Hot corrosion behavior of YSZ/ZrW2O8 composites exposed to V2O5 at 700 °C and 850 °C in air

The hot corrosion behavior of YSZ/ZrW₂O₈ composites as a promising thermal barrier coating system exposed to V₂O₅ at 700 °C and 850 °C was investigated in order to better understand the influence of the incorporated ZrW₂O₈ with isotropic negative thermal expansion performance on the corrosion resistance. Results indicate that the ZrW₂O₈ incorporation could retard the degradation of YSZ from V₂O₅ attack and the corrosion process is significantly related to the inclusion content and the temperature. The corrosion resistance could be determined by the incorporation content, while the reaction products are only temperature dependent. At 700 °C, ZrV₂O₇, YVO₄ and m-ZrO₂ were the main corrosion products, while ZrW₂O₈ recrystallized under the acidic environment provided by V₂O₅. At 850 °C, ZrW₂O₈ decomposed and only WO₃, YVO₄ and m-ZrO₂ could be detected as final corrosion products. The corrosion mechanisms of YSZ/ZrW₂O₈ composites at 700 °C and 850 °C were discussed based on the phase diagrams and Lewis acid-base rule as well as the volume compensation of the positive and negative expansion ceramics.     

Investigation of reactions between vanadium oxide and plasma-sprayed yttria-stabilized zirconia coatings

The phase evolution occurring during the reaction between corrosive V₂O₅ (T_m = 690 °C) and a plasma-sprayed 7 wt.% Y₂O₃–ZrO₂ (YSZ) coating from 700 to 900 °C has been investigated in situ by X-ray diffraction. The temperature and time of interaction between the V₂O₅ and YSZ coating determines the phases observed. Between 700 and 750 °C, reaction products of ZrV₂O₇ and YVO₄ were observed within minutes of reaching the test temperature. m-ZrO₂ was observed after 220 and 60 min at 700 and 750 °C, respectively. The simultaneous formation of both ZrV₂O₇ and YVO₄ at the beginning of the reaction along with the delay of the m-ZrO₂ formation suggests similar reactivity between both Zr and Y with V₂O₅. The weight percent of the ZrV₂O₇ phase began to diminish after 150 and 60 min at 700 and 750 °C, respectively. For reaction temperatures of 800 and 900 °C, there is a rapid decrease in the amount of t′-ZrO₂ and a rapid increase in the amount of m-ZrO₂ with reaction time. YVO₄ was also observed at these reaction temperatures. SEM and TEM microstructural observations confirmed the phases detected from the in situ XRD experiments. Reactions between YSZ and V₂O₅ suggest that the formation of a liquid phase due to the high solubility of both zirconia and yttria in vanadia is the dominate mechanism that damages the coating. The thermal conductivity of a plasma-sprayed YSZ coating reacted with up to 1 wt.% V₂O₅ did not significantly change due to the small volume affected.     

Comparison of hot corrosion behaviors of plasma-sprayed nanostructured and conventional YSZ thermal barrier coatings exposure to molten vanadium pentoxide and sodium sulfate

The purpose of the current study was evaluation and comparison of hot corrosion behaviors of plasma-sprayed conventional and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs). Hot corrosion studies were performed on the surface of coatings in the presence of a molten mixture of V₂O₅+Na₂SO₄ at 1000 °C for 30 h. Results indicated that the hot corrosion mechanisms of conventional and nanostructured YSZ coatings were similar. The reaction between corrosive salt and Y₂O₃ produced YVO₄, leaching Y₂O₃ from YSZ and causing the detrimental phase transformation of zirconia from tetragonal to monoclinic. The nanostructured coating, as compared to its conventional counterpart, in spite of a further reaction with the corrosive salt, showed a higher degradation resistance during the hot corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones.     

Hot Corrosion of Stabilized Zirconia Thermal Barrier Coatings and the Role of Mg Inhibitor

The 3–4 mol% yttria‐stabilized zirconia (YSZ) is widely used as a material for thermal barrier coating; however, the corrosive constituents present in fuel typically result in mechanical disintegration of YSZ coatings. The 3–4 mol% YSZ coatings with respective porosity of ~3% and ~22% have been undertaken with the objective to compare the hot corrosion behavior in air and sulfur‐rich atmospheres. The coatings are kept in contact with V₂O₅ + MgO powder mixture at 750°C for different dwell times of 24 and 76 h. The samples kept in air have shown intact YSZ layer for both the coatings, whereas a delamination of YSZ layer is observed for high porosity sample kept in sulfur‐rich atmosphere. XRD patterns of all the samples treated in sulfur‐rich atmosphere have indicated a phase transformation in YSZ from tetragonal to monoclinic. However, no such phase transformation has been found for samples treated in air. The V₂O₅‐induced hot corrosion attack on YSZ coating in air has been successfully inhibited by MgO, which forms a thermally stable Mg₃V₂O₈ compound. However, in sulfur‐rich atmosphere, MgO is partially consumed to form sulfates, which allows certain fraction of V₂O₅ to react with Y₂O₃ causing the degradation of top coat.     

A comparative investigation on the corrosion degradation of plasma sprayed YSZ and LnMgAl11O19 (Ln = Nd,Sm, Gd) coatings exposed to the molten V2O5 + Na2SO4 salt mixture at 1100 °C

Corrosive attack of the molten 50 wt. % V₂O₅ + 50 wt.% Na₂SO₄ salt mixture has been comparably studied for the APS YSZ and LnMgAl₁₁O₁₉ (LnMA, Ln = Nd, Sm, Gd) thermal barrier coatings upon a 10 h anneal at 1100 °C in air. The YSZ coating suffered from a deepest infiltration of the molten salt along its thickness direction through the open and connected pores as well as inter-lamellae microcracks. A large number of newly formed voids were widely distributed in the YSZ coating due to the corrosion degradation followed by the t, t’ to m-ZrO₂ phase transformation. While, a relative thin corrosion layer mainly consisting of α-Al₂O₃ and LnVO₄ were present for the corroded LnMA coatings. The much reduced number of open pores and connected microcracks together with the rapid chemical reaction between the molten salt and LnMA coatings, especially for the NdMA coating, preventing further infiltration of the molten salt, was beneficial to mitigate further attacks to the inner coating at the expense of sacrificing a thinner top layer. The presences of amorphous phases were thought to further accelerate the corrosion reaction and strengthen such a corrosion protection mode for all the APS LnMA coatings.     

Microstructural characterization of GZ/CYSZ thermal barrier coatings after thermal shock and CMAS+hot corrosion test

In this study, first, Gd₂Zr₂O₇/ceria–yttria stabilized zirconia (GZ/CYSZ) TBCs having multilayered and functionally graded designs were subjected to thermal shock (TS) test. The GZ/CYSZ functionally graded coatings displayed better thermal shock resistance than multilayered and single layered Gd₂Zr₂O₇ coatings. Second, single layered YSZ and functionally graded eight layered GZ/CYSZ coating (FG8) having superior TS life time were selected for CMAS + hot corrosion test. CMAS + hot corrosion tests were carried out in the same experiment at once. Furthermore, to generate a thermal gradient, specimens were cooled from the back surface of the substrate while heating from the top surface of the TBC by a CO₂ laser beam. Microstructural characterizations showed that the reaction products were penetrated locally inside of the YSZ. On the other hand, a reaction layer having ∼6 μm thickness between CMAS and Gd₂Zr₂O₇ was seen. This reaction layer inhibited to further penetration of the reaction products inside of the FG8.     

Thermal cycling behavior and bonding strength of single-ceramic-layer Sm2Zr2O7 and double-ceramic-layer Sm2Zr2O7/8YSZ thermal barrier coatings deposited by atmospheric plasma spraying

The single-ceramic-layer (SCL) Sm₂Zr₂O₇ (SZO) and double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZO)/8YSZ thermal barrier coatings (TBCs) were deposited by atmospheric plasma spraying on nickel-based superalloy substrates with NiCoCrAlY as the bond coat. The mechanical properties of the coatings were evaluated using bonding strength and thermal cycling lifetime tests. The microstructures and phase compositions of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that both coatings demonstrate a well compact state. The DCL SZO/8YSZ TBCs exhibits an average bonding strength approximately 1.5 times higher when compared to the SCL SZO TBCs. The thermal cycling lifetime of DCL SZO/8YSZ TBCs is 660 cycles, which is much longer than that of SCL 8YSZ TBCs (150 cycles). After 660 thermal cycling, only a little spot spallation appears on the surface of the DCL SZO/8YSZ coating. The excellent mechanical properties of the DCL LZ/8YSZ TBCs can be attributed to the underlying 8YSZ coating with the combinational structures, which contributes to improve the toughness and relieve the thermal mismatch between the ceramic layer and the metallic bond coat at high temperature.     

Thermal behaviour of multilayer and functionally-graded YSZ/Gd2Zr2O7 coatings

Zirconates with pyrochlore structure, such as Gd₂Zr₂O₇, are new promising thermal barrier coatings because of their very low thermal conductivity and good chemical resistance against molten salts. However, their coefficient of thermal expansion is low, therefore their thermal fatigue resistance is compromised. As a solution, the combination of yttria-stabilised zirconia (YSZ) and Gd₂Zr₂O₇ can reduce the thermal contraction mismatch between the thermal barrier coating parts.In the present study, two possible designs have been performed to combine YSZ/Gd₂Zr₂O₇. On the one hand, a multilayer coating was obtained where YSZ layer was deposited between a Gd₂Zr₂O₇ layer and a bond coat. On the other hand, a functionally-graded coating was designed where different layers with variable ratios of YSZ/Gd₂Zr₂O₇ were deposited such that the composition gradually changed along the coating thickness.Multilayer and functionally-graded coatings underwent isothermal and thermally-cycled treatments in order to evaluate the oxidation, sintering effects and thermal fatigue resistance of the coatings. The YSZ/Gd₂Zr₂O₇ multilayer coating displayed better thermal behaviour than the Gd₂Zr₂O₇ monolayer coating but quite less thermal fatigue resistance compared to the conventional YSZ coating. However, the functionally-graded coating displays a good thermal fatigue resistance. Hence, it can be concluded that this kind of design is ideal to optimise the behaviour of thermal barrier coatings.     

Hot corrosion behavior of double ceramic layered CaZrO3/Yttria‐stabilized zirconia coatings

A novel double ceramic layered (DCL) CaZrO₃/Yttria‐stabilized zirconia (YSZ) thermal barrier coatings (TBCs) was designed for improved service life against sulfate vanadate hot corrosion as compared with that of YSZ single layered coating. The hot corrosion behavior of DCL CaZrO₃/YSZ coatings was studied at 950°C after dry spreading 50%Na₂SO₄+50%V₂O₅ mixture onto a coated surface. The CaZrO₃ as the topmost layer in DCL CaZrO₃/YSZ coatings, served as a sacrificial layer during sulfate vanadate hot corrosion protecting the underneath YSZ coating. The corrosion reactions in this case were sluggish due to the initial formation of low melting point meta‐calcium vanadate (CaV₂O₆) that isothermally transformed to higher melting point calcium vanadates having higher calcia (CaO) content. The corrosion reaction products sealed the top surface, impeding the oxygen movement and eventually retarded the thermally grown oxide (TGO) growth. The sulfate vanadate hot corrosion life of the DCL CaZrO₃/YSZ coatings was observed to be more than double as compared with single ceramic layered YSZ coatings.     

Thermal properties of La2Zr2O7 double-layer thermal barrier coatings

La₂Zr₂O₇ is a promising thermal barrier coating (TBC) material. In this work, La₂Zr₂O₇ and 8YSZ-layered TBC systems were fabricated. Thermal properties such as thermal conductivity and coefficient of thermal expansion were investigated. Furnace heat treatment and jet engine thermal shock (JETS) tests were also conducted. The thermal conductivities of porous La₂Zr₂O₇ single-layer coatings are 0.50–0.66?W?m^?1?°C^?1 at the temperature range from 100 to 900°C, which are 30–40% lower than the 8YSZ coatings. The coefficients of thermal expansion of La₂Zr₂O₇ coatings are about 9–10?×?10^?6?°C^?1 at the temperature range from 200 to 1200°C, which are close to those of 8YSZ at low temperature range and about 10% lower than 8YSZ at high temperature range. Double-layer porous 8YSZ plus La₂Zr₂O₇ coatings show a better performance in thermal cycling experiments. It is likely because porous 8YSZ serves as a buffer layer to release stress.     

Hot-corrosion behaviors of overlay-clad yttria-stabilized zirconia coatings in contact with vanadate–sulfate salts

A dense clad overlay with chemical inertness was achieved on top of the plasma-sprayed YSZ thermal barrier coatings by laser in order to protect them from hot-corrosion attack. The Al₂O₃-clad YSZ coating exhibited good hot-corrosion behavior in contact with salt mixture of vanadium pentoxide (V₂O₅) and sodium sulfate (Na₂SO₄) for a longtime of 100 h at 1173 K. The LaPO₄-clad YSZ coating showed corrosion resistance inferior to the Al₂O₃-clad one. Yttria was leached from YSZ by reaction between Y₂O₃ and V₂O₅, which caused progressive destabilization transformation of YSZ from tetragonal (t) to monoclinic (m) phase. The chemical inertness of the clad layers and the restrained infiltration of the molten corrosive salts by the dense clad layers were primary contributions to improvement of the hot-corrosion resistances.     

Hot corrosion behavior of (Gd0.9Sc0.1)2Zr2O7 in V2O5 molten salt at 700–1000 °C

Hot corrosion behavior of (Gd_0.9Sc_0.1)₂Zr₂O₇ ceramic exposed to V₂O₅ molten salt at 700–1000 °C was investigated, providing better understanding of its corrosion resistance as a promising thermal barrier coating. Obvious corrosion reaction occurred between (Gd_0.9Sc_0.1)₂Zr₂O₇ and V₂O₅ molten salt after 4 h heat treatment, corrosion products being temperature dependent. At 700 °C, large amount of Sc₂O₃ doped ZrV₂O₇ and GdVO₄, together with a minor amount of Sc₂O₃-stabilized tetragonal ZrO₂ (t-ZrO₂), formed on the sample surfaces. With the increase of the test temperature, Sc₂O₃ doped ZrV₂O₇ turned to decompose, leading to the formation of more t-ZrO₂. At 900 °C and 1000 °C, the corrosion products were composed of GdVO₄ and t-ZrO₂. The mechanism by which the corrosion reaction occurs is proposed based on phase diagrams and Lewis acid-base rule.     

Effect of molten V2O5 salt on the corrosion behavior of micro- and nano-structured thermal sprayed SYSZ and YSZ coatings

The corrosion resistance of micro-and nano-structured scandia and yttria codoped zirconia (nano-4 mol%SYSZ and micro-8.6SYSZ) and yttria doped zirconia (4YSZ) in the presence of molten vanadium oxide were investigated. To this end, duplex TBCs (thermal barrier coatings), composed of a bond coat (NiCrAlY) and a top coat (4SYSZ or 4YSZ), were deposited on the IN738LC Ni-based supper-alloy by atmospheric plasma spraying (APS). The corrosion studies of plasma sprayed TBCs were conducted in 25 mg V₂O₅ molten salt at 910 °C for different times. The nanostructured coating, as compared to its micro-structured counterpart, in spite of a further reaction with the V₂O₅ salt, showed a higher degradation resistance during the corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones. Finally, the corrosion resistance and degradation mechanism of SYSZ and YSZ coatings were compared with the presence of molten NaVO₃ and V₂O₅ salt, respectively.     

Hot corrosion resistance of air plasma sprayed ceramic Sm2SrAl2O7 (SSA) thermal barrier coatings in simulated gas turbine environments

Samarium strontium aluminate (Sm₂SrAl₂O₇-SSA) and Yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs) were developed on NiCrAlY bond coated Inconel 718 superalloy substrate using air plasma spray process. The hot corrosion study was conducted in simulated gas turbine environments (molten mixtures of 50?wt% Na₂SO₄ + 50?wt% V₂O₅ and 90?wt% Na₂SO₄ + 5?wt% V₂O₅ + 5?wt% NaCl) for two different temperatures of 700 and 900?°C. A developed SSA TBCs showed about 8% and 22% lower lifetime at 700 and 900?°C, respectively than YSZ TBCs in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ (vanadate). The hot corrosion life of SSA TBCs being found about 13% and 39% lower than YSZ TBCs in 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl (chloride) at 700 and 900?°C, respectively. X-ray diffraction results showed the formation of SmVO₄, SrV₂O₆, and SrSO₄ as a major hot corrosion product in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ and 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl environments respectively for SSA TBCs. Similarly, YSZ TBCs also showed YVO₄ as hot corrosion product in vanadate and chloride environments. Both the TBCs suffer a more severe hot corrosion attack in chloride environment at 900?°C. The leaching of Sr²⁺ and Y³⁺ ions from SSA and YSZ respectively play a vital role in the destabilization of coating in vanadate and chloride environments at 700 and 900?°C. In both SSA and YSZ TBCs, the leaching of ion has significantly low influence as compared to attack by chloride ions at the bond coat-top coat interface in the presence of chloride environment. The hot corrosion resistance of SSA TBCs was improved three times higher in the presence of MgO and NiO inhibitor in vanadate environment at 900?°C mainly due to the formation of a stable Ni₃V₂O₈ phase at the surface.     

Hot corrosion behaviour of atmospheric and solution precursor plasma sprayed (La0.9Gd0.1)2Ce2O7 coatings in sulfate and vanadate environments

Conventional and solution precursor plasma spraying (SPPS) techniques were employed for developing gadolinium oxide doped lanthanum cerate ((La_0.9Gd_0.1)₂Ce₂O₇, Gd-LC) based double-layered thermal barrier coatings (TBCs). Hot corrosion studies of the above coatings were carried out in molten Na₂SO₄ + V₂O₅ (1:1) environment at 900 °C. The state-of-the-art yttria-stabilized-zirconia (YSZ) coating was found to be completely delaminated after 120 h by forming yttrium vanadate (YVO₄) and m-ZrO₂. The accelerated delamination of YSZ can be attributed to the undesired phase transformation during exposure to corrosive species. Double-layered APS coatings were found to last for more than 300 h without densification of underlying YSZ layer and also, show better adherence with bond coat. SPPS Gd-LC coatings were found to be completely delaminated on densifying the underlying YSZ within 300 h. Lanthanum vanadate (LaVO₄) was found to be the main corrosive product along with minor amounts of gadolinium vanadate (GdVO₄) in Gd-LC double-layer coatings.     

The influence of laser treatment on hot corrosion behavior of plasma-sprayed nanostructured yttria stabilized zirconia thermal barrier coatings

In this study, the effect of laser glazing on the hot corrosion behavior of nanostructured thermal barrier coatings (TBCs) was investigated. To this end, the hot corrosion test of plasma-sprayed and laser-glazed thermal barrier coatings conducted against 45 wt.% Na₂SO₄ + 55 wt.% V₂O₅ molten salt at 910 °C for 30 h in open air atmosphere. The results obtained from hot corrosion test showed that the reaction between Y₂O₃ and the corrosive salt produced YVO₄, leached Y₂O₃ from YSZ and led to the progressive destabilization transformation of YSZ from tetragonal to the monoclinic phase. The lifetimes of the plasma-sprayed TBCs were enhanced approximately twofold by laser glazing. Reducing the reactive specific surface area of the dense glazed layer with the molten salts and improving the stress accommodation through network cracks produced by laser glazing were the main enhancement mechanisms accounting for TBC life extension.     

Thermodynamics of reaction between gas-turbine ceramic coatings and ingested CMAS corrodents

The thermodynamic stability of ceramic coatings with respect to their reaction products is crucial to develop more durable coating materials for gas-turbine engines. Here, we report direct measurements using high-temperature solution calorimetry of the enthalpies of reaction between some relevant ceramic coatings and a corrosive molten silicate. We also report the enthalpy of mixing between the coatings and molten silicate after combining the results measured by high-temperature solution calorimetry with enthalpies of fusion measured by drop-and-catch calorimetry and differential thermal analysis. The enthalpies of solution of selected silicate and zirconia-based coatings and apatite reaction products are moderately positive except for 7YSZ, yttria-stabilized zirconia. Apatite formation is only favorable over coating dissolution in terms of enthalpy for 7YSZ. The enthalpies of mixing between the coatings and the molten silicate are less exothermic for Yb₂Si₂O₇ and CaYb₄Si₃O₁₃ than for 7YSZ, indicating lower energetic stability of the latter against molten silicate corrosion. The thermochemical results explain and support the very corrosive nature of CMAS melts in contact with ceramic coatings.     

The mechanical and thermal properties,CMAS corrosion resistance,and the wettability of novel thermal barrier material GdTaO4

Because the CMAS corrosion and phase transformation at elevated temperatures above 1250 °C have limited the applications of traditional YSZ, the design of novel thermal barrier materials is a hotspot. GdTaO₄ is considered as a type of potential novel thermal barrier material owing to its low thermal conductivity. In this study, the mechanical and thermal properties, CMAS corrosion resistance, and the wettability of the GdTaO₄ were studied and compared with that of YSZ. The results show that the coefficient of thermal expansion and hardness of GdTaO₄ are 14.1 × 10⁻⁶ K⁻¹ (1350 °C) and 534.2 Hv_0.3 respectively. The thickness of CMAS reaction layer of GdTaO₄ is ~30.8 μm after 24 h reaction at 1350 °C, which is thinner than that of YSZ. After corrosion reaction, the CMAS glass aggregated instead of completely disappearing or continuously extending over the surface of GdTaO₄. The main reaction product is Ca₂Ta₂O₇, and the anorthite phase may not be detected, which is similar to YTaO₄. By comparison, the dense substrate of YSZ became porous and CMAS glass has disappeared after 10 h. CMAS corrosion at 1350 °C. The on-line contact angle results show that the wettability of CMAS on GdTaO₄ is worse than that on YSZ at 1350 °C, while the opposite of the work of adhesion, which indicates that GdTaO₄ can remove liquid CMAS more easily than YSZ TBCs during the service. Furthermore, the corrosion depth and areas of GdTaO₄ are smaller than those of YSZ in the same situation. These findings suggest that GdTaO₄ possesses better high-temperature properties and CMAS corrosion resistance than YSZ as a kind of potential of thermal barrier material.     

Thermal cycling and hot corrosion behavior of a novel LaPO4/YSZ double-ceramic-layer thermal barrier coating

LaPO₄ powders were produced by a chemical co-precipitation and calcination method. The ceramic exhibited a monazite structure, kept phase stability at 1400?°C for 100?h, and had low thermal conductivity (~ 1.41?W/m?K, 1000?°C). LaPO₄/Y₂O₃ partially stabilized ZrO₂ (LaPO₄/YSZ) double-ceramic-layer (DCL) thermal barrier coatings (TBCs) were fabricated by air plasma spray. The LaPO₄ coating contained many nanozones. Thermal cycling tests indicated that the spallation of LaPO₄/YSZ DCL TBCs initially occurred in the LaPO₄ coating. The failure mode was similar to those of many newly developed TBCs, probably due to the low toughness of the ceramics. LaPO₄/YSZ DCL TBCs were highly resistant to V₂O₅ corrosion. Exposed to V₂O₅ at 700–900?°C for 4?h, La(P,V)O₄ formed as the corrosion product, which had little detrimental effect on the coating microstructure. At 1000?°C for 4?h, a minor amount of LaVO₄ was generated.