Optical properties of gadolinia-doped cubic yttria stabilized zirconia single crystals

Cubic zirconia single crystals stabilized with yttria and doped with Gd₂O₃ (0.10–5.00 mol%) were prepared by the optical floating zone method, and characterized by a combination of X-ray diffraction (XRD), and Raman, electron paramagnetic resonance (EPR), ultraviolet–visible (UV–Vis), photoluminescence excitation (PLE) and photoluminescence (PL) spectroscopic techniques. XRD and Raman spectroscopy showed that the crystal samples were all in the cubic phase, whereas the ceramic sample consisted of a mixture of monoclinic and cubic phases. The absorption spectrum showed four peaks at 245, 273, 308, and 314 nm in the ultraviolet region, and the optical band gap differed between samples with ≤3.00 mol% and those with >3.00 mol% Gd₂O₃. The emission spectrum showed a weak peak at 308 nm and a strong peak at 314 nm, which are attributed to the ⁶P_5/2 → ⁸S_7/2 and ⁶P_7/2 → ⁸S_7/2 transitions of Gd³⁺, respectively. The intensities of the peaks in the excitation and emission spectra increased with Gd³⁺ concentration, reached a maximum at 2.00 mol%, then decreased with higher concentrations. This quenching is considered to be the result of the electric dipole-dipole interactions, and this interpretation is supported by the Gd³⁺ EPR spectra, which showed progressive broadening with increasing Gd³⁺ concentration throughout the concentration range investigated.     

Simulation of thermal barrier coating spallation induced by the initiation/growth/coalescence of internal crack and interfacial crack based on a real image model

In the furnace cycle test, the growth of oxide film leads to the propagation and coalescence of multiple cracks near the interface, which should be responsible for the spallation of thermal barrier coatings (TBCs). A TBC model with real interface morphology is created, and the near-interface large pore is retained. The purpose of this work is to clarify the mechanism of TBC spallation caused by successive initiation, propagation, and linkage of cracks near the interface during thermal cycle. The dynamic growth of thermally grown oxide (TGO) is carried out by applying a stress-free strain. The crack nucleation and arbitrary path propagation in YSZ and TGO are simulated by the extended finite element method (XFEM). The debonding along the YSZ/TGO/BC interface is evaluated using a surface-based cohesive behavior. The large-scale pore in YSZ near the interface can initiate a new crack. The ceramic crack can propagate to the YSZ/TGO interface, which will accelerate the interfacial damage and debonding. For the TGO/BC interface, the normal compressive stress and small shear stress at the valley hinder the further crack propagation. The growth of YSZ crack and the formation of through-TGO crack are the main causes of TBC delamination. The accelerated BC oxidation increases the lateral growth strain of TGO, which will promote crack propagation and coalescence. The optimization design proposed in this work can provide another option for developing TBC with high durability.     

Exploring the influences of the counterpart materials on friction and wear behaviors of atmospheric plasma-sprayed YSZ coating

Sliding wear behaviors of atmospheric plasma-sprayed Yttria Stabilized Zirconia (YSZ) coating mated with four metallic or ceramic counterparts (Si₃N₄, Al₂O₃, GCr15 and ZrO₂) were investigated. It has been found that YSZ coatings in contact with Si₃N₄ and GCr15 show better tribological performances than the other cases, which is due to the formation of the tribolayer mainly consisting of Si₃N₄ and Fe₂O₃ respectively on the worn surfaces. In the case of YSZ coating-Al₂O₃ and YSZ coating-ZrO₂ tribopairs, the wear debris are more irregular and larger in size, resulting in severe abrasive wear and brittle fracture of debris particles. In particular, the specific wear rate of YSZ coating sliding against GCr15 is negative due to the significant material transfer of the tribo-oxide layer, while that of YSZ coating sliding against ZrO₂ is the highest. Amorphization of the wear particles appears in the four cases due to the repeated mechanical action. It has been demonstrated that the wear of YSZ coating deteriorates with the increased flash temperature between the contact surfaces during rubbing process.     

Pulsed current-driven wetting of 3YSZ by liquid Cu and its mechanisms

The wettability of 3 mol% Y₂O₃-stabilized ZrO₂ (3YSZ) by molten Cu can be greatly improved by applying pulsed currents at 1373 K. The improvement was closely related to current polarity and influenced by duty cycle and frequency. When the Cu/3YSZ interface was under cathodic condition, the wettability was mainly improved by the formation of substoichiometric ZrO_2-δ and metallic Zr at the interface. Increasing duty cycle caused the interface to change from forming protrusions to creating depression. Decreasing frequency further deepened the depression. In the opposite polarity, the adsorption and enrichment of oxygen reduced the solid-liquid and liquid-vacuum interfacial energies, thus improving the wettability. Only bubbles formed at the interface. The larger the duty cycle, the more rapidly bubbles formed and escaped. The effect of frequency at this polarity was weak. Overall, this work provides a novel and effective strategy for tailoring the wettability and interfacial chemistry between zirconia and metals.     

Corrosion behavior of air plasma spraying zirconia-based thermal barrier coatings subject to Calcium–Magnesium–Aluminum-Silicate (CMAS) via burner rig test

Three different kinds of thermal barrier coatings (TBCs) — 8YSZ, 38YSZ and a dual-layered (DL) TBCs with pure Y₂O₃ on the top of 8YSZ were produced on nickel-based superalloy substrate by air plasma spraying (APS). The Calcium–Magnesium–Aluminum-Silicate (CMAS) corrosion resistance of these three kinds of coatings were researched via burner rig test at 1350 °C for different durations. The microstructures and phase compositions of the coatings were characterized by SEM, EDS and XRD. With the increase of Y content, TBCs exhibit better performance against CMAS corrosion. The corrosion resistance against CMAS of different TBCs in descending was 8YSZ + Y₂O₃, 38YSZ and 8YSZ, respectively. YSZ diffused from TBCs into the CMAS, and formed Y-lean ZrO₂ in TBCs because of the higher diffusion rate and solubility of Y³⁺ in CMAS than Zr⁴⁺. At the same time, 38YSZ/8YSZ + Y₂O₃ reacts with CAMS to form Ca₄Y₆(SiO₄)₆O/Y_4·67(SiO₄)₃O with dense structure, which can prevent further infiltration of CMAS. The failure of 8YSZ coatings occurred at the interface between the ceramic coating and the thermally grown oxide scale (TGO)/bond coating. During the burner rig test, the Y₂O₃ layer of the DL TBCs peeled off progressively and the 8YSZ layer exposed gradually. DL coatings keep roughly intact and did not meet the failure criteria after 3 h test. 38YSZ coating was partially ablated, the overall thickness of the coating is thinned simultaneously after 2 h. Therefore, 8YSZ + Y₂O₃ dual-layered coating is expected to be a CMAS corrosion-resistant TBC with practical properties.     

Erosion behavior of EB-PVD 7YSZ coatings under corrosion/erosion regime: Effect of TBC microstructure and the CMAS chemistry

Aero-engines operating in dust-laden environments often encounter a lot of dust/sand that causes a severe problem to the TBCs by means of erosion. As the turbine entry temperatures are rising, molten sand is also a big concern to the life-time of TBCs.This paper deals with the TBC behavior under the combined influence of erosion and corrosion attack. Variations in TBC morphology, CMAS infiltration time and CMAS composition and their influence on the erosion resistance at room temperature were investigated. Two different EB-PVD 7YSZ morphologies consisting of a different porosity arrangement were tested in the erosion/corrosion regime. The more ‘Feathery’ structure has a better resistance to erosion compared to a more columnar ‘Normal’ structure, which leads to less degradation of the TBC. However, under the influence of CMAS infiltration the effect was found to be reversed. In general, CMAS-infiltrated EB-PVD TBCs exhibit a higher erosion resistance than the non-infiltrated ones.     

Image analysis of the porous yttria-stabilized zirconia (YSZ) structure for a lanthanum ferrite-impregnated solid oxide fuel cell (SOFC) electrode

Image analysis and quantification were performed on porous scaffolds for building SOFC cathodes using the two types of YSZ powders. The two powders (U1 and U2) showed different particle size distribution and sinterability at 1300?°C. AC impedance on symmetrical cells was used to evaluate the performance of the electrode impregnated with 35-wt.% La_0.8Sr_0.2FeO₃. For example, at 700?°C, the electrode from U2 powder shows a polarization resistance (R_p) of 0.21?Ω?cm², and series resistance (R_s) of 8.5?Ω?cm² for an YSZ electrolyte of 2-mm thickness, lower than the electrode from U1 powder (0.25?Ω?cm² for R_p and 10?Ω?cm² for R_s) does. The quantitative study on image of the sintered scaffold indicates that U2 powder is better at producing architecture of high porosity or long triple phase boundary (TPB), which is attributed as the reason for the higher performance of the LSF-impregnated electrode.     

EB-PVD alumina (Al2O3) as a top coat on 7YSZ TBCs against CMAS/VA infiltration: Deposition and reaction mechanisms

Al₂O₃ was deposited as a top coat on a standard 7YSZ layer (or layers) by means of EB-PVD technique and the corresponding morphology of the Al₂O₃/7YSZ coatings was studied in detail. This multi-layer TBC system was tested against calcium-magnesium-aluminium-silicate (CMAS) recession by performing infiltration experiments for different time intervals from 5?min to 50?h at 1250?°C using two types of synthetic CMAS compositions and Eyjafjallajökull volcanic ash (VA) from Iceland. The results show that the studied EB-PVD Al₂O₃/7YSZ coatings react quickly with CMAS or VA melt and form crystalline spinel (MgAl_2-xFe_xO₄) and anorthite (CaAl₂Si₂O₄) phases. The presence of Fe-oxide in the CMAS has been found to be key element in influencing the spinel formation which was proved to be more efficient against CMAS sealing in comparison to the Fe-free CMAS compositions. Even though a rapid crystallization was assured, shrinkage cracks in the EB-PVD alumina layer produced during the crystallization heat treatment have proven to be detrimental for the CMAS/VA infiltration resistance. To overcome these microstructural drawbacks, an additional alumina deposition method, namely reaction-bonded alumina oxide (RBAO), was applied on top of EB-PVD Al₂O_3. RBAO acts as a sacrificial layer forming stable reaction products inhibiting further infiltration.     

Wetting,infiltration and interaction behavior of CMAS towards columnar YSZ coatings deposited by plasma spray physical vapor

Thermal barrier coatings (TBCs) produced by electron beam physical vapor deposition (EB-PVD) or plasma spray (PS) usually suffer from molten calcium-magnesium-alumino-silicate (CMAS) attack. In this study, columnar structured YSZ coatings were fabricated by plasma spray physical vapor deposition (PS-PVD). The coatings were CMAS-infiltrated at 1250?°C for short terms (1, 5, 30?min). The wetting and spreading dynamics of CMAS melt on the coating surface was in-situ investigated using a heating microscope. The results indicate that the spreading evolution of CMAS melt can be described in terms of two stages with varied time intervals and spreading velocities. Besides, the PS-PVD columnar coating (～100?μm thick) was fully penetrated by CMAS melt within 1?min. After the CMAS attack for 30?min, the original feathered-YSZ grains (tetragonal phase) in both PS-PVD and EB-PVD coatings were replaced by globular shaped monoclinic ZrO₂ grains in the interaction regions.     

Aid of a metallic functional layer on Ni/YSZ anode for Direct Methane Fuel Cell

Aid of a metallic overlayer to nickel/yttrium-stabilized-zirconia (Ni/YSZ) anode is investigated in Direct Methane Fuel Cell. Copper modified nickel metallic overlayer shows high activity for fuel cell performance and good stability to coking in methane atmosphere. The copper-nickel overlayer provides advantages of material compatibility with the substrate and catalytic function on copper-modified nickel sites. The results suggest that the overlayer is effective for decomposition of methane and tolerant to coking by removal of deposited carbon via oxidation and gasification reaction.