Thermal conductivity of air plasma sprayed yttrium heavily-doped lanthanum zirconate thermal barrier coatings

The yttrium heavily doped La₂Zr₂O₇ solid solutions coatings, with a Y to La molar ratio of 1:1, have been successfully prepared by air plasma spraying technique. The evolution of phase composition, phase structure and thermal conductivity of such coatings with annealing at 1300?°C has been investigated. The results show that, a single pyrochlore structure can be retained for coating after annealing up to 48?h, beyond which the fluorite phase begins to precipitate out. By comparing thermal conductivities to those undoped counterparts at a similar porosity level, we find a considerably flat thermal conductivity versus temperature (k-T) curve, suggesting the existence of a strong phonon scattering source, which is inferred as rattlers. In addition, after the segmentation of the fluorite phase, the thermal conductivity of corresponding coatings rises considerably, indicating that the fluorite phase has a higher thermal conductivity than that of pyrochlore phase. Moreover, while the as-sprayed coatings show a clear indication of radiative thermal conduction beyond 1000?°C, the thermal conductivity of annealed coatings do not show such an uprising trend after 1000?°C, suggesting that the radiative thermal conduction has been greatly suppressed. The reason is proposed as the formation of local dipoles due to local enrichment of certain elements influences the propagation of electromagnetic waves and thus suppresses the radiative thermal conduction.     

Progress update on extending the durability of air plasma sprayed thermal barrier coatings

Air plasma sprayed thermal barrier coatings (TBCs) are widely used in gas turbines to provide thermal insulation for the metallic engine components. During service, the multi-layered and multi-material systems undergo thermal and mechanical degradation. The degradation mechanisms include sintering, phase transformation, residual stress, oxidation, erosion and CMAS attack. The degradation leads to the initiation and propagation of cracks at or near the interface between the topcoat and bond coat, eventually merging into large-scale delamination and resulting in failure of the TBCs. Recent progress in the development of methods for mitigating the detrimental impact of these failure mechanisms via composition and processing modifications has been reviewed. Meanwhile, the applications of newly-emerging materials with superior properties have also been discussed. The review emphasises the relationships between composition, microstructure and properties of TBCs, which is beneficial for the exploration of the advanced TBCs with higher durability.     

Laser surface modification of plasma sprayed CYSZ thermal barrier coatings

In this study, Inconel 738 LC superalloy coupons were first sprayed with a NiCoCrAlY bond coat and then with a ceria and yttria stabilized zirconia (CYSZ) top coat by air plasma spraying (APS). After that, the plasma sprayed CYSZ thermal barrier coatings (TBCs) were treated using a Nd:YAG pulsed laser. The effect of laser glazing on the microstructure of the coatings was investigated. The microstructures and surface topographies of both as-sprayed and laser glazed samples were investigated using field emission scanning electron microscope (FESEM) and atomic force microscope (AFM). The phases of the coatings were analyzed with X-ray diffractometry (XRD). The microstructural analysis results revealed that laser surface glazing of ceramic top coat reduced the surface roughness considerably, eliminated the surface porosities and produced a network of continuous cracks perpendicular to the surface. XRD patterns also showed that both as-sprayed and laser glazed top coats consisted of nonequibrium tetragonal (T′) phase.     

Thermal conductivity prediction in air plasma sprayed thermal barrier coatings containing multifarious defects

Air plasma sprayed yttria-stabilized zirconia thermal barrier coatings are widely applied in gas turbines and aviation engines, which usually contain multifarious and multiscale defects, such as pores, cracks, and amorphous layers. They all significantly lower the thermal conductivity of the coating but in drastically different ways depending on their morphologies and orientations. Establishing an accurate correlation between the microstructure and the thermal conductivity requires not only a precise separation and estimation of different kinds of defects but also a reasonable mathematic model to describe their effect on thermal conductivity. In this research, cross-section ion polishing and image analysis were chosen as a reliable assembly for characterizing multifarious defects of porous coatings, which was almost undamaged compared with the traditionally mechanical polishing. The effect of different microscale defects on the thermal conductivity was respectively and quantitatively studied to build a mathematical model. A thermal resistance induced by amorphous layers was introduced into the model, which was found to have a linear relationship with the amorphous layer concentration. It was also found a linear relationship between the amorphous layer concentration and the spraying times. The predicted thermal conductivity of porous coatings by multifarious-defect-concerned model fits the data measured using the steady heat flow method very well. This research confirms the applicability of image-analysis-based modeling as a simple, reliable, and versatile method for thermal conductivity prediction of porous coating systems.     

Thermal shock resistance of thermal barrier coatings for nickel-based superalloy by supersonic plasma spraying

Double-layer thermal barrier coatings (TBCs), including a top ZrO₂ layer and an inner CoNiCrAlY layer, were deposited on nickel-based superalloy using supersonic atmospheric plasma spraying (SAPS). Thermal shock resistance of the TBCs between 1200 °C and room temperature was investigated. After thermal shock test, the adhesive strength of the coatings was evaluated through scratch test. The SAPS–TBCs present good thermal shock resistance, exhibiting only 0.26% mass gain up to 150-time thermal cycling. Before thermal cyclic treatment, SAPS–TBCs exhibited a strong adhesion with the absence of the thermally grown oxide (TGO) between out and inner layer. With the increasing of thermal cycles, the TGO layer was formed and its thickness firstly increased and then dropped down. The critical load fell down by about 32% for topcoat–bondcoat adhesion (up to 50 cycles) and 35% or so for TBCs–substrate adhesion (up to 150 cycles) compared to the counterpart of as-sprayed specimens. The strain introduced by the existence of TGO and mixed oxides resulted in a varied adhesion for TBCs on nickel-based alloy during thermal cycling.     

Laser thermal gradient testing of air plasma sprayed multilayered,multi-material thermal barrier coatings

Air plasma sprayed (APS) thermal barrier coatings (TBCs) are a widely used technology in the gas turbine industry to thermally insulate and protect underlying metallic superalloy components. These TBCs are designed to have intrinsically low thermal conductivity while also being structurally compliant to withstand cyclic thermal excursions in a turbine environment. This study examines yttria-stabilized zirconia (YSZ) TBCs of varying architecture: porous and dense vertically cracked (DVC), which were deposited onto bond-coated superalloys and tested in a novel CO₂ laser rig. Additionally, multilayered TBCs: a two-layered YSZ (dense + porous) and a multi-material YSZ/GZO TBC were evaluated using the same laser rig. Cyclic exposure under simulative thermal gradients was carried out using the laser rig to evaluate the microstructural change of these different TBCs over time. During the test, real-time calculations of the normalized thermal conductivity of the TBCs were also evaluated to elucidate information about the nature of the microstructural change in relation to the starting microstructure and composition. It was determined that porous TBCs undergo steady increases in conductivity, whereas DVC and YSZ/GZO systems experience an initial increase followed by a monotonic decrease in conductivity. Microstructural studies confirmed the difference in coating evolution due to the cycling.     

Effect of scandia content on the thermal shock behavior of SYSZ thermal sprayed barrier coatings

Nanostructured 4SYSZ (scandia (3.5 mol%) yttria (0.5 mol%) stabilized zirconia) and 5.5 SYSZ (5 mol% scandia and 0.5 mol% yttria) thermal barrier coatings (TBCs) were deposited on nickel-based superalloy using NiCrAlY as the bond coat by plasma spraying process. The thermal shock response of both as-sprayed TBCs was investigated at 1000 °C. Experimental results indicated that the nanostructured 5.5SYSZ TBCs have better thermal shock performance in contrast to 4SYSZ TBCs due to their higher tetragonal phase content and higher fracture toughness of this coating     

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.     

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.     

Effect of substrate curvature on residual stresses and failure modes of an air plasma sprayed thermal barrier coating system

A set of aerofoil shaped air plasma sprayed thermal barrier coated (APS-TBC) specimens were adopted in this paper to investigate the stress distributions in the ceramic top coat (TC) and the thermally grown oxide (TGO), the mechanism of local crack generation and propagation at the TC/BC (bond coat) interface. The failure mode of the TBC system, the distribution of asperities at TC/BC interface, thickness of the TC and BC, and the TC microstructure were found to be influenced by substrate curvature. Residual stress was therefore measured across the thickness of the TC, along the undulating TGO and mapped at locations of asperities where failure tended to occur to interpret the initiation of local failure. The role of the TGO was investigated via its chemical bonding with the TC and the decohesion occurring at the TGO/BC interface. The crack propagation at the interface has been discussed with respect to the macro-failure of the TBC system.     

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.     

Sintering resistance of advanced plasma-sprayed thermal barrier coatings with strain-tolerant microstructures

Sintering is one of the key issues in the high temperature service of thermal barrier coatings (TBCs), considering the continuously increasing operation temperature of gas-turbine for higher energy efficiency. Based on the conventional processing method of air plasma spraying (APS), suspension plasma spraying (SPS) technique has been developed recently, in order to improve the strain tolerance of TBCs. This strain tolerance of plasma-sprayed TBCs is largely effected by the sintering behavior, which is presently not fully understood. In this work, evolution of mechanical properties, in terms of Young’s modulus and viscosity, is systematically investigated by in-situ three-point bending test at 1200?°C on free-standing coatings, including micro-cracked APS, segmented APS, vertically cracked SPS and columnar structured SPS TBCs and correlated to the microstructural evolution. Based on experimental results, power law relations are proposed for the sintering induced mechanical evolution, which deepen the understanding of the sintering behavior of plasma-sprayed TBCs.     

Microstructure analyses and thermophysical properties of nanostructured thermal barrier coatings

Nanostructured 8 wt% yttria partially stabilized zirconia coatings were deposited by air plasma spraying. Transmission electron microscopy, scanning electron microscopy, and X-ray diffraction were carried out to analyze the as-sprayed coatings and powders. Mercury intrusion porosimetry was applied to analyze the pore size distribution. Laser flash technique and differential scanning calorimetry were used to examine the thermophysical properties of the nanostructured coatings. The results demonstrate that the as-sprayed nanostructured zirconia coatings consist of the nonequilibrium tetragonal phase. The microstructure of the nanostructured coatings includes the initial nanostructure of powder and columnar grains. Moreover, micron-sized equiaxed grains were also exhibited in the nanostructured coatings. Their evolution mechanisms are discussed. The as-sprayed nanostructured zirconia coating shows a bimodal pore size distribution, and has a lower value of thermal conductivity than the conventional coating.     

Microstructure and thermal shock resistance of AlBOw- and BNw-whisker-modified thermal barrier coatings

To improve the crack propagation resistance of YSZ thermal barrier coatings during the thermal cycle, three kinds of thermal barrier coatings were prepared by atmospheric plasma spraying: YSZ, AlBOw-modified YSZ and BNW-modified YSZ. SEM, EDS and XRD were used to analyse the morphology, composition and phase composition of the sprayed powder and coating section. The phase structures of the YSZ, YSZ+AlBOw and YSZ+BNw coatings were t' phase. The cross-section of the coating presents a layered structure with pores inside. The porosity values of the YSZ, YSZ+AlBOw and YSZ+BNw coatings are 10.33%, 14.17% and 12.52%, respectively. The thermal shock resistance of three groups of coatings after 5 min at 1000 °C was analysed. The failure behaviour of the coatings after several thermal cycles was studied. The results show that the thermal shock resistance of the coatings with AlBOw is slightly lower than that of the YSZ coatings. The thermal shock resistance of the BNw coatings is 62.2% higher than that of the YSZ coatings. The whisker inhibits the crack propagation and prolongs the life of the coatings via crack deflection, whisker pull-out and whisker bridging.     

Hot corrosion resistance of air plasma sprayed ceramic Sm2SrAl2O7 (SSA) thermal barrier coatings in simulated gas turbine environments

Samarium strontium aluminate (Sm₂SrAl₂O₇-SSA) and Yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs) were developed on NiCrAlY bond coated Inconel 718 superalloy substrate using air plasma spray process. The hot corrosion study was conducted in simulated gas turbine environments (molten mixtures of 50?wt% Na₂SO₄ + 50?wt% V₂O₅ and 90?wt% Na₂SO₄ + 5?wt% V₂O₅ + 5?wt% NaCl) for two different temperatures of 700 and 900?°C. A developed SSA TBCs showed about 8% and 22% lower lifetime at 700 and 900?°C, respectively than YSZ TBCs in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ (vanadate). The hot corrosion life of SSA TBCs being found about 13% and 39% lower than YSZ TBCs in 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl (chloride) at 700 and 900?°C, respectively. X-ray diffraction results showed the formation of SmVO₄, SrV₂O₆, and SrSO₄ as a major hot corrosion product in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ and 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl environments respectively for SSA TBCs. Similarly, YSZ TBCs also showed YVO₄ as hot corrosion product in vanadate and chloride environments. Both the TBCs suffer a more severe hot corrosion attack in chloride environment at 900?°C. The leaching of Sr²⁺ and Y³⁺ ions from SSA and YSZ respectively play a vital role in the destabilization of coating in vanadate and chloride environments at 700 and 900?°C. In both SSA and YSZ TBCs, the leaching of ion has significantly low influence as compared to attack by chloride ions at the bond coat-top coat interface in the presence of chloride environment. The hot corrosion resistance of SSA TBCs was improved three times higher in the presence of MgO and NiO inhibitor in vanadate environment at 900?°C mainly due to the formation of a stable Ni₃V₂O₈ phase at the surface.     

Bimodal microstructure toughens plasma sprayed Al2O3-8YSZ-CNT coatings

Current work pursues generating controlled bimodal microstructure by plasma spraying of micrometer-sized Al₂O₃ and nanostructured spray-dried agglomerate with reinforcement of 20 wt% of 8 mol % yttria stabilized zirconia (8YSZ) and 4 wt% carbon nanotube (CNT) as potential thermal barrier coating (TBC) on the Inconel 718 substrate. Composite coatings exhibit bimodal microstructure of: (i) fully melted and resolidified microstructured region (MR), and (ii) partially melted and solid state sintered nanostructured regions (NR). Reinforcement with 8YSZ has led to an increase in hardness from ∼12.8 GPa (for μ-Al₂O₃) to ∼13.9 GPa in MR of reinforced Al₂O₃-YSZ composite. Further, with the addition of CNT in Al₂O₃-8YSZ reinforced composite, hardness of MR has remained similar ∼13.9 GPa (8YSZ reinforced) and ∼13.5 GPa (8YSZ-CNT reinforced), which is attributed to acquiescent nature and non-metallurgical bonding of CNT with MR. Indentation fracture toughness increased from 3.4 MPam^0.5 (for μ-Al₂O₃) to a maximum of 5.4 MPam^0.5 (8YSZ- CNT reinforced) showing ∼57.7% improvement, which is due to crack termination at NR, retention of t-ZrO₂ (∼3.3 vol%) crack bridging, and CNT pull-out toughening mechanisms. Modified fractal models affirmed that the introduction of bimodal microstructure (NR) i.e., nanometer-sized- Al₂O₃, nanostructured 8YSZ and CNTs in the μ-Al₂O₃ (MR) contributes ∼44.6% and ∼72% towards fracture toughness enhancement for A8Y and A8YC coatings. An enhanced contribution of nanostructured phases in toughening microstructured Al₂O₃ matrix (in plasma sprayed A8YC coating) is established via modified fractal model affirming crack deflection and termination for potential TBC applications.     

Sintering behavior of columnar thermal barrier coatings deposited by axial suspension plasma spraying (SPS)

During the last decade, Suspension Plasma Spraying (SPS) attracted a lot of interest as an alternative process to produce columnar Thermal Barrier Coatings (TBCs). In this study, columnar TBCs were deposited with SPS. After spraying, samples were isothermally annealed at 1373 K for 1 h, 3 h, 10 h and 50 h, respectively. Microstructures and mechanical properties of the ceramic coatings were investigated as a function of annealing time. Annealing resulted in healing of micro-cracks, coarsening of pores, growth of domain size, companied with a decrease of porosity within columns. The change of coating microstructure led to change of mechanical properties. In addition, residual stress in SPS coatings was also investigated. Furthermore, as-sprayed coatings and pre-annealed coatings were subjected to burner rig tests. Short time pre-annealing allowed to enhance thermal cycling lifetime of such SPS coatings. The thermal cycling results were related to microstructure modifications of coatings.     

Thermal stability and sintering behavior of plasma sprayed nanostructured 7YSZ, 15YSZ and 5.5SYSZ coatings at elevated temperatures

Nanostructured scandia, yttria doped zirconia (5.5SYSZ), 7 wt% yttria stabilized zirconia (7YSZ) and 15YSZ thermal barrier coatings (TBCs) were produced by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal stability and sintering behavior of the three as-sprayed TBCs at 1480 °C were investigated. The results indicated that the thermal stability of SYSZ and TBCs was longer than the 7YSZ TBCs due to higher amount of tetragonal phase. Furthermore, the results demonstrated that the nanostructured 7YSZ coating exhibits higher sintering resistance than 5.5SYSZ TBC.     

CMAS corrosion resistance,thermal shock resistance and numerical simulation of novel surface micromesh thermal barrier coatings

Thermal barrier coatings (TBCs) are widely used as insulating layers to protect the underlying metallic structure of gas turbine blades. However, the thermal cycling performance of TBCs is affected by their complex working environments, which may shorten their service life. Previous studies have shown that preparing a mesh structure in the bonding layer can relieve thermal stress and improve the bonding strength, thereby prolonging the service life of TBCs. In this paper, a micromesh structure was prepared on the surface of the bonding layer via wet etching. The microstructure and failure mechanism of the micromesh TBCs after CMAS (CaO-MgO-Al₂O₃-SiO₂) thermal erosion were investigated. Numerical simulation was combined with thermal shock experiments to study the stress distribution of the micromesh-structured TBCs. The results showed that the circular convex structure can effectively improve the CMAS corrosion resistance and thermal shock resistance of TBCs.     

Present status and future prospects of plasma sprayed multilayered thermal barrier coating systems

Thermal barrier coatings (TBCs) play a pivotal role in protecting the hot structures of modern turbine engines in aerospace as well as utility applications. To meet the increasing efficiency of gas turbine technology, worldwide research is focused on designing new architecture of TBCs. These TBCs are mainly fabricated by atmospheric plasma spraying (APS) as it is more economical over the electron beam physical vapor deposition (EB-PVD) technology. Notably, bi-layered, multi-layered and functionally graded TBC structures are recognized as favorable designs to obtain adequate coating performance and durability. In this regard, an attempt has been made in this article to highlight the structure, characteristics, limitations and future prospects of bi-layered, multi-layered and functionally graded TBC systems fabricated using plasma spraying and its allied techniques like suspension plasma spray (SPS), solution precursor plasma spray (SPPS) and plasma spray –physical vapor deposition (PS-PVD).