CMAS corrosion of YSZ thermal barrier coatings obtained by different thermal spray processes

Degradation of yttria-stabilized zirconia (YSZ) layers by molten CaO-MgO-Al₂O₃-SiO₂ (CMAS)-based deposits is an important failure mode of thermal barrier coating (TBC) systems in modern gas turbines. The present work aimed to understand how the chemical purity and microstructure of plasma-sprayed YSZ layers affect their response to CMAS corrosion. To this end, isothermal corrosion tests (1 h at 1250 °C) were performed on four different kinds of YSZ coatings: atmospheric plasma-sprayed (APS) layers obtained from standard- and high-purity feedstock powders, a dense – vertically cracked (DVC) layer, and a suspension plasma sprayed (SPS) one. Characterization of corroded and non-corroded samples by FEG-SEM, EBSD and micro-Raman spectroscopy techniques reveals that, whilst all YSZ samples suffered grain-boundary corrosion by molten CMAS, its extent could vary considerably. High chemical purity limits the extent of grain-boundary dissolution by molten CMAS, whereas high porosity and/or fine crystalline grain structure lead to more severe degradation.     

Architecture designs for extending thermal cycling lifetime of suspension plasma sprayed thermal barrier coatings

Suspension plasma spraying (SPS) as a relatively new spraying technology has great potential on depositing high performance thermal barrier coatings (TBCs). In some cases, however, columnar SPS TBCs show premature failure in thermal cycling test. To explain the reasons of such failure, a failure mechanism for columnar SPS TBCs was proposed in this work. The premature failure of TBCs might be related to the radial stresses in the vicinity of top coat/bond coat interface. These radial stresses were introduced by the thermal misfit and the roughness of bond coat. According to this mechanism, two architecture designs of SPS TBCs were applied to improve the thermal cycling lifetime. One was a double layered top coat design with a lamellar atmospheric plasma sprayed (APS) sub-layer and a columnar SPS top-layer. The other one was a low roughness bond coat design with a columnar SPS top coat deposited on a low roughness bond coat which was grinded before the spraying. With both designs, lifetimes of SPS TBCs were significantly extended. Especially, a lifetime even better than conventional APS TBCs was achieved with the double layered design.     

Porosity analysis and oxidation behavior of plasma sprayed YSZ and YSZ/LaPO4 abradable thermal barrier coatings

In this research, the high temperature oxidation behavior, porosity, and microstructure of four abradable thermal barrier coatings (ATBCs) consisting of micro- and nanostructured YSZ, YSZ-10%LaPO₄, and YSZ-20%LaPO₄ coatings produced by atmospheric (APS) method were evaluated. Results show that the volume percentage of porosity in the coatings containing LaPO₄ was higher than the monolithic YSZ sample. It was probably due to less thermal conductivity of LaPO₄ phases. Furthermore, the results showed that the amount of the remaining porosity in the composite coatings was higher than the monolithic YSZ at 1000 °C for 120 h. After 120 h isothermal oxidation, the thickness of thermally growth oxide (TGO) layer in composite coatings was higher than that of YSZ coating due to higher porosity and sintering resistance of composite coatings. Finally, the isothermal oxidation resistance of conventional YSZ and nanostructured YSZ coating was investigated.     

The application of small angle scattering techniques to porosity characterization in carbons

Small angle scattering (SAS) techniques offer a number of advantages for the investigation of the nature and behavior of porous materials. In particular, with respect to carbons, the essentially non-intrusive nature of SAS means that along with the more traditional, pre- and post-treatment characterization of carbons, in principle, characterization can also be performed in situ during adsorption and activation processes. In the current communication, the application of the techniques of small angle X-ray (SAXS) and neutron (SANS) scattering is reviewed specifically with respect to porosity characterization in carbons. First, the basis of these techniques is presented. More recent applications of SAXS and SANS to carbon porosity are presented, and their relative attributes are contrasted, including the related technique of contrast matching with SANS to distinguish “closed” from “open” porosity, and its application to elucidation of pore development mechanisms. Applications of other related techniques, such as μSAXS and TGA/SAXS, to carbon characterization and porosity development are also discussed.     

Design of high lifetime suspension plasma sprayed thermal barrier coatings

Thermal barrier coatings (TBCs) fabricated by suspension plasma spraying (SPS) have shown improved performance due to their low thermal conductivity and high durability along with relatively low production cost. Improvements in SPS TBCs that could further enhance their lifetime would lead to their widespread industrialisation. The objective of this study was to design a SPS TBC system with optimised topcoat microstructure and topcoat–bondcoat interface, combined with appropriate bondcoat microstructure and chemistry, which could exhibit high cyclic lifetime. Bondcoat deposition processes investigated in this study were high velocity air fuel (HVAF) spraying, high velocity oxy fuel spraying, vacuum plasma spraying, and diffusion process. Topcoat microstructure with high column density along with smooth topcoat–bondcoat interface and oxidation resistant bondcoat was shown as a favourable design for significant improvements in the lifetime of SPS TBCs. HVAF sprayed bondcoat treated by shot peening and grit blasting was shown to create this favourable design.     

Formation of vertical cracks in air plasma sprayed YSZ coatings using unpyrolyzed powder

Thick thermal barrier coatings (TTBCs) with vertical cracks deposited by air plasma spray (APS) and solution precursor plasma spray (SPPS) techniques have been widely investigated to achieve good thermal insulation along with reasonable service life. In this study, synthesized unpyrolyzed YSZ powder was air plasma sprayed in order to produce segmentation crack TTBCs. The microstructure and hardness of the deposits were then compared with those of the conventional TTBCs and dense vertically cracked (DVC)TTBCs. In this regard, spraying parameters were optimized to achieve deposits with the appropriate amount of unpyrolyzed particles in them to assist inducing vertical cracks in the deposited layers. The effect of the unpyrolyzed particles on microstructure, porosity, and microhardness of plasma sprayed coatings were also evaluated and compared. The new fabricated coating showed a bimodal structure combining non-molten sub-micron size particles and conventional splats along with segmentation cracks with higher amount of porosity and lower hardness compared to those of the DVC coatings. The results implied that, depositing unpyrolyzed powder by APS, as a new approach for achieving segmentation crack TTBCs, is very promising.     

Review of suspension and solution precursor plasma sprayed thermal barrier coatings

As one of the promising methods that can be employed to fabricate high-performance thermal barrier coatings (TBCs), suspension plasma spraying (SPS) or solution precursor plasma spraying (SPPS) has received significant attention in academic research. Enhanced performances have been shown in the SPS-/SPPS-coatings due to their special microstructures, such as uniformly distributed micro-pores, vertical cracks or columnar structures. Since there are more complexities than conventional plasma spraying methods, many works have been devoted to study the mechanism and properties of SPS-/SPPS-coatings during the past decades. In this work, the latest development of SPS or SPPS is reviewed in order to discuss some key issues in terms of preparation of suspension or solution precursor, injection mode of liquid phase, interaction between liquid and plasma jet, microstructure of as-sprayed coatings and corresponding deposition mechanism. Meanwhile, the potential application of SPS or SPPS in some new-type TBCs is introduced at the end of this paper.     

Microstructural,mechanical and tribological properties of suspension plasma sprayed YSZ/h-BN composite coating

Brittleness, relative high friction coefficient and wear rate limit the applications of ceramic coatings as wear-resistant layers. However, because embedding additives with ceramic matrix has demonstrated to be an effective way to improve coating performances, different contents and size of h-BN were added into an YSZ suspension. Afterwards, the YSZ/h-BN composite coatings were manufactured by suspension plasma spray and their tribological analysis indicated that: i) the reduction of the friction coefficient and wear rate can be achieved by incorporating h-BN into YSZ coating. ii) finer h-BN particle is more helpful to enhance the tribological properties of the coating. iii) the optimum content is dependent on h-BN particle sizes. iv) when the contents and the size of the h-BN inclusion increase, the probability distribution of the micro-hardness can become bi-modal. Three worn surface conditions were summarized and their wear mechanisms were discussed as well.     

Microstructural evaluation and thermal oxidation behaviors of YSZ/NiCoCrAlYTa coatings deposited by different thermal techniques

In this paper, two coating techniques, the high velocity oxy-fuel (HVOF) and air plasma spray (APS) techniques, were used to deposit a bond coat of NiCoCrAlYTa on the Inconel 625 substrate, followed by applying a topcoat of yttria-stabilized zirconia (YSZ). The samples were preoxidized in an argon-controlled furnace at a temperature of 1000 °C for 12 and 24 h to characterize the microstructure of a thermally grown oxide (TGO) using the two coating techniques. The most suitable preoxidized samples were further tested for isothermal oxidation at 1000 °C for up to 120 h, and a hot corrosion test was performed at 1000 °C for up to 52 h or until spalling occurred. As-sprayed and oxidized samples prepared with different coating techniques were evaluated in terms of their microstructure using different characterization methods, such as field emission scanning electron microscopy (FESEM), variable pressure scanning electron microscopy (VPSEM), energy dispersive X-ray spectroscopy (EDS) equipped with energy dispersive X-ray and X-ray diffraction (XRD) analyses. In addition, the mechanical properties of these samples were evaluated using adhesion tests. The results show that the YSZ/NiCoCrAlYTa coating applied with the HVOF technique forms a more thin and continuous layer of TGO than that obtained when applying a YSZ/NiCoCrAlYTa coating using the APS technique, indicating that a severe brittle oxidation interface exists between the two layers. The results also indicate that the mechanical strength obtained from the adhesion test of the coated samples is observably affected by the oxidation behaviors obtained with the different deposition techniques chosen.     

Effect of environmental pressure on the microstructure of YSZ thermal barrier coating via suspension plasma spraying

Suspension plasma spraying (SPS) as a potential technique to prepare thermal barrier coatings (TBCs) has been attracting more and more attention. However, most reports on SPS were carried out in the atmosphere. Given the unique features of in-flight particles and plasma jets under low pressure, the resulting coatings are expected to be different from those under atmospheric pressure. In this article, yttria-stabilized zirconia (YSZ) thermal barrier coatings were prepared using suspension plasma spraying under different environmental pressures. The results show that as the environmental pressure decreased, the column-like structural coating turned into a vertical crack segmented structure, as well as a dramatic decrease in surface roughness. More nanoparticle agglomerates were formed in the coating under lower environmental pressures. The real porosity of the coating increased with a decrease in environmental pressure.     

Interaction of CMAS on thermal sprayed ytterbium disilicate environmental barrier coatings: A story of porosity

Molten calcium magnesium alumina-silicates (CMAS) represent a challenge for the current generation of rare earth silicates environmental barrier coatings (EBCs). Their interaction with ytterbium disilicate (Yb₂Si₂O₇) free-standing coatings deposited using thermal spraying technique has been studied to further understand the reaction mechanisms. Three coatings, deposited with different porosity levels and thickness, representing traditional EBCs (<3% porosity and ～350 μm thickness) and abradable coatings (～20% porosity and 500–1000 μm thickness) were exposed to CMAS at 1350 °C. The results show that higher porosity levels facilitates CMAS infiltration in the first hour of exposure, in combination with infiltration through the inter-splat boundaries. Preferential dissolution of ytterbium monosilicate (Yb₂SiO₅) takes place, forming a 10–15 μm Ca₂Yb₈(SiO₄)₆O₂ apatite layer as the reaction product, producing a network of fine porosity (<10 μm) as the inter-splat boundary material is consumed. After exposure for 48 h, CMAS has completely infiltrated all three coatings, with apatite crystals present across the coatings, up to a depth of ～550 μm. Despite the extensive CMAS infiltration and apatite formation, no damage could be observed in any of the coatings, providing a promising first step for environmental barrier abradable coatings.     

Sintering resistance of suspension plasma sprayed 7YSZ TBC under isothermal and cyclic oxidation

This study examines sintering resistance of a thermal barrier coating (TBC), composed of a 7YSZ suspension plasma sprayed (SPS) top coat (TC), an air plasma sprayed (APS) NiCoCrAl bond coat (BC), and an INCONEL 625 substrate, under isothermal and cyclic conditions with a peak temperature of 1080 °C for 400, 800, and 1300 h/cycles. Microstructure, phase composition and microstrain were examined using SEM and XRD. Mechanical properties of fracture toughness, hardness and elastic modulus were obtained using nano-indentation. Samples under cyclic conditions presented faster sintering rate than under isothermal condition due to larger compressive strain and frequent heating and cooling cycles. Faster degradation of mechanical properties due to sintering leads to shorter lifetime of SPS coating under cyclic conditions. Moreover, vertical cracks within SPS coatings reduces compressive stress leading to a greater lifetime as compared to APS coatings exposed to similar conditions.     

Atmospheric plasma sprayed 7%-YSZ thick thermal barrier coatings with controlled segmentation crack densities and its thermal cycling behavior

Yttria-stabilized zirconia (YSZ)-coatings are deposited on Ni-based superalloy IN738 by atmospheric plasma spraying (APS). For the first time, controlled segmentation crack densities are manually developed in the coatings, even after the APS deposition. This method allows to user to control segmentation densities as well as cracks depth, which could be designed as per coating thickness and required application. Thermal cycling test shows promising strain tolerance behavior for the segmented coatings, whereas coating without segmentation could not sustain even for its first thermal cycle period. Further, microstructural studies reveal that a very thin layer of TGO was formed and obvious no coating failure or spallation was observed after thermal cycling test at 1150 °C for 500 cycles.     

Columnar and DVC-structured thermal barrier coatings deposited by suspension plasma spray: high-temperature stability and their corrosion resistance to the molten salt

High-temperature stability of SPS YSZ coatings with the columnar and deep vertically cracked (DVC) structures and their corrosion resistance to 56 wt% V₂O₅+44 wt% Na₂SO₄ molten salt mixture were investigated. Both the columnar and DVC-structured YSZ coatings were sintered at 1000 °C, but a significant increase in porosity in combination with significant reductions in Vickers’ hardness and Young's modulus were observed at the temperatures from 1200 °C to 1400 °C. The DVC-structured YSZ coating exhibited superior corrosion resistance against the molten salt mixture attack to the columnar-structured one due to its higher density behaving as a sealing protective top layer at 950 °C.     

Modelling and evaluating thermal conductivity of porous thermal barrier coatings at elevated temperatures

Thermal conductivity of various porous thermal barrier coatings (TBCs) used at elevated temperatures for gas turbines has been evaluated using the proposed six-phase model. These TBCs rely on microstructural properties and yield different types of porosities. This paper studies the thermal conductivity of TBCs based on microstructural features to evaluate the effect of different types of porosities on thermal conductivity. The first part of this paper investigates the microstructural characterization of various TBCs using image analysis (IA) technique. The second part of this paper evaluates the thermal conductivity using the image analysis. The volumetric fraction of porosities along with their orientation, shape and morphology, shows a considerable impact on the overall thermal conductivity of TBCs. The proposed six-phase model can predict thermal conductivity of porous TBCs with a good agreement with the measured values. The model results can help to better understand the effect of microstructural changes on thermal conductivity and can provide useful guide to fabricate TBCs with low thermal conductivity.     

Molten silicate interactions with plasma sprayed thermal barrier coatings: Role of materials and microstructure

Ingestion of siliceous particulate debris into both propulsion and energy turbines has introduced significant challenges in harnessing the benefits of enhanced operation efficiencies through the use of higher temperatures and thermal barrier coatings (TBCs). The so-called CMAS (for calcium-magnesium alumino-silicate) particles can melt in the gas path at temperatures greater than 1200C, where they will subsequently impact the coating surface and infiltrate through the carefully engineered porosity or cracks in a TBC. Ultimately, this CMAS attack causes premature spallation through its solidification and stiffening the ceramic during cooling. It has been noted in recent years, that TBCs based on yttria stabilized zirconia (YSZ) are completely non-resistant to CMAS attack due to their lack of reactivity with infiltrant liquid. New TBC ceramics such as Gadolinium Zirconate (GZO) show promise of CMAS resistance through rapid reaction-induced crystallization and solidification of the infiltrant, leading to its arrested infiltration. In both situations, the microstructure (porosity, micro and macro cracks) can be important differentiators in terms of the infiltration and subsequent failure mechanisms. This paper seeks to examine the interplay among microstructure, material, and CMAS attack in different scenarios. To do so, different types of YSZ & GZO single and multilayer coatings were fabricated using Air Plasma Spray (APS) and exposed to CMAS through isothermal and gradient mechanisms. In each of the cases, beyond their unique interactions with CMAS, it was observed the inherent microstructure and character of the porosity of the coating will have an additional role on the movement of the melt. For instance, vertical cracks can provide pathways for accelerated capillaric flow of the melt into both YSZ and GZO coatings. Based on these observations multilayer coatings have been proposed and realized toward potentially reducing complete coating failure and supporting multiple CMAS attack scenarios.     

Effect of molten V2O5 salt on the corrosion behavior of micro- and nano-structured thermal sprayed SYSZ and YSZ coatings

The corrosion resistance of micro-and nano-structured scandia and yttria codoped zirconia (nano-4 mol%SYSZ and micro-8.6SYSZ) and yttria doped zirconia (4YSZ) in the presence of molten vanadium oxide were investigated. To this end, duplex TBCs (thermal barrier coatings), composed of a bond coat (NiCrAlY) and a top coat (4SYSZ or 4YSZ), were deposited on the IN738LC Ni-based supper-alloy by atmospheric plasma spraying (APS). The corrosion studies of plasma sprayed TBCs were conducted in 25 mg V₂O₅ molten salt at 910 °C for different times. The nanostructured coating, as compared to its micro-structured counterpart, in spite of a further reaction with the V₂O₅ salt, showed a higher degradation resistance during the corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones. Finally, the corrosion resistance and degradation mechanism of SYSZ and YSZ coatings were compared with the presence of molten NaVO₃ and V₂O₅ salt, respectively.     

Isothermal oxidation and TGO growth behaviors of YAG/YSZ double-ceramic-layer thermal barrier coatings

In this study, yttrium aluminum garnet/yttria-stabilized zirconia (YAG/YSZ) double-ceramic-layer thermal barrier coatings (DCL TBC) and yttria-stabilized zirconia (YSZ) single-ceramic-layer thermal barrier coatings (SCL TBC) were deposited by atmosphere plasma spray (APS) on the Inconel 738 alloy substrate, and isothermal oxidation tests were performed to investigate the formation and growth behavior of thermally grown oxide (TGO). Results showed that the Al₂O₃ TGO thickness of both TBC groups increased by increasing the isothermal oxidation time,and then slowly decreased with the appearance and growth of the adverse multilayer structure comprising CoCr₂O₄, (Ni,Co)Al₂O₄, NiCr₂O₄, and NiO mixed oxides. However, since the significant inhibition effect of the YAG coating to oxygen ionic diffusion, the mixed oxides appearance time and TGO growth behaviors were delayed in the DCL TBC. As a result, the TGO thickness of the DCL TBC was always smaller than that of the SCL TBC in the entire oxidation process. And the Al₂O₃ layer thickness proportion in the total TGO of the DCL TBC was greater than or equal to that of the SCL TBC after oxidation for the same period. The results of weight gain showed that compared with the SCL TBC, the parabolic oxidation rate of the DCL TBC was decreased approximately 35%. Consequently, the DCL TBC has better high-temperature oxidation resistance than the SCL TBC.     

Comparative study on thermal shock behavior of thick thermal barrier coatings fabricated with nano-based YSZ suspension and agglomerated particles

Two kinds of segmentation-crack structured YSZ thick thermal barrier coatings (TTBCs) were deposited by suspension plasma spraying (SPS) and atmospheric plasma spraying (APS) with nano-based suspension and agglomerated particles, respectively. The phase composition, microstructure evolution and failure behavior of both TBCs before and after thermal shock tests were systematically investigated. Microstructure of the APS coating exhibits typical segmentation-crack structure in the through-thickness direction, similar with the SPS coating. The densities of segmentation-crack in APS and SPS coatings were about 3 cracks mm⁻¹ and 4 cracks mm⁻¹_, respectively. The microstructure observation also showed that the columnar and equiaxed grains existed in the SPS coating. As for the thermal shock test, the spallation life of the APS TTBCs was 146 cycles, close to that of the SPS TTBCs (166 cycles). Failure of the APS coating is due to the spallation of fringe segments and splats.     

Comparing the deposition mechanisms in suspension plasma spray (SPS) and solution precursor plasma spray (SPPS) deposition of yttria-stabilised zirconia (YSZ)

Thermal spraying using liquid feedstock has emerged as a promising technology for the deposition of finely structured ceramic coatings. In order to provide a comparative assessment of the deposition mechanisms occurring when spraying suspension or solution feedstock, suspensions of 300 nm-sized ZrO₂–4.5 mol.% Y₂O₃ particles dispersed in water and in ethanol and solutions of zirconium and yttrium salts, corresponding to ZrO₂–4.5 mol.% Y₂O₃ and ZrO₂–8 mol.% Y₂O₃ stoichiometries, were processed by plasma spraying using different parameter settings. In-flight diagnostics of sprayed droplets, together with the morphological, microstructural and phase analysis of individual lamellae collected onto polished substrates, performed by SEM, FIB, AFM and micro-Raman spectroscopy, led to the identification of deposition mechanisms, which were subsequently verified through the characterisation of complete coating layers.