Improvement strategy on thermophysical properties of A_(2)B_(2)O_(7)-type rare earth zirconates for thermal barrier coatings applications:A review

The A_(2)B_(2)O_(7)-type rare earth zirconate compounds have been considered as promising candidates for thermal barrier coating(TBC) materials because of their low sintering rate,improved phase stability,and reduced thermal conductivity in contrast with the currently used yttria-partially stabilized zirconia (YSZ) in high operating temperature environments.This review summarizes the recent progress on rare earth zirconates for TBCs that insulate high-temperature gas from hot-section components in gas turbines.Based on the first principles,molecular dynamics,and new data-driven calculation approaches,doping and high-entropy strategies have now been adopted in advanced TBC materials design.In this paper,the solid-state heat transfer mechanism of TBCs is explained from two aspects,including heat conduction over the full operating temperature range and thermal radiation at medium and high temperature.This paper also provides new insights into design considerations of adaptive TBC materials,and the challenges and potential breakthroughs are further highlighted for extreme environmental applications.Strategies for improving thermophysical performance are proposed in two approaches:defect engineering and material compositing.

Research Progress in the Failure Behavior onthe Interface of Thermal Barrier Coatings

This paper mainly introduces the research progress on interface failure behavior in high-temperature alloy surface thermal barrier coating systems.The degradation failure and structural evolution behavior during high-temperature service were analyzed for the matrix/bonding layer interface,bonding layer/TGO interface,and TGO/ceramic layer interface in thermal barrier coatings.The research focus and direction that affect the interface performance of thermal barrier coatings were proposed.

Thermal Analysis of Turbine Blades with Thermal Barrier Coatings Using Virtual Wall Thickness Method

Avirtual wall thicknessmethod is developed to simulate the temperature field of turbine bladeswith thermal barrier coatings(TBCs),to simplify the modeling process and improve the calculation efficiency.The results show that the virtualwall thickness method can improve themesh quality by 20%,reduce the number ofmeshes by 76.7%and save the calculation time by 35.5%,compared with the traditional real wall thickness method.The average calculation error of the two methods is between 0.21%and 0.93%.Furthermore,the temperature at the blade leading edge is the highest and the average temperature of the blade pressure surface is higher than that of the suction surface under a certain service condition.The blade surface temperature presents a high temperature at both ends and a low temperature in themiddle height when the temperature of incoming gas is uniformand constant.The thermal insulation effect of TBCs is the worst near the air film hole,and the best at the blade leading edge.According to the calculated temperature field of the substrate-coating system,the highest thermal insulation temperature of the TC layer is 172.01 K,and the thermal insulation proportions of TC,TGO and BC are 93.55%,1.54%and 4.91%,respectively.

A modified single edge V-notched beam method for evaluating surface fracture toughness of thermal barrier coatings

The surface fracture toughness is an important mechanical parameter for studying the failure behavior of air plasma sprayed(APS)thermal barrier coatings(TBCs).As APS TBCs are typical multilayer porous ceramic materials,the direct applications of the traditional single edge notched beam(SENB)method that ignores those typical structural characters may cause errors.To measure the surface fracture toughness more accurately,the effects of multilayer and porous characters on the fracture toughness of APS TBCs should be considered.In this paper,a modified single edge V-notched beam(MSEVNB)method with typical structural characters is developed.According to the finite element analysis(FEA),the geometry factor of the multilayer structure is recalculated.Owing to the narrower V-notches,a more accurate critical fracture stress is obtained.Based on the Griffith energy balance,the reduction of the crack surface caused by micro-defects is corrected.The MSEVNB method can measure the surface fracture toughness more accurately than the SENB method.

Study on the Attack of Molten Silicates on Plasma-Sprayed Thermal Barrier Coatings

Thermal barrier coating (TBC) revolutionized the industry by allowing higher operating temperatures for equipment, such as gas turbines in the aeronautical industry. However, at high temperatures, the TBC is exposed to the attack of molten silicates, known as CMAS (Calcium-Magnesium-Alumino-Silicate), which are particles from the environment that infiltrate the TBC, causing delamination. In this study, samples coated with TBC by thermal spray and covered with CMAS were evaluated at temperatures of 1200˚C and 1250˚C. For each temperature, exposure times of 1 h and 5 h were used. Samples with longer exposure time had a considerable volume increase. The main contribution of this work was to demonstrate the non-wettability of the CMAS, even in the 5-h heat treatments, which prevented its infiltration in the deeper regions. The conditions to guarantee the formation of the silicate and its consequent wettability are also discussed.

Effect of Al-deposition on erosion resistance of plasma sprayed thermal barrier coating

A columnar Al film was firstly deposited on the top of 7%Y2O3？stabilized zirconia （7YSZ） ceramic coating in thermal barrier coating （TBC） system by magnetron sputtering. A vacuum treatment was then carried out at 700 °C for 1 h and 900 °C for 5 h to improve the erosion resistance of Al-deposited TBC. Aα-Al2O3 layer was in situ synthesized on the top of 7YSZ coating via vacuum heat treatment. The microstructure evolution of Al-deposited TBC illustrated that a loose surface-layer and a dense sub-layer formed on the top of 7YSZ coating after vacuum treatment. The phase structures of the as-sprayed TBC and the Al-deposited TBC after vacuum heat treatment were characterized by X-ray diffraction （XRD） and transmission electron microscope （TEM） assisted with focused ion beam （FIB）. Particulate erosion resistances of the as-sprayed TBC and treated TBC were compared at room temperature. In addition, erosion mechanism and schematic diagram were proposed. The results show that the Al-deposited TBC after vacuum heat treatment has better particulate erosion resistance than the as-sprayed one.

Impedance spectroscopy study of high-temperature oxidation of Gd_2O_3-Yb_2O_3 codoped zirconia thermal barrier coatings

3Gd2O3-3Yb2O3-4Y2O3 （mole fraction, %） co-doped ZrO2 （GY-YSZ） thermal barrier coatings （TBCs） were produced by electron beam physical vapor deposition （EB-PVD）. The oxidation behavior of GY-YSZ at 1 050 ℃ was investigated using impedance spectroscopy （IS） combined with scanning electron microscopy （SEM）, Raman spectroscopy and X-ray diffractometry （XRD）. Various electrical responses observed in the impedance spectra corresponding to GY-YSZ grains and grain boundaries were explained using circuit modeling. The change in the conduction mechanism of GY-YSZ was found to be related to the O^2- vacancy and lattice distortion due to the stabilizer diffusion during the oxidation. The results also suggested that the specific oxidation information about the GY-YSZ grains and grain boundaries should be acquired at a moderate measurement temperature, which was related to the resistance value in the impedance spectra. The resistance values of the GY-YSZ grains and grain boundaries should be measured at 200 ℃ and 300 ℃, respectively.

Effects of supersonic fine particles bombarding on thermal barrier coatings after isothermal oxidation

This work was attempted to modify the current technology for thermal barrier coatings（TBCs） by adding an additional step of surface modification,namely,supersonic fine particles bombarding（SFPB） process,on bond coat before applying the topcoat.After isothermal oxidation at 1000 °C for different time,the surface state of the bond coat and its phase transformation were investigated using X-ray diffraction（XRD）,scanning electron microscopy（SEM） equipped with energy-dispersive X-ray spectrometry（EDS）,transmission electron microscopy（TEM） and Cr3＋ luminescence spectroscopy.The dislocation density significantly increases after SFPB process,which can generate a large number of diffusion channels in the area of the surface of the bond coat.At the initial stage of isothermal oxidation,the diffusion velocity of Al in the bond coat significantly increases,leading to the formation of a layer of stable α-Al2O3 phase.A great number of Cr3＋ positive ions can diffuse via diffusion channels during the transient state of isothermal oxidation,which can lead to the presence of（Al0.9Cr0.1）2O3 phase and accelerate the γ→θ→α phase transformation.Cr3＋ luminescence spectroscopy measurement shows that the residual stress increases at the initial stage of isothermal oxidation and then decreases.The residual stress after isothermal oxidation for 310 h reduces to 0.63 GPa compared with 0.93 GPa after isothermal oxidation for 26 h.In order to prolong the lifespan of TBCs,a layer of continuous,dense and pure α-Al2O3 with high oxidation resistance at the interface between topcoat and bond coat can be obtained due to additional SFPB process.

Effect of rare earth doping on thermo-physical properties of lanthanum zirconate ceramic for thermal barrier coatings

The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temperature dilatometer, DSC, and laser thermal diffusivity methods were used to analyze thermal expansion coefficient （TEC）, specific heat, and thermal diffusivity. The results showed that CeO2 doped pyrochlores La2（Zr1.8Ce0.2）2O7 and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had higher TEC than La2Zr2O7 and La1.7Dy0.3Zr2O7. La2（Zr1.8Ce0.2）2O7, La1.7Dy0.3Zr2O7, and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had lower thermal conductivity than undoped La2Zr2O7. The Dy2O3, Nd2O3, and CeO2 codoped composition showed the lowest thermal conductivity and the highest TEC. Thermo-physical results also indicated that TEC of rare earth oxide doped La2Zr2O7 ceramic was slightly higher than that of conventional ZrO2-8Wt.% Y2O3 （8YSZ）, and its thermal conductivity was lower than that of 8YSZ.

Thermal conductivity of (Sm_(1-x)La_x)_2Zr_2O_7 (x=0,0.25,0.5,0.75 and 1) oxides for advanced thermal barrier coatings

Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3＋ cation （La to Lu）, are promising candidate materials for applications as high temperature thermal barrier coatings because of their high melting points, high thermal expansion coefficients, and low thermal conductivities. In this study, oxides of Sm2Zr2O7, （Smo.75La0.25）2Zr2O7, （Sm0.5 La0.5）2 ZreO7, （Sm0.25La0.75）eZr2O7 and La2Zr2O7 were prepared by solid reactions at 1600℃ for 10 h using Sm2O3, La2O3 and ZrO2 as the reactants. The phase compositions of these ceramic materials were analyzed by X-ray diffractometer （XRD） and fourier transform infrared spectroscopy （FT-IR） methods, respectively. The microstructure was observed by scanning electron microscope （SEM）. The thermal conductivities of these ceramic materials were measured using laser-flash method. XRD and FT-IR results showed that pure ceramic materials with pyrochlore structure were prepared successfully. SEM results indicated that microstructures of these ceramic materials were dense and grain boundaries were very clean. The La2O3 doped Sm2Zr2O7 pyrochlores （Sm0.75 La0.25）2Zr2O7 and （Sm0.5 La0.5）2 Zr2O7 had lower thermal conductivity than the undoped Sm2Zr2O7. The thermal conductivity of （Sm0.25La0.75）2Zr2O7 was found to be lower than that of La2Zr2O7. The results showed that these ceramic materials had the potential to be used as candidate materials for TBCs.

Thermal stability and mechanical properties of thick thermal barrier coatings with vertical type cracks

The thermal stability and failure mechanism of thick thermal barrier coatings(TBCs) with and without vertical type cracks were investigated through the cyclic thermal exposure and thermal-shock tests. The TBC systems with thickness of about 2000 μm in the top coat were prepared by an air plasma spray(APS) on the bond coat of about 150 μm in thickness prepared by APS. The adhesive strength values of the as-prepared TBCs with and without vertical type cracks were determined to be 24.7 and 11.0 MPa, respectively, indicating the better interface stability in the TBC with vertical type cracks. The TBC with vertical type cracks shows a better thermal durability than that without vertical type cracks in the thermal cyclic exposure and thermal-shock tests. The hardness values of the as-prepared TBCs with and without vertical type cracks were found to be 6.6 and 5.3 GPa, respectively, which were increased to 9.5 and 5.5 GPa, respectively, after the cyclic thermal exposure tests. These results indicate that the vertical type cracks developed in the top coat are important in improving the lifetime performance of thick TBC in high temperature environment.

Application of Rare Earths in Thermal Barrier Coating Materials

Rare earths are a series of minerals with special properties that make them essential for applications including miniaturized electronics, computer hard disks, display panels, missile guidance, pollution controlling catalysts, H2-storage and other advanced materials. The use of thermal barrier coatings （TBCs） has the potential to extend the working temperature and the life of a gas turbine by providing a layer of thermal insulation between the metallic substrate and the hot gas. Yttria （Y203）, as one of the most important rare earth oxides, has already been used in the typical TBC material YSZ （yttria stabilized zirconia）. In the development of the TBC materials, especially in the latest ten years, rare earths have been found to be more and more important. All the new candidates of TBC materials contain a large quantity of rare earths, such as R2Zr207 （R=La, Ce, Nd, Gd）, CeO2-YSZ, RMeAI11019 （R=La, Nd; Me=Mg, Ca, Sr） and LAP04. The concept of double-ceramic- layer coatings based on the rare earth materials and YSZ is effective for the improvement of the thermal shock life of TBCs at high temperature.

Effect of Thermal Treatment on the Grain Growth of Nanostructured YSZ Thermal Barrier Coating Prepared by Air Plasma Spraying

A nanostructured thermal barrier coating is prepared by air plasma spraying using the 8wt% Y_2O_3 partially stabilized zirconia nano-powder with an average grain size of 40 nm. The microstructure and phase composition of feedstock nano-powder and coating are investigated using SEM, TEM and XRD. It is found that the as-sprayed zirconia coating has an average grain size of 67 nm and mainly consistes of metastable tetragonal phase, together with some monoclinic phase and tetragonal phase. Thermal treatment results show that the grains of the nanostructured coating grow slightly below 900℃, whereas over 1000℃ the gains grow rapidly and monoclinic phase noticeably appeares.

Porous a-Al_2O_3 thermal barrier coatings with dispersed Pt particles prepared by cathode plasma electrolytic deposition

Porous α-Al2O3 thermal barrier coatings （TBCs） containing dispersed Pt particles were prepared by cathode plasma electrolytic deposition （CPED）. The influence of the Pt particles on the microstructure of the coatings and the CPED process were studied. The prepared coatings were mainly composed of α-Al2O3. The average thickness of the coatings was approximately 100 μm. Such single-layer TBCs ex- hibited not only excellent high-temperature cyclic oxidation and spallation resistance, but also good thermal insulation properties. Porous α-Al2O3 TBCs inhibit further oxidation of alloy substrates because of their extremely low oxygen diffusion rate, provide good thermal insu- lation because of their porous structure, and exhibit excellent mechanical properties because of the toughening effect of the Pt particles and because of stress relaxation induced by deformation of the porous structure.

Preparation of Al2O3 nanowires on 7YSZ thermal barrier coatings against CMAS corrosion

The commonly-employed material for thermal barrier coatings(TBCs)is 7 wt.%Y2O3 ZrO2(7YSZ),generally deposited by electron beam-physical vapor deposition(EB-PVD).Due to the increasing demand for higher operating temperature in aero-derivative gas turbines,a lot of effort has been made to prevent the premature failure of columnar 7YSZ TBCs,which is induced by the microstructure degradation,sintering and spallation after the deposition of infiltrated siliceous mineral(consisting of calcium magnesium aluminum silicate(CaO MgO Al2O3 SiO2,i.e.,CMAS)).A new method called Al-modification for columnar 7YSZ TBCs against CMAS corrosion was present.The Al film was magnetron-sputtered on the surface of the columnar 7YSZ TBCs,followed by performing vacuum heat treatment of the Al-deposited TBCs.During the heat treatment,the molten Al reacted with ZrO2 to formα-Al2O3 overlay that effectively hindered CMAS infiltration.Moreover,the Al film could evaporate and re-nucleate,leading to the generation of Al2O3 nanowires,which further restrained the moving of molten CMAS.

Evaluation of La AlO_3 as top coat material for thermal barrier coatings

Perovskite is a versatile group of oxide materials allowing their properties to be tailored by composition towards specific requirements. La Al O3 was prepared to study and report its properties in the context of its potential in thermal barrier coatings（TBCs） technology. A citric acid method was used for synthesis and the perovskite structure was confirmed using XRD and FT-IR. Viscosity of the solution precursor was checked as well as the particle size by laser particle size analysis. Densification behavior of the material was followed by conventional sintering and by spark plasma sintering. Apparent porosity by the Archimedes method, thermal conductivity and thermal expansion coefficient were studied. Mechanical and fracture properties were measured at elevated temperatures up to 1300 ℃ For samples sintered at 1200-1400 ℃, coefficient of thermal expansion ranged from 5.5×10^-6 to 6.5×10^-6 K^-1 and thermal conductivity ranged between 2.2 and 3.4 W/（m？K）. Elastic modulus and ultimate stress were measured at 1000-1300 ℃, while by micro-indentation, fracture toughness was found to be 3 MPa·m1/2. As the sintering temperature increased from 1200 to 1500 ℃, significant densification from 3.21 to 5.81 g/cm^3 was found, indicating that material annealing should be made at least at 1400 ℃. Under this condition, negligible dimensional change in phase transition temperature of La Al O3 from the rhombohedral（R3 c） to the ideal cubic（Pm3 m） is found. Data reported in this work can be useful for comparing the mechanical and fracture behaviours of different TBCs developed involving La Al O3 as well as input for numerical simulations.

Overview on the Development of Nanostructured Thermal Barrier Coatings

Thermal barrier coatings （TBCs） have successfully been used in gas turbine engines for increasing operation temperature and improving engine efficiency. Over the past thirty years, a variety of TBC materials and TBC deposition techniques have been developed. Recently, nanostructured TBCs emerge with the potential of commercial applications in various industries. In this paper, TBC materials and TBC deposition techniques such as air plasma spray （APS）, electron beam physical vapor deposition （EB-PVD）, laser assisted chemical vapor deposition （LACVD） are briefly reviewed. Nanostructured 7-8 wt pct yttria stabilized zirconia （7-8YSZ）TBC by air plasma spraying of powder and new TBC with novel structure deposited by solution precursor plasma spray （SPPS） are compared. Plasma spray conditions, coating forming mechanisms, microstructures,phase compositions, thermal conductivities, and thermal cycling lives of the APS nanostructured TBC and the SPPS nanostructured TBC are discussed. Research opportunities and challenges of nanostructured TBCs deposited by air plasma spray are prospected.

Improvement of thermally grown oxide layer in thermal barrier coating systems with nano alumina as third layer

A thermally grown oxide （TGO） layer is formed at the interface of bond coat/top coat. The TGO growth during thermal exposure in air plays an important role in the spallation of the ceramic layer from the bond coat. High temperature oxidation resistance of four types of atmospheric plasma sprayed TBCs was investigated. These coatings were oxidized at 1000 °C for 24, 48 and 120 h in a normal electric furnace under air atmosphere. Microstructural characterization showed that the growth of the TGO layer in nano NiCrAlY/YSZ/nano Al2O3 coating is much lower than in other coatings. Moreover, EDS and XRD analyses revealed the formation of Ni（Cr,Al）2O4 mixed oxides （as spinel） and NiO onto the Al2O3 （TGO） layer. The formation of detrimental mixed oxides （spinels） on the Al2O3 （TGO） layer of nano NiCrAlY/YSZ/nano Al2O3 coating is much lower compared to that of other coatings after 120 h of high temperature oxidation at 1000 °C.

Measurement of Young's Modulus and Poisson's Ratio of Thermal Barrier Coatings

In gas turbines, thermal barrier coatings （TBCs） applied by air plasma spraying are widely used to lower the temperature of hot components. To analyze the characteristics of TBCs such as residual stress, bond strength, fracture toughness, and crack propagation ratio, the Young＇s modulus and Poisson＇s ratio are important parameters. For TBC is a brittle and thin film, it is desirable to evaluate those properties while the coatings are bonded to a substrate. An atmospheric plasma spray MCrAIY bond coat and Yttria stabilized zirconia （YSZ） top coat are deposited onto a nickel-base superalloy GH150 substrate. The Young＇s modulus and Poisson＇s ratio are measured by cantilever beam bending with NDI. The method will be developed to test the Young＇ s modulus and Poisson ratio of other multilayer systems.

Reliability assessment on interfacial failure of thermal barrier coatings

Thermal barrier coatings（TBCs） usually exhibit an uncertain lifetime owing to their scattering mechanical properties and severe service conditions. To consider these uncertainties, a reliability assessment method is proposed based on failure probability analysis. First, a limit state equation is established to demarcate the boundary between failure and safe regions, and then the failure probability is calculated by the integration of a probability density function in the failure area according to the first- or second-order moment.It is shown that the parameters related to interfacial failure follow a Weibull distribution in two types of TBC. The interfacial failure of TBCs is significantly affected by the thermal mismatch of material properties and the temperature drop in service.