THE CHARACTERISTICS OF OXIDE SCALE FORMED ON LOW PRESSURE PLASMA SPRAYED NiCrAIY COATING IN THE PRESENCE OF 5% WATER VAPOR

The oxidations of low pressure plasma sprayed (LPPS) NiCrAlY coating on nickelbase superalloy were studied at 1050C in flows of O2, and mixture of O2 and 5%H2 Ounder atmospheric pressure. Oxide formed on the surface of LPPS NiCrAlY coatingafter oxidation at 1050℃ in pure O2 consisted of NiCr2 O4, whereas oxide formed onthe surface of LPPS NiCrAlY coating after oxidation at 1000℃ in a mixture of O2 and5%H2 O is mainly composed of NiO. The effect of water vapor on the characteristicsof the oxide scale is attributed to the increase in Ni cation transport.     

水蒸气对NiCrAlY涂层抗高温氧化性能的影响

采用热重分析及现代表面分析方法研究了低压等离子喷涂Ni CrAlY涂层在纯氧以及含5%水蒸气的O2中的高温氧化行为,结果表明：在纯氧的氧化环境中 ,NiCrAlY涂层氧化动力学遵循抛物线规律,在含有5％的水蒸气的O2中,NiCrAlY涂层在氧 化至110 h后氧化动力学几乎呈直线规律.XRD及SEM分析显示,NiCrAlY涂层在O2中氧化180 h后,表面形成一层致密的Al2O3;而在含5%水蒸气的O2中氧化180 h后表面氧化层中 除了有Al2O3外,还有NiO和Cr2O3.其原因在于水蒸气中的氢在氧化物中的溶解,致 使Ni2+扩散 速度增加,使氧化层变得疏松,降低其抗氧化性.     

Cyclic-Oxidation Behavior of Thermal-barrier Coatings Exposed to NaCl Vapor

A Ni–24Cr–6Al–0.7Y (NiCrAlY) coating was deposited on a nickel-base superalloy by low-pressure plasma spraying, and the top coating, ZrO₂ partially stabilized with Y₂O₃ (7.5 wt%), was deposited on the NiCrAlY coating by air-plasma spraying. The cyclic-oxidation behavior of the NiCrAlY + YSZ coating exposed to NaCl vapor was investigated under atmospheric pressure at 1,050 °C, 1,100 °C and 1,150 °C. The cyclic-oxidation life of the NiCrAlY + YSZ coating in the presence of NaCl vapor was shortened compared with that in air. The higher the temperature is, the shorter the cyclic oxidation life. The oxide scale formed at the interface between the bond coat and the ceramic layer after exposure to NaCl vapor consisted of voluminous and non-protective NiO, Al₂O₃ and NiCr₂O₄ spinel. The failure of the TBC exposed to NaCl vapor occurs within the top coat and close to the YSZ/thermal growth oxide interface. The failure mechanism has been discussed based on the experimental results and thermodynamics.     

High-Temperature Oxidation Behavior of Sputtered IN 738 Nanocrystalline Coating

A sputtered nanocrystalline coating of IN 738 alloy was obtained by means of magnetron sputtering. The isothermal oxidation behavior at 800, 900, and 1000°C and the cyclic oxidation behavior at 950°C of the coating were studied in comparison with IN 738 cast alloy. The results indicated that a double external oxide scale was formed on the nanocrystalline coating at 900, 950, and 1000°C without internal oxide and nitride. The scale consisted in an outer mixture of Cr₂O₃, TiO₂, and NiCr₂O₄ and an inner, continuous Al₂O₃ layer, which offered good adhesive and protectiveness. However, at 800°C a continuous Al₂O₃ scale could not be formed during oxidation of nanocrystalline coating and aluminum was still oxidized internally.     

Comparison of molybdenizing and NiCrAlY coating on Ti and Ti-6Al-4V

Two surface treatments, molybdenizing and depositing NiCrAlY coating, were applied to improve the microhardness and the oxidation resistance of titanium and Ti-6Al-4V. Coupons were analyzed using optical microscopy (OM), scanning electron microscopy (SEM) with X-ray energy dispersive spectrometer (EDS), and X-ray diffraction (XRD). Vickers hardness and isothermal oxidation tests were carried out to evaluate the effects of these two surface treatments on the microhardness and oxidation resistance of the substrates. The post vacuum heat treatment of the NiCrAlY coating and the molybdenizing parameters were also discussed. It is found that molybdenizing can obviously increase the surface hardness of titanium due to the formation of β, α″, and α′ phases in the diffusion layer. As γ′ phase is formed after vacuum heat treatment, the NiCrAlY coating is effective in improving the surface hardness of Ti-6Al-4V. The NiCrAlY coating can obviously decrease the oxidation rate of Ti-6Al-4V at 700–900°C, which can be attributed to the formation of Al₂O₃ and Cr₂O₃ mixed scale during the oxidation.     

Effect of Ion Plating TiN on the Oxidation of Sputtered NiCrAlY-Coated Ti3Al-Nb in Air at 850-950°C

A single sputtered NiCrAlY coating and a complexcoating of inner ion-plated TiN and outer sputteredNiCrAlY were prepared on the intermetallic compoundTi₃Al-Nb. Their oxidation behavior wasexamined at 850, 900, and 950°C in air by thermalgravimetry combined with XRD, SEM, and EDAX. The resultsshowed that Ti₃Al-Nb followed approximatelyparabolic oxi dation, forming an outer thinAl₂O₃-rich scale and an inner TiO₂-rich layer doped withNb at the three temperatures. The TiO₂-richlayer doped with Nb dominated the oxidation reaction.The single NiCrAlY coating did not follow parabolicoxidation exactly at 850 and 950°C, but oxidizedapproximately in a parabolic manner, because theinstantaneous parabolic constants changed slightly withtime. Besides the Al₂O₃ scale,TiO₂ formed from the coating surface at the coating-substrate interface. Thedeterioration of the coating accelerated with increasingtemperature. The NiCrAlY-TiN coating showed two-stageparabolic oxidation at 850 and 900°C, and anapproximate parabolic oxidation at 950°C. The TiN layerwas effective as a barrier to inhibit coating-alloyinterdiffusion.     

The cyclic oxidation behavior of the single crystal TMS‐82+ superalloy in humidified air

The cyclic oxidation behavior of a single crystal Ni‐based superalloy TMS‐82+ was studied at 800 and 900 °C for 200 h in water vapor (air plus 15% H₂O). Regardless of the exposure temperature, time‐dependence of the growth rate of the scale for the superalloy was fitted by a subparabolic relationship. The oxidation rate was enhanced with increase in exposure temperature, which was evidenced by a higher mass gain and thicker scale. The oxides on the specimen at 800 °C consisted of (Ni,Co)O, CrTaO₄, AlTaO₄, Cr₂O₃, and θ‐Al₂O₃, whereas for the specimen exposed at 900 °C, spinels of NiCr₂O₄ and (Ni,Co)Al₂O₄ as well as α‐Al₂O₃ were observed. An innermost dense α‐Al₂O₃ layer was responsible for a stable growth rate of the scale after the initial rapid oxidation.     

Roles of Nb on the oxidation characteristics and oxide scale evolution of Fe-25Cr-35Ni-2.5Al-XNb alloys at 1000°C and 1100°C

The oxidation characteristics of Fe-25Cr-35Ni-2.5Al-_XNb (0, 0.6, and 1.2 wt%) alumina-forming austenitic alloys at 1000°C and 1100°C in air were investigated. Results show that Nb has an important effect on the high-temperature oxidation resistance. A bilayer oxide scale with a Cr₂O₃-rich outer layer and Al₂O₃-rich internal layer forms on the surface of the Nb-free alloy and exhibits a poor oxidation resistance at 1000°C and 1100°C. With Nb addition, both the 0.6Nb-addition and 1.2Nb-addition alloys exhibit better oxidation resistance at 1000°C. Because of the third element effect, Nb addition reduces the critical Al content and forms a single external protective Al₂O₃ scale, which greatly improves the oxidation resistance. After oxidation at 1100°C, niobium oxides (mainly Nb₂O₅) are formed on the surface of the 1.2Nb-addition alloy and destroy the integrity of the Al₂O₃ scale, which causes the formation of Cr-rich oxide nodules and eventually develops to be a loose bilayer oxide scale with NiCr₂O₄, Cr₂O₃, and Fe₂O₃ outer layers and Al₂O₃ inner layer.     

Characterization of oxide scales formed on high-velocity oxyfuel-sprayed Ni-Co-Cr-Al-Y + ReTa coatings

A high-velocity oxyfuel-sprayed 30 wt.% Ni-20 wt.% Co-30 wt.% Cr-10 wt.% Al-2 wt.% Y-4 wt.% Re-4 wt.% Ta coating was oxidized between 1000 and 1200 °C for up to 200 h in air, and the oxide scales were examined. The dense, sprayed coating consisted mainly of Cr₃Ni₂, Ni₃Al, Ni₃Ta, Ni, NiO, Al₅Y₃O₁₂, and Cr₂O₃. Intermetallics and some oxides formed during spraying. During oxidation, mainly αAl₂O₃, along with some Al₅Y₃O₁₂, CoAl₂O₄, CoCr₂O₄, Ta₂O₅, and Ta₂O_2.2 formed on the coating. The preferential oxidation of Al to form the Al-rich scales resulted in the formation of an Al-depleted region beneath the scales. Rhenium, being the most noble element, was distributed throughout the oxide scale and the coating, without forming any independent oxides.     

Oxidation and interfacial fracture behaviour of NiCrAlY/Al2O3 coatings on an orthorhombic-Ti2AlNb alloy

Al₂O₃ diffusion barriers of various thicknesses have been fabricated by filtered arc ion plating between the NiCrAlY coating and the O-Ti₂AlNb alloy. Isothermal oxidation tests and three-point bend tests have been conducted to investigate the influence of the Al₂O₃ diffusion barriers on the oxidation and interfacial fracture behaviour of the coatings. The results indicate that the Al₂O₃ diffusion barrier defers interdiffusion and gives oxidation resistance of the NiCrAlY coatings. The thickness of the Al₂O₃ interlayer not only influences the oxidation behaviour but also affects the interfacial fracture properties. Additionally, thermal exposure affects the critical load in three-point bend tests.     

Cyclic oxidation of Cr2AlC between 1000 and 1300 °C in air

Fully dense, monolithic ternary Cr₂AlC compounds were synthesized via a powder metallurgical route, and their cyclic oxidation behavior was investigated between 1000 and 1300 °C in air for up to 100 h. At 1000 and 1100 °C, Cr₂AlC displayed excellent cyclic oxidation resistance by forming a less than 5 μm-thick Al₂O₃ oxide layer and a narrow Cr₇C₃ underlayer. At 1200 and 1300 °C, an outer (Al₂O₃, Cr₂O₃)-mixed oxide layer, an intermediate Cr₂O₃ oxide layer, an inner Al₂O₃ oxide layer, and a Cr₇C₃ underlayer formed on the surface. From 1200 °C, scale cracking and spalling began to occur locally to a small extent. At 1300 °C, the cyclic oxidation resistance deteriorated owing to the formation of voids and the spallation of the scales.     

Relation between the residual stresses and the high-temperature oxidation resistance of superalloys protected by plasma-sprayed coatings. II

Previous studies on the oxidation behavior of two superalloys, IN100 and CMSX2, protected by LPPS MCrAlYTa coatings, were the basis to relate the high-temperature oxidation resistance to the oxidation stresses. Details are given on the choice of the X-ray diffraction conditions and on the calculations of the crystallographic elastic constants of each phase studied. Dilatometric tests were used to determine the expansion coefficient of the coatings and substrates; a difference in expansion creates stresses during cooling. It has not been possible to determine the Al₂O₃ oxidation stresses by X-ray diffraction on such systems. Calculations give an Al₂O₃ stress which agrees with values found by other authors in Al₂O₃, NiO, or Cr₂O₃, taking into account the differences in expansion coefficients of the various systems. The as-sprayed coatings are subjected to tensile stresses, due to the between the coating and the substrate. During oxidation, these stresses decrease, owing mainly to the interdiffusion phenomena between the coating and its substrate. This confirms that the more resistant system must consist of CoNiCrAlYTa-coated IN100.     

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.     

NiCoCrAlY coatings with and without an Al2O3/Al interlayer on an orthorhombic Ti2AlNb-based alloy: Oxidation and interdiffusion behaviors

The mechanism of oxidation protection of NiCoCrAlY overlay coatings on the orthorhombic Ti₂AlNb-based alloy (O alloy) Ti–22Al–26Nb (at.%) is described. While the bare alloy exhibited poor oxidation resistance at 800 °C, adding NiCoCrAlY coatings significantly improved the oxidation resistance. However, serious interdiffusion between the coatings and the substrate resulted in rapid degradation of the coating system. Several reaction layers were formed at the coating/substrate interface by interdiffusion, and non-protective scales mainly of Cr₂O₃ and TiO₂ were formed due to the degradation of the coating. In order to solve this problem, an Al₂O₃/Al interlayer was sandwiched into the coating system as a diffusion barrier. The isothermal and cyclic oxidation protection of the multilayer coating system on the Ti–22Al–26Nb substrate was evaluated at 800 and 900 °C. The results indicated that the interdiffusion was much suppressed, and the duplex coating system demonstrated improved oxidation resistance on the Ti–22Al–26Nb substrate, with a thin and adherent protective α-Al₂O₃ scale forming on the surface.     

Effect of Chemical Compositions and Surface Morphologies of MCrAlY Coating on Its Isothermal Oxidation Behavior

Chemical composition and surface morphology of MCrAlY coatings are factors which influence the oxidation behavior and the thermal durability of thermal barrier coatings. In this study, Cold-sprayed Ni20Cr10AlY and Ni23Co20Cr8.5Al4.0Ta0.6Y coatings with polished surfaces were employed to study the effect of composition on the oxidation behavior. The cold-sprayed MCrAlY coatings at the as-sprayed and shot-peened surface conditions, along with the low pressure plasma-sprayed MCrAlY coating with sputters adhered weakly on the surface, were employed to investigate the effects of surface morphologies of MCrAlY coatings on their oxidation behavior. Cold-sprayed Ni20Cr10AlY coating exhibited a two-stage oxidation behavior and a higher TGO growth rate than that of the cold-sprayed Ni23Co20Cr8.5Al4.0Ta0.6Y coating at the rapid growth stage. After 10-h oxidation, the TGO on the as-cold-sprayed coating surface was mainly constituted by Al₂O₃, while the TGO on the coating surface attached with sputters was composed of Al₂O₃ and Cr/Ni-oxides. After 500-h oxidation, Cr₂O₃ and porous spinel appeared in the TGO on the surface of the as-cold-sprayed coatings with different compositions. The growth of Cr/Ni-oxides was attributed to the Al depletion. The content of spinel decreased on the cold-sprayed NiCrAlY with a shot-peened surface compared with the as-sprayed 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.     

The combined effect of refractory coatings containing reactive elements on high temperature oxidation behavior of chromia-forming alloys

The high temperature oxidation behaviors of chromia-forming alloys (F17Ti and Fe-30Cr alloys) have been studied at 1273 K under isothermal conditions and at 1223 K under cyclic conditions, in air under the atmospheric pressure. To extend the oxidation lifetime, coatings have been applied onto the alloy surfaces. Al₂O₃ and Cr₂O₃ films doped with Sm₂O₃ or Nd₂O₃ were prepared via the metal-organic chemical vapor deposition technique. Single Cr₂O₃, Al₂O₃, Nd₂O₃ and codeposited Cr₂O₃-Nd₂O₃, Al₂O₃-Nd₂O₃, Al₂O₃-Sm₂O₃ coatings drastically improved the chromia-forming alloy high temperature oxidation behavior, since they decreased the oxidation rate and enhanced the oxide scale adhesion. Results showed that a critical amount of reactive element (Nd or Sm) in chromia or alumina coatings (11-18 at.%) was needed to observe the most effective effect. The fast precipitation of NdCrO₃ or NdTi₂₁O₃₈ and the segregation of reactive elements at the chromia grain boundaries slowing down outward cation transport and consequently blocking the chromia grain growth, was supposed to be the main reasons of the beneficial effect ascribed to the reactive elements in chromia scales.     

Oxidation resistance of sputtered Ni3(AlCr) nanocrystalline coating

Isothermal and cyclic oxidation resistance at 1000°C in air were investigated for a cast Cr-containing Ni₃Al-base alloy and its sputtered nanocrystalline coating. The results indicated that both the cast Ni₃Al alloy and its sputtered coating exhibit excellent isothermal oxidation resistance as a result of the formation of Al₂O₃ scales. However, the cast alloy possesses very poor cyclic oxidation resistance because of the spallation of the initially formed Al₂O₃ scale during cooling and subsequent formation of NiO. On the contrary, the sputtered Ni₃(AlCr) nanocrystalline coating exhibits very good cyclic oxidation resistance due to the significant improvement of the adhesion of Al₂O₃.     

Comparative study on dry sliding wear and oxidation performance of HVOF and laser re-melted Al0.2CrFeNi(Co,Cu) alloys

Al_0.2CrFeNiCo and Al_0.2CrFeNiCu high entropy alloys were deposited with high velocity oxygen fuel (HVOF) on 316L substrate. Later, a laser re-melting (LR) process was applied to enhancing the coating microstructure. LR process effects on dry sliding wear and oxidation behaviors were investigated. The mixture of powders with free elements led to the formation of inner oxides in HVOF coatings. The oxide and porosity were eliminated using LR. After LR, FCC was the dominant phase in both alloys, while BCC, sigma and Cr₂O₃ phases were observed in Al_0.2CrFeNiCo alloy. The hardnesses of the Al_0.2CrFeNiCo and Al_0.2CrFeNiCu coatings after HVOF were HV 591 and HV 361, respectively. After LR, the hardnesses decreased to HV 259 and HV 270, respectively. Although HVOF coatings were most affected by increased load, they showed the highest wear resistance compared to other samples. The lowest wear resistance could be seen in the substrate. After the oxidation tests, HVOF coating layer was completely oxidized and also, the coating layer was delaminated from the substrate after 50 h oxidation due to its porous structure. LR coatings exhibited better oxidation performance. Al_0.2CrFeNiCo was dominantly composed of Cr₂O₃, exhibiting a slower-growing tendency at the end of the oxidation tests, while Al_0.2CrFeNiCu was composed of spinel phases.     

Corrosion behavior of an alumina forming austenitic steel exposed to supercritical carbon dioxide

Microstructure characterization of corrosion behavior of an alumina forming austenitic (AFA) steel exposed to supercritical carbon dioxide was conducted at 450–650 °C and 20 MPa. At low temperature and short exposure times, the oxidation kinetics were parabolic and the oxide scales were mainly composed of protective and continuous Al₂O₃ and (Cr, Mn)-rich oxide layers. As the temperature and exposure time increased, the AFA steel gradually suffered breakaway oxidation and its oxide scales showed a multilayer structure mainly composed of Fe₃O₄, (Cr, Fe)₃O₄, NiFe/FeCr₂O₄/Cr₂O₃/Al₂O₃, FeCr₂O₄/Al₂O₃, and NiFe/Cr₂O₃/Al₂O₃, in sequence. The corrosion mechanism based on the microstructure evolution is discussed in detail.