Low Thermal Conductivity Coatings for Gas Turbine Applications

Plasma spraying of thermal barrier coatings (TBCs) on gas turbine parts is widely used today either to enable higher-turbine inlet temperatures with consequent improvement of combustion efficiency or to reduce the requirements for the cooling system and increase component life-time. Development of low conductivity TBCs, which allows us to further increase gas turbine efficiency and availability, is an ongoing challenge. In order to get low thermal conductivity values an experimental program was conducted. Yttria partially stabilized zirconia (YPSZ) and dysprosia partially stabilized zirconia (DyPSZ) were used to study the influence of power input in the plasma torch and powder feed rate on coating properties. Microstructure evaluations were performed to evaluate the influence of the spraying parameters on the coating morphology and porosity level. Laser Flash (LF) and Transient Plane Source (TPS) methods were utilized to evaluate the coatings thermal conductivity and a comparison between the two methods conducted as well as a correlation study between coating microstructure/composition and thermal conductivity (TC).     

Next Generation Thermal Barrier Coatings for the Gas Turbine Industry

The aim of this study is to develop the next generation of production ready air plasma sprayed thermal barrier coating with a low conductivity and long lifetime. A number of coating architectures were produced using commercially available plasma spray guns. Modifications were made to powder chemistry, including high purity powders, dysprosia stabilized zirconia powders, and powders containing porosity formers. Agglomerated & sintered and homogenized oven spheroidized powder morphologies were used to attain beneficial microstructures. Dual layer coatings were produced using the two powders. Laser flash technique was used to evaluate the thermal conductivity of the coating systems from room temperature to 1200 °C. Tests were performed on as-sprayed samples and samples were heat treated for 100 h at 1150 °C. Thermal conductivity results were correlated to the coating microstructure using image analysis of porosity and cracks. The results show the influence of beneficial porosity on reducing the thermal conductivity of the produced coatings.     

The effects of heat treatment and gas atmosphere on the thermal conductivity of APS and EB-PVD PYSZ thermal barrier coatings

The effects of heat treatment and gas atmosphere on thermal conductivity of atmospheric plasma sprayed (APS) and electron beam physical vapor deposited (EB-PVD) partially Y₂O₃ stabilized ZrO₂ (PYSZ) thermal barrier coatings (TBCs) were investigated. Two-layer samples that had an EB-PVD coating deposited on bond coated nickel-base superalloy IN625 substrates, free-standing APS and EB-PVD coatings as well as a quasi-free-standing EB-PVD PYSZ coating (coating on semitransparent sapphire) were included in the study. Thermal diffusivity measurements for determining thermal conductivity were made from room temperature up to 1150 °C in vacuum and under argon gas using the laser flash technique. To investigate the effect of heat treatment on thermal conductivity, coatings were annealed at 1100 °C in air. For both the APS and EB-PVD PYSZ coatings the first 100 h heat treatment caused a significant increase in thermal conductivity that can be attributed to microstructural changes caused by sintering processes. Compared to the measurements in vacuum, the thermal conductivity of APS coatings increased by about 10% under argon gas at atmospheric pressure, whereas for the EB-PVD coatings, the influence of gas on thermal conductivity was relatively small. The effect of gas on the thermal conductivity of APS and EB-PVD PYSZ coatings can be attributed to amount, shape, and spatial arrangement of pores in the coating material.     

Influence of dopant on the thermal properties of two plasma-sprayed zirconia coatings Part I: Relationship between powder characteristics and coating properties

Plasma- sprayed coatings produced with two zirconia powders (− 90 + 10 μm, spray dried and partially sintered) that were stabilized (9 wt %) with dysprosia (DSZ) and ytterbia (YbSZ) were compared to coat-ings sprayed with a yttria (7 wt %) stabilized zirconia (YSZ) powder (45 + 22 μm, fused and crushed). The YSZ particles in the coating were almost fully molten (less than 0.2 % monoclinic m- phase), with excellent contact between the layered splats (adhesion of 54 MPa). The DSZ particles were only partially melted (3.1 % m- phase), with coating adhesion greater than 34 MPa; the YbSZ particles were less melted (6.1 % m- phase), with coating adhesion of 27 MPa. The thermal properties (diffusivity, a; specific heat, c_p; and thermal conductivity, κ) of the coatings were about the same. Under thermal cycling (1 h heating at 1100 °C in a furnace followed by fast cooling for approximately 3 min by air jets) of the coatings sprayed on FeCrAl alloy manufactured by powder metallurgy, the behavior of the DSZ coating was simi-lar to that of the YSZ, whereas the YbSZ coating was partially detached. However, in all cases the percent-age of the monoclinic phase decreased and the ratio of the hexagonal structure increased to 1.013 of the nontransformable tetragonal phase t′.     

Thermal conductivity of a zirconia thermal barrier coating

The conductivity of a thermal-barrier coating composed of atmospheric plasma sprayed 8 mass percent yttria partially stabilized zirconia has been measured. This coating was sprayed on a substrate of 410 stainless steel. An absolute, steady-state measurement method was used to measure thermal conductivity from 400 to 800 K. The thermal conductivity of the coating is 0.62 W/(m×K). This measurement has shown to be temperature independent.     

Microstructure and Thermal Properties of Plasma Sprayed Thermal Barrier Coatings from Nanostructured YSZ

Nanostructured yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs) were produced by atmospheric plasma spraying. The microstructure of the sprayed coating was characterized by transmission electron microscope (TEM) and scanning electron microscope (SEM). The nano-coating had a higher porosity of ~25% than the conventional coating, which is mainly attributed to the large amount of intersplat gaps in the nano-coating. The thermal conductivity for the nano-coating was in the level of 0.8-1.1 W/m·K, about 40% lower than that for the conventional coating, indicating a better thermal insulation performance. The nano-TBC exhibited a thermal cycling lifetime of more than 500 cycles, whereas spallation failure of the conventional TBC occurred within 200 cycles. Accelerated sintering could be one of the reasons for the failure of the nano-TBC.     

Microstructure and Thermal Behavior of Thermal Barrier Coatings

Yttria stabilized zirconia thick coatings were thermally sprayed from two different feedstock powders. Coating characteristics such as density, crystalline phase composition, and microstructure were evaluated. The thermal expansion coefficient and thermal diffusivity were measured as a function of temperature up to 800 °C and analyzed in terms of the microstructural features. The ability of available models to relate the measured thermal properties to the microstructural features as characterized by readily available methods was assessed. The importance of pore shape and orientation on the thermal conductivity was evidenced. The thermal contact resistance between the substrate and the coating in these samples was estimated from the thermal diffusivity data, and found to change during cooling from 800 °C.     

Impact of Impurity Content on the Sintering Resistance and Phase Stability of Dysprosia- and Yttria-Stabilized Zirconia Thermal Barrier Coatings

Dysprosia-stabilized zirconia (DySZ) is a promising candidate to replace yttria-stabilized zirconia (YSZ) as a thermal barrier coating due to its lower inherent thermal conductivity. It is also suggested in studies that DySZ may show greater stability to high temperature phase changes compared to YSZ, possibly allowing for coatings with extended lifetimes. Separately, the impurity content of YSZ powders has been proven to influence high-temperature sintering behavior. By lowering the impurity oxides within the spray powder, a coating more resistant to sintering can be produced. This study presents both high purity and standard purity dysprosia and YSZ coatings and their performance after a long heat treatment. Coatings were produced using powder with the same morphology and grain size; only the dopant and impurity content were varied. Samples have been heat treated for exposure times up to 400 h at a temperature of 1150 °C. Samples were measured for thermal conductivity to plot the evolution of coating thermal properties with respect to exposure time. Thermal conductivity has been compared to microstructure analysis and porosity measurement to track structural changes. Phase analysis utilizing x-ray diffraction was used to determine differences in phase degradation of the coatings after heat treatment.     

Deposition and Characteristics of Submicrometer-Structured Thermal Barrier Coatings by Suspension Plasma Spraying

In the field of thermal barrier coatings (TBCs) for gas turbines, suspension plasma sprayed (SPS) submicrometer-structured coatings often show unique mechanical, thermal, and optical properties compared to conventional atmospheric plasma sprayed ones. They have thus the potential of providing increased TBC performances under severe thermo-mechanical loading. Experimental results showed the capability of SPS to obtain yttria stabilized zirconia coatings with very fine porosity and high density of vertical segmentation cracks, yielding high strain tolerance, and low Young??s modulus. The evolution of the coating microstructure and properties during thermal cycling test at very high surface temperature (1400?°C) in our burner rigs and under isothermal annealing was investigated. Results showed that, while segmentation cracks survive, sintering occurs quickly during the first hours of exposure, leading to pore coarsening and stiffening of the coating. In-situ measurements at 1400?°C of the elastic modulus were performed to investigate in more detail the sintering-related stiffening.     

Study of microstructure and thermal shock behavior of two types of thermal barrier coatings

Gas turbines provide one of the most severe environments challenging material systems nowadays. Only an appropriate coating system can supply protection particularly for turbine blades. This study was made by comparison of properties of two different types of thermal barrier coatings (TBCs) in order to improve the surface characteristics of high temperature components. These TBCs consisted of a duplex TBC and a five layered functionally graded TBC. In duplex TBCs, 0.35 mm thick yittria partially stabilized zirconia top coat (YSZ) was deposited by air plasma spraying and ～0.15 mm thick NiCrAlY bond coat was deposited by high velocity oxyfuel spraying. ～0.5 mm thick functionally graded TBC was sprayed by varying the feeding ratio of YSZ/NiCrAlY powders. Both coatings were deposited on IN 738LC alloy as a substrate. Microstructural characterization was performed by SEM and optical microscopy whereas phase analysis and chemical composition changes of the coatings and oxides formed during the tests were studied by XRD and EDX. The performance of the coatings fabricated with the optimum processing conditions was evaluated as a function of intense thermal cycling test at 1100 °C. During thermal shock test, FGM coating failed after 150 and duplex coating failed after 85 cycles. The adhesion strength of the coatings to the substrate was also measured. Finally, it is found that FGM coating has a larger lifetime than the duplex TBC, especially with regard to the adhesion strength of the coatings.     

纳米氧化锆热障涂层组织结构和高温稳定性能分析

采用大气等离子喷涂技术制备了纳米氧化锆热障涂层.利用FESEM和XRD对纳米氧化锆热障涂层的微观组织和物相组成进行研究.微观组织分析结果表明,纳米氧化锆热障涂层展现出独特的微观复合结构,包括未熔纳米颗粒和柱状晶组织.物相分析结果表明,纳米氧化锆热障涂层主要由非平衡四方相组成.纳米氧化锆热障涂层高温稳定性能试验结果表明,涂层晶粒度随着服役温度和服役时间的增加而增加,但仍保持纳米结构;涂层物相组成不随服役环境的变化而变化.     

新型锆酸盐基热障涂层材料的研究进展

简要回顾了传统7±1 %Y_2O_3稳定的ZrO_2(YSZ)热障涂层的研究现状,指出YSZ涂层在高温热循环下存在着相变,抗烧结能力差等缺点.鉴于新型稀土锆酸盐系列由于具有热导率低、抗烧结能力强等优点而被认为有望作为新一代热障涂层候选材料,重点概述了目前国内外在这种热障涂层材料的陶瓷块体制备及涂层材料方面的研究现状,并进一步探讨了未来新型稀土锆酸盐基热障涂层的发展方向.     

Analysis of the Microstructure and Thermal Shock Resistance of Laser Glazed Nanostructured Zirconia TBCs

Nanostructured zirconia thermal barrier coatings (TBCs) have been prepared by atmospheric plasma spraying using the reconstituted nanosized yttria partially stabilized zirconia powder. Field emission scanning electron microscope was applied to examine the microstructure of the resulting TBCs. The results showed that the TBCs exhibited a unique, complex structure including nonmelted or partially melted nanosized particles and columnar grains. A CO₂ continuous wave laser beam has been applied to laser glaze the nanostructured zirconia TBCs. The effect of laser energy density on the microstructure and thermal shock resistance of the as-glazed coatings has been systematically investigated. SEM observation indicated that the microstructure of the as-glazed coatings was very different from the microstructure of the as-sprayed nanostructured TBCs. It changed from single columnar grain to a combination of columnar grains in the fracture surface and equiaxed grains on the surface with increasing laser energy density. Thermal shock resistance tests have showed that laser glazing can double the lifetime of TBCs. The failure of the as-glazed coatings was mainly due to the thermal stress caused by the thermal expansion coefficient mismatch between the ceramic coat and metallic substrate.     

Thermal Cycling Behavior of Quasi-Columnar YSZ Coatings Deposited by PS-PVD

Columnar-structured thermal barrier coatings, owing to their high strain tolerance, are expected for their potential possibilities to substantially extend turbine lives and improve engine efficiencies. In this paper, plasma spray-physical vapor deposition (PS-PVD) process was used to deposit yttria partially stabilized zirconia (YSZ) coatings with quasi-columnar structures. Thermal cyclic tests on burner rigs and thermal shock tests by heating and water-quenching method were involved to evaluate the thermal cycling and thermal shock behaviors of such kind of structured thermal barrier coatings (TBCs). Evolution of the microstructures, phase composition, residual stresses and failure behaviors of quasi-columnar YSZ coatings before and after the thermal tests was investigated. The quasi-columnar coating obtained had an average life of around 623 cycles when the spallation area reached about 10% of the total coating surface during burner rig tests with the coating surface temperature of ~1250 °C. Failure of the coating is mainly due to the break and pull-out of center columnar segments.     

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.     

Thermal modeling of various thermal barrier coatings in a high heat flux rocket engine

One- and two-dimensional thermal models were developed to predict the thermal response of tubes with and without thermal barrier coatings (TBCs) tested for short durations in a H₂/O₂ rocket engine. Temperatures were predicted using median thermophysical property data for traditional air plasma sprayed ZrO₂–Y₂O₃ TBCs, as well as air plasma sprayed and low pressure plasma sprayed ZrO₂–Y₂O₃/NiCrAlY cermet coatings. Good agreement was observed between predicted and measured metal temperatures. It was also shown that the variation in the reported values of the thermal conductivity of plasma sprayed ZrO₂–Y₂O₃ coatings can result in temperature differences of up to 180°C at the ceramic/metal interface. In contrast, accounting for the presence of the bond coat or radiation from the ceramic layer had only a small effect on substrate temperatures (<20°C). The thermal models were also used to show that for the short duration test conditions of this study, a 100 μm thick ZrO₂–Y₂O₃ coating would provide a metal temperature benefit of approximately 300°C over an uncoated tube while a 200 μm thick coating would provide a benefit greater than 500°C. The difference in the thermal response between tubes and rods was also predicted and used to explain the previously-observed increased life of TBCs on rods over that on tubes.     

Low conductivity plasma sprayed thermal barrier coating using hollow psz spheres: Correlation between thermophysical properties and microstructure

Life and thermal properties of plasma sprayed TBCs - widely used in gas turbine engines - are closely related to the microstructure of the ceramic top coating. Especially, the thermal behaviour of this coating is induced by the void shapes and networks which are in turn determined by both the spraying conditions and the feedstock material.A specific hollow yttria partially stabilised zirconia powder was produced in a one-step process by spray drying and an experimental statistical design study was conducted to investigate the influence of spraying variables (primary and secondary gas flow rates, arc current, spraying distance, spraying angle and traverse speed) on structure and properties of resulting plasma sprayed coatings. The coatings were characterized with respect to deposition efficiency, roughness, porosity and thermal conductivity. A reduction of 25% of the thermal conductivity was achieved by improving the spray and powder parameters. A quantitative characterization of the porous structure using image analysis of polished cross-sections was implemented. The parameters that have relevant influence on the coating porous structure were identified, and their relative importance was determined. An attempt was made to identify morphological criteria of the porous network (coarse/fine porosity ratio, cracks total length, cracks orientation) correlating with the thermal conductivity values.     

La2O3-modified YSZ coatings: High-temperature stability and improved thermal barrier properties

Lanthana precursor was coated on yttria-stabilized-zirconia (YSZ) powders by wet chemical infiltration, and was introduced to the crystalline structure and grain boundaries of YSZ after plasma spraying of thermal barrier coatings (TBCs). The microstructural stability and thermal barrier properties of this new kind of TBCs were studied under different annealing conditions. It demonstrates that the La₂O₃ surface coating restrains grain growth of YSZ during both deposition and post-annealing processes, compared to a TBC obtained from commercially available unmodified YSZ powders. According to the composition analysis, lanthana partially dissolved in the zirconia matrix after heat treatment. The thermal diffusivity of YSZ coating significantly decreased after lanthana modification, typically from 0.354 mm² s^− 1 for an unmodified sample to 0.243 mm² s^− 1, reflecting a decrease of 31%. Even after annealed at 1200 °C for 50 h, the thermal diffusivity of modified coatings still shows a reduction of 25% than unmodified samples.     

Oxidation resistant coatings in combination with thermal barrier coatings on γ-TiAl alloys for high temperature applications

Titanium aluminide alloys based on γ-TiAl are considered of growing interest for high temperature applications due to their attractive properties. To extend the service temperatures above 750 °C, the oxidation behaviour has to be improved predominantly by protective layers. In the present study environmental and thermal protection coatings on gamma titanium aluminides were investigated. Nitride and metallic overlay coatings based on Ti-Al-Cr-Y-N and Ti-Al-Cr, respectively, were produced by magnetron sputtering techniques. Thermal barrier coatings (TBCs) of partially yttria stabilized zirconia were deposited onto Ti-45Al-8Nb, either pre-oxidized or coated with protective layers, applying electron beam physical vapour deposition (EB-PVD).Cyclic oxidation tests were performed at 900 °C and 950 °C in air. The nitride coating exhibited poor oxidation resistance when exposed at 900 °C providing no protection for γ-TiAl. The oxidation behaviour of the Ti-Al-Cr coating was reasonable at both exposure temperatures. During prolonged exposure the coating was depleted in chromium, resulting in the breakdown of the protective alumina scale. EB-PVD zirconia coatings deposited on γ-TiAl exhibited promising lifetime, particularly when specimens were coated with Ti-Al-Cr. The adherence of the TBC on the thermally grown oxide scales was excellent; failure observed was associated with spallation of the oxide scale. At 950 °C, TBCs on specimens coated with Ti-Al-Cr spalled after less than 200 thermal cycles caused by severe oxidation of γ-TiAl and reactions between the zirconia coatings and the thermally grown oxides.     

热障涂层失效机理、改进方法及未来发展方向

热障涂层(Thermal Barrier Coatings,TBCs)是用于航空发动机及燃气轮机的一种高效功能性隔热涂层,常用材料为氧化钇(质量分数6％～8％)部分稳定氧化锆(YSZ).首先,从TGO生长、高温烧结、CMAS腐蚀、盐雾腐蚀和热膨胀失配等方面介绍了YSZ的失效机理,以上因素会从不同程度上造成涂层分层、开裂乃至失效.其次,介绍了通过控制界面反应速度和元素扩散速度,改变涂层化学成分及结构等方法,改善YSZ性能.为适应下一代超高温热障涂层的发展要求,近年来,国内外针对制备工艺的改善和新材料性能进行了研究.通过调控等离子物理气相沉积的喷距,能得到不同微观结构的热障涂层,运用纳米粉体再造粒技术,能制备出抗热震性能、耐磨抗腐蚀性、韧性以及可加工性更为优异的纳米结构涂层.ABO3型钙钛矿结构钡盐、钽酸盐、石榴石结构稀土铝酸盐、磁铅石结构稀土铝酸盐、独居石结构稀土磷酸盐等新型陶瓷层材料的研究是一大热点.与传统YSZ相比,新陶瓷层材料有优异的高温相稳定性、高热膨胀系数、高热导率等性能,但存在断裂韧性低、组分复杂等缺点.最后,为热障涂层未来研究指出了方向,并展望了其面临的挑战.