Effect of morphology on thermal conductivity of EB-PVD PYSZ TBCs

Partially yttria stabilized zirconia (PYSZ) based thermal barrier coatings (TBC) manufactured by electron beam-physical vapour deposition (EB-PVD) protect turbine blades, working under severe service conditions in aero engines and stationary turbines. These coatings show a high strain tolerance relying on their unique morphology which is comprised of weakly bonded, preferred-oriented columns, voids between feather-like sub-columns and, finally, of intra-columnar closed pores.The results obtained in this work demonstrate that variation of the EB-PVD process parameters alters the resulting columnar morphology and porosity of the coatings. The physical properties and, most importantly, thermal conductivity, are greatly affected by these morphological alterations. This study investigates three morphologically different EB-PVD PYSZ TBC top coats in terms of the spatial and geometrical characteristics of their porosity and correlates those with the thermal conductivity values measured in as-coated state and after heat treatment at 1100 °C for 1 h and 100 h. Changes in the open and closed porosity caused by heat-treatment are characterized by small-angle neutron scattering (SANS), Brunauer-Emmett-Teller Method (BET) and scanning electron microscope (SEM). Correlation of shape and surface-area changes in all porosity types of the analysed coatings revealed that the thermal conductivity of these coatings is influenced primarily by size and shape distribution of the pores and secondarily by the pore surface-area available at the cross section perpendicular to the heat flux.     

Application of USAXS analysis and non-interacting approximation to determine the influence of process parameters and ageing on the thermal conductivity of electron-beam physical vapor deposited thermal barrier coatings

Electron-beam physical vapor deposited (EB-PVD) thermal barrier coatings (TBCs) display a lower thermal conductivity compared with the deposited bulk material. This effect is achieved due to the presence of pores within these films. The spatial and geometrical characteristics of the porosity influence directly the magnitude of the achieved reduction of the thermal conductivity. In this work, three EB-PVD coating containing different microstructures were manufactured by varying the manufacturing process parameters during the deposition process. Their corresponding thermal conductivities were measured via the laser flash analysis method (LFA) in both the as-coated state and after ageing (1100 °C/100 h). Analysis of the pore formation during processing was carried out by ultrasmall-angle X-ray scattering (USAXS). This technique is supported with a computer based modeling developed by researchers at Advanced Photon Source (APS) in ANL, USA, and in National Institute of Standards and Technology (NIST), USA. The model enables the characterization of the size, shape, volume and orientation of each of the pore populations in EB-PVD TBCs. The effect of these spatial and geometrical characteristics of the porosity on the thermal conductivity of the EB-PVD coatings were studied via a non-interacting approximation based on Maxwell's model. Results of LFA measurements and the applied approximation indicate an interrelation between the microstructure and the thermal properties of the analyzed EB-PVD coatings. Microstructures containing a higher volume fraction of fine anisotropic intra-columnar pores, and larger voids between feather-arms oriented at lower angles toward the substrate plane correspond to lower thermal conductivity values. Inter-columnar gaps do no significantly contribute to lowering the thermal conductivity due to their orientation parallel to the heat flux and their lower volume fraction compared with the volume occupied by the primary columns. On heat treatment, the deepest section of the gaps between feather-arms break-up into arrays of nano-sized low aspect ratio voids. The anisotropic, elongated intra-columnar pores evolve toward low aspect ratio shapes that are less effective in reducing the thermal conductivity.     

Evolution of thermal properties of EB-PVD 7YSZ thermal barrier coatings with thermal cycling

During high-temperature exposure, the microstructure of thermal barrier coatings evolves, leading to increased thermal conductivity. We describe the evolution in the thermal properties of a 7 wt.% Y₂O₃ stabilized ZrO₂ electron beam-physical vapor deposited (EB-PVD) thermal barrier coating with thermal cycling between room temperature and 1150 °C until failure. The thermal diffusivity and conductivity of the coating were evaluated non-destructively based on the analysis of its photothermal infrared emission. Although the coating density does not increase significantly with thermal cycling, the thermal diffusivity and conductivity of the coating increased substantially, particularly during the first 20 1 h cycles. The values then approach a limiting value. Complementary Raman spectroscopy suggests that the increase is accompanied by a reduction in the defect concentration in the coating and that there is also a correlation between the width of the Raman lines and the thermal conductivity.     

Non-contact sensing of TBC/BC interface temperature in a thermal gradient

Luminescence lifetimes of rare-earth ions in yttria-stabilized zirconia have been shown to exhibit temperature sensitivity from 500-1150 °C [Gentleman, M.M. and Clarke, D.R. (2005) Surface and Coatings Technology 200, 1264; Gentleman, M.M. and Clarke, D.R. (2004) Surface and Coatings Technology 188-189, 93.]. These doped zirconias can be deposited along with standard thermal barrier coatings to create thin temperature sensing layers within the coating. Of particular interest is the temperature at the coating/bond coat interface as the oxidation life of a TBC system is exponentially dependent on this temperature. In this study, thin (∼ 10 μm) layers of europia-doped yttria-stabilized zirconia were deposited by EB-PVD onto bond-coated CMSX-4 superalloy buttons to achieve sensor layers located next to the TBC/BC interface. These coatings were then used to measure the interface temperature in a thermal gradient. Combined with pyrometric measurements of the coating-surface temperature and metal-surface temperature, the thermal conductivity of the coating (1.5 W/mK) and heat flux (∼ 1 MW/m²) in the tests were calculated.     

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.     

Thermal conductivity of nanoporous ZrO2-4 mol% Y2O3 multilayer coatings fabricated by EB-PVD

The effect of multilayer configurations on the thermal conductivity of 4 mol% Y₂O₃⁻ stabilized ZrO₂ coatings fabricated by EB-PVD has been investigated. The deposited coating layers consist of columnar grains containing nano-sized pores. Multilayer specimens are found to contain many pores at the interfaces between layers. The density and thermal conductivity of the multilayer coatings decreases with increasing number of coating layers for one to six layers. The thermal conductivities of coatings deposited onto rotating substrates are lower than those of coatings deposited on stationary substrates. The decreased thermal conductivity of multilayer coatings is ascribed to the increased total porosity resulting from an increase in the number of interface pores concomitant with the formation of non-uniform interfaces between layers, which causes increased phonon scattering.     

Superior thermal barrier coatings using solution precursor plasma spray

A novel process, solution precursor plasma spray (SPPS), is presented for depositing thermal barrier coatings (TBCs), in which aqueous chemical precursors are injected into a standard direct current plasma spray system. The resulting coatings microstructure has three unique features: (1) ultra fine splats (1 μm), (2) nanometer and micron-sized interconnected porosity, and (3) closely spaced, through-thickness cracks. Coatings over 3 mm thick can be readily deposited using the SPPS process. Coating durability is excellent, with SPPS coatings showing, in furnace cycling tests, 2.5 times the spallation life of air plasma coatings (APS) and 1.5 times the life of electron beam physical vapor deposited (EB-PVD) coatings. The conductivity of SPPS coatings is lower than EB-PVD coatings and higher than the best APS coatings. Manufacturing cost is expected to be similar to APS coatings and much lower than EB-PVD coatings. The SPPS deposition process includes droplet break-up and material arriving at the deposition surface in various physical states ranging from aqueous solution, gel phase, to fully-molten ceramic. The relation between the arrival state of the material and the microstructure is described.     

High sintering resistance of a novel thermal barrier coating

Sintering resistance of a novel thermal barrier coating Nd_xZr_1 − xO_y with Z dissolved in, where 0 < x < 0.5, 1.75 < y < 2 and Z is an oxide of a metal selected from Y, Mg, Ca, Hf and mixtures thereof, was studied. The coatings of Nd_xZr_1 − xO_y and typical 7YSZ were deposited by electron beam physical vapor deposition (EB-PVD) and air plasma spray (APS). The samples with the coating system of EB-PVD Nd_xZr_1 − xO_y or 7YSZ overlaid onto a MCrAlY bond coat were cyclically sintered at 1107 °C for 706 hours. The freestanding coatings of EB-PVD Nd_xZr_1 − xO_y and 7YSZ were isothermally sintered at 1371 °C for 500 hours. The microstructure of EB-PVD Nd_xZr_1 − xO_y before and after the sintering was evaluated and compared with EB-PVD 7YSZ. The sintering resistance of freestanding APS Nd_xZr_1 − xO_y coating was also investigated after isothermal sintering at 1200 °C for 50 and 100 hours. The results demonstrated that the new coatings of Nd_xZr_1 − xO_y applied with both EB-PVD and APS have higher sintering resistance than EB-PVD and APS 7YSZ, respectively.     

Failure of physical vapor deposition/plasma-sprayed thermal barrier coatings during thermal cycling

ZrO₂-7 wt.% Y₂O₃ plasma-sprayed (PS) coatings were applied on high-temperature Ni-based alloys precoated by physical vapor deposition with a thin, dense, stabilized zirconia coating (PVD bond coat). The PS coatings were applied by atmospheric plasma spraying (APS) and inert gas plasma spraying (IPS) at 2 bar for different substrate temperatures. The thermal barrier coatings (TBCs) were tested by furnace isothermal cycling and flame thermal cycling at maximum temperatures between 1000 and 1150 °C. The temperature gradients within the duplex PVD/PS thermal barrier coatings during the thermal cycling process were modeled using an unsteady heat transfer program. This modeling enables calculation of the transient thermal strains and stresses, which contributes to a better understanding of the failure mechanisms of the TBC during thermal cycling. The adherence and failure modes of these coating systems were experimentally studied during the high-temperature testing. The TBC failure mechanism during thermal cycling is discussed in light of coating transient stresses and substrate oxidation.     

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.     

Effect of Oxidation Behavior on the Mechanical and Thermal Properties of Plasma Sprayed Tungsten Coatings

Tungsten (W) coatings have been prepared via air (APS) and vacuum plasma spraying (VPS) technologies, respectively. The microstructures and chemical compositions of the coatings were comparatively studied; meanwhile, the mechanical and thermal properties were evaluated. The results obtained showed that oxide content in the VPS-W coating was apparently lower than that of the APS-W coating because of the different surrounding atmosphere, which influenced the mechanical and thermal properties of the coatings directly. Similar microstructures were observed for the VPS-W and the APS-W coating, but the VPS-W coating was much denser. The bonding strength of the VPS-W coating was much higher than that of the APS-W coating. Thermal conductivity of the VPS-W coating was 59.3 W/m · K at room temperature while the APS-W coating was 32.2 W/m  K. Thermal loading experiments of electron beam showed that the VPS-W coating could withstand the heat load of 10.75 MW/m², while the APS-W coating formed serious cracks on its surface at the load of 7.5 MW/m².     

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.     

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

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

Thermal conductivity of EB-PVD ZrO2-4 mol% Y2O3 films using the laser flash method

The variation in thermal conductivity and thermal diffusivity of ZrO₂-4 mol% Y₂O₃ coatings deposited onto Inconel substrates by EB-PVD is examined as a function of coating thickness using the laser flash method. The coatings are found to consist of columnar grains with a feather-like microstructure. The thermal conductivities of the coatings are calculated using two methods: the first involves separating the coating from the substrate and measuring the thermal diffusivity directly; the second uses thermal diffusion results from coatings still attached to the substrate and is based on the response function method. The results of both methods are in excellent agreement, and show that the thermal conductivities of the coatings increase with increasing coating thickness. The results also confirm that the double layer method can be used successfully to calculate the thermal conductivities of thin film coatings.     

Synthesis and characterization of Y3Al5O12 and ZrO2-Y2O3 thermal barrier coatings by combustion spray pyrolysis

Y₃Al₅O₁₂ and ZrO₂-Y₂O₃ (8 mol% YSZ) coatings for potential application as thermal barrier coatings were prepared by combustion spray pyrolysis. Thermal cycling of as deposited coatings on stainless steel and FeCrAlY bond coat substrates was carried out at 1000 °C and 1200 °C to determine the thermal fatigue response. Structural and morphological studies on Y₃Al₅O₁₂ and 8 mol% YSZ coatings before and after thermal cycling have been carried out. It has been noted that the coatings on FeCrAlY substrates remain intact after 50 cycles between room temperature and 1200 °C, whereas the coatings on stainless steel show some minor damage such as peeling off near the periphery after 50 cycles at 1000 °C. Thermal diffusivity values of Y₃Al₅O₁₂ and 8 mol% YSZ films were measured by using photo thermal deflection spectroscopy and the values are lower than those of coatings produced by conventional techniques such as EBPVD and APS.     

Effect of Thermal Treatment on High-Temperature Mechanical Properties Enhancement in LPPS, HVOF, and APS CoNiCrAlY Coatings

The mechanical properties of a MCrAlY coating significantly influence the initiation of cracks in the superalloy substrate under thermomechanical-fatigue conditions. Previous studies have developed a convenient method for evaluating the mechanical properties of sprayed coatings by lateral compression of a circular tube coating. This method does not need chucking, and manufacturing the free-standing coating is quite straightforward. In this study, the mechanical properties of the free-standing CoNiCrAlY coatings prepared using low-pressure plasma spraying (LPPS), high-velocity oxyfuel (HVOF) spraying, and atmospheric plasma spraying (APS) were systematically measured with the lateral compression method at room temperature through to 920 °C. The effect of postspray thermal treatments, in vacuum and in air, on the mechanical properties was investigated in the 400 to 1100 °C temperature range. It was found that high-temperature thermal treatment in air was effective in increasing the bending strength and Young’s modulus. It was especially effective on the APS coatings, which were produced using powders with average size 60 μm, and on HVOF coating, whose bending strengths increased by approximately three times. On the contrary, the enhancement in the LPPS and APS coatings produced with powders 21 μm in size was found to be approximately 1.6 times.     

Corrosion behaviour of thermal sprayed nitinol coatings

NiTi alloy is here investigated as an alternative coating to stainless steel since it is considered to possess good corrosion properties. Three different thermal spray techniques (high velocity oxy-fuel -HVOF-, vacuum plasma spray -VPS- and atmospheric plasma spray quenching -APS+Q-) have been used for building the coatings, and electrochemical tests have been carried out for corrosion evaluation. Open-circuit tests have revealed that the VPS-coating shows fairly good corrosion resistance, both in the as-sprayed and polished forms. The HVOF coatings however, showed a strong dependence on the surface conditions and APS+Q is dominated by electrolyte penetration through coating cracks, thus exhibiting a higher i_corr.     

Effect of Thermal Aging on Microstructure and Functional Properties of Zirconia-Base Thermal Barrier Coatings

Thermal barrier coating (TBCs) systems made of plasma sprayed zirconia are commonly used in gas turbine engines to lower metal components surface temperature and allow higher combustion temperature that results in higher fuel efficiency and environmentally cleaner emissions. Low thermal conductivity and long service life are the most important properties of these coatings. The objective of this work was to study the influence of a long-term heat treatment (i.e., 1200 °C/2000 h) on different characteristics of atmospheric plasma sprayed TBCs. Two zirconia feedstock materials were evaluated, namely, yttria partially stabilized zirconia and dysprosia partially stabilized zirconia. Several spray conditions were designed and employed to achieve different coating morphologies. Microstructure analyses revealed that the coating microstructure was significantly dependent on both operating conditions and heat treatment conditions. Significant changes in coatings porosity occurred during heat treatment. The lowest thermal conductivity was reached with the dysprosia partially stabilized zirconia material. Heat treatment affected TBCs adhesion strength as well.     

Neodymium-cerium oxide as new thermal barrier coating material

Neodymium-cerium oxide (Nd₂Ce₂O₇) was proposed as a new thermal barrier coating material in this work. Monolithic Nd₂Ce₂O₇ powder was prepared by the solid-state reaction at 1400 °C. The phase composition, thermal stability and thermophysical properties of Nd₂Ce₂O₇ were investigated. Nd₂Ce₂O₇ with fluorite structure was thermally stable in the temperature range of interest for TBC applications. The results indicated that the thermal expansion coefficient (TEC) of Nd₂Ce₂O₇ was higher than that of YSZ (6-8 wt.% Y₂O₃ + ZrO₂) and even more interesting was the TEC change as a function of temperature paralleling that of the superalloy bond coat. Moreover, the thermal conductivity of Nd₂Ce₂O₇ is 30% lower than that of YSZ, which was discussed based on the theory of heat conduction. Thermal barrier coating of Nd₂Ce₂O₇ was produced by atmospheric plasma spraying (APS) using the spray-dried powder. The thermal cycling was performed with a gas burner test facility to examine the thermal stability of the as-prepared coating.     

Development and microstructure optimization of atmospheric plasma-sprayed NiO/YSZ anode coatings for SOFCs

In this paper, preparation and characterization of porous anode layers with uniform phase distribution are discussed for solid oxide fuel cell (SOFC) application. The Ni/8YSZ cermet coatings were fabricated by atmospheric plasma spray (APS) process using oxidized nickel coated graphite (Ni-graphite) and 8 mol% yittria — stabilized zirconia (8YSZ) blend as feedstock. To control the microstructure of the coating, the nickel coated graphite with low density was used as a starting feedstock instead of conventional pure nickel (Ni) powder. To balance the conductivity, uniform porosity, and structural stability of the coatings, the effects of process parameters such as hydrogen gas flow rate, stand off distance and pore formation precursor (graphite) addition on the microstructures of the resulting coatings are investigated. The results show that the anode coatings with high conductivity, structural stability and porosity could be deposited with moderate hydrogen gas flow rate and short stand off distance.