Xiufu Sun, Anke Hagen, Mogens B. Mogensen

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Solid oxide electrolysis cells have an immense potential in converting CO2 and H2O into syngas during co-electrolysis operation. The produced syngas can be further converted into hydrocarbons. This kind of technology is called power-to-gas or power-to-liquid. To produce hydrocarbons via this route, durability of the cells is still a challenge, which needs to be further investigated in order to improve the cells. In this work, various nickel-yttria stabilized zirconia (Ni-YSZ) fuel electrode supported or YSZ electrolyte supported cells, cerium gadolinium oxide (CGO) barrier layer, and an oxygen electrode are investigated for durability under co-electrolysis conditions in both galvanostatic and potentiostatic conditions. While changing the gas on the oxygen electrode, keeping the fuel electrode gas composition constant, a change in the gas concentration arc was observed by impedance spectroscopy. Measurements of open circuit potential revealed the presence of leaks in the setup. It is speculated that the change in concentration impedance may be related to the leaks. Furthermore, the cells were also tested under pressurized conditions to find an inter-play between the leak rate and the pressure. A mathematical modeling together with electrochemical and microscopy analysis is presented.

Keywords: co-electrolysis, durability, leaks, gas concentration arc

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17 Preparation and Conductivity Measurements of LSM/YSZ Composite Solid Oxide Electrolysis Cell Anode Materials

Authors: Christian C. Vaso, Rinlee Butch M. Cervera

Abstract:

One of the most promising anode materials for solid oxide electrolysis cell (SOEC) application is the Sr-doped LaMnO3 (LSM) which is known to have a high electronic conductivity but low ionic conductivity. To increase the ionic conductivity or diffusion of ions through the anode, Yttria-stabilized Zirconia (YSZ), which has good ionic conductivity, is proposed to be combined with LSM to create a composite electrode and to obtain a high mixed ionic and electronic conducting anode. In this study, composite of lanthanum strontium manganite and YSZ oxide, La0.8Sr0.2MnO3/Zr0.92Y0.08O2 (LSM/YSZ), with different wt.% compositions of LSM and YSZ were synthesized using solid-state reaction. The obtained prepared composite samples of 60, 50, and 40 wt.% LSM with remaining wt.% of 40, 50, and 60, respectively for YSZ were fully characterized for its microstructure by using powder X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), and Scanning electron microscope/Energy dispersive spectroscopy (SEM/EDS) analyses. Surface morphology of the samples via SEM analysis revealed a well-sintered and densified pure LSM, while a more porous composite sample of LSM/YSZ was obtained. Electrochemical impedance measurements at intermediate temperature range (500-700 °C) of the synthesized samples were also performed which revealed that the 50 wt.% LSM with 50 wt.% YSZ (L50Y50) sample showed the highest total conductivity of 8.27x10-1 S/cm at 600 oC with 0.22 eV activation energy.

Keywords: ceramics, microstructure, fuel cells, electrochemical impedance spectroscopy

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16 Nano-Structured Hydrophobic Silica Membrane for Gas Separation

Authors: Sajid Shah, Yoshimitsu Uemura, Katsuki Kusakabe

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Sol-gel derived hydrophobic silica membranes with pore sizes less than 1 nm are quite attractive for gas separation in a wide range of temperatures. A nano-structured hydrophobic membrane was prepared by sol-gel technique on a porous α–Al₂O₃ tubular support with yttria stabilized zirconia (YSZ) as an intermediate layer. Bistriethoxysilylethane (BTESE) derived sol was modified by adding phenyltriethoxysilylethane (PhTES) as an organic template. Six times dip coated modified silica membrane having a thickness of about 782 nm was characterized by field emission scanning electron microscopy. Thermogravimetric analysis, together along contact angle and Fourier transform infrared spectroscopy, showed that hydrophobic properties were improved by increasing the PhTES content. The contact angle of water droplet increased from 37° for pure to 111.5° for the modified membrane. The permeance of single gas H₂ was higher than H₂:CO₂ ratio of 75:25 binary feed mixtures. However, the permeance of H₂ for 60:40 H₂:CO₂ was found lower than single and binary mixture 75:25 H₂:CO₂. The binary selectivity values for 75:25 H₂:CO₂ were 24.75, 44, and 57, respectively. Selectivity had an inverse relation with PhTES content. Hydrophobicity properties were improved by increasing PhTES content in the silica matrix. The system exhibits proper three layers adhesion or integration, and smoothness. Membrane system suitable in steam environment and high-temperature separation. It was concluded that the hydrophobic silica membrane is highly promising for the separation of H₂/CO₂ mixture from various H₂-containing process streams.

Keywords: gas separation, hydrophobic properties, silica membrane, sol–gel method

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15 Calculating Approach of Thermal Conductivity of 8 YSZ in Different Relative Humidities Corresponding to Low Water Contents

Authors: Yun Chol Kang, Myong Nam Kong, Nam Chol Yu, Jin Sim Kim, Un Yong Paek, Song Ho Kim

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This study focuses on the calculating approach of the thermal conductivity of 8 mol% yttria-stabilized zirconia (8YSZ) in different relative humidity corresponding to low water contents. When water content in 8YSZ is low, water droplets can accumulate in the neck regions. We assume that spherical water droplets are randomly located in the neck regions formed by grains and surrounded by the pores. Based on this, a new hypothetical pore constituted by air and water is proposed using the microstructural modeling. We consider 8YSZ is a two-phase material constituted by the solid region and the hypothetical pore region where the water droplets are penetrated in the pores, randomly. The results showed that the thermal conductivity of the hypothetical pore is calculated using the parallel resistance for low water contents, and the effective thermal conductivity of 8YSZ material constituted by solid and hypothetical pore in different relative humidities using EMPT. When the numbers of water layers on the surface of 8YSZ are less than 1.5, the proposed approach gives a good interpretation of the experimental results. When the theoretical value of the number of water layers on 8YSZ surface is 1, the water content is not enough to cover the internal solid surface completely. The proposed approach gives a better interpretation of the experimental results in different relative humidities that numbers of water layers on the surface of 8YSZ are less than 1.5.

Keywords: 8YSZ, microstructure, thermal conductivity, relative humidity

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14 Steam Reforming of Acetic Acid over Microwave-Synthesized Ce0.75Zr0.25O2 Supported Ni Catalysts

Authors: Panumard Kaewmora, Thirasak Rirksomboon, Vissanu Meeyoo

Abstract:

Due to the globally growing demands of petroleum fuel and fossil fuels, the scarcity or even depletion of fossil fuel sources could be inevitable. Alternatively, the utilization of renewable sources, such as biomass, has become attractive to the community. Biomass can be converted into bio-oil by fast pyrolysis. In water phase of bio-oil, acetic acid which is one of its main components can be converted to hydrogen with high selectivity over effective catalysts in steam reforming process. Steam reforming of acetic acid as model compound has been intensively investigated for hydrogen production using various metal oxide supported nickel catalysts and yet they seem to be rapidly deactivated depending on the support utilized. A catalyst support such as Ce1-xZrxO2 mixed oxide was proposed for alleviating this problem with the anticipation of enhancing hydrogen yield. However, catalyst preparation methods play a significant role in catalytic activity and performance of the catalysts. In this work, Ce0.75Zr0.25O2 mixed oxide solid solution support was prepared by urea hydrolysis using microwave as heat source. After that nickel metal was incorporated at 15 wt% by incipient wetness impregnation method. The catalysts were characterized by several techniques including BET, XRD, H2-TPR, XRF, SEM, and TEM as well as tested for the steam reforming of acetic acid at various operating conditions. Preliminary results showed that a hydrogen yield of ca. 32% with a relatively high acetic conversion was attained at 650°C.

Keywords: acetic acid, steam reforming, microwave, nickel, ceria, zirconia

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13 Development of LSM/YSZ Composite Anode Materials for Solid Oxide Electrolysis Cells

Authors: Christian C. Vaso, Rinlee Butch M. Cervera

Abstract:

Solid oxide electrolysis cell (SOEC) is a promising technology for hydrogen production that will contribute to the sustainable energy of the future. An important component of this SOEC is the anode material and one of the promising anode material for such application is the Sr-doped LaMnO3 (LSM) and Yttrium-stabilized ZrO2 (YSZ) composite material. In this study, LSM/YSZ with different weight percent compositions of LSM and YSZ were synthesized using solid-state reaction method. The obtained samples, 60LSM/40YSZ, 50LSM/50YSZ, and 40LSM/60YSZ, were fully characterized for its microstructure using X-ray diffraction, FTIR, and SEM/EDS. EDS analysis confirmed the elemental composition and distribution of the synthesized samples. Surface morphology of the sample using SEM exhibited a well sintered and densified samples and revealed a beveled cube-like LSM morphology while the YSZ phase appeared to have a sphere-like microstructure. Density measurements using Archimedes principle showed relative densities greater than 90%. In addition, AC impedance measurement of the synthesized samples have been investigated at intermediate temperature range (400-700 °C) in an inert and oxygen gas flow environment. At pure states, LSM exhibited a high electronic conductivity while YSZ demonstrated an ionic conductivity of 3.25 x 10-4 S/cm at 700 °C under Oxygen gas environment with calculated activation energy of 0.85eV. The composite samples were also studied and revealed that as the YSZ content of the composite electrode increases, the total conductivity decreases.

Keywords: ceramic composites, fuel cells, strontium lanthanum manganite, yttria partially-stabilized zirconia

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12 Performance and Processing Evaluation of Solid Oxide Cells by Co-Sintering of GDC Buffer Layer and LSCF Air Electrode

Authors: Hyun-Jong Choi, Minjun Kwak, Doo-Won Seo, Sang-Kuk Woo, Sun-Dong Kim

Abstract:

Solid Oxide Cell(SOC) systems can contribute to the transition to the hydrogen society by utilized as a power and hydrogen generator by the electrochemical reaction with high efficiency at high operation temperature (>750 ℃). La1-xSrxCo1-yFeyO3, which is an air electrode, is occurred stability degradations due to reaction and delamination with yittria stabilized zirconia(YSZ) electrolyte in a water electrolysis mode. To complement this phenomenon SOCs need gadolinium doped ceria(GDC) buffer layer between electrolyte and air electrode. However, GDC buffer layer requires a high sintering temperature and it causes a reaction with YSZ electrolyte. This study carried out low temperature sintering of GDC layer by applying Cu-oxide as a sintering aid. The effect of a copper additive as a sintering aid to lower the sintering temperature for the construction of solid oxide fuel cells (SOFCs) was investigated. GDC buffer layer with 0.25-10 mol% CuO sintering aid was prepared by reacting GDC power and copper nitrate solution followed by heating at 600 ℃. The sintering of CuO-added GDC powder was optimized by investigating linear shrinkage, microstructure, grain size, ionic conductivity, and activation energy of CuO-GDC electrolytes at temperatures ranging from 1100 to 1400 ℃. The sintering temperature of the CuO-GDC electrolyte decreases from 1400 ℃ to 1100 ℃ by adding the CuO sintering aid. The ionic conductivity of the CuO-GDC electrolyte shows a maximum value at 0.5 mol% of CuO. However, the addition of CuO has no significant effects on the activation energy of GDC electrolyte. GDC-LSCF layers were co-sintering at 1050 and 1100 ℃ and button cell tests were carried out at 750 ℃.

Keywords: Co-Sintering, GDC-LSCF, Sintering Aid, solid Oxide Cells

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11 Self-Organized TiO₂–Nb₂O₅–ZrO₂ Nanotubes on β-Ti Alloy by Anodization

Authors: Muhammad Qadir, Yuncang Li, Cuie Wen

Abstract:

Surface properties such as topography and physicochemistry of metallic implants determine the cell behavior. The surface of titanium (Ti)-based implant can be modified to enhance the bioactivity and biocompatibility. In this study, a self-organized titania–niobium pentoxide–zirconia (TiO₂–Nb₂O₅–ZrO₂) nanotubular layer on β phase Ti35Zr28Nb alloy was fabricated via electrochemical anodization. Energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement techniques were used to investigate the nanotubes dimensions (i.e., the inner and outer diameters, and wall thicknesses), microstructural features and evolution of the hydrophilic properties. The in vitro biocompatibility of the TiO₂–Nb₂O₅–ZrO₂ nanotubes (NTs) was assessed by using osteoblast cells (SaOS2). Influence of anodization parameters on the morphology of TiO₂–Nb₂O₅–ZrO₂ NTs has been studied. The results indicated that the average inner diameter, outer diameter and the wall thickness of the TiO₂–Nb₂O₅–ZrO₂ NTs were ranged from 25–70 nm, 45–90 nm and 5–13 nm, respectively, and were directly influenced by the applied voltage during anodization. The average inner and outer diameters of NTs increased with increasing applied voltage, and the length of NTs increased with increasing anodization time and water content of the electrolyte. In addition, the size distribution of the NTs noticeably affected the hydrophilic properties and enhanced the biocompatibility as compared with the uncoated substrate. The results of this study could be considered for developing nano-scale coatings for a wide range of biomedical applications.

Keywords: Titanium alloy, TiO₂–Nb₂O₅–ZrO₂ nanotubes, anodization, surface wettability, biocompatibility

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10 Partially Phosphorylated Polyvinyl Phosphate-PPVP Composite: Synthesis and Its Potentiality for Zr (IV) Extraction from an Acidic Medium

Authors: Khaled Alshamari

Abstract:

Synthesized partially phosphorylated polyvinyl phosphate derivative (PPVP) was functionalized to extract Zirconium (IV) from Egyptian zircon sand. The specifications for the PPVP composite were approved effectively via different techniques, namely, FT-IR, XPS, BET, EDX, TGA, HNMR, C-NMR, GC-MS, XRD and ICP-OES analyses, which demonstrated a satisfactory synthesis of PPVP and zircon dissolution from Egyptian zircon sand. Factors controlling parameters, such as pH values, shaking time, initial zirconium concentration, PPVP dose, nitrate ions concentration, co-ions, temperature and eluting agents, have been optimized. At 25 ◦C, pH 0, 20 min shaking, 0.05 mol/L zirconium ions and 0.5 mol/L nitrate ions, PPVP has an exciting preservation potential of 195 mg/g, equivalent to 390 mg/L zirconium ions. From the extraction–distribution isotherm, the practical outcomes of Langmuir’s modeling are better than the Freundlich model, with a theoretical value of 196.07 mg/g, which is more in line with the experimental results of 195 mg/g. The zirconium ions adsorption onto the PPVP composite follows the pseudo-second-order kinetics with a theoretical capacity value of 204.08 mg/g. According to thermodynamic potential, the extraction process was expected to be an exothermic, spontaneous and beneficial extraction at low temperatures. The thermodynamic parameters ∆S (−0.03 kJ/mol), ∆H (−12.22 kJ/mol) and ∆G were also considered. As the temperature grows, ∆G values increase from −2.948 kJ/mol at 298 K to −1.941 kJ/mol at 338 K. Zirconium ions may be eluted from the working loaded PPVP by 0.025M HNO₃, with a 99% efficiency rate. It was found that zirconium ions revealed good separation factors towards some co-ions such as Hf⁴+ (28.82), Fe³+ (10.64), Ti⁴+ (28.82), V⁵+ (86.46) and U⁶+ (68.17). A successful alkali fusion technique with NaOH flux followed by the extraction with PPVP is used to obtain a high-purity zirconia concentrate with a zircon content of 72.77 % and a purity of 98.29%. As a result of this, the improved factors could finally be used.

Keywords: zirconium extraction, partially phosphorylated polyvinyl phosphate (PPVP), acidic medium, zircon

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9 Investigations into the Efficiencies of Steam Conversion in Three Reactor Chemical Looping

Authors: Ratnakumar V. Kappagantula, Gordon D. Ingram, Hari B. Vuthaluru

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This paper analyzes a three reactor chemical looping process for hydrogen production from natural gas, allowing for carbon dioxide capture through chemical looping technology. An oxygen carrier is circulated to separate carbon dioxide, to reduce steam for hydrogen production and to supply oxygen for combustion. In this study, the emphasis is placed on the steam conversion in the steam reactor by investigating the hydrogen efficiencies of the complete system at steam conversions of 15.8% and 50%. An Aspen Plus model was developed for a Three Reactor Chemical Looping process to study the effects of operational parameters on hydrogen production is investigated. Maximum hydrogen production was observed under stoichiometric conditions. Different conversions in the steam reactor, which was modelled as a Gibbs reactor, were found when Gibbs-identified products and user identified products were chosen. Simulations were performed for different oxygen carriers, which consist of an active metal oxide on an inert support material. For the same metal oxide mass flowrate, the fuel reactor temperature decreased for different support materials in the order: aluminum oxide (Al2O3) > magnesium aluminate (MgAl2O4) > zirconia (ZrO2). To achieve the same fuel reactor temperature for the same oxide mass flow rate, the inert mass fraction was found to be 0.825 for ZrO2, 0.7 for MgAl2O4 and 0.6 for Al2O3. The effect of poisoning of the oxygen carrier was also analyzed. With 3000 ppm sulfur-based impurities in the feed gas, the hydrogen product energy rate of the process were found to decrease by 0.4%.

Keywords: aspen plus, chemical looping combustion, inert support balls, oxygen carrier

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8 Optimal Sputtering Conditions for Nickel-Cermet Anodes in Intermediate Temperature Solid Oxide Fuel Cells

Authors: Waqas Hassan Tanveer, Yoon Ho Lee, Taehyun Park, Wonjong Yu, Yaegeun Lee, Yusung Kim, Suk Won Cha

Abstract:

Nickel-Gadolinium Doped Ceria (Ni-GDC) cermet anodic thin films were prepared on Scandia Stabilized Zirconia (ScSZ) electrolyte supports by radio frequency (RF) sputtering, with a range of different sputtering powers (50 – 200W) and background Ar gas pressures (30 – 90mTorr). The effects of varying sputtering power and pressure on the properties of Ni-GDC films were studied using Focused Ion Beam (FIB), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Energy Dispersive X-ray (EDX), and Atomic Force Microscopy (AFM) techniques. The Ni content was found to be always higher than the Ce content, at all sputtering conditions. This increased Ni content was attributed to significantly higher energy transfer efficiency of Ni ions as compared to Ce ions with Ar background sputtering gas. The solid oxide fuel cell configuration was completed by using lanthanum strontium manganite (LSM/YSZ) cathodes on the other side of ScSZ supports. Performance comparison of cells was done by Voltage-Current-Power (VIP) curves, while the resistances of various cell components were observed by nyquist plots. Initial results showed that anode films made by higher powered RF sputtering performed better than lower powered ones for a specific Ar pressure. Interestingly, however, anodes made at highest power and pressure, were not the ones that showed the maximum power output at an intermediate solid oxide fuel cell temperature of 800°C. Finally, an optimal sputtering condition was reported for high performance Ni-GDC anodes.

Keywords: intermediate temperature solid oxide fuel cells, nickel-cermet anodic thin films, nyquist plots, radio frequency sputtering

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7 Experimental Optimization in Diamond Lapping of Plasma Sprayed Ceramic Coatings

Authors: S. Gowri, K. Narayanasamy, R. Krishnamurthy

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Plasma spraying, from the point of value engineering, is considered as a cost-effective technique to deposit high performance ceramic coatings on ferrous substrates for use in the aero,automobile,electronics and semiconductor industries. High-performance ceramics such as Alumina, Zirconia, and titania-based ceramics have become a key part of turbine blades,automotive cylinder liners,microelectronic and semiconductor components due to their ability to insulate and distribute heat. However, as the industries continue to advance, improved methods are needed to increase both the flexibility and speed of ceramic processing in these applications. The ceramics mentioned were individually coated on structural steel substrate with NiCr bond coat of 50-70 micron thickness with the final thickness in the range of 150 to 200 microns. Optimal spray parameters were selected based on bond strength and porosity. The 'optimal' processed specimens were super finished by lapping using diamond and green SiC abrasives. Interesting results could be observed as follows: The green SiC could improve the surface finish of lapped surfaces almost as that by diamond in case of alumina and titania based ceramics but the diamond abrasives could improve the surface finish of PSZ better than that by green SiC. The conventional random scratches could be absent in alumina and titania ceramics but in PS those marks were found to be less. However, the flatness accuracy could be improved unto 60 to 85%. The surface finish and geometrical accuracy were measured and modeled. The abrasives in the midrange of their particle size could improve the surface quality faster and better than the particles of size in low and high ranges. From the experimental investigations after lapping process, the optimal lapping time, abrasive size, lapping pressure etc could be evaluated.

Keywords: atmospheric plasma spraying, ceramics, lapping, surface qulaity, optimization

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6 BI- And Tri-Metallic Catalysts for Hydrogen Production from Hydrogen Iodide Decomposition

Authors: Sony, Ashok N. Bhaskarwar

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Production of hydrogen from a renewable raw material without any co-synthesis of harmful greenhouse gases is the current need for sustainable energy solutions. The sulfur-iodine (SI) thermochemical cycle, using intermediate chemicals, is an efficient process for producing hydrogen at a much lower temperature than that required for the direct splitting of water. No net byproduct forms in the cycle. Hydrogen iodide (HI) decomposition is a crucial reaction in this cycle, as the product, hydrogen, forms only in this step. It is an endothermic, reversible, and equilibrium-limited reaction. The theoretical equilibrium conversion at 550°C is just a meagre of 24%. There is a growing interest, therefore, in enhancing the HI conversion to near-equilibrium values at lower reaction temperatures and by possibly improving the rate. The reaction is relatively slow without a catalyst, and hence catalytic decomposition of HI has gained much significance. Bi-metallic Ni-Co, Ni-Mn, Co-Mn, and tri-metallic Ni-Co-Mn catalysts over zirconia support were tested for HI decomposition reaction. The catalysts were synthesized via a sol-gel process wherein Ni was 3wt% in all the samples, and Co and Mn had equal weight ratios in the Co-Mn catalyst. Powdered X-ray diffraction and Brunauer-Emmett-Teller surface area characterizations indicated the polycrystalline nature and well-developed mesoporous structure of all the samples. The experiments were performed in a vertical laboratory-scale packed bed reactor made of quartz, and HI (55 wt%) was fed along with nitrogen at a WHSV of 12.9 hr⁻¹. Blank experiments at 500°C for HI decomposition suggested conversion of less than 5%. The activities of all the different catalysts were checked at 550°C, and the highest conversion of 23.9% was obtained with the tri-metallic 3Ni-Co-Mn-ZrO₂ catalyst. The decreasing order of the performance of catalysts could be expressed as: 3Ni-Co-Mn-ZrO₂ > 3Ni-2Co-ZrO₂ > 3Ni-2Mn-ZrO₂ > 2.5Co-2.5Mn-ZrO₂. The tri-metallic catalyst remained active till 360 mins at 550°C without any observable drop in its activity/stability. Among the explored catalyst compositions, the tri-metallic catalyst certainly has a better performance for HI conversion when compared to the bi-metallic ones. Owing to their low costs and ease of preparation, these trimetallic catalysts could be used for large-scale hydrogen production.

Keywords: sulfur-iodine cycle, hydrogen production, hydrogen iodide decomposition, bi-, and tri-metallic catalysts

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5 Investigating the Effect of Ceramic Thermal Barrier Coating on Diesel Engine with Lemon Oil Biofuel

Authors: V. Karthickeyan

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The demand for energy is anticipated to increase, due to growing urbanization, industrialization, upgraded living standards and cumulatively increasing human population. The general public is becoming gradually aware of the diminishing fossil fuel resources along with the environmental issues, and it has become clear that biofuel is intended to make significant support to the forthcoming energy needs of the native and industrial sectors. Nowadays, the investigation on biofuels obtained from peels of fruits and vegetables have gained the consideration as an environment-friendly alternative to diesel. In the present work, biofuel was produced from non-edible Lemon Oil (LO) using steam distillation process. LO is characterized by its beneficial aspects like low kinematic viscosity and enhanced calorific value which provides better fuel atomization and evaporation. Furthermore, the heating values of the biofuels are approximately equal to diesel. A single cylinder, four-stroke diesel engine was used for this experimentation. An engine modification technique namely Thermal Barrier Coating (TBC) was attempted. Combustion chamber components were thermally coated with ceramic material namely partially stabilized zirconia (PSZ). The benefit of thermal barrier coating is to diminish the heat loss from engine and transform the collected heat into piston work. Performance characteristics like Brake Thermal Efficiency (BTE) and Brake Specific Fuel Consumption (BSFC) were analyzed. Combustion characteristics like in-cylinder pressure and heat release rate were analyzed. In addition, the following engine emissions namely nitrogen oxide (NO), carbon monoxide (CO), hydrocarbon (HC), and smoke were measured. The acquired performance combustion and emission characteristics of uncoated engine were compared with PSZ coated engine. From the results, it was perceived that the LO biofuel may be considered as the prominent alternative in the near prospect with thermal barrier coating technique to enrich the performance, combustion and emission characteristics of diesel engine.

Keywords: ceramic material, thermal barrier coating, biofuel and diesel engine

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4 Improving Performance of K₂CO₃ Sorbent Using Core/Shell Alumina-Based Supports in a Multicycle CO₂ Capture Process

Authors: S. Toufigh Bararpour, Amir H. Soleimanisalim, Davood Karami, Nader Mahinpey

Abstract:

The continued increase in the atmospheric concentration of CO2 is expected to have great impacts on the climate. In order to reduce CO2 emission to the atmosphere, an efficient and cost-effective technique is required. Using regenerable solid sorbents, especially K2CO3 is a promising method for low-temperature CO2 capture. Pure K2CO3 is a delinquent substance that requires modifications before it can be used for cyclic operations. For this purpose, various types of additives and supports have been used to improve the structure of K2CO3. However, hydrophilicity and reactivity of the support materials with K2CO3 have a negative effect on the CO2 capture capacity of the sorbents. In this research, two kinds of alumina supports (γ-Alumina and Boehmite) were used. In order to decrease the supports' hydrophilicity and reactivity with K2CO3, nonreactive additives such as Titania, Zirconia and Silisium were incorporated into their structures. These materials provide a shell around the alumina to protect it from undesirable reactions and improve its properties. K2CO3-based core/shell-supported sorbents were fabricated using two preparation steps. The sol-gel method was applied for shelling the supports. Then the shelled supports were impregnated on K2CO3. The physicochemical properties of the sorbents were determined using SEM and BET analyses, and their CO2 capture capacity was quantified using a thermogravimetric analyzer. It was shown that type of the shell's material had an important effect on the water adsorption capacity of the sorbents. Supported K2CO3 modified by Titania shell showed the lowest hydrophilicity among the prepared samples. Based on the obtained results, incorporating nonreactive additives in Boehmite had an outstanding impact on the CO2 capture performance of the sorbent. Incorporation of Titania into the Boehmite-supported K2CO3 enhanced its CO2 capture capacity significantly. Therefore, further study of this novel fabrication technique is highly recommended. In the second phase of this research project, the CO2 capture performance of the sorbents in fixed and fluidized bed reactors will be investigated.

Keywords: CO₂ capture, core/shell support, K₂CO₃, post-combustion

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3 A Selective and Fast Hydrogen Sensor Using Doped-LaCrO₃ as Sensing Electrode

Authors: He Zhang, Jianxin Yi

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As a clean energy, hydrogen shows many advantages such as renewability, high heat value, and extensive sources and may play an important role in the future society. However, hydrogen is a combustible gas because of its low ignition energy (0.02mJ) and wide explosive limit (4% ~ 74% in air). It is very likely to cause fire hazard or explosion once leakage is happened and not detected in time. Mixed-potential type sensor has attracted much attention in monitoring and detecting hydrogen due to its high response, simple support electronics and long-term stability. Typically, this kind of sensor is consisted of a sensing electrode (SE), a reference electrode (RE) and a solid electrolyte. The SE and RE materials usually display different electrocatalytic abilities to hydrogen. So hydrogen could be detected by measuring the EMF change between the two electrodes. Previous reports indicate that a high-performance sensing electrode is important for improving the sensing characteristics of the sensor. In this report, a planar type mixed-potential hydrogen sensor using La₀.₈Sr₀.₂Cr₀.₅Mn₀.₅O₃₋δ (LSCM) as SE, Pt as RE and yttria-stabilized zirconia (YSZ) as solid electrolyte was developed. The reason for selecting LSCM as sensing electrode is that it shows the high electrocatalytic ability to hydrogen in solid oxide fuel cells. The sensing performance of the fabricated LSCM/YSZ/Pt sensor was tested systemically. The experimental results show that the sensor displays high response to hydrogen. The response values for 100ppm and 1000ppm hydrogen at 450 ºC are -70 mV and -118 mV, respectively. The response time is an important parameter to evaluate a sensor. In this report, the sensor response time decreases with increasing hydrogen concentration and get saturated above 500ppm. The steady response time at 450 ºC is as short as 4s, indicating the sensor shows great potential in practical application to monitor hydrogen. An excellent response repeatability to 100ppm hydrogen at 450 ˚C and a good sensor reproducibility among three sensors were also observed. Meanwhile, the sensor exhibits excellent selectivity to hydrogen compared with several interfering gases such as NO₂, CH₄, CO, C₃H₈ and NH₃. Polarization curves were tested to investigate the sensing mechanism and the results indicated the sensor abide by the mixed-potential mechanism.

Keywords: fire hazard, H₂ sensor, mixed-potential, perovskite

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2 Cartilage Mimicking Coatings to Increase the Life-Span of Bearing Surfaces in Joint Prosthesis

Authors: L. Sánchez-Abella, I. Loinaz, H-J. Grande, D. Dupin

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Aseptic loosening remains as the principal cause of revision in total hip arthroplasty (THA). For long-term implantations, submicron particles are generated in vivo due to the inherent wear of the prosthesis. When this occurs, macrophages undergo phagocytosis and secretion of bone resorptive cytokines inducing osteolysis, hence loosening of the implanted prosthesis. Therefore, new technologies are required to reduce the wear of the bearing materials and hence increase the life-span of the prosthesis. Our strategy focuses on surface modification of the bearing materials with a hydrophilic coating based on cross-linked water-soluble (meth)acrylic monomers to improve their tribological behavior. These coatings are biocompatible, with high swelling capacity and antifouling properties, mimicking the properties of natural cartilage, i.e. wear resistance with a permanent hydrated layer that prevents prosthesis damage. Cartilage mimicking based coatings may be also used to protect medical device surfaces from damage and scratches that will compromise their integrity and hence their safety. However, there are only a few reports on the mechanical and tribological characteristics of this type of coatings. Clear beneficial advantages of this coating have been demonstrated in different conditions and different materials, such as Ultra-high molecular weight polyethylene (UHMWPE), Polyethylene (XLPE), Carbon-fiber-reinforced polyetheretherketone (CFR-PEEK), cobalt-chromium (CoCr), Stainless steel, Zirconia Toughened Alumina (ZTA) and Alumina. Using routine tribological experiments, the wear for UHMWPE substrate was decreased by 75% against alumina, ZTA and stainless steel. For PEEK-CFR substrate coated, the amount of material lost against ZTA and CrCo was at least 40% lower. Experiments on hip simulator allowed coated ZTA femoral heads and coated UHMWPE cups to be validated with a decrease of 80% of loss material. Further experiments on hip simulator adding abrasive particles (1 micron sized alumina particles) during 3 million cycles, on a total of 6 million, demonstrated a decreased of around 55% of wear compared to uncoated UHMWPE and uncoated XLPE. In conclusion, CIDETEC‘s hydrogel coating technology is versatile and can be adapted to protect a large range of surfaces, even in abrasive conditions.

Keywords: cartilage, hydrogel, hydrophilic coating, joint

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1 Detailed Degradation-Based Model for Solid Oxide Fuel Cells Long-Term Performance

Authors: Mina Naeini, Thomas A. Adams II

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Solid Oxide Fuel Cells (SOFCs) feature high electrical efficiency and generate substantial amounts of waste heat that make them suitable for integrated community energy systems (ICEs). By harvesting and distributing the waste heat through hot water pipelines, SOFCs can meet thermal demand of the communities. Therefore, they can replace traditional gas boilers and reduce greenhouse gas (GHG) emissions. Despite these advantages of SOFCs over competing power generation units, this technology has not been successfully commercialized in large-scale to replace traditional generators in ICEs. One reason is that SOFC performance deteriorates over long-term operation, which makes it difficult to find the proper sizing of the cells for a particular ICE system. In order to find the optimal sizing and operating conditions of SOFCs in a community, a proper knowledge of degradation mechanisms and effects of operating conditions on SOFCs long-time performance is required. The simplified SOFC models that exist in the current literature usually do not provide realistic results since they usually underestimate rate of performance drop by making too many assumptions or generalizations. In addition, some of these models have been obtained from experimental data by curve-fitting methods. Although these models are valid for the range of operating conditions in which experiments were conducted, they cannot be generalized to other conditions and so have limited use for most ICEs. In the present study, a general, detailed degradation-based model is proposed that predicts the performance of conventional SOFCs over a long period of time at different operating conditions. Conventional SOFCs are composed of Yttria Stabilized Zirconia (YSZ) as electrolyte, Ni-cermet anodes, and LaSr₁₋ₓMnₓO₃ (LSM) cathodes. The following degradation processes are considered in this model: oxidation and coarsening of nickel particles in the Ni-cermet anodes, changes in the pore radius in anode, electrolyte, and anode electrical conductivity degradation, and sulfur poisoning of the anode compartment. This model helps decision makers discover the optimal sizing and operation of the cells for a stable, efficient performance with the fewest assumptions. It is suitable for a wide variety of applications. Sulfur contamination of the anode compartment is an important cause of performance drop in cells supplied with hydrocarbon-based fuel sources. H₂S, which is often added to hydrocarbon fuels as an odorant, can diminish catalytic behavior of Ni-based anodes by lowering their electrochemical activity and hydrocarbon conversion properties. Therefore, the existing models in the literature for H₂-supplied SOFCs cannot be applied to hydrocarbon-fueled SOFCs as they only account for the electrochemical activity reduction. A regression model is developed in the current work for sulfur contamination of the SOFCs fed with hydrocarbon fuel sources. The model is developed as a function of current density and H₂S concentration in the fuel. To the best of authors' knowledge, it is the first model that accounts for impact of current density on sulfur poisoning of cells supplied with hydrocarbon-based fuels. Proposed model has wide validity over a range of parameters and is consistent across multiple studies by different independent groups. Simulations using the degradation-based model illustrated that SOFCs voltage drops significantly in the first 1500 hours of operation. After that, cells exhibit a slower degradation rate. The present analysis allowed us to discover the reason for various degradation rate values reported in literature for conventional SOFCs. In fact, the reason why literature reports very different degradation rates, is that literature is inconsistent in definition of how degradation rate is calculated. In the literature, the degradation rate has been calculated as the slope of voltage versus time plot with the unit of voltage drop percentage per 1000 hours operation. Due to the nonlinear profile of voltage over time, degradation rate magnitude depends on the magnitude of time steps selected to calculate the curve's slope. To avoid this issue, instantaneous rate of performance drop is used in the present work. According to a sensitivity analysis, the current density has the highest impact on degradation rate compared to other operating factors, while temperature and hydrogen partial pressure affect SOFCs performance less. The findings demonstrated that a cell running at lower current density performs better in long-term in terms of total average energy delivered per year, even though initially it generates less power than if it had a higher current density. This is because of the dominant and devastating impact of large current densities on the long-term performance of SOFCs, as explained by the model.

Keywords: degradation rate, long-term performance, optimal operation, solid oxide fuel cells, SOFCs

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