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.

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.

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.

Review of Numerical Simulation of TGO Growth in Thermal Barrier Coatings

Thermally grown oxide(TGO)is a critical factor for the service life of thermal barrier coatings(TBC).Numerical simulations of the growth process of TGO have become an effective means of comprehensively understanding the progressive damage of the TBC system.At present,technologies of numerical simulation to TGO growth include two categories:coupled chemical-mechanical methods and mechanical equivalent methods.The former is based on the diffusion analysis of oxidizing elements,which can describe the influence of bond coat(BC)consumption and phase transformation in the growth process of TGO on the mechanical behavior of each layer of TBC,and has high accuracy for the thickness evolution of TGO,but they cannot describe the lateral growth of TGO and the rumpling phenomenon induced.The latter focuses on describing the final stress and strain state after the growth of a specific TGO rather than the complete growth processes of TGO.Based on the measured TGO thickness growth curve,simulations of thickening and lateral growth can be achieved by directly applying anisotropic volumetric strain to oxidized elements and switching elements properties from the BC to the TGO.

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.

DETERMINATION OF CREEP PROPERTIES OF THERMAL BARRIER COATING(TBC)SYSTEMS FROM THE INDENTATION CREEP TESTING WITH ROUND FLAT INDENTERS

Indentation creep behavior with cylindrical flat indenters on the thermal barrier coating (TBC) was studied by finite element method (FEM). On ike constant applied indentation creep stress, there is a steady creep rate for each case studied for different creep properties of the TBC system. The steady creep depth rate depends on the applied indentation creep stress and size of the indenters as well as the creep properties of the bond coat of the TBC and the substrate. The possibilities to determine the creep properties of a thermal barrier system from indention creep testing were discussed. As an example, with two different size indenters, the creep properties of bond coat of the TBC system can be derived by an inverse FEM method. This study not only provides a numerical method to obtain the creep properties of the TBC system, but also extends the application of indentation creep method with cylindrical flat indenters.

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.

Effects of Shot Peening Process on Thermal Cycling Lifetime of TBCs Prepared by EB-PVD

Conventional two-layered thermal barrier coatings （TBCs） are prepared by electron beam physical vapor deposition （EB-PVD） with ZrO2-8 wt% Y2O3 （8YSZ） as top coat and CoCrAlY as bond coat on disk-shaped Ni based super-alloy. In this paper, three kinds of shot peening process with different lengths of operating time were adopted for bond coating. As a result, changes took place in its surface roughness and the surface micro-hardness. A thermal cycling test at 1 273 Kx55 rain and another at room temperature for 5 min were performed to study the effects of shot peening process on the thermal cycling lifetime of TBCs. It is found that a moderate shot peening process will be able to prolong the life time. The oxidation dynamic of the as-processed TBCs basically accords with the parabolic rule, and the oxidation test also attests to the spallation between YSZ and thermal growth oxide （TGO） responsible mainly for the failure of TBCs.

THE INFLUENCE OF Mo DIFFUSION ON THE THERMAL BEHAVIOR OF TBCs ON Ni_3Al BASED ALLOY IC-6

Conventional two-layered structure thermal barrier coatings (TBCs) were prepared onto γ'-Ni3Al based alloy IC-6 by electron beam physical vapor deposition (EB-PVD). Isothermal oxidation and thermal cycling tests were carried out to investigate the effect of Mo content at the interface between bond coat and ceramic top coat caused by diffusion. It has been found that the alloy coated with TBCs presented the lowest oxidation weight gain value for the reason that the ceramic top coat in TBC system can effectively stop Mo oxides evaporating. The life time of TBCs has close relation with Mo content at the interface between the bond coat and top coat. Spaliation of ceramic top coat occurred during thermal cyclic testing when Mo atoms accumulated at the interface up to certain amount to decline the combination between the bond coat and top coat.

Mechanical properties and simulated thermal conductivity of biomimetic structured PS-PVD(Gd_(0.9)Yb_(0.1))_(2)Zr_(2)O_(7) thermal barrier coatings

Plasma spray physical vapor deposition(PS-PVD)(Gd_(0.9)Yb_(0.1))_(2)Zr_(2)O_(7)(GYbZ)thermal barrier coatings(TBCs)exhibited better silicate-phobicity than coatings produced by electron beam physical vapor depo-sition.In combination with PS-PVD and ultrafast laser direct writing technology,biomimetic structured GYbZ TBCs,with a triple-scale micro/nano surface microstructure,were obtained.Laser ablating on the PS-PVD GYbZ coating enhanced the surface roughness,improving its wear resistance without increasing the surface hardness.Furthermore,during the laser ablation processing,numerous nanoparticles were deposited in-situ in the gaps between columns of the coating,reducing the coating Young’s modulus.The simulated temperature field and heat flux field demonstrated that the presence of numerous interfaces between small columns of the PS-PVD coatings is beneficial to thermal insulation.However,laser ablation decreased the coating thickness,reducing the thermal insulation by around 20%-30%as compared to its PS-PVD counterpart,suggesting that a moderate increase in the coating thickness should be considered when designing an efficient TBC system.

Microstructures and Adhesive Strength of Three Kinds of Ceramic Coatings

In gas turbine engine, the study of ceramic thermal resistance coating has always been paid more attention because it can effectively reduce metal interface temperatures, improve corrosion and/or oxidation resistance and extend life. The microstructures, SEM microfractographs and adhesive strength of three kinds of zirconia plasma-sprayed ceramic coating were investigated. The results indicated that nanostructured zirconia coating have higher adhesive strength and better micro-cracking resistance properties compared with magnesia or yttria stabilized zirconia coating because its less quantities laminar internal structures and closed packed structures with less quantities and uniform distribution cavities. The sprayed power is also an important factor affecting adhesive strength of nanostructured zirconia coating.

Corrosion behavior of Gd_(2)Zr_(2)O_(7)thermal barrier coatings under Fe-containing environmental sediment attack

Environmental sediments mainly consisting of CaO–MgO–Al_(2)O_(3)–SiO_(2)(CMAS)corrosion are a serious threat to thermal barrier coatings(TBCs),in which Fe element is usually ignored.Gd_(2)Zr_(2)O_(7)TBCs are famous for their excellent CMAS resistance.In this study,the characteristics of Fe-containing environmental sediments(CMAS-Fe)and their corrosiveness to Gd_(2)Zr_(2)O_(7)coatings were investigated.Four types of CMAS-Fe glass with different Fe contents were fabricated.Their melting points were measured to be 1322–1344℃,and the high-temperature viscosity showed a decreasing trend with increasing Fe contents.The corrosion behavior of four types of CMAS-Fe to Gd_(2)Zr_(2)O_(7)coatings at 1350℃was investigated.At the initial corrosion stage(0.1 h),anorthite was precipitated in CMAS-Fe with a high Ca:Si ratio,while Fe-garnet was formed in the melt with the highest Fe content.Prolonging the corrosion time resulted in the formation of a reaction layer,which exhibited an interpenetrating network composed of Gd-oxyapatite,ZrO_(2),and residual CMAS-Fe.Some spinel was precipitated within the reaction layer.After 1 h or even longer time,the reaction layers tended to be stable and compact,which had comparable hardness and fracture toughness to those of Gd_(2)Zr_(2)O_(7)coatings.Under the cyclic CMAS-Fe attack,the residual CMAS-Fe in the interpenetrating network provided a pathway for the redeposited CMAS-Fe infiltration,resulting in the continuous growth of the reaction layer.As a result,the Gd_(2)Zr_(2)O_(7)coatings had a large consumption in the thickness,degrading the coating performance.Therefore,the Gd_(2)Zr_(2)O_(7)coatings exhibit unsatisfactory corrosion resistance to CMAS-Fe attack.

Microwave-absorbing functionalization of LaMgAl_(11)O_(19)composite thermal barrier coatings by atmospheric plasma spraying

Thermal protection of the hot-end components of ultra-high-flying vehicles requires the microwave absorption of thermal barrier coating(TBC).In this work,the microwave-absorbing functionalization of LaMgAl_(11)O_(19)(LMA)TBC was successfully realized by adding FeSiAl(FSA)absorber to the LMA thermal barrier ceramic matrix to adjust electromagnetic parameters.Due to the formation of the layered lamellae structure during atmospheric plasma spraying(APS),LMA-FSA composite TBCs have better electromagnetic wave(EMW)absorbing properties than feed powder.EMW absorption of TBCs is mainly controlled by the magnetic loss,and the natural resonance is the main mechanism of magnetic loss.TBCs exhibit a minimum reflection loss(RL)value of-13.4 dB,and effective absorption bandwidth(EAB)of RL<-10 dB is up to 3.11 GHz at a simulated thickness of 2 mm.Phase and structure stability of the TBCs and microwave absorption property could be relatively well preserved even after heat treatments at 600-1000℃ for 3-50 h.Thermal conductivity of the LMA-FSA composite TBCs with FSA contents of 30-50 wt%are about 2.84-3.05 W·m^(-1)·K^(-1)at 800℃.LMA-FSA composite TBCs with heat-resistant,heat-insulation,and EMW absorbing properties might find attractive potential applications in the thermal protection for the light alloy hot-end components in civil and military industry.

CMAS-phobic and infiltration-inhibiting protective layer material for thermal barrier coatings

Calcium-magnesium-alumina-silicate(CMAS)corrosion has attracted special attention in the thermal barrier coating(TBC)field.At high temperatures,when CMAS melts,it adheres to the coating surface and penetrates the interior,severely destroying the TBC.In this study,a promising CMAS-phobic and infiltration-inhibiting material,GdPO4,on which molten CMAs is difficult to wet and penetrate,was proposed.These desirable attributes are explained by analyzing the material characteristics of GdPO_(4) and its interfacial reaction with CMAS.GdPO4 is demonstrated to have low surface energy,making it difficult for molten CMAS to wet and adhere to the surface.When in contact with molten CMAS,a double-layer structured reaction layer consisting of an acicular upper sublayer and a compact lower sublayer is formed on the GdPO4 surface,which can effectively impede molten CMAS spreading and penetration.First-principles calculation results revealed that the reaction layer has low surface energy and low adhesion to CMAS,which are favorable for molten CMAS phobicity.Additionally,the formation of the reaction layer increases the viscosity of the molten CMAS,which can increase melt wetting and penetration.Hence,GdPO4,which exhibits excellent CMAS-phobicity and infiltration-inhibiting ability,is a promising protective layer material for TBCs against CMAS adhesion and attack.

Understanding of degradation-resistant behavior of nanostructured thermal barrier coatings with bimodal structure

Nanostructured thermal barrier coatings(TBCs) often provide high degradation resistance, as well as extended lifetime. However, the underlying mechanism has not been fully understood. In this study, the sintering characteristics of nanostructured yttria-stabilized zirconia(YSZ) coatings were investigated,and compared with those of the conventional YSZ coatings. Multiscale characterizations of the changes in microstructures and properties were performed. Results showed that the enhanced high-performance durability was mainly attributed to different sintering mechanisms of lamellar zones and nanozones.Sintering characteristics of the lamellar zones were similar to those of the conventional coatings. Stagesensitive healing of two-dimensional(2 D) pores dominated the sintering behavior of the lamellar zones.However, the differential densification rates between nanozones and lamellar zones of the nanostructured TBCs led to the formation of coarse voids. This counteractive effect, against healing of 2 D pores, was the main factor contributing to the retardation of the performance degradation of bimodal TBCs during thermal exposure. Based on the understanding of the performance-degradation resistance, an outlook towards TBCs with higher performances was presented.

Effect of Sintering on Thermal Conductivity and Thermal Barrier Effects of Thermal Barrier Coatings

Thermal barrier coatings （TBCs） are mostly applied to hot components of advanced turbine engines to insulate the compo- nents from hot gas. The effect of sintering on thermal conductivity and thermal barrier effects of conventional plasma sprayed and nanostructured yttria stabilized zirconia （YSZ） thermal barrier coatings （TBCs） are investigated. Remarkable increase in thermal conductivity occurs to both typical coatings after heat treatment, The change of porosity is just the opposite. The grain size of the nanostructured zirconia coating increases more drastically with annealing time compared to that of the conventional plasma sprayed coating, which indicates that coating sintering makes more contributions to the thermal conductivity of the nanostructured coating than that of the conventional coating. Thermal barrier effect tests using temperature difference technique are performed on both coatings. The thermal barrier effects decrease with the increase of thermal conductivity after heat treat- ment and the decline seems more drastic in low thermal conductivity range. The decline in thermal barrier effects is about 80℃ for nanostructured coating after 100 h heat treatment, while the conventional coating reduces by less than 60 ℃ compared to the as-sprayed coating.

Progress in ceramic materials and structure design toward advanced thermal barrier coatings

Thermal barrier coatings(TBCs)can effectively protect the alloy substrate of hot components in aeroengines or land-based gas turbines by the thermal insulation and corrosion/erosion resistance of the ceramic top coat.However,the continuous pursuit of a higher operating temperature leads to degradation,delamination,and premature failure of the top coat.Both new ceramic materials and new coating structures must be developed to meet the demand for future advanced TBC systems.In this paper,the latest progress of some new ceramic materials is first reviewed.Then,a comprehensive spalling mechanism of the ceramic top coat is summarized to understand the dependence of lifetime on various factors such as oxidation scale growth,ceramic sintering,erosion,and calcium–magnesium–aluminium–silicate(CMAS)molten salt corrosion.Finally,new structural design methods for high-performance TBCs are discussed from the perspectives of lamellar,columnar,and nanostructure inclusions.The latest developments of ceramic top coat will be presented in terms of material selection,structural design,and failure mechanism,and the comprehensive guidance will be provided for the development of next-generation advanced TBCs with higher temperature resistance,better thermal insulation,and longer lifetime.

Experimental and numerical investigation on the thermal and mechanical behaviours of thermal barrier coatings exposed to CMAS corrosion

Calcium-magnesium-alumino-silicate(CMAS)corrosion is a critical factor which causes the failure of thermal barrier coating(TBC).CMAS attack significantly alters the temperature and stress fields in TBC,resulting in their delamination or spallation.In this work,the evolution process of TBC prepared by suspension plasma spraying(SPS)under CMAS attack is investigated.The CMAS corrosion leads to the formation of the reaction layer and subsequent bending of TBC.Based on the observations,a corrosion model is proposed to describe the generation and evolution of the reaction layer and bending of TBC.Then,numerical simulations are performed to investigate the corrosion process of free-standing TBC and the complete TBC system under CMAS attack.The corrosion model constructs a bridge for connecting two numerical models.The results show that the CMAS corrosion has a significant influence on the stress field,such as the peak stress,whereas it has little influence on the steady-state temperature field.The peak of stress increases with holding time,which increases the risk of the rupture of TBC.The Mises stress increases nonlinearly along the thick direction of the reaction layer.Furthermore,in the traditional failure zone,such as the interface of the top coat and bond coat,the stress obviously changes during CMAS corrosion.