Yttria stabilized zirconia corrosion destabilization followed by Raman mapping

The incidence of V₂O₅ corrosion on yttria stabilized zirconia (YSZ) thermal barrier coatings has been studied as a function of application methods and powder initial granulometry. Commercial fused-and-crushed 8 wt.% yttria-stabilized zirconia was sprayed by Atmospheric Plasma Spraying (APS) and High Frequency Pulse Detonation. Hollow Spherical Powder (HOSP™) with the same composition was sprayed by APS. The coatings where covered with V₂O₅ powder and treated at 1000 °C for different times. The extent of corrosion was followed by X-ray diffraction, scanning electron microscopy and Raman micro-spectrometry. A relationship between coating porosity and corrosion resistance is explored: the HOSP coating presented deeper penetration of corrosion than the other coatings. The authors present the extended capabilities of Raman semi-quantitative phase analysis to describe the depth and density of yttria leaching by vanadia leading to YSZ destabilization.     

Microstructural analysis of YSZ and YSZ/Al2O3 plasma sprayed thermal barrier coatings after high temperature oxidation

Air plasma sprayed TBCs usually include lamellar structure with high interconnected porosities which transfer oxygen from YSZ layer towards bond coat and cause TGO growth and internal oxidation of bond coat.The growth of thermally grown oxide (TGO) at the interface of bond coat and ceramic layer and internal oxidation of bond coat are considered as the main destructive factors in thermal barrier coatings.Oxidation phenomena of two types of plasma sprayed TBC were evaluated: (a) usual YSZ (yttria stabilized zirconia), (b) layer composite of (YSZ/Al₂O₃) which Al₂O₃ is as a top coat over YSZ coating. Oxidation tests were carried out on these coatings at 1100°C for 22, 42 and 100h. Microstructure studies by SEM demonstrated the growth of TGO underneath usual YSZ coating is higher than for YSZ/Al₂O₃ coating. Also cracking was observed in usual YSZ coating at the YSZ/bond coat interface. In addition severe internal oxidation of the bond coat occurred for usual YSZ coating and micro-XRD analysis revealed the formation of the oxides such as NiCr₂O₄, NiCrO₃ and NiCrO₄ which are accompanied with rapid volume increase, but internal oxidation of the bond coat for YSZ/Al₂O₃ coating was lower and the mentioned oxides were not detected.     

Hot corrosion behaviour of plasma sprayed alumina + YSZ particle composite coating

Hot corrosion is one of the damage mechanisms in thermal barrier coatings (TBCs) due to the molten salt effects as a result of combustion of low quality fuel. In this study, the hot corrosion behaviour of alumina–yttria stabilized zirconia particle composite coatings produced by thermal spraying for use as a thermal barriers on industrial gas turbines and in jet engines was evaluated. Plasma sprayed coatings with three different amounts of alumina- yttria stabilized zirconia particle composite have been exposed to 50 wt % Na₂SO₄ + 50 wt % V₂O₅ corrosive molten salt temperatures at 1050°C for 60 hours. Damages in the coatings surface and cross section after hot corrosion tests have been studied by using a scanning electron microscope to observe the microstructure and x-ray diffraction techniques to analyze the phase composition. The results have shown that the amount of YVO₄ crystals on the surface of YSZ coatings decrease while Al₂O₃ increases in YSZ + Al₂O₃ composition, therefore, the hot corrosion resistance of TBC improves with the addition of Al₂O₃.     

Hot corrosion behaviour of plasma sprayed YSZ/Al2O3 dispersed NiCrAlY coatings on Inconel-718 superalloy

Oxide dispersed NiCrAlY bond coatings have been developed for enhancing thermal life cycles of thermal barrier coatings (TBCs). However, the role of dispersed oxides on high temperature corrosion, in particular hot corrosion, has not been sufficiently studied. Therefore, the present study aims to improve the understanding of the effect of YSZ dispersion on the hot corrosion behaviour of NiCrAlY bond coat. For this, NiCrAlY, NiCrAlY + 25 wt.% YSZ, NiCrAlY + 50 wt.% YSZ and NiCrAlY + 75 wt.% YSZ were deposited onto Inconel-718 using the air plasma spraying (APS) process. Hot corrosion studies were conducted at 800 °C on these coatings after covering them with a 1:1 weight ratio of Na₂SO₄ and V₂O₅ salt film. Hot corrosion kinetics were determined by measuring the weight gain of the specimens at regular intervals for a duration of 51 h. X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy techniques were used to determine the nature of phases formed, examine the surface attack and to carry out microanalysis of the hot corroded coatings respectively. The results show that YSZ dispersion causes enhanced hot corrosion of the NiCrAlY coating. Leaching of yttria leads not only to the formation of the YVO₄ phase but also the destabilization of the YSZ by hot corrosion. For the sake of comparison, the hot corrosion behaviour of a NiCrAlY + 25 wt.% Al₂O₃ coating was also examined. The study shows that the alumina dispersed NiCrAlY bond coat offers better hot corrosion resistance than the YSZ dispersed NiCrAlY bond coat, although it is also inferior compared to the plain NiCrAlY bond coat.     

Microstructures and Properties of Laser-Glazed Plasma-Sprayed ZrO2-YO1.5/Ni-22Cr-10AI-1Y Thermal Barrier Coatings

Thermal barrier coatings (TBCs) consisting of two layers with various yttria contents (ZrO ₂- YO_1.5/Ni-22Cr-10Al- lY) were plasma sprayed, and parts of the various specimens were glazed by using a pulsed CO₂ laser. All the specimens were then subjected to furnace thermal cycling tests at 1100 °C; the effect of laser glazing on the durability and failure mechanism of the TBCs was then evaluated. From these results, two models were developed to show the failure mechanism of as- sprayed and laser- glazed TBCs: model A, which is thermal-stress dominant, and model V, which is oxidation-stress dominant. For top coats containing cubic phase, cubic and monoclinic phases, or tetragonal and a relatively larger amount of monoclinic phases, whose degradation is thermal- stress dominant, laser glazing improved the durability of TBCs by a factor of about two to six. Segmented cracks that occurred during glazing proved beneficial for accommodating thermal stress and raising the tolerance to oxidation, which resulted in a higher durability. Thermal barrier coatings with top coats containing tetragonal phase had the highest durability. Degradation of such TBCs resulted mainly from oxidation of the bond coats. For top coats with a greater amount of monoclinic phase, thermal mismatch stress occurred during cooling and detrimentally affected durability.     

An investigation on hot corrosion behavior of YSZ-Ta2O5 in Na2SO4 + V2O5 salt at 1100 °C

This study compares the hot corrosion performance of yttria stabilized zirconia (YSZ), and YSZ-Ta₂O₅ (TaYSZ) composite samples in the presence of molten mixture of Na₂SO₄ + V₂O₅ at 1100 °C. For YSZ, the reaction between NaVO₃ and Y₂O₃ produces YVO₄ and leads to the transformation of tetragonal ZrO₂ to monoclinic ZrO₂. For TaYSZ, minor amounts of NaTaO₃, TaVO₅ and Ta₉VO₂₅ are formed as the hot corrosion products with only traceable amounts of YVO₄. Due to the synergic effect of doping of zirconia with both Y₂O₃ and Ta₂O₅, the TaYSZ sample has a much better hot corrosion resistance than YSZ.     

Hot corrosion behaviour of plasma sprayed YSZ/LaMgAl11O19 composite coatings in molten sulfate–vanadate salt

Hot corrosion studies of thermal barrier coatings (TBCs) with different YSZ/LaMgAl₁₁O₁₉ (LaMA) composite coating top coats were conducted in 50 wt.% Na₂SO₄ + 50 wt.% V₂O₅ molten salt at 950 °C for 60 h. Results indicate that TBCs with composite coating top coats exhibit superior oxidation and hot corrosion resistances to the TBC with the traditional YSZ top coat, especially for which has a LaMA overlay. The presence of LaMA can effectively restrain the destabilization of YSZ at the expense of its own partial degradation. The hot corrosion mechanism of LaMA coating and the composite coatings have been explored.     

Sealing procedures for thick thermal barrier coatings

Zirconia-based 8Y₂O₃-ZrO₂ and 22MgO-ZrO₂ thick thermal barrier coatings (TTBC, 1000 μm), were studied with different sealing methods for diesel engine applications. The aim of the sealing procedure was to improve hot corrosion resistance and mechanical properties of porous TBC coatings. The surface of TTBCs was sealed with three different methods: (1) impregnation with phosphate-based sealant, (2) surface melting by laser glazing, and (3) spraying of dense top coating with a detonation gun. The thicknesses of the densified top layers were 50–400 μm, depending on the sealing procedure. X-ray diffraction (XRD) analysis showed some minor phase changes and reaction products caused by phosphate-based sealing treatment and some crystal orientation changes and phase changes in laser-glazed coatings. The porosity of the outer layer of the sealed coating decreased in all cases, which led to increased microhardness values. The hot corrosion resistance of TTBCs against 60Na₂SO₄-40V₂O₅ deposit was determined in isothermal exposure at 650 °C for 200 h. Corrosion products and phase changes were studied with XRD after the test. A short-term engine test was performed for the reference coatings (8Y₂O₃-ZrO₂ and 22MgO-ZrO₂) and for the phosphate-sealed coatings. Engine tests, duration of 3 h, were performed at the maximum load of the engine and were intended to evaluate the thermal cycling resistance of the sealed coatings. All of the coatings passed the engine test, but some vertical cracks were detected in the phosphate-sealed coatings.     

High‐temperature corrosion behavior of some post‐plasma‐spraying‐gas‐nitrided metallic coatings on a Fe‐based superalloy

The objective of the present study is to propose a cost‐effective process for modifying commercially available coatings by gas nitriding using commonly available equipment and starting materials. Al–Cr and Ti–Al metallic coatings were deposited on Superfer 800H (Fe‐based superalloy) using a plasma spray process. Then the gas nitriding of the coatings was done in the lab and the parameters were optimized after conducting several trials on plasma‐sprayed‐coated specimens. Characterization and high‐temperature corrosion behavior of coatings after exposure to air and molten salt at 900°C were studied under cyclic conditions. Techniques like XRD, SEM/EDX, and X‐ray mapping analysis were used for the characterization of the coatings and analysis of the oxide scale. Both the coatings successfully protected the substrate and were effective in decreasing the corrosion rate when subjected to cyclic oxidation (Type‐I hot corrosion) at 900°C for 50 cycles in air and molten salt (a salt mixture of Na₂SO₄–60%V₂O₅ dissolved in distilled water). Based on the findings of the present study, the coatings under study are recommended for tapplications to super‐heater and reheater tubes of boilers and all those surfaces that face fireside corrosion, such as fluidized beds, industrial waste incinerators, internal combustion engines, gas turbines or steam turbines, to provide protection against degradation in these environments. The cost of the product/process is approximately Rs. 0.62 per mm² in case of Al–Cr coating and Rs. 1.86 per mm² in case of Ti–Al coating.     

Effect of yttria(Y<Subscript>2</Subscript>O<Subscript>3</Subscript>) coating for high temperature oxidation resistance of 9Cr-1Mo steel

This paper investigates the effect of yttria (Y₂O₃) coating on high temperature oxidation behaviour of low alloy 9 Cr–1Mo steel. The superficial coating is Y₂O₃ was prepared for experimental investigation. The isothermal corrosion study of uncoated and coated specimens was carried out in air oxidation environment at 973 K for 8 h. The corrosion rate and reaction kinetics were studied and the post corroded scales were characterized in SEM, EDS and XRD. The results clearly indicate that Y₂O₃ coated specimen improves the high temperature oxidation resistance than uncoated specimens. The improvement of oxidation resistance in presence of Y₂O₃ coating can be attributed to the changed mechanism of scale growth from outer cation migration to inner anion migration and enhancement of scale adhesion with the substrate. Further, enhancement of scale adhesion with the substrate in case of Y₂O₃ coating also improves the oxidation resistance. The detail mechanism of the oxidation of Y₂O₃ coated and uncoated specimen is further discussed in this paper.     

Air Plasma-Sprayed Yttria and Yttria-Stabilized Zirconia Thermal Barrier Coatings Subjected to Calcium-Magnesium-Alumino-Silicate (CMAS)

Yttria (Y₂O₃) and zirconia (ZrO₂) stabilized by 8 and 20 wt.%Y₂O₃ thermal barrier coatings (TBCs) subjected to calcium-magnesium-alumino-silicate (CMAS) have been investigated. Free-standing Y₂O₃, 8 and 20 wt.%YSZ coatings covered with synthetic CMAS slurry were heated at 1300 °C in air for 24 h in order to assess the effect of Y₂O₃ on the corrosion resistance of the coatings subjected to CMAS. The microstructures and phase compositions of the coatings were characterized by SEM, EDS, XRD, RS, and TEM. TBCs with higher Y₂O₃ content exhibited better CMAS corrosion resistance. Phase transformation of ZrO₂ from tetragonal (t) to monoclinic (m) occurred during the interaction of 8YSZ TBCs and CMAS, due to the depletion of Y₂O₃ in the coating. Some amounts of original c-ZrO₂ still survived in 20YSZ TBCs along with a small amount of m-ZrO₂ that appeared after reaction with CMAS. Furthermore, Y₂O₃ coating was found to be particularly highly effective in resisting the penetration of molten CMAS glass at high temperature (1300 °C). This may be ascribed to the formation of sealing layers composed of Y-apatite phase [based on Ca₄Y₆ (SiO₄)₆O and Y_4.67(SiO₄)₃O] by the high-temperature chemical interactions of Y₂O₃ coating and CMAS glass.     

The yttrium effect on the corrosion resistance of CO2-laser processed MCrAlY coatings

To improve the corrosion resistance and to study the effect of yttrium in the behavior of coatings produced by thermal spraying MCrAlY (M=Ni, Co) powders, CO₂ laser processing was conducted. Three methods were used: (1) a combination of gas flame and plasma spraying in air followed by laser glazing in argon, (2) low-pressure plasma spraying (LPPS) and laser glazing in argon, and (3) LPPS and laser-gas (O₂) alloying. Laser glazing in argon of the MCrAlY coatings sprayed in air promoted formation of weakly adherent agglomerates of Al–Y oxides and an alumina-chromia solid solution. Glazing in argon atmosphere of LPPS CoNiCrAlY and NiCrAlY coatings caused the formation of nickel aluminides besides the formation of Y–Al compounds. Gas (O₂)-alloying of these coatings produces continuous and adherent (yttrium-containing) alumina and chromia layers. The effects of yttrium on the characteristics of the oxides formed in the coatings during laser glazing, laser-gas alloying, and high-temperature oxidation is discussed. This work also investigated the oxidation resistance of the laser-processed MCrAlY coatings in air and in the presence of 85 mol/o V₂O₅–Na₂SO₄ fused salt at 900°C.     

Hot corrosion behavior of detonation gun sprayed Cr3C2–NiCr coatings on Ni and Fe-based superalloys in Na2SO4–60% V2O5 environment at 900 °C

The present work investigates the hot corrosion resistance of detonation gun sprayed (D-gun) Cr₃C₂–NiCr coatings on Superni 75, Superni 718 and Superfer 800 H superalloys. The deposited coatings on these superalloy substrates exhibit nearly uniform, adherent and dense microstructure with porosity less than 0.8%. Thermogravimetry technique is used to study the high temperature hot corrosion behavior of bare and Cr₃C₂–NiCr coated superalloys in molten salt environment (Na₂SO₄–60% V₂O₅) at high temperature 900 °C for 100 cycles. The corrosion products of the detonation gun sprayed Cr₃C₂–NiCr coatings on superalloys are analyzed by using XRD, SEM, and FE-SEM/EDAX to reveal their microstructural and compositional features for elucidating the corrosion mechanisms. It is shown that the Cr₃C₂–NiCr coatings on Ni- and Fe-based superalloy substrates are found to be very effective in decreasing the corrosion rate in the given molten salt environment at 900 °C. Particularly, the coating deposited on Superfer 800 H showed a better hot corrosion protection as compared to Superni 75 and Superni 718. The coatings serve as an effective diffusion barrier to preclude the diffusion of oxygen from the environment into the substrate superalloys. It is concluded that the hot corrosion resistance of the D-gun sprayed Cr₃C₂–NiCr coating is due to the formation of desirable microstructural features such as very low porosity, uniform fine grains, and the flat splat structures in the coating.     

Effect of Nano-Si<Subscript>3</Subscript>N<Subscript>4</Subscript> Additives and Plasma Treatment on the Dry Sliding Wear Behavior of Plasma Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-8YSZ Ceramic Coatings

In this paper, the effect of nano-Si₃N₄ additives and plasma treatment on the wear behavior of Al₂O₃-8YSZ ceramic coatings was studied. Nano-Al₂O₃, nano-8YSZ (8 wt.% Y₂O₃-stabilized ZrO₂) and nano-Si₃N₄ powders were used as raw materials to fabricate four types of sprayable feedstocks. Plasma treatment was used to improve the properties of the feedstocks. The surface morphologies of the ceramic coatings were observed. The mechanical properties of the ceramic coatings were measured. The dry sliding wear behavior of the Al₂O₃-8YSZ coatings with and without Si₃N₄ additives was studied. Nano-Si₃N₄ additives and plasma treatment can improve the morphologies of the coatings by prohibiting the initiation of micro-cracks and reducing the unmelted particles. The hardness and bonding strength of AZSP (Al₂O₃-18 wt.% 8YSZ-10 wt.% Si₃N₄-plasma treatment) coating increased by 79.2 and 44% compared to those of AZ (Al₂O₃-20 wt.% 8YSZ) coating. The porosity of AZSP coating decreased by 85.4% compared to that of AZ coating. The wear test results showed that the addition of nano-Si₃N₄ and plasma treatment could improve the wear resistance of Al₂O₃-8YSZ coatings.     

Effect of Y2O3 content in the pack on microstructure and hot corrosion resistance of Y–Co-modified aluminide coating

Y–Co-modified aluminide coatings on nickel base superalloys were prepared by pack cementation method. Effect of Y₂O₃ content in the pack mixture on microstructure and hot corrosion resistance of the coatings was investigated. The results show that with the increase in Y₂O₃ content, the content of Co in the coatings increases. The mass gain of the coatings with Y₂O₃ addition of 1, 2 and 3 wt.% is 0.6, 0.55 and 0.42 mg/cm² after hot corrosion at 1173 K for 100 h, respectively. Y₂O₃ addition accelerates the diffusion of Co and thus increases the hot corrosion resistance of the coating.     

Advances in High Velocity Suspension Flame Spraying (HVSFS)

Three suspensions, containing oxide nanoparticle single phases, (Al₂O₃, 3YSZ and Cr₂O₃) were prepared and sprayed using High Velocity Suspension Flame Spraying (HVSFS) technique. The coatings were characterized concerning their mechanical properties by means of nano indenter hardness measurements (all coatings) and ball on disk tribometry (Al₂O₃, 3YSZ).APS and HVOF sprayed Al₂O₃ coatings were characterized under same conditions for comparison. X-ray diffraction analysis was performed on HVSF sprayed Al₂O₃ and Cr₂O₃ coatings and a plasma-sprayed Cr₂O₃ coating for comparison. A Williamson-Hall line profile analysis was performed to estimate and compare crystallite size in the coatings.     

Thermal conductivity and phase stability of plasma sprayed ZrO2–Y2O3–La2O3 coatings

Thermal conductivity and phase stability of La₂O₃,Y₂O₃ stabilized ZrO₂ plasma sprayed coatings were investigated. La₂O₃ was selected as a stabilizer because it had a significant effect on reducing densification of Y₂O₃ stabilized ZrO₂ (YSZ). The developed coating showed low thermal conductivity even after high temperature exposure due to its high resistance to sintering. However, phase stability and thermal cycle life of the coating decreased as the amount of La₂O₃ was increased. It was concluded that optimum amount of La₂O₃ addition was about 1 mol% to suppress sintering with little degradation of other properties.     

Comparison of corrosion resistance between Al2O3 and YSZ coatings against high temperature LiCl-Li2O molten salt

In this study, the high-temperature corrosion resistance of plasma-sprayed ceramic oxide coatings has been evaluated in a LiCl-Li₂O molten salt under an oxidizing environment. Al₂O₃ and YSZ coatings were manufactured by atmospheric plasma spraying onto a Ni alloy substrate. Both the plasma-sprayed Al₂O₃ and YSZ coatings had a typical splat quenched microstructure which contained various types of defects, including incompletely filled pores, inter-splat pores and intra-splat microcracks. Corrosion resistance was evaluated by the thickness reduction of the coating as a function of the immersion time in the LiCl-Li₂O molten salt at a temperature of 650 °C. A linear corrosion kinetic was found for the Al₂O₃ coating, while no thickness variation with time occurred for the YSZ coating. The ceramic oxide coatings were reacted with LiCl-Li₂O molten salt to form a porous reaction layer of LiAl, Li₅AlO₄ and LiAl₅O₈ for the Al₂O₃ coating and a dense reaction layer of non-crystalline phase for the YSZ coating. The reaction products were also formed along the inside coating of the porous channel. The superior corrosion resistance of the YSZ coating was attributed to the formation of a dense protective oxide layer of non-crystalline reaction products on the surface and at the inter-splat pores of the coating.     

The hot corrosion behaviour of HVOF sprayed MCrAlX coatings under Na2SO4 (+NaCl) salt films

The hot corrosion behaviour of two NiCoCrAlYTa and CoCrAlYSi HVOF sprayed coatings and a CoCrAlY VPS coating were investigated under laboratory conditions at 900°C using a synthetic gas atmosphere containing sulphur as an impurity. All the coatings tested showed good protection under Na₂SO₄ salt films. In the presence of NaCl in the Na₂SO₄ salt films, the corrosion rates of low Al containing coatings increased considerably but the NiCoCrAlYTa coating with higher Al content still revealed good performance. It is suggested that NaCl in the salt film causes premature failure of the protective scale and reduces the incubation period of corrosion in the coatings of lower Al content. Furthermore, it seems that the finely dispersed Al rich oxide particles in the sprayed and heat‐treated HVOF coating microstructure do not lead to internal corrosion. The experimental investigations include short‐term corrosion kinetic measurements and SEM analyses.     

Preparation of Al2O3–ZrO2–Y2O3 Composite Coatings by a Modified Sol–Gel Technique for Thermal Barrier Application

Spatial-network Al₂O₃–ZrO₂–Y₂O₃ composite coatings were prepared by a modified sol–gel technique, so-called thermal pressure and filtration of sol–gel paint. The composite coatings were derived from a composite paint of yttria partially stabilized zirconia (YSZ) particles, Al₂O₃ particles and Al₂O₃–Y₂O₃ sol. Their microstructure showed that YSZ particles were covered with spatial-network Al₂O₃–Y₂O₃ blanket. Cyclic oxidation at 1,050 °C in air for 200 h demonstrates that the oxygen diffusion rate in the coatings could be effectively inhibited. Meanwhile, suitable coefficients of thermal expansion (CTE) gave the composite coatings better spallation resistance than that of Al₂O₃–Y₂O₃ or ZrO₂–Y₂O₃ coatings. The positive results of cyclic oxidation indicated that the composite coating can be used as an interlayer between the bond coat and the top ceramic layer in traditional TBCs. Not only the depletion rate of aluminum-rich phase in MCrAlY alloy could be slowed down by spatial-network Al₂O₃–Y₂O₃, but also different thermal expansion between thermally grown oxides layer and top layer could be relieved by suitable CTE. In this paper, the mechanisms of the inhibition of oxygen diffusion and thermal match between ceramic coating and alloy are also discussed.