Double-ceramic-layer thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/La2Ce2O7 deposited by electron beam-physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and La₂Ce₂O₇ (LC) were deposited by electron beam-physical vapor deposition (EB-PVD). The composition, interdiffusion, surface and cross-sectional morphologies, cyclic oxidation behavior of DCL coating were studied. Energy dispersive spectroscopy and X-ray diffraction analyses indicate that both LZ7C3 and LC coatings are effectively fabricated by a single LZ7C3 ingot with properly controlling the deposition energy. The chemical compatibility of LC coating and thermally grown oxide (TGO) layer is unstable. LaAlO₃ is formed due to the chemical reaction between LC and Al₂O₃ which is the main composition of TGO layer. Additionally, the thermal cycling behavior of DCL coating is influenced by the interdiffusion of Zr and Ce between LZ7C3 and LC coatings. The failure of DCL coating is a result of the sintering of LZ7C3 coating surface, the chemical incompatibility of LC coating and TGO layer and the abnormal oxidation of bond coat. Since no single material that has been studied so far satisfies all the requirements for high temperature applications, DCL coating is an important development direction of TBCs.     

Preparation and characteristics of three-layer YSZ-(YSZ/Al2O3)-YSZ TBCs

Novel three-layer YSZ-(YSZ/Al₂O₃)-YSZ (6 wt.% Y₂O₃ partially stabilized ZrO₂) thermal barrier coatings (TBCs) were successfully prepared on Ni-based superalloy substrate using composite sol-gel and pressure filtration microwave sintering (PFMS) techniques. The coatings were evaluated for the cyclic oxidation resistance, thermal barrier effect and the presences of phases and microstructures. FE-SEM results indicate that the coatings were dense and crack-free. The coatings maintained their structural integrity when they were exposed at 1100 for 100 h. They exhibited superior oxidation resistance, spallation resistance and thermal insulation property compared with single-layer YSZ coatings. Moreover, the detailed mechanisms were discussed in order to understand the improved performance of the three-layer TBCs.     

High performance nanostructured ZrO2 based thermal barrier coatings deposited by high efficiency supersonic plasma spraying

In this paper, the nanostructured zirconia (ZrO₂) based thermal barrier coatings (TBCs) deposited by high efficiency supersonic atmospheric plasma spraying (SAPS), were described. The phase composition, microstructure, thermal conductivity and thermal shock resistance of as-sprayed coating were studied. The results revealed that the as-sprayed coating was composed of tetragonal zirconia and consisted of some unmelted nanoparticles (30-50 nm) and nanograins (60-110 nm), and the latter was the main microstructure of the coating. The nanograins and homogeneously distributed micro-cracks of coating resulted in not only low thermal conductivity, but also high thermal cycling lives. Besides, the failure process of coating during thermal cycles was also investigated in the present work.     

Influence of pores on the surface microcompression mechanical response of thermal barrier coatings fabricated by atmospheric plasma spray—Finite element simulation

Surface microcompression is a very important technique to characterize the mechanical properties of film and coating systems. In this paper, surface microcompression simulation for La₂Zr₂O₇ (LZ) thermal barrier coatings (TBCs) was implemented by finite element method, especially, the influence of pores on the surface microcompression mechanical response of the thermal barrier coatings fabricated by atmospheric plasma spray (APS) was focused on. The simulation results indicate that the pores not only affect the stress distribution beneath the contact area between the indenter and coating surface, but also affect the shape of the force-displacement curve and the plastic deformation behavior of TBCs. The micromechanism was discussed in detail in this study. At the same time, by using the surface microcompression technique, a new direction or method was proposed to characterize the pore content of the coating quantitatively.     

Effect of Young's modulus evolution on residual stress measurement of thermal barrier coatings by X-ray diffraction

Subjected to thermal cycling, the apparent Young's modulus of air plasma-sprayed (APS) 8 wt.% Y₂O₃-stabilized ZrO₂ (8YSZ) thermal barrier coatings (TBCs) was measured by nanoindentation. Owing to the effects of sintering and porous microstructure, the apparent Young's modulus follows a Weibull distribution and changes from 50 to 93 GPa with an increase of thermal cycling. The evolution of residual stresses in the top coating of an 8YSZ TBC system was determined by X-ray diffraction (XRD). The residual stresses derived from the XRD data are well consistent with that obtained by the Vickers indention. It is shown that the evolution of Young's modulus plays an important role in improving the measurement precision of residual stresses in TBCs by XRD.     

Influence of Co(CH3COO)2 concentration on thermal emissivity of coatings formed on titanium alloy by micro-arc oxidation

Ceramic thermal protection coatings on Ti6Al4V alloy were achieved by micro-arc oxidation (MAO) in the presence of Co(CH₃COO)₂. The morphology, crystallographic structure and chemical composition of the coating were characterized by various techniques. The thermal emission of the coating was measured by Fourier transform spectrometer apparatus. The bonding strength between the coating and substrate was studied, together with the thermal shock resistance of the coating. The results indicate that the content of Co in the coating layer significantly affects its thermal emissivity. Higher concentration of Co(CH₃COO)₂ in electrolytes leads to more Co ions into the coating, which enhances the emissivity of the coating. All the coatings show bonding strength higher than 10 MPa. In addition, the coating remains stable over 40 cycles of thermal shocking. The coating formed at 4 g/L Co(CH₃COO)₂ displays an average spectral emissivity value more than 0.9 and bonding strength about 10.4 MPa.     

激光重熔对等离子喷涂ZrO_2-20%Y_2O_3热障涂层隔热性能的影响

采用大气等离子喷涂(APS)技术在铝基体表面制备氧化锆(ZrO2-20%Y2O3,质量分数)热障涂层,并用脉冲激光对其进行重熔处理,研究了激光重熔对涂层组织形貌、物相转变和隔热性能的影响。研究结果表明激光的比能量对涂层的成型及性能有重要影响,过高的比能量会使涂层表面粗糙度增加,涂层成型变差。在选用合适的低比能量激光重熔条件下,扫描电镜观察结果表明经激光重熔可消除喷涂态涂层的孔隙和层状结构。对粉末和重熔前后的涂层进行了X射线衍射分析,结果表明喷涂及重熔过程中都没有发生相变;隔热试验结果表明重熔后涂层的隔热温度有所下降。     

Ultrasonic characterization of thermally grown oxide in thermal barrier coating by reflection coefficient amplitude spectrum

The thermally grown oxide (TGO) growth at the interface of ceramic coating/bond coating in thermal barrier coatings (TBCs) was evaluated by ultrasonic reflection coefficient amplitude spectrum (URCAS). A theoretical analysis was performed about the influence of acoustic impedance match relationship between the ceramic coating and its adjacent media on URCAS. The immersion ultrasonic narrow pulse echo method was carried out on the TBC specimen before and after oxidation under 1050 °C × 1 h for 15 cycles. The resonant peaks of URCAS obtained before and after oxidation showed that TGO which generated between the ceramic coating and bond coating due to the oxidation, changed the acoustic impedance match between the ceramic coating and its adjacent media. This method is able to nondestructively characterize the generation of TGO in TBCs, and is important to practical engineering application.     

Microscopic observation of laser glazed yttria-stabilized zirconia coatings

Thermal barrier coatings (TBCs) are frequently used as insulation system for hot components in gas-turbine, combustors and power plant industries. The corrosive gases which come from combustion of low grade fuels can penetrate into the TBCs and reach the metallic components and bond coat and cause hot corrosion and erosion damage. Glazing the top coat by laser beam is advanced approach to seal TBCs surface. The laser beam has the advantage of forming a dense thin layer composed of micrograins. Plasma-sprayed yttria-stabilized zirconia (YSZ) coating was glazed with Nd-YAG laser at different operating conditions. The surface morphologies, before and after laser treatment, were investigated by scanning electron microscopy. Laser beam assisted the densification of the surface by remelting a thin layer of the exposed surface. The laser glazing converted the rough surface of TBCs into smooth micron-size grains with size of 2-9 μm and narrow grain boundaries. The glazed surfaces showed higher Vickers hardness compared to as-sprayed coatings. The results revealed that the hardness increases as the grain size decreases.     

Influence of FeSO4 concentration on thermal emissivity of coatings formed on titanium alloy by micro-arc oxidation

Ceramic coatings with high emission were fabricated on Ti6Al4V alloy by microarc oxidation (MAO) with additive FeSO₄ into the electrolyte. The microstructure, chemical composition and chemical state of the coatings were determined by SEM, XRD, EDS and XPS, respectively. The bonding strength between the coating and substrate was studied by tensile strength test, together with the thermal shock resistance of the coating. The results showed that Fe content in the coating layer significantly affect its thermal emissivity. The relative content of Fe in the coatings surface increased at first and then decreased with increasing the concentration of FeSO₄ in electrolytes, so does the emissivity of the coatings. The bonding strength became weaker with increasing the concentration of FeSO₄. In addition, the coating remains stable over 40 cycles of thermal shocking. The coating formed at 3 g/L FeSO₄ demonstrates the highest an average spectral emissivity value around of 0.87, and bonding strength higher than 33 MPa.     

Numerical study on the thermo-stress of ZrO2 thermal and barrier coatings by high-intensity pulsed ion beam irradiation

This paper studies numerically the thermo-mechanical effects of ZrO2 thermal barrier coatings (TBCs) irradiated by a high-intensity pulsed ion beam in consideration of the surface structure.Taking the deposited energy of ion beams in TBCs as the source term in the thermal conduction equation,the distribution of temperature in TBCs was simulated.Then,based on the distribution,the evolution of thermal stress was calculated by the finite element method.The results show that tensile radial stress formed at the valley of TBC surfaces after irradiation by HIPIB.Therefore,if cracks happen,they must be at valleys instead of peaks.As for the stress waves,no matter whether through peak or valley position,tensile and compressive stresses are present alternately inside TBCs along the depth direction,and the strength of stress decreases with time.     

Anomalies of the photo-response and thermal boundary resistance of a YBaCuO/YSZ structure

The photoresponse of a YBaCuO/ZrO₂ bolometric structure was measured under modulated (λ = 630 nm) and pulsed (τ ≈ 7 – 8 ns; λ = 337 nm) laser excitation. The shape of the measured photoresponse was interpreted by a thermal model; nevertheless, the pulse amplitude for vanishing YBaCuO film resistance was 5–6 times greater than predicted; the thermal boundary resistance R_Bd between YBaCuO and YSZ was evaluated ? 10^?2 K × cm²/Watt, which is considerably larger than estimated theoretically for the similar situation of YBaCuO/MgO [5].     

Microstructure, bonding strength and thermal shock resistance of ceramic coatings on steels prepared by plasma electrolytic oxidation

Ceramic coatings were successfully prepared on steel by plasma electrolytic oxidation (PEO) in aluminate electrolyte and silicate electrolyte, respectively. The microstructure of the coatings including surface morphology, phase and element composition were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The bonding strength between the ceramic coating and the substrate was tested using different methods including tensile tests and shearing tests. The thermal shock resistance of the coatings was also evaluated. The results indicated that coatings obtained in both electrolytes were porous and coarse. The average diameters of the pores were below 10 μm. PEO coatings obtained in aluminate electrolyte were composed of Fe₃O₄ and FeAl₂O₄, while those obtained in silicate electrolyte were in a noncrystal state. PEO coatings obtained in aluminate electrolyte showed similar change trend of tensile strength and shearing strength with increasing treating time, namely, a relatively high values with middle time treating and low value with short and long time treating. The best coating was the samples treated with 30 min, whose tensile strength was 20.6 MPa and shearing strength was 16 MPa. The tensile strength and shearing strength of coatings obtained in silicate electrolyte were not strongly influenced by the treating time, the values of which were range in 14 ± 2 MPa and 11 ± 2 MPa, respectively. Coatings obtained in both electrolytes showed the best thermal shock resistance with middle time treating. Coatings obtained in silicate electrolyte show a little better thermal shock resistance than those obtained in aluminate electrolyte.     

Characterization and oxidation behavior of NiCoCrAlY coating fabricated by electrophoretic deposition and vacuum heat treatment

Electrophoretic deposition (EPD) was showed to be a feasible and convenient method to fabricate NiCoCrAlY coatings on nickel based supperalloys. The microstructure and composition of the NiCoCrAlY coatings after vacuum heat treatment were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDAX). Isothermal-oxidation test was performed at 1100 °C in static air for 100 h. The results show that the major phases in electrophoretic deposited and vacuum heat treated NiCoCrAlY coating are γ-Ni and γ′-Ni₃Al phases, also there is an extremely small quantity of Al₂O₃ in the coating. Composition fluctuations occur in the coating and a certain amount of titanium diffuse from the superalloy substrate to the top of the coating during vacuum heat treatment. The oxidation test results exhibit that the oxidation kinetics of this coating has two typical stages. The protective oxide layer is mainly formed in the initial linear growth stage and then the oxide layer hinders further oxidation of the coating in the subsequent parabolic growth stage. The coating can effectively protect the superalloy substrate from oxidation. A certain amount of rutile TiO₂ is formed in the coating during oxidation and it is adverse to the oxidation resistance of the coating.     

Specific features of residual stress measurements in thermal barrier coatings

Techniques for measuring the residual stresses in bilayer thermal barrier coatings of a NiCrAlY alloy metal sublayer and 8-wt% stabilized ZrO₂–8Y₂O₃ ceramic upper layer are developed with the inhomogeneous composition and stress relaxation upon removal of the top layers taken into account. The outer ceramic layer is shown to undergo quenching-induced tensile stress up to 200 MPa, whereas the metal sublayer is subjected to compressive stress of 600 MPa which is associated with an increase in the specific volume as a result of the formation of a thermally grown oxide (TGO).     

Preparation and properties of composite ceramic coating containing Al2O3–ZrO2–Y2O3 on AZ91D magnesium alloy by plasma electrolytic oxidation

A composite ceramic coating containing Al₂O₃–ZrO₂–Y₂O₃ was successfully prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) technique in an alkaline aluminate electrolyte. The morphology, elemental and phase composition, corrosion behavior and thermal stability of the uncoated and coated samples were studied by environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electrochemical corrosion test, high temperature oxidation test and thermal shock test. The results showed that the composite ceramic coating was composed of Al₂O₃, c-ZrO₂, t-ZrO₂, Y₂O₃ and some magnesium compounds, such as MgO, MgF₂ and MgAl₂O₄. After PEO treatment, the corrosion potential of AZ91D alloy was increased and the corrosion current density was significantly reduced. Besides, the coated magnesium alloys also showed excellent high temperature oxidation resistance and thermal shock resistance at 500 °C environment.     

Development and properties of nanostructured thermal spray coatings

Nanostructured thermal spray coatings have been intensively studied because of their potential in a wide variety of industrial applications. In the present paper, current development status of nanostructured thermal spray coatings is presented, mainly based on the results of the authors. In the nanostructured WC–Co wear-resistant coatings, the influence of feedstock characteristics on the coating properties was discussed to suggest the desirable morphology of feedstock for thermal spraying. For the nanostructured Cr₂O₃ based solid-lubricant coatings, the advanced feedstock has been developed in order to solve the inhomogeneity problem of the conventional coatings. Various properties of the nanostructured coatings were evaluated and compared with those of the conventional counterparts. These results clearly demonstrate that the significant improvement in coating performance can be achieved by utilizing proper nanostructured coatings.     

Large room temperature magnetoresistance in YSZ doped La0.67Ba0.33MnO3 composite

The temperature dependence of the resistivity for composite samples of (1−x)La_0.67Ba_0.33MnO₃+xYSZ(LBMO/YSZ) with different YSZ doping level of x has been investigated in a magnetic field range of 0-7000 Oe, where the YSZ represents yttria-stabilized zirconia (8 mol% Y₂O₃+92 mol% ZrO₂). With increasing YSZ doping level, the range of 0-10%, the metal-insulator transition temperature (T_P) decreases. However, the resistivity, specially the low temperature resistivity, increases. Results also show that the YSZ doping level has an important effect on a low field magnetoresistance (LFMR). In the magnetic field of 7000 Oe, a room temperature magnetoresistance value of 20% was observed for the composite with a YSZ doping level of 2%, which is encouraging for potential application of CMR materials at room temperature and low field.     

Modified YSZ/Ni structures with improved stability

The modification of the YSZ/Ni interface by the addition of lower surface energy oxides such as TiO₂, Cr₂O₃ and Mn₃O₄ on the YSZ-surface or alloying Ni-metal with Cr or Pd influences positively the interfacial bonding between ceramic and metallic phases. Wetting experiments in the modified-YSZ/liquid Ni and YSZ/liquid Ni-based alloys systems at 1773K in Ar+4vol%H₂ atmosphere gave contact angle values lower than that of the unmodified YSZ/liquid-Ni system. The present wettability results together with literature data were used for the determination of the surface energies for the modified YSZ-ceramics and the liquid Ni-based alloys as well as the interfacial energies of the ceramic-liquid metal systems examined. Lower interfacial energy values were achieved in the case of the modified YSZ-ceramics. The modification of the YSZ-surface was found to contribute positively also to the interfacial bonding of the ceramic-solid Ni interface, decreasing in this way the agglomeration rate of the metallic phase, when this is deposited as a thin layer onto the ceramic surface. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 16, 1996     

Electrode reaction at platinum / ceria surface modified YSZ interface

The electrode reaction was examined on ceria coated YSZ by a platinum point electrode in H₂-H₂O atmosphere at 973 K- 1173 K. The thickness of the ceria coating layer was altered from 0 to 2.5 μm, fabricated by a laser ablation and by a vacuum vapor deposition method on YSZ single crystals. The electrode / electrolyte interface conductivity increased with 1/4 powers ofp(H₂) andp(H₂O) on both ceria coated and non-coated YSZ. The interface conductivity was significantly improved on a thicker ceria coating surface than 1 μm. The effective electrode reaction radius also increased in a thick ceria coating. The¹⁸O/¹⁶O exchange experiment at low oxygen partial pressure revealed that the oxygen surface exchange rate of ceria is not high compared with that of YSZ. It can be concluded that the bulk ionic conduction of ceria makes a more effective contribution to the electrode reaction than the surface catalytic activity in H₂-H₂O atmosphere. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997