Compositionally graded YSZ–NiO composites by surface laser melting

Laser surface melting has been applied to near eutectic NiO–YSZ sintered ceramics. The objective is to generate a functional gradient composite material with graded microstructure and composition. At low solidification rates the resultant material has a graded composition, with a severe NiO segregation towards the surface. A thick NiO layer whose thickness depends on the travelling speed is formed. Below this layer the microstructure is eutectic like with composition varying with depth. In contact with the ceramic, excess YSZ coming from the hypereutectic composition forms an almost continuous YSZ layer. The thickness of both segregated layers, NiO and YSZ can be controlled by traverse speed. Thickness decreases as travelling speed increases until a limiting travelling rate of 110 mm/h, at which no more segregation is found. Possible causes to explain the relevant NiO segregation towards the surface are discussed.     

Development of stabilized zirconia–alkali salts dual membranes for carbon dioxide capture

Molten Na₂CO₃–K₂CO₃ (NKC, 56–44 mol%) eutectic compositions were vacuum-impregnated, at the eutectic temperature, into two porous ZrO₂:8.6 mol% MgO (magnesium-partially stabilized zirconia, MgPSZ) and ZrO₂:8 mol% Y₂O₂ (yttria-fully stabilized zirconia, 8YSZ) ceramics. Thermogravimetric analyses were performed in mixtures of that composition with MgPSZ and 8YSZ ceramic powders. Before impregnation, porosity was achieved in the two compounds by addition and thermal removal of 30 vol.% NKC. To ascertain the carbonates had filled up through the ceramic body, both sides of the parallel and fracture surfaces of the disk-shaped impregnated compositions were observed in a scanning electron microscope and analyzed by energy-dispersive X-ray spectroscopy. The electrical conductivity of the two ceramics, before and after impregnation, was evaluated by electrochemical impedance spectroscopy in the 5 Hz–13 MHz frequency range from approximately 530 to 740°C. The permeation of the carbonate ions through the membranes via the eutectic composition was assessed by the threshold temperatures of the onset of the carbonate ion percolation. The objectives were to prepare dual-phase membranes for the separation of carbon dioxide and for the development of carbon dioxide sensors.     

Performance and Evaluation of Cu‐based Nano‐composite Anodes for Direct Utilisation of Hydrocarbon Fuels in SOFCs

The anodes for direct utilisation of hydrocarbon fuels have been developed by using Cu/Ceria‐based nano‐composite powders. The CuO/GDC/YSZ–YSZ or CuO/GDC‐GDC nano‐composite powders were synthesised by coating nano‐sized CuO and CeO₂ particles on the YSZ or GDC core particles selectively by the Pechini process. Their microstructures and electrical properties have been investigated with long‐term stability in reactive gases of dry methane and air. The anodes fabricated using Cu‐based nano‐composite anodes showed almost no carbon deposition until 500 h in dry CH₄ atmosphere. The type of an electrolyte‐supported single cell in conjunction with the Cu/Ceria‐based anode must be selected together for the low melting temperature of Cu/CuO. The GDC electrolyte supported unit cell with the Cu/GDC–GDC anode showed the maximum power density of 0.1 Wcm^–2 and long‐term stability for more than 500 h under electronic load of 0.05 Acm^–2 at 650 °C in dry methane atmosphere.     

Ni–YSZ cermet micro-tubes with textured surface

Tubular Ni–YSZ porous cermets, with the external surface textured in the form of submicron size alternating YSZ and porous Ni lamellae aligned perpendicular to the tube surface have been fabricated. The surface of the ceramic tubes of eutectic composition was directionally solidified in the radial direction using the laser zone melting procedure where the power of the laser was adjusted to melt a thin surface layer. The melt solidified in the very high thermal growth radial gradient produced by radiation losses and convention cooling. A crack free layer with typical eutectic lamellar microstructure, with domains aligned perpendicular to the tube surface, was produced along the external surface of the tubes. The porous cermet tubes were prepared by thermo-chemical reduction of the NiO phase in the previously textured binary NiO–YSZ eutectic precursors. After reduction, porous Ni leaves of about 100 nm lateral dimension were confined between the YSZ lamellae in the textured layer. The influence of growth parameters over microstructure size and morphology is discussed.     

Degradation of Spark Plasma Sintered Yttria Stabilized Zirconia (YSZ) and CeO2‐YSZ Ceramics in Supercritical Water

Zirconia ceramics are often considered in the nuclear industry for high temperature applications due to their radiation resistance, chemical inertness, high thermal stability and low thermal conductivity. However, wide application of zirconia ceramics is hindered by their degradation behavior in aqueous media. In this research, moderately dense 8 mol% Yttria Stabilized Zirconia (YSZ) as well as YSZ based ceramics containing 5, 10 and 15 mol% CeO₂ were fabricated via Spark Plasma Sintering (SPS). Sintered ceramics were subjected to static degradation testing in supercritical water at 400°C and 31 MPa. The weight loss and microstructural changes of the ceramics associated with supercritical water exposure were studied, and the results suggest that the addition of CeO₂ significantly reduced the degradation rate and improved the bulk structural stability of the ceramic composite. This behavior was attributed to the enhanced stabilization of the zirconia lattice, preventing the evolution of the undesirable monoclinic‐ZrO₂ phase.     

Boosting intermediate temperature performance of solid oxide fuel cells via a tri-layer ceria–zirconia–ceria electrolyte

Using cost-effective fabrication methods to manufacture a high-performance solid oxide fuel cell (SOFC) is helpful to enhance the commercial viability. Here, we report an anode-supported SOFC with a three-layer Gd_0.1Ce_0.9O_1.95 (gadolinia-doped-ceria [GDC])/Y_0.148Zr_0.852O_1.926 (8YSZ)/GDC electrolyte system. The first dense GDC electrolyte is fabricated by co-sintering a thin, screen-printed GDC layer with the anode support (NiO–8YSZ substrate and NiO–GDC anode) at 1400°C for 5 h. Subsequently, two electrolyte layers are deposited via physical vapor deposition. The total electrolyte thickness is less than 5 μm in an area of 5 × 5 cm², enabling an area-specific ohmic resistance as low as 0.125 Ω cm⁻² at 500°C (under open circuit voltage), and contributing to a power density as high as 1.2 W cm⁻² at 650°C (at an operating cell voltage of 0.7 V, using humidified [10 vol.% H₂O] H₂ as fuel and air as oxidant). This work provides an effective strategy and shows the great potential of using GDC as an electrolyte for high-performance SOFC at intermediate temperature.     

Processing and characterisation of a fine nickel oxide/zirconia/composite prepared by polymeric complex solution synthesis

A homogeneous dispersion of nickel in a YSZ ceramic matrix by the polymeric organic complex solution method was achieved. A YSZ powder was added to the polymeric gel containing Ni²⁺ cations leading to an organic resin in which the YSZ particles were embedded. By further heat treatment a composite of ultrafine nickel oxide dispersed in the YSZ matrix was attained. After sintering and reducing treatment of nanocrystalline NiO/YSZ composite, the microstructure of the Ni/YSZ cermet showed a uniform distribution of the porous metallic Ni particles of about 1–2 μm surrounded by a microporous space. The electrical properties of NiO/YSZ (55/45 wt.%) composites were studied using impedance spectroscopy in the temperature range from 100 to about 700 °C. Variations in activation energy were in agreement to the NiO electrical behaviour with increasing temperatures for polymer complex solution NiO/YSZ prepared composite, which indicates a uniform and fine-grained microstructure, in which the YSZ–YSZ and/or the NiO–NiO particle contacts were predominant.     

Influence of Deposition Temperature of GDC Interlayer Deposited by RF Magnetron Sputtering on Anode‐Supported SOFC

Gadolinia‐doped ceria (GDC) film, as a barrier layer to prevent chemical reaction between yttria‐stabilized zirconia (YSZ) electrolyte and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–δ (BSCF)–GDC cathode, is deposited by radio frequency (RF) magnetron sputtering on YSZ electrolyte, and the influence of deposition temperature on Ni–YSZ/YSZ/GDC/BSCF–GDC single cell performance is investigated. The SEM results show that the GDC film deposited at 30 °C exhibits a porous structure, whereas the GDC film deposited at 400 °C has a dense structure. The single cells show excellent performance when the deposition temperature is above 250 °C, whereas the single cells show poor performance when the deposition temperature is below 200 °C. The large difference in cell performance occurs from their large difference in polarization resistance. The porous structure of GDC interlayer, which cannot well prevent the reaction between BSCF and YSZ, is responsible for the poor performance of the cells with GDC interlayer deposited at a temperature below 200 °C.     

Synergetic effect of NiO and SiO2 on the sintering and properties of 8 mol% yttria-stabilized zirconia electrolytes

Yttria-doped zirconia electrolytes (e.g., 8 mol% yttria-stabilized ZrO₂, 8YSZ) have been considered to be the most promising candidates for applications in solid oxide fuel cells (SOFC). Due to the ubiquitous presence of SiO₂ impurities and wide use of Ni-containing anodes, it is therefore of great technical importance to understand the synergetic effect of NiO and SiO₂ on densification, grain growth and ionic conductivities (especially the grain boundary (GB) conduction) of zirconia electrolytes. In this study, three groups of 8YSZ ceramics, with Si contents of ∼30, ∼500 and ∼3000 ppm, have been designed. 1 at% NiO was added into these materials by a wet chemical method. The addition of SiO₂ has a negative effect on the sintering and densification, while the introduction of 1 at% NiO reduced the sintering temperature and promotes grain growth of the zirconia ceramics. However, the presence of small amount of NiO prevented full densification of 8YSZ ceramics. NiO also led to a decrease by ∼33% in grain interior (GI) conductivity, with little effect on the GB conduction of high-purity 8YSZ (∼30 ppm SiO₂). However, the coexistence of NiO and SiO₂ is extremely detrimental to total conductivity by significantly reducing the GB conduction. Moreover, it is observed that, unlike the 8YSZ-doped SiO₂ with only, whose GB conduction increases greatly with increasing sintering temperature, the GB conduction of the NiO and SiO₂ codoped samples is less sensitive to sintering temperature.     

Interaction of a ceria‐based anode functional layer with a stabilized zirconia electrolyte: Considerations from a materials perspective

We report on the materials interaction of gadolinium‐doped ceria (GDC) and yttria‐stabilized zirconia (YSZ) in the context of high‐temperature sintering during manufacturing of anode supported solid oxide fuel cells (AS–SOFC). While ceria‐based anodes are expected to show superior electrochemical performance and enhanced sulfur and coking tolerance in comparison to zirconia‐based anodes, we demonstrate that the incorporation of a Ni–GDC anode into an ASC with YSZ electrolyte decreases the performance of the ASC by approximately 50% compared to the standard Ni–YSZ cell. The performance loss is attributed to interdiffusion of ceria and zirconia during cell fabrication, which is investigated using powder mixtures and demonstrated to be more severe in the presence of NiO. We examine the physical properties of a GDC–YSZ mixed phase under reducing conditions in detail regarding ionic and electronic conductivity as well as reducibility, and discuss the expected impact of cation intermixing between anode and electrolyte.     

Wet Atomisation of Gd‐doped CeO2 Electrolyte Slurries for Intermediate Temperatures' Microtubular SOFC Applications

A wet atomising system has been employed as a novel method to prepare ultrafine Gd‐doped CeO₂ (GDC) electrolyte slurries. By changing the fluid flow pressure and repeating the atomisation process several times for the same atomised slurries, we have obtained optimised ultrafine GDC slurry with high‐dispersed and homogeneous distribution. The sizes of the particles of GDC were in the range of tens of nanometres. A highly dense electrolyte layer (membrane) was prepared using the ultrafine GDC slurries for intermediate temperatures microtubular solid oxide fuel cell (SOFC) applications. The SOFC was fabricated by using supporting porous anode tubes of NiO and GDC, and the cathode consisted of La_0.6Sr_0.4Co_0.2Fe_0.8O_3–y and GDC. A dense 10 μm GDC electrolyte layer was obtained at a lower sintering temperature of 1,250 °C for 1 h. The SOFC was tested with humidified (3% H₂O) hydrogen as a fuel and the static air as an oxidant, and the tubular cell maintained its high performance even at 500 °C.     

Synthesis of Highly Porous Yttria-Stabilized Zirconia by Tape-Casting Methods

Porous ceramics of Y₂O₃-stabilized ZrO₂ (YSZ) were prepared by tape-casting methods using both pyrolyzable pore formers and NiO followed by acid leaching. The porosity of YSZ wafers increased in a regular manner with the mass of graphite or polymethyl methacrylate (PMMA) to between 60% and 75% porosity. SEM indicated that the shape of the pores in the final ceramic was related to the shape of the pore formers, so that the pore size and microstructure of YSZ wafers could be controlled by the choice of pore former. Dilatometry measurements showed that measurable shrinkage started at 1300 K, and a total shrinkage of 26% was observed, independent of the amount or type of pore former used. Temperature-programmed oxidation (TPO) measurements on the green tapes demonstrated that the binders and dispersants were combusted between 550 and 750 K, that PMMA decomposed to methyl methacrylate between 500 and 700 K, and that graphite combusted above 900 K. The porosity of YSZ ceramics prepared by acid leaching of nickel from NiO–YSZ, with 50 wt% NiO, was studied as a function of NiO and YSZ particle size. Significant changes in pore dimension were found when NiO particle size was changed.     

Performance of mix‐impregnated CeO2‐Ni/YSZ Anodes for Direct Oxidation of Methane in Solid Oxide Fuel Cells

CeO₂‐Ni/YSZ anodes for methane direct oxidation were prepared by the vacuum mix‐impregnation method. By this method, NiO and CeO₂ are obtained from nitrate decomposition and high temperature sintering is avoided, which is different from the preparation of conventional Ni‐yttria‐stabilised zirconia(YSZ) anodes. Impregnating CeO₂ into the anode can improve the cell performance, especially, when CH₄ is used as fuel_. The investigation indicated that CeO₂‐Ni/YSZ anodes calcined at higher temperature exhibited better stability than those calcined at lower temperature. Under the testing temperature of 1,073 K, the anode calcined at 1,073 K exhibited the best performance. The maximum power density of a cell with a 10 wt.‐%CeO₂‐25 wt.‐%Ni anode calcined at 1,073 K reached 480 mW cm^–2 after running on CH₄ for 5 h. At the same time, high discharge current favoured cell operation on CH₄ when using these anodes. No obvious carbon was found on the CeO₂‐Ni anode after testing in CH₄ as revealed from SEM and corresponding linear EDS analysis. In addition, cell performance decreased at the beginning of discharge testing which was attributed to the anode microstructure change observed with SEM.     

Synthesis and characterization of mullite-ZrO2 porous fibrous ceramic for highly efficient oil-water separation

This work aimed to proposing a new strategy for preparing the mullite-ZrO₂ porous fibrous ceramic used as alternative matrix material for oil-water separation by the aqueous gel-casting method. The properties of the fabricated porous fibrous ceramics in terms of microstructure, phase composition, apparent porosity, bulk density and compressive strength were investigated and the separation behavior was predicted by analyzing the structural changes. It is demonstrated that the phase composition of green bodies consisted of bayerite, boehmite, ZrSiO₄ and YSZ, and the sintered sample contained mullite, ZrO₂ and YSZ. As the YSZ fibers increased, the porosity of the fabricated porous ceramic increased with the maximum value of 70.65% due to the formation of more pores caused by YSZ fibers. Moreover, a significant increase in compressive strength (up to 9.52–21.86 MPa) was observed with the increase of YSZ fibers. Therefore, the fabricated porous ceramics could be appropriative for advanced applications of separation membranes for oil-water separation.     

Effect of variation of NiO on properties of NiO/GDC (gadolinium doped ceria) nano-composites

In the present work, systematic study of series of NiO_x GDC_(1?x) where x = 0.1–0.6; has been reported for the first time. For the synthesis of homogeneous NiO–GDC nanocomposite powders, the nano-powders of NiO and Ce_0.9Gd_0.1O_1.95 (GDC10) synthesized by solution combustion synthesis were mixed in mol % proportion. NiO–GDC nanocomposite can be reduced in situ to form Ni–GDC cermet anode. Hence the Ni–GDC cermet anode combines the catalytic activity and high electronic conduction property of Ni and ionic conductivity of GDC. Nano-crystalline constituents in the NiO–GDC nano composite are believed to give better anodic performance than microcrystalline constituents. Hence the efficient study of the atomistic structure and the accurate characterization of the structural parameters, such as crystallite size and internal strains, are of considerable interest. Therefore the NiO_x–GDC10_1?x nanocomposite powders were characterized by XRD and FTIR spectroscopy. Further these powders were pelletized, sintered and characterized by FE-SEM and d.c. conductivity.     

Effect of GDC addition method on the properties of LSM–YSZ composite cathode support for solid oxide fuel cells

Equal amounts of Gd_0.1Ce_0.9O_2−δ (GDC) were added to La_0.65Sr_0.3MnO_3−δ/(Y₂O₃)_0.08(ZrO₂)_0.92 (LSM/YSZ) powder either by physical mixing or by sol–gel process, to produce a porous cathode support for solid oxide fuel cells (SOFCs). The effect of the GDC mixing method was analyzed in view of sinterability, thermal expansion coefficient, microstructure, porosity, and electrical conductivity of the LSM/YSZ composite. GDC infiltrated LSM/YSZ (G-LY) composite showed a highly porous microstructure when compared with mechanically mixed LSM/YSZ (LY) and LSM/YSZ/GDC (LYG) composites. The cathode support composites were used to fabricate the button SOFCs by slurry coating of YSZ electrolyte and a nickel/YSZ anode functional layer, followed by co-firing at 1250 °C. The G-LY composite cathode-supported SOFC showed maximum power densities of 215, 316, and 396 mW cm⁻² at 750, 800, and 850 °C, respectively, using dry hydrogen as fuel. Results showed that the GDC deposition by sol–gel process on LSM/YSZ powder before sintering is a promising technique for producing porous cathode support for the SOFCs.     

Directly fabricated Al2O3/GdAlO3 eutectic ceramic with large smooth surface by selective laser melting: Rapid solidification behavior and thermal field simulation

Selective laser melting (SLM), a novel approach for one-step melting and solidifying ceramic powder beds layer by layer without post-process of degreasing and sintering, has been developed to directly prepare highly dense (>95 %) Al₂O₃/GdAlO₃(GAP) eutectic composite ceramics with large smooth surfaces. Compact net-shaped plates with the maximum size of 73 × 24 × 5 mm³ are obtained by different strategies of laser pre-heating and multi-tracks’ deposition without any binders. Combined with the finite element thermodynamic coupling simulation results, it is proved that the stress between the substrate and depositions during SLM can be greatly reduced by the step-up preheating, and thus effectively improving the ceramic forming quality. The macro-morphology, microstructure evolution, rapid solidification behavior and mechanical properties of the SLM-ed eutectic ceramics are systematically investigated at different laser processing parameters. The microstructure transforms from ultra-fine irregular eutectic to complex regular eutectic with the increase of the scanning rate. The average eutectic spacing, and solidification rate has an approximately linear relationship consistent with the Jackson-Hunt (JH) model. The microhardness and fracture toughness can reach 17.1 ± 0.2 GPa and 4.5 ± 0.1 MPa·m^1/2, respectively. The results indicate that SLM method is a highly effective technique for fabricating high-performance net-shaped structural composite ceramics.     

Microwave Dielectric Properties of SrO–2CeO2–nTiO2 (n=4 and 5) Ceramics

SrO–2CeO₂–nTiO₂ ceramics with n=4 and 5 have been prepared through conventional solid-state ceramic route. Structural and microstructural characterizations of the sintered ceramics were carried out using X-ray diffraction, laser Raman, and scanning electron microscopic studies. Microwave dielectric properties have been measured using postresonator and resonant cavity techniques. SrO–2CeO₂–4TiO₂ and SrO–2CeO₂–5TiO₂ ceramics showed dielectric constants of 71.3 and 71.7, respectively, around 4 GHz together with a relatively high unloaded quality factor.     

Stability properties and microstructure properties of microwave-sintered CeO2 doped zirconia ceramics

Nanosized CeO₂–ZrO₂ powders prepared by atmospheric pressure pyrolysis were used as raw materials to prepare CeO₂–ZrO₂ ceramics using microwave sintering. The samples were characterised using bulk density measurements, X-ray diffraction (XRD), Fourier Transform Infrared Spectrometer (FT-IR), Raman, and scanning electron microscopy (SEM). The purpose was to determine the optimised microwave sintering process for CeO₂–ZrO₂ ceramics and reveal the corresponding mechanism. The results show that with a CeO₂ addition content above 5 mol%, the tetragonal phase peak appeared obviously in the sample. The results show that the tetragonal phase peak appears when the CeO₂ content is more than 5 mol%. The dopants, namely CeO₂, have reduced the solid solution's phase transformation temperature with the assistance of microwave heating. Additionally, the grain size of the CeO₂–ZrO₂ ceramics has shown a negative relationship with Ce content at a temperature of 900 °C. The reason is that the rapid sintering due to microwave sintering and the oxygen vacancies generated by CeO₂ can effectively inhibit grain growth. The regulation mechanism on microwave sintering of CeO₂–ZrO₂ ceramic was clarified, and the technical prototype of controlled prepared CeO₂–ZrO₂ ceramics by microwave sintering was constructed.     

Electrochemical performance of intermediate temperature micro-tubular solid oxide fuel cells using porous ceria barrier layers

We describe the manufacture and electrochemical characterization of micro-tubular anode supported solid oxide fuel cells (mT-SOFC) operating at intermediate temperatures (IT) using porous gadolinium-doped ceria (GDC: Ce_0.9Gd_0.1O_2−δ) barrier layers. Rheological studies were performed to determine the deposition conditions by dip coating of the GDC and cathode layers. Two cell configurations (anode/electrolyte/barrier layer/cathode): single-layer cathode (Ni–YSZ/YSZ/GDC/LSCF) and double-layer cathode (Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF) were fabricated (YSZ: Zr_0.92Y_0.16O_2.08; LSCF: La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ). Effect of sintering conditions and microstructure features for the GDC layer and cathode layer in cell performance was studied. Current density–voltage (j–V) curves and impedance spectroscopy measurements were performed between 650–800 °C, using wet H₂ as fuel and air as oxidant. The double-cathode cells using a GDC layer sintered at 1400 °C with porosity about 50% and pores and grain sizes about 1 μm, showed the best electrochemical response, achieving maximum power densities of up to 160 mW cm⁻² at 650 °C and about 700 mW cm⁻² at 800 °C. In this case GDC electrical bridges between cathode and electrolyte are preserved free of insulating phases. A preliminary test under operation at 800 °C shows no degradation at least during the first 100 h. These results demonstrated that these cells could compete with standard IT-SOFC, and the presented fabrication method is applicable for industrial-scale.