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.     

Microstructural evaluation and thermal oxidation behaviors of YSZ/NiCoCrAlYTa coatings deposited by different thermal techniques

In this paper, two coating techniques, the high velocity oxy-fuel (HVOF) and air plasma spray (APS) techniques, were used to deposit a bond coat of NiCoCrAlYTa on the Inconel 625 substrate, followed by applying a topcoat of yttria-stabilized zirconia (YSZ). The samples were preoxidized in an argon-controlled furnace at a temperature of 1000 °C for 12 and 24 h to characterize the microstructure of a thermally grown oxide (TGO) using the two coating techniques. The most suitable preoxidized samples were further tested for isothermal oxidation at 1000 °C for up to 120 h, and a hot corrosion test was performed at 1000 °C for up to 52 h or until spalling occurred. As-sprayed and oxidized samples prepared with different coating techniques were evaluated in terms of their microstructure using different characterization methods, such as field emission scanning electron microscopy (FESEM), variable pressure scanning electron microscopy (VPSEM), energy dispersive X-ray spectroscopy (EDS) equipped with energy dispersive X-ray and X-ray diffraction (XRD) analyses. In addition, the mechanical properties of these samples were evaluated using adhesion tests. The results show that the YSZ/NiCoCrAlYTa coating applied with the HVOF technique forms a more thin and continuous layer of TGO than that obtained when applying a YSZ/NiCoCrAlYTa coating using the APS technique, indicating that a severe brittle oxidation interface exists between the two layers. The results also indicate that the mechanical strength obtained from the adhesion test of the coated samples is observably affected by the oxidation behaviors obtained with the different deposition techniques chosen.     

喷涂功率对YSZ涂层的力学性能和抗铝硅熔体腐蚀性能的影响

热浸镀Al–Si合金涂层是一种有效的现代钢铁防腐涂层，但熔融Al–Si合金腐蚀已成为热浸镀Al–Si合金生产线沉没辊及其备件亟待解决的关键问题之一。本工作采用大气等离子喷涂技术制备Y2O3部分稳定ZrO2(YSZ)/NiCrAlY防护涂层，研究了喷涂功率对YSZ涂层组织和力学性能的影响和涂层在700℃下Al–Si熔体中的腐蚀行为。结果表明，YSZ涂层是由板条和层间柱状晶粒组成的典型层状结构，随着喷涂功率从37 kW增至46 kW，层间柱状结晶呈长大趋势；YSZ涂层主要由t-ZrO2相和少量m-ZrO2相组成，喷涂功率对涂层相组成无明显影响；喷涂功率为40 kW的YSZ涂层具有较高的显微硬度642.4 HV0.3和结合强度62 MPa。此外，当带有涂层的样品在700℃的Al–Si熔液中腐蚀240 h后，YSZ涂层与高温Al–Si熔液之间的界面没有反应层生成，同时Al–Si合金熔液中的Al和Si元素也未渗透进YSZ涂层内部，表明YSZ/NiCrAlY防护涂层有效地将Al–Si合金熔体阻挡在涂层表面。     

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.     

Microstructure and permeability of porous YSZ ceramics fabricated by freeze casting of oil-in-water suspension

Porous yttria-stabilized zirconia (YSZ) ceramics are fabricated through freeze casting of oil-in-water suspension followed by sintering at 1250−1550 °C. The pore structure, compressive strength and permeability of porous YSZ ceramics are tailored via altering the emulsion content and sintering temperature. The samples obtained using higher emulsion content or at lower sintering temperature show larger Darcian and non-Darcian constants due to their higher open porosity and larger pore size. Furthermore, the investigation on individual contributions of viscous and inertial resistances on the total pressure drop during permeation process indicates that the viscous resistance increases but the inertial resistance decreases with increasing the emulsion content or decreasing the sintering temperature for samples. Porous YSZ ceramics obtained in this work with a k₁ range of 3.14 × 10⁻¹³–1.12 × 10⁻¹² m² are appropriate for applications in filters and membrane supports.     

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.