Development of a Thermal Transport Database for Air Plasma Sprayed ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Thermal Barrier Coatings

Thermal diffusivities of air plasma sprayed (APS) thermal barrier coatings (TBCs) were measured by the laser flash method. The data were used to calculate thermal conductivity of TBCs when provided with density and specific heat data. Due to the complicated microstructure and other processing-related parameters, thermal diffusivity of TBCs can vary as much as three- to four-fold. Data collected from over 200 free-standing ZrO₂-7-8wt.%Y₂O₃ TBCs are presented. The large database gives a clear picture of the expected “band” of thermal diffusivity values. When this band is used as a reference for thermal diffusivity of a specific TBC, the thermal transport property of the TBC can be more precisely described. This database is intended to serve researchers and manufacturers of TBCs as a valuable resource for the evaluation of TBCs.     

Application of Plasma-Sprayed Complex Perovskites as Thermal Barrier Coatings

In an effort to improve the performance of heat engines at high temperatures, advanced surface coatings have been developed from complex perovskites. Materials of Ba(Mg_1/3Ta_2/3)O₃ and La(Al_1/4Mg_1/2Ta_1/4)O₃ composition were synthesized and applied as ceramic topcoats of thermal barrier coating (TBC) systems by atmospheric plasma spraying (APS) in single layer and in double-layer combination with conventional yttria stabilized zirconia (YSZ). Microstructural and phase analyses reveal that plasma spraying of complex perovskites is accompanied with the formation of vertical crack networks and secondary oxide phases which influence the failure mechanism of the TBCs. The low value of fracture toughness for the complex perovskites and the thermally grown oxide at the topcoat-bondcoat interface of the TBCs are, however, the major factors which lead to the coating failure on thermal cycling at about 1250 °C.     

Development of a Pre-Oxidation Treatment to Improve the Adhesion between Thermal Barrier Coatings and NiCoCrAlY Bond Coatings

High-temperature coating systems, consisting of a René N5 superalloy, a Ni–23Co–23Cr–19Al–0.2Y (at.%) bond coating (BC), and a yttria (7 wt%)-stabilized zirconia (YSZ) thermal barrier coating (TBC), were thermally cycled to failure for seven different controlled pre-oxidation treatments and one commonly employed industrial pre-oxidation treatment to establish the preferred microstructures of the thermally-grown oxide (TGO) on a NiCoCrAlY bond coating after pre-oxidation. It was found that the failure of the coating system occurred along the TGO/BC interface when the TGO attained a critical thickness, except if a NiAl₂O₄ spinel layer developed contiguous to the TBC/TGO interface. Then, the coating system failed at a smaller TGO thickness along the NiAl₂O₄/α-Al₂O₃ interface. The value for the TGO thickness at failure increased for a larger area fraction of Y-rich oxide pegs at the TGO/BC interface after pre-oxidation. A desired slow-growing oxide layer on the BC surface was promoted when the presence of the oxides NiAl₂O₄, θ-Al₂O₃, Y₃Al₅O₁₂ at the TGO surface after pre-oxidation was avoided. The α-Al₂O₃ layer, which developed adjacent to the BC upon thermal cycling, grew at a low rate if the initial oxide at the onset of oxidation consisted of θ-Al₂O₃ instead of α-Al₂O₃. Based on these results a pre-oxidation treatment is proposed for which the lifetime of the entire coating system during service is enhanced.     

Higher Temperature Thermal Barrier Coatings with the Combined Use of Yttrium Aluminum Garnet and the Solution Precursor Plasma Spray Process

Gas-turbine engines are widely used in transportation, energy and defense industries. The increasing demand for more efficient gas turbines requires higher turbine operating temperatures. For more than 40 years, yttria-stabilized zirconia (YSZ) has been the dominant thermal barrier coating (TBC) due to its outstanding material properties. However, the practical use of YSZ-based TBCs is limited to approximately 1200 °C. Developing new, higher temperature TBCs has proven challenging to satisfy the multiple property requirements of a durable TBC. In this study, an advanced TBC has been developed by using the solution precursor plasma spray (SPPS) process that generates unique engineered microstructures with the higher temperature yttrium aluminum garnet (YAG) to produce a TBC that can meet and exceed the major performance standards of state-of-the-art air plasma sprayed YSZ, including: phase stability, sintering resistance, CMAS resistance, thermal cycle durability, thermal conductivity and erosion resistance. The temperature improvement for hot section gas turbine materials (superalloys & TBCs) has been at the rate of about 50 °C per decade over the last 50 years. In contrast, SPPS YAG TBCs offer the near-term potential of a > 200 °C improvement in temperature capability.     

Magnetoresistance of the La<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> single crystal

The dependence of the resistance ρ of the La_0.7Ca_0.3MnO₃ single crystal on the temperature (in a range of 77 < T < 410 K) and magnetic field H is studied. The dependence of the magnetoresistance Δρ/ρ of the ferromagnetic phase on the field is shown to be determined by the competition of two mechanisms. In low magnetic fields, the magnetoresistance is positive Δρ/ρ > 0 and is determined by changes in the resistance with changing magnetization orientation with respect to the crystallographic axes; in high magnetic fields, the magnetoresistance is negative Δρ/ρ < 0, since it is the suppression of spin fluctuations in the magnetic field that plays the principal role. The phase transition from the ferromagnetic to paramagnetic state is a first-order transition close to the second-order one. In the transition range, the magnetoresistance is determined by the resistivity in the zero field ρ(T) and by the shift of the transition temperature T _C(H) in the magnetic field. In the paramagnetic state, the resistivity ρ(T) has an activation character; similarly to the magnetoresistance of other lanthanum manganites, the magnetoresistance of this single crystal is controlled by a change in the activation energy in the magnetic field.     

Thermal Fatigue Behavior of Thick and Porous Thermal Barrier Coatings Systems

High-temperature thermal fatigue causes the failure of thermal barrier coating (TBC) systems. This paper addresses the development of thick TBCs, focusing on the microstructure and the porosity of the yttria partially stabilized zirconia (YPSZ) coating, regarding its resistance to thermal fatigue. Thick TBCs, with different porosity levels, were produced by means of a CoNiCrAlY bond coat and YPSZ top coat, both had been sprayed by air plasma spray. The thermal fatigue resistance of new TBC systems and the evolution of the coatings before and after thermal cycling was then evaluated. The limit of thermal fatigue resistance increases depending on the amount of porosity in the top coat. Raman analysis shows that the compressive in-plane stress increases in the TBC systems after thermal cycling, nevertheless the increasing rate has a trend which is contrary to the porosity level of top coat. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Isothermal oxidation of physical vapor deposited partially stabilized zirconia thermal barrier coatings

Thermal barrier coatings (TBCs), consisting of physical vapor deposited (PVD) partially stabilized zirconia (PSZ, 8 wt.%Y₂O₃) and a diffusion aluminide bond coat, were characterized as a function of time after oxidative isothermal heat treatment at 1373 K in air. The experimental characterizations was conducted by X-ray diffraction analysis and scanning electron microscopy (SEM) with energy-dispersive spectroscopy. During cooling to room temperature, spallation of the PSZ ceramic coatings occurred after 200 and 350 h of isothermal heat treatment. This failure was always sudden and violent, with the TBC popping from the substrate. The monoclinic phase of zirconia was first observed on the bottom surface of the PVD PSZ after 200 h of isothermal heat treatment. The failure of TBCs occurred either in the bond coat oxidation products of αAl₂O₃ and rutile TiO₂ or at the interface between the oxidation products and the diffusion aluminide bond coat or the PSZ coating.     

Mechanical Properties of LaTi<Subscript>2</Subscript>Al<Subscript>9</Subscript>O<Subscript>19</Subscript> and Thermal Cycling Behaviors of Plasma-Sprayed LaTi<Subscript>2</Subscript>Al<Subscript>9</Subscript>O<Subscript>19</Subscript>/YSZ Thermal Barrier Coatings

Recently, extensive efforts have been made to develop new thermal barrier coating (TBC) materials which can operate at temperatures above 1523 K over a long term. In this article, LaTi₂Al₉O₁₉ (LTA) was synthesized by solid-state reaction at 1773 K, and the mechanical properties of the LTA bulk were evaluated. The microhardness is about 14 GPa, comparable to that of YSZ bulk, whereas the Young’s modulus is about 44 GPa, lower than the value of YSZ. However, the fracture toughness of 0.8-1 MPa m^1/2 is much lower than that of bulk YSZ. A double-ceramic-layer LTA/YSZ TBC structure was proposed and the TBC sprayed by plasma spraying. Thermal cycling tests of the TBC specimens were performed at 1373 K with a dwell time of 10 min. The LTA remained good stability with ZrO₂ and Al₂O₃. However, the single layer LTA TBC was cracked at the LTA/bond coat interface after about 300 cycles, due to its poor thermal shock resistance, while the YSZ TBC yielded a lifetime of about 1000 cycles. The LTA/YSZ TBC remained intact even after 3000 cycles, exhibiting a promising potential as new TBC materials.     

The Effect of Heat Treatment on the Oxidation Behavior of HVOF and VPS CoNiCrAlY Coatings

Free-standing VPS and HVOF CoNiCrAlY coatings were produced. The as-sprayed HVOF coating retained the γ/β microstructure of the feedstock powder, and the VPS coating consisted of a single (γ) phase. A 3-h, 1100 °C heat treatment in vacuum converted the single-phase VPS coating to a two-phase γ/β microstructure and coarsened the γ/β microstructure of the HVOF coating. Oxidation of free-standing as-sprayed and heat-treated coatings of each type was carried out in air at 1100 °C for a duration of 100 h. Parabolic rate constant(s), K _p, were determined for free-standing, as-sprayed VPS and HVOF coatings as well as for free-standing coatings that were heat treated prior to oxidation. The observed increase in K _p following heat treatment is attributed to a sintering effect eliminating porosity from the coating during heat treatment. The lower K _p values determined for both HVOF coatings compared to the VPS coatings is attributed to the presence of oxides in the HVOF coatings, which act as the barrier to diffusion. Oxidation of the as-sprayed coatings produced a dual-layer oxide consisting of an inner α-Al₂O₃ layer and outer spinel layer. Oxidation of the heat-treated samples resulted in a single-layer oxide, α-Al₂O₃. The formation of a thin α-Al₂O₃ layer during heat treatment appeared to prevent nucleation and growth of spinel oxides during subsequent oxidation.     

Surface Modification of Thermal Barrier Coatings by Single-Shot Defocused Laser Treatments

Thermal barrier coatings (TBC) consisting of atmospheric plasma-sprayed ZrO₂-8 wt.% Y₂O₃ and a high velocity oxygen fuel-sprayed metallic bond coat were subjected to CO₂ continuous wave laser treatments. The effects of laser power on TBCs were investigated as was the thermally grown oxide (TGO) layer development of all as-sprayed and laser-treated coatings after thermal oxidation tests in air environment for 50, 100, and 200 h at 1100 °C. The effects of laser power on TBCs were investigated. TGO layer development was examined on all as-sprayed and laser-treated coatings after thermal oxidation tests in air environment for 50, 100, and 200 h at 1100 °C. Melted and heat-affected zone regions were observed in all the laser-treated samples. Oxidation tests showed a stable alumina layer and mixed spinel oxides in the TGO layers of the as-sprayed and laser-treated TBCs.     

Erosion Performance of Gadolinium Zirconate-Based Thermal Barrier Coatings Processed by Suspension Plasma Spray

7-8 wt.% Yttria-stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used by the gas turbines industry due to its excellent thermal and thermo-mechanical properties up to 1200 °C. The need for improvement in gas turbine efficiency has led to an increase in the turbine inlet gas temperature. However, above 1200 °C, YSZ has issues such as poor sintering resistance, poor phase stability and susceptibility to calcium magnesium alumino silicates (CMAS) degradation. Gadolinium zirconate (GZ) is considered as one of the promising top coat candidates for TBC applications at high temperatures (>1200 °C) due to its low thermal conductivity, good sintering resistance and CMAS attack resistance. Single-layer 8YSZ, double-layer GZ/YSZ and triple-layer GZdense/GZ/YSZ TBCs were deposited by suspension plasma spray (SPS) process. Microstructural analysis was carried out by scanning electron microscopy (SEM). A columnar microstructure was observed in the single-, double- and triple-layer TBCs. Phase analysis of the as-sprayed TBCs was carried out using XRD (x-ray diffraction) where a tetragonal prime phase of zirconia in the single-layer YSZ TBC and a cubic defect fluorite phase of GZ in the double and triple-layer TBCs was observed. Porosity measurements of the as-sprayed TBCs were made by water intrusion method and image analysis method. The as-sprayed GZ-based multi-layered TBCs were subjected to erosion test at room temperature, and their erosion resistance was compared with single-layer 8YSZ. It was shown that the erosion resistance of 8YSZ single-layer TBC was higher than GZ-based multi-layered TBCs. Among the multi-layered TBCs, triple-layer TBC was slightly better than double layer in terms of erosion resistance. The eroded TBCs were cold-mounted and analyzed by SEM.     

Microstructure Evolution and Interface Stability of Thermal Barrier Coatings with Vertical Type Cracks in Cyclic Thermal Exposure

In this study, the effects of intrinsic feature of microstructure in thermal barrier coatings (TBCs) with and without vertical cracks on the microstructure and mechanical properties were investigated in cyclic thermal exposure. The hardness values of TBCs with vertical cracks were higher than those without vertical cracks, showing a good agreement with microstructure. The TBC prepared without vertical cracks using the 204-NS was delaminated after 250 cycles in the cyclic thermal exposure test. The TBCs with and without vertical cracks prepared with 204 C-NS and the TBC with vertical cracks prepared with 204 NS showed a sound condition without any cracking at the interface or spalling of top coat. After the thermal exposure of 381 cycles, the hardness values were increased in the survived TBC specimens, and the thicknesses of TGO layer for the TBCs with 204 C-NS and 204 NS were measured as in the ranges of 5-9 and 3-7 μm, respectively. In the thermal shock test, the advantage of vertical cracks for thermal durability of TBC could be well investigated, showing relatively longer sustained cycles in the TBCs with vertical cracks. The TBCs with vertical cracks are more efficient in improving thermal durability than those without vertical cracks in cyclic thermal exposure.     

Thermo-Physical Properties and Thermal Shock Resistance of Segmented La2Ce2O7/YSZ Thermal Barrier Coatings

La₂Ce₂O₇ (LCO)/yttria-stabilized zirconia (YSZ) thermal barrier coating (TBC) with segmentation crack structure was produced by atmospheric plasma spraying. Thermo-physical properties, such as thermal diffusivities and thermal conductivities, and thermal cycling performance of the segmented LCO/YSZ TBC were investigated. The thermal conductivity of the segmented coating was measured to be around 1.02 W/mK at 1200 °C, relatively lower than that of the non-segmented coating, respectively. The segmented LCO/YSZ TBC exhibited a thermal cycling lifetime of around 2100 cycles, improving the durability by nearly 50% as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Thermal barrier coatings for industrial gas turbine applications: An industrial note

Thermal barrier coatings (TBCs) have been used in high-thrust aircraft engines for many years to pro-vide thermal protection and increase engine efficiencies. TBC life requirements for aircraft engines are typically less than those required for industrial gas turbines. This paper describes current and future ap-plications of TBCs in industrial gas turbine engines. Early testing and applications of TBCs are reviewed. Areas of concern from the engine designer’s and materials engineer’s perspective are identified and evaluated. This paper focuses on the key factors that are expected to influence utilization of TBCs in ad-vanced industrial gas turbine engines. It is anticipated that reliable, durable, and highly effective coating systems will be produced that will ultimately improve engine efficiency and performance.     

Investigation of interfacial properties of atmospheric plasma sprayed thermal barrier coatings with four-point bending and computed tomography technique

A modified four-point bending test has been employed to investigate the interfacial toughness of atmospheric plasma sprayed (APS) yttria stabilised zirconia (YSZ) thermal barrier coatings (TBCs) after isothermal heat treatments at 1150 °C. The delamination of the TBCs occurred mainly within the TBC, several to tens of microns above the interface between the TBC and bond coat. X-ray diffraction analysis revealed that the TBC was mainly tetragonal in structure with a small amount of the monoclinic phase. The calculated energy release rate increased from ~ 50 J/m^− 2 for as-sprayed TBCs to ~ 120 J/m^− 2 for the TBCs exposed at 1150 °C for 200 h with a loading phase angle about 42°. This may be attributed to the sintering of the TBC. X-ray micro-tomography was used to track in 3D the evolution of the TBC microstructure non-destructively at a single location as a function of thermal exposure time. This revealed how various types of imperfections develop near the interface after exposure. The 3D interface was reconstructed and showed no significant change in the interfacial roughness after thermal exposure.     

An experimental investigation on thermo-mechanical buckling delamination failure characteristic of air plasma sprayed thermal barrier coatings

The primary intention of this work is to investigate the thermo-mechanical buckling delamination failure characteristic of air plasma sprayed thermal barrier coatings (TBCs) under compression tests at high temperature. The TBCs samples with a pre-delamination were firstly designed and they had been successfully prepared by air plasma sprayed technique. The main novelty of this paper is that the first work to validate and obtain three kinds of the interface failure forms in TBCs system during compression tests, i.e. buckling delamination, edge delamination and global buckling failure. The effects of the initial delamination length, temperature gradient and applied mechanical load on the delamination resistance of the TBCs system were discussed in detail. It is difficult to observe buckling delamination or edge delamination failure phenomena until the initial delamination length in TBCs reaches or exceeds 4 mm or more. For edge delamination failure, the interface fracture toughness (Γ_i^II), energy release rate (G_ss^edge) and stress intensity factor (K_II) between the TBC/TGO interface were 35 J m^− 2, 38.8 J m^− 2 and 0.97 MPa at high temperature gradient, respectively. Using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX), it was inferred that the delamination fracture located within the ceramic coating close to the TBC/TGO interface. The results agree well with other experimental and theoretical results.     

Mechanistic Study on the Degradation of Thermal Barrier Coatings Induced by Volcanic Ash Deposition

Thermal stress generated on thermal barrier coatings (TBCs) by volcanic ash (VA) deposition was assessed measuring the tip deflection of a multilayered beam structure as a function of temperature. The TBC in this study was deposited onto the surface of a blade utilized in a land-based gas turbine which is composed of 8 wt.%Y₂O₃-ZrO₂/CoNiCrAlY on a Ni-based superalloy. The VA-deposited TBC sample was heated at 1453 K, and the effect of VA deposition on TBC delamination was examined in comparison with a TBC sample without VA deposition as a reference. On the basis of the VA attack damage mechanism which was investigated via the tip deflection measurement and a comprehensive microstructure examination, a damage-coupled constitutive model was proposed. The proposed model was based on the infiltration of the molten VA inside pores and phase transformations of yttria -tabilized zirconia in the TBC system. The numerical analysis results, which were simulated utilizing the finite element code installing the developed constitutive model, showed us that VA attack on the TBC sample induced near-interfacial cracks because of a significant increasing in the coating stress.     

镍基合金涡轮叶片热障涂层研究进展

热障涂层技术是提升航空发动机性能的关键因素之一,随着航空发动机技术的发展,对热障涂层也提出了更高的要求。为适应镍基合金涡轮叶片热胀涂层的使用要求,热胀涂层的陶瓷面层发展出（YSZ+A2B2O7）结构涂层。热障涂层陶瓷面层常用的制备方法包括等离子喷涂技术和电子束物理气相沉积技术,金属粘结层常用的制备方法包括真空电弧镀技术和化学气相沉积技术。热障涂层低膨胀系数金属粘结层技术、热障涂层修复技术、新一代热障涂层材料、建立科学的热障涂层性能评价体系等是未来热障涂层的主要发展方向。     

Failure Analysis of Multilayered Suspension Plasma-Sprayed Thermal Barrier Coatings for Gas Turbine Applications

Improvement in the performance of thermal barrier coatings (TBCs) is one of the key objectives for further development of gas turbine applications. The material most commonly used as TBC topcoat is yttria-stabilized zirconia (YSZ). However, the usage of YSZ is limited by the operating temperature range which in turn restricts the engine efficiency. Materials such as pyrochlores, perovskites, rare earth garnets are suitable candidates which could replace YSZ as they exhibit lower thermal conductivity and higher phase stability at elevated temperatures. The objective of this work was to investigate different multilayered TBCs consisting of advanced topcoat materials fabricated by suspension plasma spraying (SPS). The investigated topcoat materials were YSZ, dysprosia-stabilized zirconia, gadolinium zirconate, and ceria–yttria-stabilized zirconia. All topcoats were deposited by TriplexPro-210^TM plasma spray gun and radial injection of suspension. Lifetime of these samples was examined by thermal cyclic fatigue and thermal shock testing. Microstructure analysis of as-sprayed and failed specimens was performed with scanning electron microscope. The failure mechanisms in each case have been discussed in this article. The results show that SPS could be a promising route to produce multilayered TBCs for high-temperature applications.     

基于磁过滤技术的热障涂层表面Al2O3 覆盖层抗CMAS腐蚀性能

为了提高热障涂层（TBC）的抗沉积物（主要成分为CaO、MgO、Al₂O₃和SiO₂,简称CMAS）腐蚀性能,采用磁过滤阴极真空电弧（FCVA）技术在TBC表面上制备了致密的Al₂O₃覆盖层,比较和分析了Al₂O₃改性TBC和沉积态TBC的润湿行为和抗CMAS腐蚀性能。结果表明：使用FCVA技术制备Al₂O₃覆盖层的过程对7%（质量分数）氧化钇稳定的氧化锆（7YSZ）相的结构无明显影响,且经Al₂O₃改性的TBC综合性能均优于沉积态TBC。在1250 ℃、CMAS腐蚀条件下,Al₂O₃覆盖层有效地限制了熔融CMAS在TBC表面上的扩散行为。同时,Al₂O₃填充了7YSZ柱状晶之间的间隔并且阻碍了熔融CMAS的渗透,证明了FCVA可作为一种制备Al₂O₃涂层的新方法以提高TBC的抗CMAS腐蚀性能,且Al₂O₃涂层及其制备过程对TBC的热震性能均无消极影响。