Hot Corrosion Performance of AlO-CrO/NiCoCrAlYTa and AlO/NiCoCrAlYTa Coatings Deposited by Atmospheric Plasma Spraying

AlO-CrO/NiCoCrAlYTa and AlO/NiCoCrAlYTa coatings were deposited on 316L stainless steel substrate using atmospheric plasma spraying, respectively, in order to improve the oxidation and corrosion resistance. The hot corrosion performance of the coatings at 700 and 900 °C were studied, and the detailed microstructures and phase composition of the coatings were analyzed using x-ray diffraction, scanning electron microscope with energy dispersive spectrometer, and transmission electron microscope. The results show that both coatings are structurally featured by slatted layers, consisting of amorphous phase, Cr₂O₃, Ni₃Al, and Al₂O₃. The hot corrosion resistance of AlO-CrO/NiCoCrAlYTa coating is better than that of AlO/NiCoCrAlYTa coating. This improvement is attributed to lower porosity and more compact Cr₂O₃ in AlO-CrO/NiCoCrAlYTa coating which performs better than Al₂O₃ in blocking further inward progress of corrosion and oxidization.     

Microstructure and Thermal Properties of Nanostructured 4?wt.%Al2O3-YSZ Coatings Produced by Atmospheric Plasma Spraying

Microstructure and phase composition of the nanostructured Al₂O₃ doped YSZ coatings by atmospheric plasma spraying method have been characterized with XRD, TEM and SEM. The nanostructured 4AlYSZ coatings consist mainly of t-ZrO₂, crystalline Al₂O₃ phase is absent in the coatings and the grain size of the 4AlYSZ coating is about 65 nm. The APS 4AlYSZ coating is characterized by nanozones, dense area and voids. After doping, the coefficient of thermal expansion of YSZ is decreased to 10.928 × 10⁻⁶/K. The addition of Al₂O₃ has a great influence on decreasing the thermal conductivity of nano-YSZ, which is mainly caused by the point defect scattering and grain-boundary scattering. The lifetime of nanostructured 4AlYSZ coating is about 1000 cycles at 1100 °C.     

Oxidation and hot corrosion behaviors of HVAF-sprayed conventional and nanostructured NiCrC coatings

The oxidation and hot corrosion behaviors of HVAF-sprayed conventional and nanostructured NiCrC coatings were studied. The oxidation experiment was conducted in air, and the hot corrosion was conducted in the Na₂SO₄–30%K₂SO₄ environment, in the temperature range of 550–750 °C for periods up to 160 h. The corrosion kinetics was tested with the thermogravimetric method. The corrosion products were characterized by scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffractometry (XRD). As indicated by the results, both types of coatings possess high corrosion resistance, especially the nanostructured NiCrC coating. The enhanced grain boundary diffusion in the nanostructured coating not only promotes the formation of a denser Cr₂O₃ scale with a higher rate, but also helps to mitigate the Cr depletion at the metal/scale interface. The less porosity of the nanostructured coating is also thought to be beneficial to the anti-corrosion properties.     

Impedance Analysis of 7YSZ Thermal Barrier Coatings During High-Temperature Oxidation

ZrO₂-7 wt.%Y₂O₃ (7YSZ) thermal barrier coatings (TBCs) were prepared by atmospheric plasma spraying. High-temperature oxidation of 7YSZ TBCs was accomplished at 950 °C and characterized by impedance spectroscopy and scanning electron microscopy with energy-dispersive spectrometry. The results indicated that the thermally grown oxide (TGO) mainly contained alumina. The increase of the thickness of the TGO layer appeared to follow a parabolic law. Impedance analysis demonstrated that the resistance of the TGO increased with increasing oxidation time, also following a parabolic law, and that characterization of the TGO thickness based on fitting an equivalent circuit to its measured resistance is feasible. The YSZ grain-boundary resistance increased due to increasing cracks within the coating for oxidation time less than 50 h. However, beyond 150 h, the YSZ grain-boundary resistance slightly decreased, mainly due to sintering of the coating during the oxidation process.     

Resistance of Nanostructured Environmental Barrier Coatings to the Movement of Molten Salts

Corrosion of components in a recovery boiler is a major problem faced by the pulp and paper industry. The superheater tubes become severely corroded due to the presence of sulfidic gases in the boiler and molten salts which are deposited on the surface of the tubes. As a result, the boiler must be decommissioned for expensive maintenance and repairs. Yttria-stabilized zirconia (YSZ) coatings have been shown to provide corrosion resistance when applied on gas turbines operating at high temperatures. Air plasma-sprayed YSZ environmental barrier coatings on Type 309 stainless steel were exposed to three different corrosive environments: Test A??600?°C, salt vapors, flue gases, 168?h; Test B??600?°C, molten salt, air, 168?h; and Test C??600?°C, molten salt, flue gases, 168?h. Two different types of YSZ coatings??conventional YSZ and nanostructured YSZ??were tested to study their resistance to corrosion and molten salt penetration. The performances of both types of coatings were evaluated, and a comparative study was conducted. It was found that the nanostructured YSZ samples protected the stainless steel substrate better than their conventional counterparts. This superior performance was attributed to the presence of semi-molten nano-agglomerates present in the coating microstructure, which acted as collection points for the penetrating molten salts.     

Behaviour and mechanisms of alkali-sulphate-induced hot corrosion on composite coatings at 900 °C

Three coating systems (one single MCrAlY, two composite coatings with/without the Cr-rich interlayer) have been prepared by the arc ion plating (AIP) and electroplating methods. Hot corrosion of the coatings at 900 °C by alkali sulphates shows that a composite coating with a chromium-rich interlayer exhibits the best corrosion resistance. The MCrAlY coating was severely deteriorated in 100 h since its non-productive (Ni,Co)Al₂O₄ and Cr₂O₃ scales induce internal sulfidation and oxidation. However, the microstructural involutions seldom occur within composite coatings, especially for the one with the Cr-rich interlayer. Mechanisms of hot corrosion of the three coatings are discussed.     

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.     

Synthesis and oxidation behavior of nanocrystalline MCrAlY bond coatings

Thermal barrier coating systems protect turbine blades against high-temperature corrosion and oxidation. They consist of a metal bond coat (MCrAlY, M = Ni, Co) and a ceramic top layer (ZrO₂/Y₂O₃). In this work, the oxidation behavior of conventional and nanostructured high-velocity oxyfuel (HVOF) NiCrAlY coatings has been compared. Commercially available NiCrAlY powder was mechanically cryomilled and HVOF sprayed on a nickel alloy foil to form a nanocrystalline coating. Freestanding bodies of conventional and nanostructured HVOF NiCrAlY coatings were oxidized at 1000 °C for different time periods to form the thermally grown oxide layer. The experiments show an improvement in oxidation resistance in the nanostructured coating when compared with that of the conventional one. The observed behavior is a result of the formation of a continuous Al₂O₃ layer on the surface of the nanostructured HVOF NiCrAlY coating. This layer protects the coating from further oxidation and avoids the formation of mixed oxide protrusions present in the conventional coating. The original version of this article was published as part of the ASM Proceedings, Thermal Spray 2003: Advancing the Science and Applying the Technology, International Thermal Spray Conference (Orlando, FL), May 5–8 2003, Basil R. Marple and Christian Moreau, Ed., ASM International, 2003.     

Hot corrosion properties of composite coatings in the presence of NaCl at 700 and 900 °C

Cyclic hot corrosion tests have been carried out on three coatings (one NiCoCrAlY and two composite coatings) at 700 and 900 °C. The kinetic curves and evolution of microstructure show that the composite coating with a Cr-base interlayer performs best. The Cr₂O₃ scale is more effective to protect the coating at 700 °C than that at 900 °C. The corrosion process is accelerated by NaCl via forming volatile MCl_x and inducing the formation of molten voids in the coating or extra oxidation at the interface of fusant/oxide scale, determined by the temperature and the compositions of the coating.     

Effects of Al and Ni doping on oxidation and corrosion resistance of electrophoretic deposited YSZ coatings

Yttria-stablized zirconia (YSZ)/(Ni,Al) coatings were deposited on Inconel 600 alloy substrate by the electrophoretic deposition combined with vacuum sintering technique. The effects of isothermal oxidation at 1100 °C on the composition of the coatings and the crack healing were investigated, and the corrosion resistance of the coatings in 3.5% NaCl (mass fraction) solution was also studied. The results showed that the cracks on the coating gradually healed up with the increase of the isothermal oxidation time. During isothermal oxidation process, the coating composed of Ni₃Al was transformed to α-Al₂O₃ particulates. The α-Al₂O₃ particulates can seal the defects such as pores and cracks, and meanwhile prevent the oxygen diffusion into the coatings. The polarization curves and EIS results indicated that the coatings oxidized for 40 h had a more positive corrosion potential, higher breakdown potential, higher impedance module at low frequency and much lower corrosion current density compared with YSZ coated and uncoated Inconel 600 alloys.     

Elevated Temperature Solid Particle Erosion Performance of Plasma-Sprayed Co-based Composite Coatings with Additions of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and CeO<Subscript>2</Subscript>

In this paper, investigation into solid particle erosion behavior of atmospheric plasma-sprayed composite coating of CoCrAlY reinforced with Al₂O₃ and CeO₂ oxides on Superni 76 at elevated temperature of 600 °C is presented. Alumina particles are used as erodent at two impact angles of 30° and 90°. The microstructure, porosity, hardness, toughness and adhesion properties of the as-sprayed coatings are studied. The effects of temperature and phase transformation in the coatings during erosion process are analyzed using XRD and EDS techniques. Optical profilometer is used for accurate elucidation of erosion volume loss. CoCrAlY/CeO₂ coating showed better erosion resistance with a volume loss of about 50% of what was observed in case of CoCrAlY/Al₂O₃/YSZ coating. Lower erosion loss is observed at 90° as compared to 30° impact angle. The erosion mechanism evaluated using SEM micrograph revealed that the coatings experienced ductile fracture exhibiting severe deformation with unusual oxide cracks. Reinforced metal oxides provide shielding effect for erodent impact, enabling better erosion resistance. The oxidation of the coating due to high-temperature exposure reforms erosion process into oxidation-modified erosion process.     

Influence of laser‐glazing on hot corrosion resistance of yttria‐stabilized zirconia TBC in molten salt mixture of V2O5 and Na2SO4

Plasma‐sprayed 8YSZ (zirconia stabilized with 8 wt% yttria)/NiCoCrAlYTa thermal barrier coatings (TBCs) were laser‐glazed using a continuous‐wave CO₂ laser. Open pores within the coating surface were eliminated and an external densified layer was generated by laser‐glazing. The hot corrosion resistances of the plasma‐sprayed and laser‐glazed coatings were investigated. The two specimens were exposed for the same period of 100 h at 900 °C to a salt mixture of vanadium pentoxide (V₂O₅) and sodium sulfate (Na₂SO₄). Serious crack and spallation occurred in the as‐sprayed coating, while the as‐glazed coating exhibited good hot corrosion behavior and consequently achieved a prolonged lifetime. The results showed that the as‐sprayed 8YSZ coating achieved remarkably improved hot corrosion resistance by laser‐glazing. Changes in the coatings were studied by scanning electron microscopy (SEM) to observe the microstructure and X‐ray diffraction (XRD) technique to analyze the phase composition. XRD results showed that the reaction between yttria (Y₂O₃) and V₂O₅ produced yttrium vanadate (YVO₄), leaching Y₂O₃ from YSZ and causing the progressive destabilization transformation from the tetragonal (t) to monoclinic (m) phase. The external dense layer produced by laser‐glazing restrained the penetration of the molten salt, to a certain extent, into the coating, which led to a relatively low m‐ZrO₂ content in the coating after the hot corrosion test. Additionally, the segmented cracks in the coating surface induced by laser‐glazing were helpful to the improvement of strain tolerance of the coating. The two factors were important contributions to the significant enhancement of hot corrosion resistance of the as‐glazed YSZ coating.     

Performance of high-velocity oxyfuel-sprayed coatings on an Fe-based superalloy in Na2SO4-60%V2O5 environment at 900 °C part II: Hot corrosion behavior of the coatings

NiCrBSi, Cr₃C₂-NiCr, Ni-20Cr, and Stellite-6 coatings were deposited on an Fe-based superalloy by the high-velocity oxyfuel (HVOF) thermal spray process. The hot corrosion behavior of the coatings in an aggressive environment of Na₂SO₄-60%V₂O₅ at 900 °C under cyclic conditions was studied. The thermogravimetric technique was used to establish the kinetics of corrosion. X-ray diffraction, scanning electron microscopy/energy-dispersive x-ray and electron probe microanalysis techniques were used to analyze the corrosion products. Hot corrosion resistances of all the coatings were found to be better than the uncoated superalloy. The Ni-20Cr coating was found to be the most protective, followed by Cr₃C₂-NiCr coatings. The Ni-20Cr coating had reduced the mass gain by 90% of that gained by the uncoated superalloy. The hot corrosion resistance shown by the Cr₃C₂-NiCr coating was slightly better compared with the NiCrBSi coating; however, both of the coatings performed better than the Stellite-6 coating. The Stellite-6 coating was the least effective among the coatings studied, but it was still successful in decreasing the mass gain to about one fourth compared with the uncoated superalloy. The formation of oxides and spinels of nickel, chromium, or cobalt may be contributing to the development of hot corrosion resistance in the coatings. This article focuses on the hot corrosion behavior of HVOF coatings. The characterization of these coatings has been presented in part I included in this issue.     

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.     

Oxidation and Hot Corrosion Behavior of Plasma-Sprayed MCrAlY–Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> Coatings

The oxidation and hot corrosion behavior of two atmospheric plasma-sprayed NiCoCrAlY–Cr₂O₃ and CoNiCrAlY–Cr₂O₃ coatings, which are primarily designed for wear applications at high temperature, were investigated in this study. The two coatings were exposed to air and molten salt (75%Na₂SO₄–25%NaCl) environment at 800 °C under cyclic conditions. Oxidation and hot corrosion kinetic curves were obtained by thermogravimetric technique. X-ray diffraction analysis and scanning electron microscopy with energy-dispersive x-ray spectrometry were employed to characterize the coatings’ microstructure, surface oxides, and composition. The results showed that both coatings provided the necessary oxidation resistance with oxidation rates of about 1.03 × 10^?2 and 1.36 × 10^?2 mg/cm² h, respectively. The excellent oxidation behavior of these two coatings is attributed to formation of protective (Ni,Co)Cr₂O₄ spinel on the surface, while as-deposited Cr₂O₃ in the coatings also acted as a barrier to diffusion of oxidative and corrosive substances. The greater presence of Co in the CoNiCrAlY–Cr₂O₃ coating restrained internal diffusion of sulfur and slowed down the coating’s degradation. Thus, the CoNiCrAlY–Cr₂O₃ coating was found to be more protective than the NiCoCrAlY–Cr₂O₃ coating under hot corrosion condition.     

超音速大气等离子喷涂TiB2-SiC涂层的抗氧化性及耐熔盐腐蚀性能

采用超音速大气等离子喷涂制备全包覆TiB₂-SiC涂层,研究了TiB₂-SiC涂层在400和800 ℃的氧化性能,并探究其氧化机理。对TiB₂-SiC涂层在900 ℃下的抗铝熔盐腐蚀性能进行研究,并探讨其耐熔盐腐蚀机理。结果表明,超音速大气等离子喷涂制备的TiB₂-SiC涂层具有良好的抗氧化性,在400 ℃的氧化速率常数为1.92×10^-5 mg²·cm^-4·s^-1,在800 ℃的氧化速率常数为1.82×10^-4 mg²·cm^-4·s^-1。超音速大气等离子喷涂制备的TiB₂-SiC涂层在900 ℃下具有良好的抗熔盐腐蚀性能,熔盐腐蚀后TiB₂-SiC涂层都保持致密结构,未发生涂层的开裂及剥落。     

Stepwise Depletion of Coating Elements as a Result of Hot Corrosion of NiCrAlY Coatings

Present investigation deals with the hot corrosion behaviour of the NiCrAlY coatings deposited by HVOF technique on Superni76 under cyclic conditions at 900  °C in the presence of Na₂SO₄ + 60% V₂O₅ salt. The weight change behaviour of the coatings was followed with time up to 200 cycles and K _p value was calculated for the hot corrosion process. Surface and cross-section of the corroded samples were examined by FESEM/EDS and XRD to follow the progress of corrosion up to 200 cycles. In earlier cycles, the corrosive species oxidised top surface of the coatings. With increasing number of cycles, oxidation of the coatings occurred up to 40-μm depth. A Cr-depleted band was seen below the oxide scale. Further increase in number of cycles led to migration and oxidation of Al to form Al₂O₃ sublayer at coating/scale interface, thereby leading to formation of Al-depleted zone in the coating below the Al₂O₃ sublayer. The corrosion resistance of the NiCrAlY coatings is attributed to the formation of the continuous and dense Al₂O₃ sublayer at the coating/scale interface, which acts as barrier to the migration of Cr to the surface. The appearance of Al₃Y after 100 and 200 cycles also contributes to the increased corrosion resistance of coatings after 100 and 200 cycles.     

Improving high temperature oxidation and hot corrosion resistance of Ni-base super alloy INC738LC with Cr-Si-RE modified aluminide coatings produced by single step pack cementation process

The Cr-Si-Zr (or Y) modified aluminide coatings were produced on Ni-base INC738 by a novel single step pack cementation process and their behavior was evaluated in cyclic oxidation and hot corrosion conditions. A dual layer pack with different composition was applied to produce Cr-Si-Zr or Cr-Si-Y modified aluminide coatings. A mixture of salts 75%Na₂SO₄-20%NaCl-5%V₂O₅ at 950°C was used as a hot corrosion environment. The results show that oxidation and corrosion rate of Cr-Si-Zr or Cr-Si-Y modified aluminide coatings produced by dual layer pack process are lower than those of uncoated or simple aluminide coatings. Coatings with higher Al content and uniformly dispersed Cr-Si rich phases show better hot corrosion resistance.     

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.     

Improvement of thermally grown oxide layer in thermal barrier coating systems with nano alumina as third layer

A thermally grown oxide (TGO) layer is formed at the interface of bond coat/top coat. The TGO growth during thermal exposure in air plays an important role in the spallation of the ceramic layer from the bond coat. High temperature oxidation resistance of four types of atmospheric plasma sprayed TBCs was investigated. These coatings were oxidized at 1000 °C for 24, 48 and 120 h in a normal electric furnace under air atmosphere. Microstructural characterization showed that the growth of the TGO layer in nano NiCrAlY/YSZ/nano Al₂O₃ coating is much lower than in other coatings. Moreover, EDS and XRD analyses revealed the formation of Ni(Cr,Al)₂O₄ mixed oxides (as spinel) and NiO onto the Al₂O₃ (TGO) layer. The formation of detrimental mixed oxides (spinels) on the Al₂O₃(TGO) layer of nano NiCrAlY/YSZ/nano Al₂O₃ coating is much lower compared to that of other coatings after 120 h of high temperature oxidation at 1000 °C.