Thermal cycling failure of new LaMgAl11O19/YSZ double ceramic top coat thermal barrier coating systems

New LaMgAl₁₁O₁₉ (LaMA)/YSZ double ceramic top coat thermal barrier coatings (TBCs) with the potential application in advanced gas-turbines and diesel engines to realize improved efficiency and durability were prepared by plasma spraying, and their thermal cycling failure were investigated. The microstructure evolutions as well as the crystal chemistry characteristics of LaMA coating which seemed to have strong influences on the thermal cycling failure of LaMA and the new double ceramic top coat TBCs based on LaMA/YSZ system were studied. For double ceramic top coat TBC system, interface modification of LaMA/YSZ by preparing thin composite coatings seemed to be more preferred due to the formations of multiple cracks during thermal cycling making the TBC to be more strain tolerant and as well as resulting in an improved thermal cycling property. The effects of the TGO stresses on the failure behavior of the TBCs were discussed through fluorescence piezo-spectroscopy analysis.     

Hot corrosion behaviour of plasma sprayed YSZ/LaMgAl11O19 composite coatings in molten sulfate–vanadate salt

Hot corrosion studies of thermal barrier coatings (TBCs) with different YSZ/LaMgAl₁₁O₁₉ (LaMA) composite coating top coats were conducted in 50 wt.% Na₂SO₄ + 50 wt.% V₂O₅ molten salt at 950 °C for 60 h. Results indicate that TBCs with composite coating top coats exhibit superior oxidation and hot corrosion resistances to the TBC with the traditional YSZ top coat, especially for which has a LaMA overlay. The presence of LaMA can effectively restrain the destabilization of YSZ at the expense of its own partial degradation. The hot corrosion mechanism of LaMA coating and the composite coatings have been explored.     

Fabrication and Characteristics of YSZ�CYSZ/Al2O3 Double-Layer TBC

A novel YSZ?CYSZ/Al₂O₃ (YSZ means 6 wt% yttria partially stabilized zirconia) double-layer thermal barrier coating was fabricated using composite sol?Cgel and pressure filtration microwave sintering (PFMS) technologies. In this double-layer coating, the top layer was YSZ ceramics with a thickness of about 150 ??m and the bottom layer was composed of micro-sized YSZ particles packed by nano-sized ??-Al₂O₃ films and had a thickness of about 10 ??m. Cyclic oxidation tests indicated that this coating possessed superior properties to resist oxidation of alloy and spallation of coating. These beneficial effects could be mainly attributed to that, the alloy substrate could be sealed completely by ??-Al₂O₃ phase and the thermal stress could be decreased by means of better thermal matching and nano/micron structure in YSZ/Al₂O₃ layer. Moreover, thermal insulation capability tests indicated that the thermal barrier effect was improved due to the application of YSZ/Al₂O₃ layer. YSZ/Al₂O₃ layer could be considered as a promising bond coat in TBCs.     

Preparation of Al2O3–ZrO2–Y2O3 Composite Coatings by a Modified Sol–Gel Technique for Thermal Barrier Application

Spatial-network Al₂O₃–ZrO₂–Y₂O₃ composite coatings were prepared by a modified sol–gel technique, so-called thermal pressure and filtration of sol–gel paint. The composite coatings were derived from a composite paint of yttria partially stabilized zirconia (YSZ) particles, Al₂O₃ particles and Al₂O₃–Y₂O₃ sol. Their microstructure showed that YSZ particles were covered with spatial-network Al₂O₃–Y₂O₃ blanket. Cyclic oxidation at 1,050 °C in air for 200 h demonstrates that the oxygen diffusion rate in the coatings could be effectively inhibited. Meanwhile, suitable coefficients of thermal expansion (CTE) gave the composite coatings better spallation resistance than that of Al₂O₃–Y₂O₃ or ZrO₂–Y₂O₃ coatings. The positive results of cyclic oxidation indicated that the composite coating can be used as an interlayer between the bond coat and the top ceramic layer in traditional TBCs. Not only the depletion rate of aluminum-rich phase in MCrAlY alloy could be slowed down by spatial-network Al₂O₃–Y₂O₃, but also different thermal expansion between thermally grown oxides layer and top layer could be relieved by suitable CTE. In this paper, the mechanisms of the inhibition of oxygen diffusion and thermal match between ceramic coating and alloy are also discussed.     

Microstructural analysis of YSZ and YSZ/Al2O3 plasma sprayed thermal barrier coatings after high temperature oxidation

Air plasma sprayed TBCs usually include lamellar structure with high interconnected porosities which transfer oxygen from YSZ layer towards bond coat and cause TGO growth and internal oxidation of bond coat.The growth of thermally grown oxide (TGO) at the interface of bond coat and ceramic layer and internal oxidation of bond coat are considered as the main destructive factors in thermal barrier coatings.Oxidation phenomena of two types of plasma sprayed TBC were evaluated: (a) usual YSZ (yttria stabilized zirconia), (b) layer composite of (YSZ/Al₂O₃) which Al₂O₃ is as a top coat over YSZ coating. Oxidation tests were carried out on these coatings at 1100°C for 22, 42 and 100h. Microstructure studies by SEM demonstrated the growth of TGO underneath usual YSZ coating is higher than for YSZ/Al₂O₃ coating. Also cracking was observed in usual YSZ coating at the YSZ/bond coat interface. In addition severe internal oxidation of the bond coat occurred for usual YSZ coating and micro-XRD analysis revealed the formation of the oxides such as NiCr₂O₄, NiCrO₃ and NiCrO₄ which are accompanied with rapid volume increase, but internal oxidation of the bond coat for YSZ/Al₂O₃ coating was lower and the mentioned oxides were not detected.     

Evolution of Lamellar Interface Cracks During Isothermal Cyclic Test of Plasma-Sprayed 8YSZ Coating with a Columnar-Structured YSZ Interlayer

The failure of plasma-sprayed thermal barrier coatings (TBC) usually occurs through spalling of ceramic coating. The crack evolution during thermal cycling of TBC is directly associated with its spalling. In this paper, the cracks in TBC along the direction of the interface between ceramic coating and bond coat were examined from cross-section of TBC experienced different numbers of thermal cycle, and crack number and the total length of cracks were measured to aim at understanding the failure mechanism. TBC consists of cold-sprayed NiCoCrAlTaY bond coat on IN738 superalloy and double layered plasma-sprayed 8YSZ with a columnar grain structured YSZ interlayer of about 20 μm thick and about 230 μm lamellar YSZ. With each isothermal cyclic test, the TBC samples were kept at 1150 °C for 26 min hold and then cooled down to a temperature less than 80 °C in 4 min by air forced cooling. Results showed that cracks propagated primarily within lamellar-structured YSZ over the columnar YSZ along lamellar interface. The measurement from the cross-section revealed that crack number and total crack length apparently increased with the increase of the number of thermal cycle. It was found that cracks with a length less than a typical size of 200 μm accounted for the majority of cracks despite the number of thermal cycle during the test. A crack initiation and propagation model for plasma-sprayed TBC is proposed with a uniform distribution of circular cracks. The propagatable cracks form homogeneously within plasma-sprayed porous YSZ coating at the early stage of thermal cycling and propagate at an identical rate during thermal cycling. Only a few of large cracks are formed before most cracks reach to the critical size for multi-cracks linking-up. The propagation of most cracks to the critical size will leads to the rapid crack bridging and subsequent spalling of top ceramic TBC.     

Microstructural and Mechanical Property Evolutions of Plasma-Sprayed YSZ Coating During High-Temperature Exposure: Comparison Study Between 8YSZ and 20YSZ

Plasma-sprayed YSZ coatings, serving as the thermal insulating top coating for thermal barrier coatings, involve thermally activated microstructural evolution, which may change the physical and mechanical properties and thereby influence the thermal barrier performance and service lifetime. In this study, 8YSZ and 20YSZ coatings annealed at 1300 °C were comparatively investigated to understand the effects of phase structure on the sintering behavior. Results show that, compared with the 20YSZ coating consisting of mainly thermodynamically stable cubic phase, the as-sprayed 8YSZ coating presented a multiphase structure mainly composed of thermodynamically metastable tetragonal phase, and significant phase transformation occurred during high-temperature exposure. The lamellar bonding had significantly improved because of the healing of intersplat pores. Fracture toughness, microhardness, and elastic modulus increased with sintering duration. The 8YSZ coating exhibiting the thermodynamically metastable tetragonal phase structure experienced a slower sintering kinetics than the 20YSZ coatings consisting mainly of thermodynamically stable cubic phase.     

Structure and durability evaluation of YSZ + Al2O3 composite TBCs with APS and HVOF bond coats under thermal cycling conditions

Plasma sprayed thermal barrier coatings (TBCs) are applied to gas turbine components for providing thermal insulation and oxidation resistance. The TBC systems currently in use on superalloy substates typically consists of a metallic MCrAlY based bond coat and an insulating Y₂O₃ partially stabilized ZrO₂ as a ceramic top coat (ZrO₂ 7–8 wt.% Y₂O₃). The oxidation of bond coat underlying yttria stabilized zirconia (YSZ) is a significant factor in controlling the failure of TBCs. The oxidation of bond coat induces to the formation of a thermally grown oxide (TGO) layer at the bond coat/YSZ interface. The thickening of the TGO layer increases the stresses and leads to the spallation of TBCs. If the TGO were composed of a continuous scale of Al₂O₃, it would act as a diffusion barrier to suppress the formation of other detrimental mixed oxides during the extended thermal exposure in service, thus helping to protect the substrate from further oxidation and improving the durability. The TBC layers are usually coated onto the superalloy substrate using the APS (Atmospheric plasma spray) process because of economic and practical considerations. As well as, HVOF (High velocity oxygen fuel) bond coat provides a good microstructure and better adhesion compared with the APS process. Therefore, there is a need to understand the cycling oxidation characteristic and failure mode in TBC systems having bond coat prepared using different processes. In the present investigation, the growth of TGO layers was studied to evaluate the cyclic oxidation behavior of YSZ/Al₂O₃ composite TBC systems with APS-NiCrAlY and HVOF-NiCrAlY bond coats. Interface morphology is significantly effective factor in occurrence of the oxide layer. Oxide layer thickening rate is slower in APS bond coated TBCs than HVOF bond coated systems under thermal cycle conditions at 1200 °C. The YSZ/Al₂O₃ particle composite systems with APS bond coat have a higher thermal cycle life time than with the HVOF bond coating.     

Effect of Suspension Plasma-Sprayed YSZ Columnar Microstructure and Bond Coat Surface Preparation on Thermal Barrier Coating Properties

Suspension plasma spraying (SPS) is identified as promising for the enhancement of thermal barrier coating (TBC) systems used in gas turbines. Particularly, the emerging columnar microstructure enabled by the SPS process is likely to bring about an interesting TBC lifetime. At the same time, the SPS process opens the way to a decrease in thermal conductivity, one of the main issues for the next generation of gas turbines, compared to the state-of-the-art deposition technique, so-called electron beam physical vapor deposition (EB-PVD). In this paper, yttria-stabilized zirconia (YSZ) coatings presenting columnar structures, performed using both SPS and EB-PVD processes, were studied. Depending on the columnar microstructure readily adaptable in the SPS process, low thermal conductivities can be obtained. At 1100 °C, a decrease from 1.3 W m^?1 K^?1 for EB-PVD YSZ coatings to about 0.7 W m^?1 K^?1 for SPS coatings was shown. The higher content of porosity in the case of SPS coatings increases the thermal resistance through the thickness and decreases thermal conductivity. The lifetime of SPS YSZ coatings was studied by isothermal cyclic tests, showing equivalent or even higher performances compared to EB-PVD ones. Tests were performed using classical bond coats used for EB-PVD TBC coatings. Thermal cyclic fatigue performance of the best SPS coating reached 1000 cycles to failure on AM1 substrates with a β-(Ni,Pt)Al bond coat. Tests were also performed on AM1 substrates with a Pt-diffused γ-Ni/γ′-Ni₃Al bond coat for which more than 2000 cycles to failure were observed for columnar SPS YSZ coatings. The high thermal compliance offered by both the columnar structure and the porosity allowed the reaching of a high lifetime, promising for a TBC application.     

Comparative Structure,Oxidation Resistance and Thermal Stability of CoNiCrAlY Overlay Coatings With and Without Pt and Their Performance in Thermal Barrier Coatings on a Ni-Based Superalloy

It is demonstrated that the addition of Pt to CoNiCrAlY overlay coating can significantly improve its oxidation resistance and thermal stability as well as its performance in thermal barrier coatings. The addition of Pt is found to stabilize a surface layer with composition based upon NiAlPt₂ with L1_o superlattice in addition to enhancing a more favorable distribution of Y and restricting the outward diffusion of detrimental substrate elements particularly Ta and Ti. Due to these beneficial effects, utilizing the Pt-modified bond coating in a TBC system with top coating of zirconia stabilized by yttria is found to extend its lifetime from 410 ± 42 h to 956 ± 48 h as determined from cycling oxidation tests at 1150 °C. However, spallation of the top coatings in the two systems has been correlated with loss of oxide adherence to the bond coatings.     

Reaction, transformation and delamination of samarium zirconate thermal barrier coatings

The rare earth zirconates have attracted interest for thermal barrier coatings (TBCs) because they have very low intrinsic thermal conductivities, are stable above 1200 °C and are more resistant to sintering than yttria-stabilized zirconia (YSZ). Samarium zirconate (SZO) has the lowest thermal conductivity of the rare earth zirconates and its pyrochore structure is stable to 2200 °C but little is known about its response to thermal cycling. Here, columnar morphology SZO coatings have been deposited on bond coated superalloy substrates using a directed vapor deposition method that facilitated the incorporation of pore volume fractions of 25 to 45%. The as-deposited coatings had a fluorite structure which transformed to the pyrochlore phase upon thermal cycling between 100 and 1100 °C. This cycling eventually led to delamination of the coatings, with failure occurring at the interface between the TGO and a “mixed zone” that formed between the thermally grown alumina oxide (TGO) and the SZO. While the delamination lifetime increased with coating porosity (reduction in coating modulus), it was significantly less than that of similar YSZ coatings applied to the same substrates. The reduced life resulted from a reaction between the rare earth zirconate and the alumina-rich bond coat TGO, leading to the formation of a mixed zone consisting of SZO and SmAlO₃. Thermal strain energy calculations show that the delamination driving force increases with TGO and mixed layer thicknesses and with coating modulus. The placement of a 10 μm thick YSZ layer between the TGO and SZO layers eliminated the mixed zone and restored the thermal cyclic life to that of YSZ structures.     

Influence of TGO Composition on the Thermal Shock Lifetime of Thermal Barrier Coatings with Cold-sprayed MCrAlY Bond Coat

NiCoCrAlTaY bond coat was deposited by cold spraying to assemble thermal barrier coatings (TBCs). The microstructure of the cold-sprayed bond coat was examined using scanning electron microscopy. TBCs consisting of cold-sprayed bond coat and plasma-sprayed YSZ were pretreated at different conditions to form different thermally grown oxides (TGOs) before thermal cycling test. The influence of the TGO composition on the thermal cyclic lifetime was quantitatively examined through the measurement of the coverage ratio of the mixed oxides on the bond coat surface. The results showed that the bond coat exhibited a dense oxidation-free microstructure, and TGOs in different morphologies and constituents were present after thermal cyclic test. The formation of TGOs was significantly influenced by pretreatment conditions. Two kinds of TGO were detected on the surface of bond coat after the spallation of YSZ coatings. One is the α-Al₂O₃-based TGO and the other is the mixed oxide. It was found that the thermal cyclic lifetime is inversely proportional to the coverage ratio of the mixed oxides formed at the bond coat/YSZ interface. The high coverage ratio of the mixed oxide on the interface leads to the early spalling of YSZ coating.     

Novel thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and yttria stabilized zirconia (YSZ) were deposited by electron beam-physical vapor deposition (EB-PVD). The thermal cycling test at 1373 K in an air furnace indicates the DCL coating has a much longer lifetime than the single layer LZ7C3 coating, and even longer than that of the single layer YSZ coating. The superior sintering-resistance of LZ7C3 coating, the similar thermal expansion behaviors of YSZ interlayer with LZ7C3 coating and thermally grown oxide (TGO) layer, and the unique growth modes of columns within DCL coating are all very helpful to the prolongation of thermal cycling life of DCL coating. The failure of DCL coating is mainly a result of the reduction-oxidation of cerium oxide, the crack initiation, propagation and extension, the abnormal oxidation of bond coat, the degradation of t′-phase in YSZ coating and the outward diffusion of Cr alloying element into LZ7C3 coating.     

Impedance Analysis of 7YSZ Thermal Barrier Coatings During High-Temperature Oxidation

ZrO₂-7 wt.%Y₂O₃ (7YSZ) thermal barrier coatings (TBCs) were prepared by atmospheric plasma spraying. High-temperature oxidation of 7YSZ TBCs was accomplished at 950 °C and characterized by impedance spectroscopy and scanning electron microscopy with energy-dispersive spectrometry. The results indicated that the thermally grown oxide (TGO) mainly contained alumina. The increase of the thickness of the TGO layer appeared to follow a parabolic law. Impedance analysis demonstrated that the resistance of the TGO increased with increasing oxidation time, also following a parabolic law, and that characterization of the TGO thickness based on fitting an equivalent circuit to its measured resistance is feasible. The YSZ grain-boundary resistance increased due to increasing cracks within the coating for oxidation time less than 50 h. However, beyond 150 h, the YSZ grain-boundary resistance slightly decreased, mainly due to sintering of the coating during the oxidation process.     

Novel thermal barrier coatings based on La2Ce2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Novel thermal barrier coatings based on La₂Ce₂O₇/8YSZ double-ceramic-layer (DCL) systems, which were deposited by electron beam physical vapor deposition (EB-PVD), were found to have a longer lifetime compared to the single layer La₂Ce₂O₇ (LC) system, and even much longer than that of the single layer 8YSZ system under burner rig test. The DCL coating structure design can effectively alleviate the thermal expansion mismatch between LC coating and bond coat, as well as avoid the chemical reaction between LC and Al₂O₃ in thermally grown oxide (TGO), which occurs above 1000 °C as determined by differential scanning calorimetry (DSC) analysis. The failure mechanism of LC/8YSZ DCL coating is mainly due to the sintering of LC coating surface after long-term thermal cycling.     

Cyclic-Oxidation Behavior of Thermal-barrier Coatings Exposed to NaCl Vapor

A Ni–24Cr–6Al–0.7Y (NiCrAlY) coating was deposited on a nickel-base superalloy by low-pressure plasma spraying, and the top coating, ZrO₂ partially stabilized with Y₂O₃ (7.5 wt%), was deposited on the NiCrAlY coating by air-plasma spraying. The cyclic-oxidation behavior of the NiCrAlY + YSZ coating exposed to NaCl vapor was investigated under atmospheric pressure at 1,050 °C, 1,100 °C and 1,150 °C. The cyclic-oxidation life of the NiCrAlY + YSZ coating in the presence of NaCl vapor was shortened compared with that in air. The higher the temperature is, the shorter the cyclic oxidation life. The oxide scale formed at the interface between the bond coat and the ceramic layer after exposure to NaCl vapor consisted of voluminous and non-protective NiO, Al₂O₃ and NiCr₂O₄ spinel. The failure of the TBC exposed to NaCl vapor occurs within the top coat and close to the YSZ/thermal growth oxide interface. The failure mechanism has been discussed based on the experimental results and thermodynamics.     

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.     

Mechanical Behavior of Air Plasma-Sprayed YSZ Functionally Graded Mullite Coatings Investigated via Instrumented Indentation

Yttria-stabilized zirconia (YSZ)-mullite multilayer architectures with compositional grading between the bond coat and YSZ top coat are envisioned as solutions to ease their coefficient of thermal expansion mismatch induced stress. In this work, two different types of mullite powder (spray-dried and freeze-granulated) and a mullite-YSZ 75/25 vol.% mixture spray-dried powder were employed. Using instrumented indentation with loads between 10 and 500 mN, the role of the powder characteristics on the mechanical behavior of air plasma-sprayed mullite bond coats deposited on SiC substrates was investigated. Hardness (H) and elastic modulus (E) were measured for the as-sprayed coatings and for coatings heat-treated at 1300 °C, in water vapor environment, for periods up to 500 h. Both H and E values of the coatings are found to be highly dependent on the size distribution of the starting powders. It is aimed the fabrication of an efficient and cost-effective EBC prototype based on YSZ compositionally graded mullite.     

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.     

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′.