Role of oxygen pressure on the stability of lanthanum strontium manganite–yttria stabilized zirconia composite

We have investigated the structural and chemical stability of La_0.8Sr_0.2MnO₃ (LSM)–8 mol.% yttria stabilized zirconia (YSZ) composite. LSM and YSZ powders were mixed and sintered at 1400 °C for 10 h in controlled atmosphere (PO₂ = 0.21 to 10^?6 atm). The unit cell volume of LSM increases during exposure to reduced oxygen partial pressure while it remains unchanged for YSZ. During reduction in the oxygen partial pressure from 0.21 atm to 10^?6 atm, the solubility of manganese in YSZ increases from ～10 at.% to ～15 at.%. Lower oxygen partial pressure also results in the grain growth and formation of La₂Zr₂O₇ and MnO_x (Mn₃O₄) compounds lowering the stability of the LSM–YSZ composite. On subsequent sintering in 0.21 atm PO₂, the La₂Zr₂O₇ and MnO_x compounds tend to disappear indicating the reversibility of the interaction. The reversibility of LSM–YSZ reaction has been independently confirmed using La₂Zr₂O₇ and MnO_x.     

Evolution of hot corrosion resistance of YSZ,Gd2Zr2O7, and Gd2Zr2O7 + YSZ composite thermal barrier coatings in Na2SO4 + V2O5 at 1050 °C

This paper compares the hot corrosion performance of yttria stabilized zirconia (YSZ), Gd₂Zr₂O₇, and YSZ + Gd₂Zr₂O₇ composite coatings in the presence of molten mixture of Na₂SO₄ + V₂O₅ at 1050 °C. These YSZ and rare earth zirconate coatings were prepared by atmospheric plasma spray (APS). Chemical interaction is found to be the major corrosive mechanism for the deterioration of these coatings. Characterizations using X-ray diffraction (XRD) and scanning electron microscope (SEM) indicate that in the case of YSZ, the reaction between NaVO₃ and Y₂O₃ produces YVO₄ and leads to the transformation of tetragonal ZrO₂ to monoclinic ZrO₂. For the Gd₂Zr₂O₇ + YSZ composite coating, by the formation of GdVO₄, the amount of YVO₄ formed on the YSZ + Gd₂Zr₂O₇ composite coating is significantly reduced. Molten salt also reacts with Gd₂Zr₂O₇ to form GdVO₄. Under a temperature of 1050 °C, Gd₂Zr₂O₇ based coatings are more stable, both thermally and chemically, than YSZ, and exhibit a better hot corrosion resistance.     

Properties evolution of plasma-sprayed La2Zr2O7 coating induced by pore structure evolution during thermal exposure

To study the inter-lamellar pores evolution under thermal exposure and how it affects the coating properties, free standing atmospheric plasma sprayed (APS) La₂Zr₂O₇ (LZO) coating was subjected to thermal exposure at the temperatures of 1200 °C and 1300 °C for different durations. It was found that APS LZO coating experiences a rapid sintering during the early 5–20 h of thermal exposure. Such microstructure evolution behavior was attributed to the presence of the lamellar structure, which contains most 2D pores with a small inter-lamellar spacing. As a result, the density, inter-lamellar bonding ratio, mechanical properties and thermal conductivity of the LZO coating remarkably increase in about 20 h of thermal exposure. It was revealed that the evolution of the properties of the APS LZO coating during high temperature exposure is mainly ascribed to the shape change of the inter-lamellar pores for the formation of grain bridging in inter-lamellar pores.     

Characterisation of the microstructure and thermal properties of Nd2Zr2O7 and Nd2Zr2O7/YSZ thermal barrier coatings

The microstructure of following thermal barrier coatings (TBC) was characterised in this paper: monolayer coatings Nd₂Zr₂O₇ and 8YSZ; a double ceramic layered (DCL) coating. Coatings were characterised by thicknesses that did not exceed 300 μm and porosities of approx. 5%. The chemical and phase composition analysis of the DCL layers revealed an external Nd₂Zr₂O₇ ceramic layer approx. 80 μm thick, a transitional zone approx. 120 μm thick and an internal 8YSZ layer 100 μm thick. For the case of the monolayer coating, the Nd₂Zr₂O₇ pyrochlore phase was the only one-phase component. The surface topography of both TBC systems was typical for plasma sprayed coatings, and compressive stress state had a value of approx. 5–10 MPa. Measurements of the thermal parameters, i.e., thermal diffusivity, point to considerably better insulative properties for both new types of layers when compared to the standard 8YSZ layers.     

Thermal shock behavior of 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The single-ceramic-layer (SCL) 8YSZ (conventional and nanostructured 8YSZ) and double-ceramic-layer (DCL) La₂Zr₂O₇ (LZ)/8YSZ thermal barrier coatings (TBCs) were fabricated by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal shock behavior of the three as-sprayed TBCs at 1000 °C and 1200 °C was investigated. The results indicate that the thermal cycling lifetime of LZ/8YSZ TBCs is longer than that of SCL 8YSZ TBCs due to the fact that the DCL LZ/8YSZ TBCs further enhance the thermal insulation effect, improve the sintering resistance ability and relieve the thermal mismatch between the ceramic layer and the metallic layer at high temperature. The nanostructured 8YSZ has higher thermal shock resistance ability than that of the conventional 8YSZ TBC which is attributed to the lower tensile stress in plane and higher fracture toughness of the nanostructured 8YSZ layer. The pre-existed cracks in the surface propagate toward the interface vertically under the thermal activation. The nucleation and growth of the horizontal crack along the interface eventually lead to the failure of the coating. The crack propagation modes have been established, and the failure patterns of the three as-sprayed coatings during thermal shock have been discussed in detail.     

Influence of the deposition energy on the composition and thermal cycling behavior of La2(Zr0.7Ce0.3)2O7 coatings

Lanthanum–zirconium–cerium composite oxide (La₂(Zr_0.7Ce_0.3)₂O₇, LZ7C3) coatings were prepared under different conditions by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, surface and cross-sectional morphologies, cyclic oxidation behavior of these coatings were studied. Elemental analysis indicates that the coating composition has partially deviated from the stoichiometry of the ingot, and the existence of excess La₂O₃ is also observed. The optimized composition of LZ7C3 coatings could be effectively achieved by the addition of excess CeO₂ into the ingot or by properly controlling the deposition energy. Meanwhile, when the deposition energy is 1.15 × 10⁴–1.30 × 10⁴ J/cm², the coating has a similar X-ray diffraction (XRD) pattern to the ingot, and the thermal cycling life of the coating is also superior to other coatings. The spallation of the coatings occurs either within the ceramic layer approximately 6–10.5 μm above its thermally grown oxide (TGO) layer or at the interface between ceramic layer and bond coat.     

Improvement on the phase stability,mechanical properties and thermal insulation of Y2O3-stabilized ZrO2 by Gd2O3 and Yb2O3 co-doping

Gd₂O₃ and Yb₂O₃ co-doped 3.5 mol% Y₂O₃–ZrO₂ and conventional 3.5 mol% Y₂O₃–ZrO₂ (YSZ) powders were synthesized by solid state reaction. The objective of this study was to improve the phase stability, mechanical properties and thermal insulation of YSZ. After heat treatment at 1500 °C for 10 h, 1 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (1Gd1Yb-YSZ) had higher resistance to destabilization of metastable tetragonal phase than YSZ. The hardness of 5 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (5Gd1Yb-YSZ) was higher than that of YSZ. Compared with YSZ, 1Gd1Yb-YSZ and 5Gd1Yb-YSZ exhibited lower thermal conductivity and shorter phonon mean free path. At 1300 °C, the thermal conductivity of 5Gd1Yb-YSZ was 1.23 W/m K, nearly 25% lower than that of YSZ (1.62 W/m K). Gd₂O₃ and Yb₂O₃ co-doped YSZ can be explored as a candidate material for thermal barrier coating applications.     

A simple non-destructive method to indicate the spallation and damage degree of the double-ceramic-layer thermal barrier coating of La2(Zr0.7Ce0.3)2O7 and 8YSZ:Eu

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and Eu³⁺-doped zirconia, which was partially stabilised by 8 wt% yttria (8YSZ:Eu), were prepared by atmospheric plasma spraying. A thermal cycling test was carried out. The 8YSZ:Eu sublayer exposed during thermal cycling could produce visible luminescence under ultraviolet (UV) illumination, providing an indication of the spallation and damage degree of the coating. The result shows that the application of a Eu³⁺-doped luminescence sublayer can be a very simple and useful non-destructive technique to indicate the spallation and damage degree of DCL coatings.     

Improvement in thermal shock resistance of gadolinium zirconate coating by addition of nanostructured yttria partially-stabilized zirconia

Gadolinium zirconate (Gd₂Zr₂O₇, GZ) as one of the promising thermal barrier coating materials for high-temperature application in gas turbine was toughened by nanostructured 3 mol% yttria partially-stabilized zirconia (YSZ) incorporation. The fracture toughness of the composite of 90 mol% GZ-10 mol% YSZ (GZ–YSZ) was increased by about 60% relative to the monolithic GZ. Both the GZ and GZ–YSZ composite coatings were deposited by atmospheric plasma spraying on Ni-base superalloys and then thermal-shock tested under the same conditions. The thermal-shock lifetime of GZ–YSZ composite coating was improved, which is believed to be mainly attributed to the enhancement of fracture toughness by the addition of YSZ. In addition, the failure mechanisms of the thermal-shock tested GZ–YSZ composite coatings were discussed.     

The effect of La2O3 on the microstructure and room temperature mechanical properties of t-ZrO2

Structural and mechanical properties of La₂O₃ added (up to 5 wt%) t-ZrO₂ compacts were examined with the aim of optimizing hardness and fracture toughness for room temperature applications. Structural examinations were performed using an X-ray diffractometer and a scanning electron microscope. Mechanical properties of the compacts were determined as modulus of elasticity, hardness and fracture toughness by conducting Vickers indentation tests under test loads of 0.5, 1 and 10 kg. Addition of 0.5 wt% La₂O₃ deteriorated the room temperature stability of t-ZrO₂ by forming m-ZrO₂ and coarse polygonal grains in the matrix. Higher concentrations (2 and 5 wt% La₂O₃) caused precipitation of La₂Zr₂O₇ at the grain boundaries, which also accompanied by a reduction in hardness. Fracture toughness increased with increasing La₂O₃ content of the compact. Finally, an optimum combination between hardness and fracture toughness was obtained for the 0.5 wt% La₂O₃ containing compact.     

Microstructure and thermal properties of nanostructured gadolinia doped yttria-stabilized zirconia thermal barrier coatings produced by air plasma spraying

In this article, the nanostructured 2 mol% Gd₂O₃-4.5 mol% Y₂O₃-ZrO₂(2GdYSZ) coating was developed by the atmospheric plasma spraying technique. And the microstructure and thermal properties of plasma-sprayed 2GdYSZ coating were investigated. The result from the investigation indicates that the as-sprayed coating is characterized by typical microstructure consisting of melted zones, nano-zones, splats, nano-pores, high-volume spheroidal pores and micro-cracks. The 2GdYSZ coating shows a lower resistance to destabilization of the metastable tetragonal (t′) phase compared to the yttria stabilized zirconia(YSZ). The thermal diffusivity and thermal conductivity of the nano-2GdYSZ coating at room temperature are 0.431 mm² s⁻¹ and 1.042 W/m K, respectively. Addition of gadolinia to the nano-YSZ can significantly reduce the thermal conductivity compared to the nano-YSZ and the conventional YSZ. The reduction is mainly attributed to the synergetic effect of gadolinia doping along with nanostructure.     

Constrained sintering of YSZ/Al2O3 composite coatings on metal substrates produced from eletrophoretic deposition

Yttria stabilized zirconia/alumina (YSZ/Al₂O₃) composite coatings were prepared from electrophoretic deposition (EPD), followed by sintering. The constrained sintering of the coatings on metal substrates was characterized with microstructure examination using electron microscopy, mechanical properties examination using nanoindentation, and residual stress measurement using Cr³⁺ fluorescence spectroscopy. The microstructure close to the coating/substrate interface is more porous than that near the surface of the EPD coatings due to the deposition process and the constrained sintering of the coatings. The sintering of the YSZ/Al₂O₃ composite coating took up to 200 h at 1250 °C to achieve the highest density due to the constraint of the substrate. When the coating was sintered at 1000 °C after sintering at 1250 °C for less than 100 h, the compressive stress was generated due to thermal mismatch between the coating and metal substrate, leading to further densification at 1000 °C because of the ‘hot pressing’ effect. The relative densities estimated based on the residual stress measurements are close to the densities measured by the Archimedes method, which excludes an open porosity effect. The densities estimated from the hardness and the modulus measurements are lower than those from the residual stress measurement and the Archimedes method, because it takes account of the open porosity.     

Molten salt synthesis of La2Zr2O7 ultrafine powders

Ultrafine powders of pyrochlore-type La₂Zr₂O₇ were synthesized via a simple molten salt mediated process using zirconium oxide and lanthanum oxide as raw materials, and sodium chloride, potassium chloride and sodium fluoride to form a reaction medium. The effects of reaction temperature, salt/reactant ratio and salt type on the La₂Zr₂O₇ formation were investigated. Among the three attempted salt assemblies (KCl–LiCl, Na₂CO₃–K₂CO₃, and NaCl–KCl–NaF), NaCl–KCl–NaF showed the best accelerating effect on the La₂Zr₂O₇ formation. At a given temperature, the La₂Zr₂O₇ content in the final products increased with the increase in the salt amount. Phase pure submicron sized La₂Zr₂O₇ ultrafine powders were obtained after 3 h firing at 1100 °C with the salt/reactant weight ratio of 5:1 or at 1200 °C with salt/reactant weight ratio of 3:1. The synthesis temperature (1100 °C) was much lower than that required by the conventional solid-state mixing method or a wet chemical method. The “dissolution–precipitation” mechanism had dominated the synthesis process.     

Structural characterization of YSZ/Al2O3 nanostructured composite coating fabricated by electrophoretic deposition and reaction bonding

Suspension of YSZ and Al particles in acetone in presence of 1.2 g/l iodine as dispersant was used for electrophoretic deposition of green form YSZ/Al coating. Results revealed that applied voltage of 6 V and deposition time of 3 min were appropriate for deposition of green composite form coating. After deposition, a nanostructured dense YSZ/Al₂O₃ composite coating was fabricated by oxidation of Al particles at 600 °C for 2 h and subsequently sintering heat treatment at 1000 °C for 2 h. Melting and oxidation of Al particles in the green form composite coating not only caused reaction bonding between the particles but also lowered the sintering temperature of the ceramic coating about 200 °C. The EDS maps confirmed that the composition of fabricated coating was uniform and Al₂O₃ particles were dispersed homogenously in YSZ matrix.     

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.     

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.     

Microstructural characterization of GZ/CYSZ thermal barrier coatings after thermal shock and CMAS+hot corrosion test

In this study, first, Gd₂Zr₂O₇/ceria–yttria stabilized zirconia (GZ/CYSZ) TBCs having multilayered and functionally graded designs were subjected to thermal shock (TS) test. The GZ/CYSZ functionally graded coatings displayed better thermal shock resistance than multilayered and single layered Gd₂Zr₂O₇ coatings. Second, single layered YSZ and functionally graded eight layered GZ/CYSZ coating (FG8) having superior TS life time were selected for CMAS + hot corrosion test. CMAS + hot corrosion tests were carried out in the same experiment at once. Furthermore, to generate a thermal gradient, specimens were cooled from the back surface of the substrate while heating from the top surface of the TBC by a CO₂ laser beam. Microstructural characterizations showed that the reaction products were penetrated locally inside of the YSZ. On the other hand, a reaction layer having ∼6 μm thickness between CMAS and Gd₂Zr₂O₇ was seen. This reaction layer inhibited to further penetration of the reaction products inside of the FG8.     

Effects of manganese oxide addition and reductive atmosphere annealing on the phase stability and microstructure of yttria stabilized zirconia

The effects of Mn₃O₄ addition and reductive atmosphere (N₂:H₂ = 97:3) annealing on the microstructure and phase stability of yttria stabilized zirconia (YSZ) ceramics during sintering at 1500 °C for 3 h in air and subsequent annealing in a reductive atmosphere were investigated. Mn₃O₄ added 6 mol% YSZ (6YSZ) and 10 mol% YSZ (10YSZ) ceramics were prepared via the conventional solid-state reaction processes. The X-ray diffraction results showed that a single cubic phase of ZrO₂ was obtained in 1 mol% Mn₃O₄ added 6YSZ ceramic at a sintering temperature of 1500 °C for 3 h. A trace amount of monoclinic ZrO₂ phases were observed for 1 mol% Mn₃O₄ added 6YSZ ceramics after annealing at 1300 °C for 60 cycles in a reductive atmosphere by transmission electron microscopy. Furthermore, a single cubic ZrO₂ phase existed stably as Mn₃O₄ added 10YSZ ceramics was annealed at 1300 °C for 60 cycles in reductive atmosphere.     

New double-ceramic-layer thermal barrier coatings based on zirconia–rare earth composite oxides

A series of La₂O₃–ZrO₂–CeO₂ composite oxides were synthesized by solid-state reaction. The final product keeps fluorite structure when the molar ratio Ce/Zr ≥ 0.7/0.3, and below this ratio only mixtures of La₂Zr₂O₇ (pyrochlore) and La₂O₃–CeO₂ (fluorite) exist. Averagely speaking, the increase of CeO₂ content gives rise to the increase of thermal expansion coefficient and the reduction of thermal conductivity, but La₂(Zr_0.7Ce_0.3)₂O₇ has the lowest sintering ability and the lowest thermal conductivity which could be explained by the theory of phonon scattering. Based on the large thermal expansion coefficient of La₂Ce_3.25O_9.5, the low thermal conductivities and low sintering abilities of La₂Zr₂O₇ and La₂(Zr_0.7Ce_0.3)₂O₇, double-ceramic-layer thermal barrier coatings were prepared. The thermal cycling tests indicate that such a design can largely improve the thermal cycling lives of the coatings. Since no single material that has been studied so far satisfies all the requirements for high temperature thermal barrier coatings, double-ceramic-layer coating may be an important development direction of thermal barrier coatings.     

Electrochemical decomposition of NO over composite electrodes on YSZ electrolyte

NO decomposition over electrochemical cells that involve a bilayered composite electrode has been investigated. NO was decomposed only after a minimum current density was applied and its conversion increased abruptly with increasing applied current. The compositions of phases and their spatial distribution on the cathode strongly influenced the decomposition activity as a function of the current density since they are directly correlated with the site and number densities of the triple-phase boundary and the electrochemically induced active site, i.e., F-center. The [(La₂Sn₂O₇ + YSZ)/Pt] electrode could convert more than 85% of NO into N₂ at 200 mA/cm² whereas only 27% was decomposed over the platinum electrode although the latter was more electrochemically active at lower current ∼70 mA/cm². The addition of Pt into the [(La₂Sn₂O₇ + YSZ)/Pt] composite electrode not only expands the densities of the tpb and F-centers but also enhances competitive NO adsorption as indirectly confirmed by impedance spectroscopy, both of which promote NO conversion at the lower current density.