Miniaturized bend tests on partially stabilized EB-PVD ZrO2 thermal barrier coatings

The elastic properties of thermal barrier coatings (TBCs) are important for modelling the lifetime of these coatings. A new test setup has been developed to measure the system modulus of electron-beam enhanced physical vapour deposited (EB-PVD) TBC coatings by miniaturized bend tests.Due to the brittleness, low stiffness and small thickness of the top coat and its complex microstructure, it is difficult to measure its Young's modulus by standard mechanical testing. For this reason, a special sample material has been prepared which consists of a 1 mm thick layer of EB-PVD TBC. This material was isothermally heat treated for different times at 950 °C, 1100 °C and 1200 °C and then tested in a specially developed miniaturized bend test. The bend test setup permits mechanical tests with a high resolution in stress and strain, where the strain is measured by digital image correlation. So the stiffness of the free-standing TBC samples could be measured with a high accuracy and the sintering behaviour of the EB-PVD TBC and the consequent rise of Young's modulus could be determined. The results show a significant increase of the system modulus with heat treatment time and temperature caused by sintering of the coating. An activation energy of 220 kJ/mol for the process has been determined.In addition, the material was tested by nanoindentation in order to measure Young's modulus on a local scale, and the porosity of the samples was determined by quantitative image analysis.     

Investigation of interfacial properties of atmospheric plasma sprayed thermal barrier coatings with four-point bending and computed tomography technique

A modified four-point bending test has been employed to investigate the interfacial toughness of atmospheric plasma sprayed (APS) yttria stabilised zirconia (YSZ) thermal barrier coatings (TBCs) after isothermal heat treatments at 1150 °C. The delamination of the TBCs occurred mainly within the TBC, several to tens of microns above the interface between the TBC and bond coat. X-ray diffraction analysis revealed that the TBC was mainly tetragonal in structure with a small amount of the monoclinic phase. The calculated energy release rate increased from ~ 50 J/m^− 2 for as-sprayed TBCs to ~ 120 J/m^− 2 for the TBCs exposed at 1150 °C for 200 h with a loading phase angle about 42°. This may be attributed to the sintering of the TBC. X-ray micro-tomography was used to track in 3D the evolution of the TBC microstructure non-destructively at a single location as a function of thermal exposure time. This revealed how various types of imperfections develop near the interface after exposure. The 3D interface was reconstructed and showed no significant change in the interfacial roughness after thermal exposure.     

Correlation between spraying conditions and microcrack density and their influence on thermal cycling life of thermal barrier coatings

It is generally known that the porosity of thermal barrier coatings is essential to guarantee a sufficiently high strain tolerance of the coating during thermal cycling. However, much less is known about the influence of the specific morphology of porosity, such as microcracks and typically larger pores, on the performance of the coatings. Both features are usually formed during plasma spraying of yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs). In this investigation, the influence of microcracks on the thermal cycling behavior was studied. The amount of microcracks within YSZ thermal barrier coatings was changed by changing the powder-feeding rate. Only small changes of the total porosity were observed. Mercury porosimetry served as a tool to investigate both the amount of microcracks and pores in the coating. Additionally, microcrack densities were determined from metallographical investigations. A linear dependence between the amount of fine pores determined by Hg porosimetry and the crack density was obtained for one set of coatings. Thermal cycling TBC specimens with different microcrack densities were produced and tested in a gas burner test facility. At high surface temperatures (above 1300 °C), failure occurred in the ceramic close to the surface. Under these conditions, the samples with increased horizontal microcrack densities showed a significant increase of thermal cycling life.     

Tensile fracture behavior of thermal barrier coatings on superalloy

Tensile fracture behavior of thermal barrier coatings (TBCs) on superalloy was investigated in air at room temperature (RT), 650 °C and 850 °C. The bond coat NiCrAlY was fabricated by either high velocity oxygen fuel (HVOF) or air plasma spraying (APS), and the top coat 7%Y₂O₃-ZrO₂ was deposited by APS. Thus two kinds of the TBC system were formed. It was shown that the coating had little effect on tensile stress-strain curves of the substrate and similar tensile strength was obtained in two kinds of the TBC system. However, the cracking behavior in the two kinds of TBC system at RT was different, which was also different from that at 650 °C and 850 °C by scanning electron microscopy. The interface fracture toughness of the two kinds of TBC system was evaluated by the Suo-Hutchinson model and the stress distribution in the coating and substrate was analyzed by the shear lag model.     

Oxidation resistant coatings in combination with thermal barrier coatings on γ-TiAl alloys for high temperature applications

Titanium aluminide alloys based on γ-TiAl are considered of growing interest for high temperature applications due to their attractive properties. To extend the service temperatures above 750 °C, the oxidation behaviour has to be improved predominantly by protective layers. In the present study environmental and thermal protection coatings on gamma titanium aluminides were investigated. Nitride and metallic overlay coatings based on Ti-Al-Cr-Y-N and Ti-Al-Cr, respectively, were produced by magnetron sputtering techniques. Thermal barrier coatings (TBCs) of partially yttria stabilized zirconia were deposited onto Ti-45Al-8Nb, either pre-oxidized or coated with protective layers, applying electron beam physical vapour deposition (EB-PVD).Cyclic oxidation tests were performed at 900 °C and 950 °C in air. The nitride coating exhibited poor oxidation resistance when exposed at 900 °C providing no protection for γ-TiAl. The oxidation behaviour of the Ti-Al-Cr coating was reasonable at both exposure temperatures. During prolonged exposure the coating was depleted in chromium, resulting in the breakdown of the protective alumina scale. EB-PVD zirconia coatings deposited on γ-TiAl exhibited promising lifetime, particularly when specimens were coated with Ti-Al-Cr. The adherence of the TBC on the thermally grown oxide scales was excellent; failure observed was associated with spallation of the oxide scale. At 950 °C, TBCs on specimens coated with Ti-Al-Cr spalled after less than 200 thermal cycles caused by severe oxidation of γ-TiAl and reactions between the zirconia coatings and the thermally grown oxides.     

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.     

Post-deposition treatment of zirconia thermal barrier coatings using Sol-Gel alumina

This article addresses the problem of gas permeability of thermal sprayed yttria-stabilized zirconia thermal barrier coatings (TBC)s. The objective of this study was to decrease the open porosity of TBCs through deposition of dense alumina ceramic on the surface of the pores. A simple infiltration technique was used, beginning with aluminum isopropoxide as sol precursor, subsequently hydrated to aluminum hydroxide sol, which decomposed at relatively low temperatures to extra-fine, readily sinterable aluminum oxide. In some experiments, the sol-gel (SG) precursor was combined with fine grains of calcined alumina, constituting high solid-yield composite sol-gel (CSG) deposits within the pores of TBCs. Sinterability in the model systems, including aluminum hydroxide sol-calcined alumina and aluminum hydroxide sol-calcined alumina-zirconia, has been studied. A number of TBC specimens were impregnated with suspensions of alumina sols and CSG. It is shown that these ceramics effectively penetrated into the pores and cracks of TBCs and reduced the coating permeability to gases. The overall reduction of porosity was however small (from ∼12 to ∼11%), preserving the strain and thermal shock tolerance of the coatings. Burner rig tests showed an increase in sealed coating lifetime under thermomechanical fatigue conditions.     

Air-plasma-sprayed thermal barrier coatings that are resistant to high-temperature attack by glassy deposits

Thermal barrier coatings (TBCs) used in gas-turbine engines afford higher operating temperatures, resulting in enhanced efficiencies and performance. However, at these high operating temperatures, environmentally ingested airborne sand/ash particles melt on the hot TBC surfaces and form calcium–magnesium–aluminosilicate (CMAS) glass deposits. The molten CMAS glass penetrates the TBCs, leading to loss of strain tolerance and TBC failure. Here we demonstrate the use of the commercial manufacturing method of air-plasma-spray (APS) to fabricate CMAS-resistant yttria-stabilized zirconia (YSZ)-based TBCs containing Al and Ti in solid solution. Results from thermal stability studies of these new TBCs and CMAS/TBC interaction experiments are presented, together with a discussion of the CMAS mitigation mechanisms. The ubiquity of airborne sand/ash particles and the ever-increasing demand for higher operating temperatures in future high efficiency/performance gas-turbine engines will necessitate CMAS resistance in all hot-section components of those engines. In this context the versatility, ease of processing, and low cost offered by the APS method has broad implications for the design and fabrication of next-generation CMAS-resistant TBCs for future engines.     

Evidence of accelerated thermal cycling test schedules influencing the ranking of zirconia-base thermal barrier coatings

Thermal barrier coatings (TBCs) often encounter temperature cycling in the course of normal operation. In the absence of actual or simulated engine test facilities, accelerated furnace thermal cycling experiments are frequently devised to evaluate the response of various TBCs. This study, which deals with yttria-stabilized and magnesia-stabilized zirconia systems, shows that the performance of a TBC is significantly governed by the severity of the time-temperature schedule employed. More importantly, the ranking of the two zirconia-base TBCs also is influenced by the adopted thermal cycling test schedule. These findings have ramifications in the design of suitable accelerated tests for TBC evaluation.     

Preparation of YSZ coatings by thermal pressure and filtration of sol-gel paint (TPFSP) for thermal barrier application

Thick YSZ ceramic coatings were prepared by thermal pressure and filtration of sol-gel paint (TPFSP), a modified sol-gel composite coating technique. SEM results show that the coatings were dense and crack-free by using paints of high mass ratios of YSZ powder to Zr-Y oxide in sol and high pressures. And the cross-sectional detail of coatings exhibited that the microstructure was consisted of micro/nano-size ceramic particles and micro-pores. The thermal insulation tests indicated that mass ratio of YSZ powder to Zr-Y oxide in sol was in inversely linear relationship with temperature drop per micron thickness. The coating showed good adherence with alloy substrate and maintained structural integrity when exposed at 1050 °C for 200 h. The cyclic oxidation test also indicated that both of oxidation resistance and spallation resistance for YSZ coated specimens were greatly improved. The TPFSP process could be a promising method to prepare TBCs for wide applications.     

An investigation into the correlation between nano-impact resistance and erosion performance of EB-PVD thermal barrier coatings on thermal ageing

Nanomechanical testing (nano-impact and nanoindentation mapping) has been carried out on the top surfaces of as-received and aged 8 wt.% yttria stabilised zirconia (YSZ) thermal barrier coatings (TBCs) produced by electron-beam physical vapour deposition (EB-PVD). The correlation between the nanomechanical test results and the previously reported erosion resistance of the TBCs has been investigated. The experimental results revealed that aged TBCs on zirconia for 24 h at 1500 °C or on alumina for 100 h at 1100 °C resulted in large increases in their hardness (H), modulus (E), H/E and H³/E² ratios but their erosion resistance was reduced. Nano-impact tests showed a dramatic decrease in impact resistance following the ageing of these TBCs, which is consistent with the erosion results. The strong correlation between the nano-impact and erosion resistances has confirmed the premise that rapid laboratory impact tests must produce deformation with similar contact footprint to that produced in the erosion tests.     

Proto-TGO formation in TBC systems fabricated by spark plasma sintering

Thermal barrier coatings (TBC) are commonly used in modern gas turbines for aeronautic and energy production applications. The conventional methods to fabricate such TBCs are EB-PVD or plasma spray deposition. Recently, the spark plasma sintering (SPS) technique was used to prepare new multilayered coatings. In this study, complete thermal barrier systems were fabricated on single crystal Ni-based superalloy (AM1®) substrate in a one-step SPS process. The lifetime of TBC systems is highly dependent on its ability to form during service a dense, continuous, slow-growing alumina layer (TGO) between an underlying bond coating and a ceramic top coat. In the present paper, we show that such kind of layer (called proto-TGO in the following) can be in situ formed during the SPS fabrication of TBC systems. This proto-TGO is continuous, dense and its nature has been determined using TEM-EDS-SAD and Raman spectroscopy. This amorphous oxide layer in the as-fabricated samples transforms to α-Al₂O₃ during thermal treatment under laboratory air at 1100 °C. Oxidation kinetics during annealing are in good agreement with the formation of a protective α-Al₂O₃ layer.     

La2O3-modified YSZ coatings: High-temperature stability and improved thermal barrier properties

Lanthana precursor was coated on yttria-stabilized-zirconia (YSZ) powders by wet chemical infiltration, and was introduced to the crystalline structure and grain boundaries of YSZ after plasma spraying of thermal barrier coatings (TBCs). The microstructural stability and thermal barrier properties of this new kind of TBCs were studied under different annealing conditions. It demonstrates that the La₂O₃ surface coating restrains grain growth of YSZ during both deposition and post-annealing processes, compared to a TBC obtained from commercially available unmodified YSZ powders. According to the composition analysis, lanthana partially dissolved in the zirconia matrix after heat treatment. The thermal diffusivity of YSZ coating significantly decreased after lanthana modification, typically from 0.354 mm² s^− 1 for an unmodified sample to 0.243 mm² s^− 1, reflecting a decrease of 31%. Even after annealed at 1200 °C for 50 h, the thermal diffusivity of modified coatings still shows a reduction of 25% than unmodified samples.     

Effects of defects on the thermal fatigue behavior of detonation-gun sprayed thermal barrier coatings

The effects of coating defects, such as pores and cracks, on the thermal fatigue behavior of zirconia based thermal barrier coatings (TBCs) have been investigated. Duplex TBCs, which are composed of an 8 wt.% Y₂O₃ stabilized ZrO₂ (YSZ) layer on top of a NiCrAlY bond layer were produced by detonation gun spraying. Thermal fatigue tests were conducted on three different TBC specimens, the YSZ layers of which were varied in terms of porosity and crack morphology, and failure analyses were subsequently carried out on the tested specimens. From these results, the roles of the defects on the thermal and mechanical degradation behavior of the TBCs were investigated.     

Deposition and Characteristics of Submicrometer-Structured Thermal Barrier Coatings by Suspension Plasma Spraying

In the field of thermal barrier coatings (TBCs) for gas turbines, suspension plasma sprayed (SPS) submicrometer-structured coatings often show unique mechanical, thermal, and optical properties compared to conventional atmospheric plasma sprayed ones. They have thus the potential of providing increased TBC performances under severe thermo-mechanical loading. Experimental results showed the capability of SPS to obtain yttria stabilized zirconia coatings with very fine porosity and high density of vertical segmentation cracks, yielding high strain tolerance, and low Young??s modulus. The evolution of the coating microstructure and properties during thermal cycling test at very high surface temperature (1400?°C) in our burner rigs and under isothermal annealing was investigated. Results showed that, while segmentation cracks survive, sintering occurs quickly during the first hours of exposure, leading to pore coarsening and stiffening of the coating. In-situ measurements at 1400?°C of the elastic modulus were performed to investigate in more detail the sintering-related stiffening.     

Bilayer Suspension Plasma-Sprayed Thermal Barrier Coatings with Enhanced Thermal Cyclic Lifetime: Experiments and Modeling

Suspension plasma spraying (SPS) has been shown as a promising process to produce porous columnar strain tolerant coatings for thermal barrier coatings (TBCs) in gas turbine engines. However, the highly porous structure is vulnerable to crack propagation, especially near the topcoat-bondcoat interface where high stresses are generated due to thermal cycling. A topcoat layer with high toughness near the topcoat-bondcoat interface could be beneficial to enhance thermal cyclic lifetime of SPS TBCs. In this work, a bilayer coating system consisting of first a dense layer near the topcoat-bondcoat interface followed by a porous columnar layer was fabricated by SPS using Yttria-stabilised zirconia suspension. The objective of this work was to investigate if the bilayer topcoat architecture could enhance the thermal cyclic lifetime of SPS TBCs through experiments and to understand the effect of the column gaps/vertical cracks and the dense layer on the generated stresses in the TBC during thermal cyclic loading through finite element modeling. The experimental results show that the bilayer TBC had significantly higher lifetime than the single-layer TBC. The modeling results show that the dense layer and vertical cracks are beneficial as they reduce the thermally induced stresses which thus increase the lifetime.     

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.     

Oxidation behavior of thermal barrier coatings with HVOF and detonation-sprayed NiCrAlY bondcoats

The high-velocity oxygen-fuel (HVOF) technology was employed to deposit the bondcoat of a thermal barrier coating (TBC) system. The isothermal oxidation rate at 1100 °C of the TBC system with the HVOF bondcoat is two times lower than that of the TBC system with the detonation-sprayed bondcoat. The better isothermal oxidation resistance of the TBCs with HVOF sprayed bondcoats demonstrates that unlike alumina dispersoids in the HVOF sprayed bondcoat, rough surface of the detonation-sprayed bondcoat is undesirable for the detonation-sprayed TBC system concerning oxidation due to a large specific surface area and unfavorable oxides on the bondcoat.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

Thermal cycling behavior and interfacial stability in thick thermal barrier coatings

The thermal cycling behavior of thermal barrier coatings (TBCs), which were prepared by two different air-plasma spray (APS) guns of 9 MB and TriplexPro™-200, was investigated to understand the effects of the microstructure on the interfacial stability and fracture behavior of TBCs. The porosities of the top coats could be controlled by changing the gun, showing porosity of about 15% using the 9 MB and 19% using the TriplexPro™-200, which decreased slightly with thermal exposure. Defects, such as interlamellar cracks, vertical cracks, and intrasplat cracks, were freshly produced in both TBCs after thermal exposure, showing delamination in the case of 2000 μm TBCs prepared using the TriplexPro™-200. The adhesive strength values of TBCs with 600 and 2000 μm thicknesses were about 8 and 6 MPa, respectively, indicating that the adhesive strength values of TBCs were affected by the coating thickness, independent of the gun. The hardness values increased after thermal exposure, and the TBCs prepared using the TriplexPro™-200 showed higher values than those prepared using the 9 MB for both thicknesses. The toughness values were not dependent on the gun, only showing an effect from coating thickness. The increase in coating thickness enhanced the densification, resulting in higher hardness and toughness values, and the microstructure could be controlled by changing the gun.