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.     

TEM analysis of the microstructure of thermal barrier coatings after isothermal oxidation

Thermal barrier coatings (TBCs) are extensively used to protect metallic components in applications where the operating conditions include an aggressive environment at high temperatures. The most important factor controlling TBC durability is the nucleation, and subsequent thickening, of a thermally grown oxide (TGO) layer which is formed during high-temperature oxidation. For this reason, the aim of this work is to analyse the TGO microstructure evolution during isothermal oxidation to explain the macroscopic oxidation behaviour. To this end, transmission electron microscopy (TEM) was used to evaluate the TGO fine microstructure. ZrO₂(Y₂O₃) top coat and NiCrAlY bond coating were air plasma sprayed onto an Inconel 600 Ni base alloy. The TBCs were isothermally oxidized in air at 950 and 1050 °C for 24, 48, 72, 144 and 336 h and the principal differences in TGO composition were analysed. α-Al₂O₃ was the main TGO constituent in the TBC treated at 950 °C. On the other hand, Al was rapidly consumed in the TBC oxidized at 1050 °C leading to the formation of NiAl₂O₄ spinels, after 72 h exposure, and NiO, after 336 h. The TGO growth kinetics followed a power law, controlled by Al³⁺ diffusion, in the samples treated at 950 °C. However, two different power laws fitted the TGO growth kinetics in the coatings treated at 1050 °C as the diffusion of Ni²⁺ is relevant after 72 h exposure.     

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.     

CoNiCrAlY黏结层结构设计及其对热障涂层结合强度和抗热震性能的影响

目的 设计热障涂层黏结层结构,改善涂层结合强度和抗热震性能。方法 制备了5种结构的CoNiCrAlY黏结层,即超音速火焰喷涂(HVOF)底层+等离子喷涂(APS)上层的双层结构黏结层试样,对其进行1 050℃真空热处理3 h后的试样,APS黏结层试样,HVOF黏结层试样及其真空热处理试样。再在以上5种试样表面制备Y₂O₃部分稳定ZrO₂(YSZ)陶瓷层,研究黏结层的表面粗糙度、相组成、微观组织结构及其对涂层试样结合强度、热震性能的影响。结果 制备态的黏结层由γ/γ’和β-NiAl两相组成,真空热处理后β相含量增多,表面粗糙度下降。在所有涂层试样中,双黏结层的涂层试样的结合强度最低,为28.43 MPa;对其真空热处理后得到的涂层试样的结合强度最高,达到39.42 MPa,主要原因在于热处理促进了两黏结层之间的扩散,提高了界面强度。双黏结层的涂层试样的抗热震性能最好,200次热震后涂层无明显剥落,而APS黏结层的涂层试样的抗热震性能最差,涂层抗热震性能的差异在于黏结层微观结构的不同。结论 双黏结层的结构设计综合了APS、H...     

TGO Growth and Crack Propagation in a Thermal Barrier Coating

In thermal barrier coating (TBC) systems, a continuous alumina layer developed at the ceramic topcoat/bond coat interface helps to protect the metallic bond coat from further oxidation and improve the durability of the TBC system under service conditions. However, other oxides such as spinel and nickel oxide, formed in the oxidizing environment, are believed to be detrimental to TBC durability during service at high temperatures. It was shown that in an air-plasma-sprayed (APS) TBC system, postspraying heat treatments in low-pressure oxygen environments could suppress the formation of the detrimental oxides by promoting the formation of an alumina layer at the ceramic topcoat/bond coat interface, leading to an improved TBC durability. This work presents the influence of postspraying heat treatments in low-pressure oxygen environments on the oxidation behavior and durability of a thermally sprayed TBC system with high-velocity oxy-fuel (HVOF)-produced Co-32Ni-21Cr-8Al-0.5Y (wt.%) bond coat. Oxidation behavior of the TBCs is evaluated by examining their microstructural evolution, growth kinetics of the thermally grown oxide (TGO) layers, and crack propagation during low-frequency thermal cycling at 1050 °C. The relationship between the TGO growth and crack propagation will also be discussed.     

Investigation of TBCs on turbine blades by photoluminescence piezospectroscopy

Thermal barrier coating (TBC) blade specimens with Pt diffusion bond coats were subjected to thermal cycling with periodic measurements of the residual stress in the thermally grown oxide (TGO) using photoluminescence piezospectroscopy. Two distinct stress levels were generally found to coexist in the probed volume, i.e. a high stress (～4 GPa) and a low stress (～500 MPa) level. Both the high and low stress levels were independent of the curvature of the blade surface, in agreement with numerical modelling based on a composite cylinder stress model. The relative contributions of the two stress levels appear to be correlated with the θ-Al₂O₃ content of the TGO, which was dependent on the position on the blade. The TBCs tended to fail along the TGO/bond coat interface in thermal cycling. This was modified by the presence of mixed transition metal oxides in the TGO. The results are interpreted in terms of a likely failure mechanism.     

TGO growth behaviour in TBCs with APS and HVOF bond coats

The growth of thermally grown oxide (TGO) layers and their influence on crack formation were studied for two thermal barrier coating (TBC) systems with CoNiCrAlY bond coats produced by (i) air plasma spray (APS) and (ii) high-velocity oxy-fuel (HVOF) techniques. All samples received a vacuum heat treatment and were subsequently subjected to thermal cycling in air. The TGOs were predominantly comprised of layered alumina, along with some oxide clusters of chromia, spinel and nickel oxide. However, after extended oxidation, the alumina layer formed in the APS-CoNiCrAlY bond coat transformed to chromia/spinel, while that formed in the HVOF-CoNiCrAlY bond coat remained stable. TGO thickening in the APS-CoNiCrAlY bond coat generally exhibited a three-stage growth behavior, which resembles a high temperature creep curve, whereas growth of the alumina layer in the HVOF-CoNiCrAlY bond coat showed an extended steady-state stage. Crack propagation in these two TBCs was found to be related to the growth and coalescence of oxide-induced cracking, connecting with pre-existing discontinuities in the topcoat. Hence, crack propagation during thermal cycling appeared to be controlled by TGO growth.     

Delamination resistance of thermal barrier coatings containing embedded ductile layers

Micromechanical models are developed to explore the effect of embedded metal layers upon thermal cycling delamination failure of thermal barrier coatings (TBCs) driven by thickening of a thermally grown oxide (TGO). The effects of reductions in the steady-state (i.e. maximum) energy release rate (ERR) controlling debonding from large interface flaws and decreases in the thickening kinetics of TGO are investigated. The models are used to quantify the dependence of the ERR and delamination lifetime upon the geometry and constitutive properties of metal/TBC/TGO multilayers. Combinations of multilayer properties are identified which maximize the increase in delamination lifetime. It is found that even in the absence of TGO growth rate effects, the delamination lifetime of TBC systems with weak TGO/bond coat interfaces can be more than doubled by replacing 10–20% of the ceramic TBC layer with a metal whose ambient temperature yield stress is in the ～100–200 MPa range.     

Simultaneous synthesis by spark plasma sintering of a thermal barrier coating system with a NiCrAlY bond coat

As-fabricated thermal barrier coating (TBC) systems generally consist of a superalloy substrate, a MCrAlY bond coat (M = Ni, Co, Fe), and a ceramic (usually partially stabilized zirconia) top coat. The conventional methods for producing the two coating layers generally derive from thermal spray and physical vapor deposition techniques. Thermal exposure leads to the formation of an additional layer: the thermally grown oxide (TGO) between the bond coat and top coat. In the present work, a TBC system is synthesized through the application of spark plasma sintering (SPS), which provides not only the opportunity to synthesize all three layers at once, but the process is quite rapid and can produce dense layers. More specifically, this paper describes the application of this method to an yttria-stabilized ZrO₂ (YSZ) top coat and a NiCrAlY bond coat on a Ni-base Hastelloy X substrate. A one-micron thick Al₂O₃ TGO layer is also created from the reaction between an Al foil layer inserted in the stack prior to sintering and the ZrO₂ in the top coat. The effects of select process conditions are considered. The resulting multi-layer system is characterized with optical microscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray analysis (EDAX) and X-ray diffraction (XRD). Differential thermal analysis (DTA) is used to investigate the reaction between the Al foil and the YSZ top coat.     

Thermal barrier coating bonded by (Al2O3–Y2O3)/(Y2O3-stabilized ZrO2) laminated composite coating prepared by two-step cyclic spray pyrolysis

Thermal barrier coating bonded by (Al₂O₃–Y₂O₃)/(Y₂O₃-stabilized ZrO₂) (YSZ) laminated coating has been developed on Ni-based superalloy by two-step cyclic pyrolysis. It is demonstrated, from cyclic oxidation tests at 1100 °C, that YSZ top coat and alloy substrate can be bonded together effectively by the (Al₂O₃–Y₂O₃)/YSZ laminated coating, showing good resistance to oxidation, cracking, spallation and buckling. These beneficial effects can be attributed to the sealing effect of the designed multi-sealed compact bond coat with α-Al₂O₃ layers, the decrease of thermal stresses, the increase of fracture toughness in such bond coat and no interdiffusion between the substrate and bond coat.     

Degradation of a TBC with HVOF-CoNiCrAlY Bond Coat

Thermal barrier coatings (TBCs) provide both thermal insulation and oxidation and corrosion protection to the substrate metal, and their durability is influenced by delamination near the interface between the ceramic topcoat and the metallic bond coat, where a layer of thermally grown oxide (TGO) forms during service exposure. In the present work, the degradation process of a TBC with an air-plasma-spray ZrO₂-8 wt.%Y₂O₃ topcoat and a high-velocity oxy-fuel CoNiCrAlY bond coat was studied, in terms of TGO growth kinetics and aluminum depletion in the bond coat, as well as cracking behavior. The results show that the TGO growth kinetics can be described by a transient oxidation stage with δ³ = k ₁ t followed by a steady-state oxidation stage with δ² = c + k ₂ t. Significant aluminum depletion was observed in the bond coat after extended thermal exposure; however, chemical failure of the bond coat did not occur even after the aluminum content near the TGO/CoNiCrAlY interface decreased to 4.5 at.%. A power-law relationship between the maximum crack length in the TBC and the TGO thickness was observed, which may serve as the basis for TBC life prediction.     

Cyclic oxidation behavior of HVOF bond coatings deposited on La- and Y-doped superalloys

One suggested strategy for improving the performance of thermal barrier coating (TBC) systems used to protect hot section components in gas turbines is the addition of low levels of dopants to the Ni-base superalloy substrate. To quantify the benefit of these dopants, the oxidation behavior of three commercial superalloys with different Y and La contents was evaluated with and without a NiCoCrAlYHfSi bond coating deposited by high velocity oxygen fuel (HVOF) spraying. Cyclic oxidation experiments were conducted in dry O₂ at 1050°, 1100° and 1150 °C. At the highest temperature, the bare superalloy without La showed more attack due to its lower Al content but no difference in oxidation rate or scale adhesion was noted at lower temperatures. With a bond coating, the alumina scale was non-uniform in thickness and spalled at each temperature. Among the three coated superalloys, no clear difference in oxide growth rate or scale adhesion was observed. Evaluations with a YSZ top coat and a bond coating without Hf are needed to better determine the effect of superalloy dopants on high temperature oxidation performance.     

Thermal Failure of Nanostructured Thermal Barrier Coatings with Cold-Sprayed Nanostructured NiCrAlY Bond Coat

Nanostructured thermal barrier coatings (TBCs) were deposited by plasma spraying using agglomerated nanostructured YSZ powder on Inconel 738 substrate with cold-sprayed nanostructured NiCrAlY powder as bond coat. The isothermal oxidation and thermal cycling tests were applied to examine failure modes of plasma-sprayed nanostructured TBCs. For comparison, the TBC consisting of conventional microstructure YSZ and conventional NiCrAlY bond coat was also deposited and subjected to the thermal shock test. The results showed that nanostructured YSZ coating contained two kinds of microstructures; nanosized zirconia particles embedded in the matrix and microcolumnar grain structures of zirconia similar to those of conventional YSZ. Although, after thermal cyclic test, a continuous, uniform thermally grown oxide (TGO) was formed, cracks were observed at the interface between TGO/BC or TGO/YSZ after thermal cyclic test. However, the failure of nanostructured and conventional TBCs mainly occurred through spalling of YSZ. Compared with conventional TBCs, nanostructured TBCs exhibited better thermal shock resistance.     

Surface Modification of Thermal Barrier Coatings by Single-Shot Defocused Laser Treatments

Thermal barrier coatings (TBC) consisting of atmospheric plasma-sprayed ZrO₂-8 wt.% Y₂O₃ and a high velocity oxygen fuel-sprayed metallic bond coat were subjected to CO₂ continuous wave laser treatments. The effects of laser power on TBCs were investigated as was the thermally grown oxide (TGO) layer development of all as-sprayed and laser-treated coatings after thermal oxidation tests in air environment for 50, 100, and 200 h at 1100 °C. The effects of laser power on TBCs were investigated. TGO layer development was examined on all as-sprayed and laser-treated coatings after thermal oxidation tests in air environment for 50, 100, and 200 h at 1100 °C. Melted and heat-affected zone regions were observed in all the laser-treated samples. Oxidation tests showed a stable alumina layer and mixed spinel oxides in the TGO layers of the as-sprayed and laser-treated TBCs.     

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.     

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.     

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.     

The effect of silicon on thermal shock performance of aluminide-thermal barrier coatings

The failure of air-plasma-sprayed thermal barrier coatings (APS TBCs) with conventional pack aluminide and slurry Si-modified aluminide bond coats on superalloy In-738LC was investigated during a thermal-shock test. Thermal shock experiments consisted of rapid thermal cycling between 1100 °C and 300 °C for 120 times. It was found that the lifetime of APS TBCs on aluminide bond coats can be extended by introducing silicon into aluminide structure. Silicon improved the bond coat oxidation resistance as well as the stability of β-NiAl phase, which is critical to the coating life enhancement.     

Failure Mechanism for Thermal Fatigue of Thermal Barrier Coating Systems

Thick thermal barrier coatings (TBCs), consisting of a CoNiCrAlY bond coat and yttria-partially stabilized zirconia top coat with different porosity values, were produced by air plasma spray (APS). The thermal fatigue resistance limit of the TBCs was tested by furnace cycling tests (FCT) according to the specifications of an original equipment manufacturer (OEM). The morphology, residual stresses, and micromechanical properties (microhardness, indentation fracture toughness) of the TBC systems before and after FCT were analyzed. The thermal fatigue resistance increases with the amount of porosity in the top coat. The compressive in-plane stresses increase in the TBC systems after thermal cycling; nevertheless the increasing rate has a trend contrary to the porosity level of top coat. The data suggest that the spallation happens at the TGO/top coat interface. The failure mechanism of thick TBCs was found to be similar to that of conventional thin TBC systems made by APS.     

Oxidation and Degradation of EB–PVD Thermal–Barrier Coatings

Thermal–barrier coatings (TBCs) consist of a magnetron-sputtered Ni–30Cr–12Al–0.3Y (wt.%) bond coat to protect the substrate superalloy from oxidation/hot corrosion and an electron-beam physical-vapor deposited (EB–PVD) 7 wt.% yttria partially stabilized zirconia (YPSZ) top coat. The thermal cyclic life of the TBC system was assessed by furnace cycling at 1050°C. The oxidation kinetics were evaluated by thermogravimetric analysis (TGA) at 900, 1000, and 1100°C for up to 100 hr. The results showed that the weight gain of the specimens at 1100°C was the smallest in the initial 20 hr, and the oxide scale formed on the sputtered Ni–Cr–Al–Y bond coat is only Al₂O₃ at the early stage of oxidation. With aluminum depletion in the bond coat, NiO, Ni(Cr,Al)₂O₄, and other spinel formed near the bond coat. During thermal cycling, microcracks were initiated preferentially in the YPSZ top coat along columnar grain boundaries and then extended through and along the top coat. The growth stress of TGO added to the thermal stress imposed by cycling, lead to the separation at the bond coat–TGO interface. The ceramic top coat spalled with the oxide scale still adhering to the YPSZ after specimens had been cycled at 1050°C for 300 cycles. The failure mode of the EB–PVD ZrO₂–7 wt.% Y₂O₃ sputtered Ni–Cr–Al–Y thermal-barrier coating was spallation at the bond coat–TGO interface.