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.

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.

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.

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.

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.

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.

Effects of heat treatment on the corrosion resistance of carbon steel coated with LaMgAl_(11)O_(19) thermal barrier coatings

LaMgAl11O19thermal barrier coatings（TBCs） were applied to carbon steels with a NiCoCrAlY bond coat by plasma spraying. The effects of heat treatment on the corrosion resistance of carbon steel coated with LaMgAl11O19TBCs were investigated in 3.5wt% Na Cl solution using polarization curves, electrochemical impedance spectroscopy（EIS）, scanning electron microscopy（SEM）, and X-ray diffraction（XRD）. The results show that a large number of cracks are found in the LaMgAl11O19TBCs after the samples are heat-treated, including some through-thickness cracks. The corrosion forms of the as-sprayed and heat-treated TBCs are uniform corrosion and pitting corrosion, respectively. The as-sprayed TBCs exhibit three EIS time constants after being immersed for less than 7 d, and then a new time constant appears because of steel substrate corrosion. When the immersion time is increased to 56 d, a Warburg impedance（W） component appears in the EIS data. The EIS data for the heat-treated TBCs exhibit only two time constants after the samples are immersed for less than 14 d, and a new time constant appears when the immersion time is increased further. The heat treatment reduces the corrosion resistance of carbon steel coated with LaMgAl11O19TBCs. The corrosion products are primarily γ-Fe OOH and Fe3O4.

Premature failure induced by non-equilibrium grain-boundary tantalum segregation in air-plasma sprayed ZrO_(2)-YO_(1.5)-TaO_(2.5)thermal barrier coatings

ZrO_(2)-YO_(1.5)-TaO_(2.5)(ZYTO)is a promising top-coat material for thermal barrier coatings(TBCs).The bulk properties of ZYTO have been reported by several studies,but its performances as TBCs are less-well understood.In this work,ZYTO TBCs were prepared by air plasma spraying(APS)and their thermal cycling performances were investigated at 1150℃.Despite of the good bulk properties,APS ZYTO TBCs present an extremely short thermal fatigue life.This is attributed to the non-equilibrium grain-boundary segregation of TaO_(2.5) induced by limited solubility and rapid quenching during APS process,resulting in a tetragonal(t)to cubic(c)and metastable-tetragonal(tm)phase transformation in ZYTO TBCs.The volume shrinkage(~0.74vol%)of phase transformation leads to many cracks at the c/tm phase boundaries after deposition.On the other hand,the formation of cubic phase with massive grain-boundary Ta segregation induces a large intergranular embrittlement and a weak bonding strength(~5.3 MPa),resulting in the premature failure of the ZYTO TBCs.

Acoustic emission assessment of interface cracking in thermal barrier coatings

In this paper,acoustic emission（AE） and digital image correlation methods were applied to monitor interface cracking in thermal barrier coatings under compression.The interface failure process can be identifie via its AE features,including buckling,delamination incubation and spallation.According to the Fourier transformation of AE signals,there arefourdifferentfailuremodes：surfaceverticalcracks,opening and sliding interface cracks,and substrate deformation.The characteristic frequency of AE signals from surface vertical cracks is 0.21 MHz,whilst that of the two types of interface cracks are 0.43 and 0.29 MHz,respectively.The energy released of the two types of interface cracks are 0.43 and 0.29 MHz,respectively.Based on the energy released from cracking and the AE signals,a relationship is established between the interface crack length and AE parameters,which is in good agreement with experimental results.

Quantitative assessment of the surface crack density in thermal barrier coatings

In this paper, a modified shear-lag model is developed to calculate the surface crack density in thermal barrier coatings（TBCs）. The mechanical properties of TBCs are also measured to quantitatively assess their surface crack density. Acoustic emission（AE） and digital image correlation methods are applied to monitor the surface cracking in TBCs under tensile loading. The results show that the calculated surface crack density from the modified model is in agreement with that obtained from experiments. The surface cracking process of TBCs can be discriminated by their AE characteristics and strain evolution. Based on the correlation of energy released from cracking and its corresponding AE signals, a linear relationship is built up between the surface crack density and AE parameters, with the slope being dependent on the mechanical properties of TBCs.

Failure of EB-PVD Thermal Barrier Coatings Subjected to Thermo-Mechanical Loading

Thermal barrier coatings （TBCs） were developed to protect metallic blades and vanes working in turbo-engines. The two-layered structure TBCs, consisting of NiCoCrAlY bond coat and yttria stabilized zirconia （YSZ）, were deposited on a cylinder of superalloy substrate by the electron beam-physical vapor deposition （EB-PVD）. The failure mechanism of the TBCs was investigated with a thermo-mechanical fatigue testing system under the service condition similar to that for turbine blades. Non-destructive evaluation of the coated specimens was conducted through the impedance spectroscopy. It is found that the crack initiation mainly takes place on the top coat at the edge of the heated zones.

Characterization of functionally graded ZrO_2 thermal barrier coatings sprayed by supersonic plasma spray with dual powder feed ports

The functionally graded thermal barrier coatings （FG-TBCs） with 80%ZrO2-13%CeO2-7%Y2O3 （C-YSZ）/NiCoCrAlY were prepared using a recently developed supersonic plasma spraying（S-PS） with dual powder feed ports system. The thermal shock experiment of FG-TBCs specimens was carried out by means of the automatic thermal cycle device, in which the samples were heated to 1200℃ by oxygen-acetylene flame jet then water-quenched to ambient temperature. The temperature—time curves of specimens and photographs can be watched on-line and recorded by a computer during the test. The results show that the totally 1mm-thick FG-TBCs have excellent thermal shock resistance due to the fact that the coatings have no any peeling-off after 200 thermal cycles. The microstructures and morphologies of FG-TBCs were characterized and analyzed by SEM.

Characterization of Failure Mechanisms of Duplex and Graded Thermal Barrier Coatings Exposed to Thermal Shock Test

The beginning of failure of a (ZrO2-7%Y2O3)/(Ni-22%Co-17%Cr-12.5%Al-0.6%Y) duplex andgraded coating systems on lnconel 617 and IN738LC in burner rig tests has been characterized.The test conditions are 40 s heating up to 75O℃ substrate temperature followed by 80 s aircooling. Failure is considered at the appearance of the first bright spot during heating period.Stresses due to thermal expansion mismatch strains on cooling are the probable cause of life-limiting in this conditions of testing.

Influence of the Thermal Barrier Coatings Design on the Oxidation Behavior

The properties of two different types of thermal barrier coatings （TBCs） were compared to improve the surface characteristics on high temperature components. These TBCs consisted of a duplex TBC and a five-layered functionally graded TBC. NiCrAIY bond coats were deposited on a number of Inconel-738LC specimens using high velocity oxy-fuel spraying （HVOF） technique. For duplex coating, a group of these specimens were coated with yttria stabilized zirconia （YSZ） using plasma spray technique. Functionally graded NiCrAIY/YSZ coatings were fabricated by plasma spray using co-injection of the two different powders in a single plasma torch. The amount of zirconia in functionally graded coatings were gradually increased from 30 to 100 vol. pct. Microstructural changes, thermally grown oxide （TGO） layer growth and damage initiation of the coatings were investigated as a function of isothermal oxidation test at 970℃. As a complementary test, the performance of the fabricated coatings by the optimum processing conditions was evaluated as a function of intense thermal cycling test at 1100℃. Also the strength of the adhesive coatings of the substrate was also measured. Microstructural characterization was analyzed by scanning electron microscopy （SEM） and optical microscopy whereas phase analysis and chemical composition changes of the coatings and oxides formed during the tests were studied by XRD （X-ray diffraction） and EDS （energy dispersive spectrometer）. The results showed that microstructure and compositions gradually varied in the functionally graded coatings. By comparison of duplex and functionally graded TBCs oxidation behavior （duplex failure after 1700 h and funcitionally graded TECs failure after 2000 h）, thermal shock test and adhesion strength of the coatings, the functionally graded TBC had better performance and more durability.