Evolution of hot corrosion resistance of conventional CSZ and MoSi2 self-healing thermal barrier coatings in Na2SO4+V2O5 at 950 °C

ZrO₂-based hot corrosion-resistant thermal barrier coatings (TBCs) with MoSi₂+Al₂O₃ have gained increasing attention. In this research, a novel dual-layer TBC (CSZ: ZrO₂-25 wt% CeO₂-2.5 wt% Y₂O₃/MAC: MoSi₂ + Al₂O₃ + CSZ) was developed, and its hot corrosion was compared to a single-layer CSZ. The atmospheric plasma spray (APS) process was utilized to apply CSZ/MAC and CSZ TBCs on NiCrAlY, as a bond coat to nickel-based superalloy (IN738LC). Different investigations, including hot corrosion test, field emission scanning electron microscopy (FESEM/EDS), and X-ray diffraction (XRD) analyses, were used to reveal why the MAC overlayer improves the CSZ hot corrosion behavior. A medium of Na₂SO₄-55 wt% V₂O₅ was used to analyze the hot corrosion; a temperature of 950 °C for 2 h was considered in every single cycle. The results exposed that there is a big difference between the hot corrosion resistance of the dual-layer CSZ/MAC TBC in comparison with the single-layer CSZ. Based on the FESEM analysis, this can be related to the very low diffusion of Na₂SO₄-55 wt% V₂O₅ into the dual-layer TBC where the infiltration of aggressive molten salt was diminished. According to the XRD results, two reasons are leading to the degradation of the aforementioned TBCs: (i) the tetragonal to the monoclinic transformation of ZrO₂ and (ii) the formation of hot corrosion products, i.e., CeVO₄ and YVO₄ crystals.     

Hot corrosion behavior of V2O5-coated Gd2Zr2O7 ceramic in air at 700–850 °C

Gd₂Zr₂O₇ ceramic was prepared by solid state reaction at 1650 °C for 10 h in air, and exhibited a defect fluorite-type structure. Reaction between molten V₂O₅ and Gd₂Zr₂O₇ ceramic was investigated at temperatures ranging from 700 to 850 °C using an X-ray diffractometer (XRD) and scanning electron microscopy (SEM). Molten V₂O₅ reacted with Gd₂Zr₂O₇ to form ZrV₂O₇ and GdVO₄ at 700 °C; however, in a temperature range of 750–850 °C, molten V₂O₅ reacted with Gd₂Zr₂O₇ to form GdVO₄ and m-ZrO₂. Two different reactions observed at 700 °C and 750–850 °C could be explained based on the thermal instability of ZrV₂O₇.     

Interactions of Na2SO4 and yttrium-silicate environmental barrier coatings at 825°C

Yttrium-silicates (Y₂Si₂O₇ and Y₂SiO₅) are candidate environmental barrier coating (EBC) materials for silicon carbide ceramic matrix composites (SiC-CMCs). These materials’ high-temperature, high-velocity steam, and siliceous debris resistance are well studied. However, Na₂SO₄-induced hot corrosion mechanisms are less understood. Free-standing atmospheric plasma sprayed Y₂Si₂O₇ and Y₂SiO₅ coupons were exposed to 2.5 mg/cm² of Na₂SO₄ at 825°C in 0.1% SO₂-O₂ (g). Scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and inductively coupled plasma-optical emission spectrometry were used to identify a previously unknown damage mechanism. Water-soluble Y and Na-Y sulfates and oxysulfates formed in reaction with Na₂SO₄, causing significant damage to the yttrium-silicate EBCs materials.     

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.     

Failure mechanisms of (Gd0.9Yb0.1)2Zr2O7/Yb2SiO5/Si thermal/environmental barrier coatings during thermal exposure at 1300 °C/1400 °C

A novel tri-layer (Gd_0.9Yb_0.1)₂Zr₂O₇/Yb₂SiO₅/Si (GYbZ/YbMS/Si) thermal and environmental barrier coatings (TEBCs) was first proposed for protecting SiC-based ceramic matrix composites (CMCs). Wherein, the GYbZ layer by plasma spray physical vapor deposition (PS-PVD) was quasi-columnar structured while the YbMS and the Si layers by atmospheric plasma spray (APS) were lamellar structured. The oxidation behavior and the failure mechanisms of the GYbZ/YbMS/Si TEBCs at 1300 °C/1400 °C are revealed. At 1300 °C, the mud-cracks penetrated through the GYbZ/YbMS layer and transversely deflected in the Si layer are responsible for the oxidation at YbMS/Si interface. When the temperature increased to 1400 °C, the propagation of mud-cracks, cavities, and TGO channel cracks occurred due to the sintering of GYbZ and the fast growth of cristobalite. Eventually, these defects caused delaminating failure at interface. Moreover, another de-bonding failure of the coating was observed resulting from the significant thickening of oxide scale at the edge region.     

Synthesis and thermal stability of Re2Zr2O7, (Re = La,Gd) and La2(Zr1−xCex)2O7−δ compounds under reducing and oxidant atmospheres for thermal barrier coatings

Rare-earth zirconates and cerates have attracted particular interest for thermal barrier coating (TBC) applications due to their advantageous thermal properties, such as a low conductivity and efficient phase stability at elevated temperatures. This study focuses on synthesising La₂Zr₂O₇, Gd₂Zr₂O₇, La₂Ce₂O_7?γ and La₂(Zr_0.7Ce_0.3)O_7?γ compounds via two soft chemistry processes, alkoxide and citrate synthesis. Thermal analysis, X-ray diffraction (XRD) and scanning electron microscope observations were used to analyse the powder after calcinations under air. Chemical reactivity tests under a reducing atmosphere were performed at 1400 °C and investigated by XRD analysis. It was found that the lanthanum and gadolinium zirconates are the most stable and interesting materials under an Ar_(g)/3%H_2(g) atmosphere.     

The corrosion behaviors of thermal barrier material of M-YTaO4 attacked by CMAS at 1250 °C

The corrosion of YSZ TBCs attacked by calcium–magnesium–aluminosilicate (CMAS) is a serious problem. Yttrium tantalite (YTaO₄), a new kind of potential thermal barrier ceramic material, was expected to replace the YSZ to manufacture the TBCs because of its great thermophysical characteristics. In this study, porous YTaO₄ ceramic pellets, instead of actual TBCs, were used to investigate the CMAS corrosion resistance at 1250 °C. Results indicated that CMAS couldn't cover the whole surface of YTaO₄ pellets homogeneously because of low wettability between liquid CMAS and YTaO₄, in addition, there was almost no reaction layer after 4 h reaction. The XRD results showed that M-YTaO₄, M′-YTaO₄, Ca₂Ta₂O₇ and Y₂Si₂O₇ were the main four phases after reaction and there was no phase containing the elements of Mg and Al. Compared with YSZ TBCs, this new kind of potential thermal barrier ceramic material showed well resistance to CMAS corrosion.     

Thermal cycling performance of La2Ce2O7/50 vol.% YSZ composite thermal barrier coating with CMAS corrosion

La₂Ce₂O₇ (LC) is receiving increasing attention due to its lower thermal conductivity, better phase stability and higher sintering resistance than yttria partially stabilized zirconia (YSZ). However, the low fracture toughness and the sudden drop of CTE at approximately 350?°C greatly limit its application. In this study, the LC/50?vol.% YSZ composite TBC was deposited by supersonic atmospheric plasma spraying (SAPS). Compared to YSZ or double layered LC/YSZ coating, the thermal cycling life of LC/50?vol.% YSZ coating with CMAS attack increased by 93% or 91%. The latter possessed higher fracture toughness (1.48?±?0.26?MPa?m^1/2) than LC (0.72?±?0.15?MPa?m^1/2) and better CMAS corrosion resistance than YSZ owing to the formation of Ca₂(La_xCe_1-x)₈(SiO₄)₆O_6–4x with <001> orientation perpendicular to the coating surface. The sudden CTE decrease of LC was fully suppressed in LC/50?vol.% YSZ coating due to the change of temperature dependent residual stresses induced by YSZ.     

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.     

Hot corrosion of V2O5-coated NdMgAl11O19 ceramic in air at 950 °C

NdMgAl₁₁O₁₉ ceramic was prepared by solid-state reaction at 1700 °C for 10 h in air, and exhibited a single phase of magnetoplumbite structure. Reaction between molten V₂O₅ and NdMgAl₁₁O₁₉ was investigated at 950 °C using an X-ray diffractometer, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Molten V₂O₅ reacts with NdMgAl₁₁O₁₉ to form α-Al₂O₃, NdVO₄ and MgAl₂O₄ at 950 °C in air. After hot corrosion at 950 °C for 50 h, α-Al₂O₃ is the main corrosion product. The thickness of the corrosion layer gradually increases with increasing corrosion time from 10 to 50 h.     

Evolution mechanism of the microstructure and mechanical properties of plasma-sprayed yttria-stabilized hafnia thermal barrier coating at 1400 °C

Yttria stabilized hafnia (Hf_0.84Y_0.16O_1.92, YSH16) coatings were sprayed by atmospheric plasma spraying (APS). The effects of thermal aging at 1400 °C on the microstructures, mechanical properties and thermal conductivity of the coatings were studied. The results show that the as-sprayed coating was composed of the cubic phase, and the nano-sized monoclinic (M) phase was precipitated in the annealed coating. The presence of M phase effectively constrained the sintering of the coating due to its superior sintering-resistance. The Young's modulus kept at a nearly same level of ~78 GPa even after annealing, and the coating annealed for 6 h yielded a maximum value of hardness but revealed a declining tendency in the Vicker's hardness with prolonged sintering time. The thermal conductivity increased from 0.8-0.95 W m^-1 K^-1 at as-sprayed state to 1.6 W m^-1 K^-1 after annealing at 1400 °C for 96 h. The dual-phase coating is promising to serve at temperatures above 1400 °C due to its excellent thermal stability and mechanical properties.     

Hot corrosion behavior of Cr2AlC MAX phase and CoNiCrAlY compounds at 950 °C in presence of Na2SO4+V2O5 molten salts

In this research, a high-purity Cr₂AlC MAX phase sample was prepared via spark plasma sintering (SPS) method with the hot corrosion behavior investigated in the presence of Na₂SO₄+V₂O₅ molten salts at 950 °C. Also, the hot corrosion resistance of this MAX phase was compared with a hot corrosion-resistant SPS-processed CoNiCrAlY sample. The results of the hot corrosion test after 30 h revealed that the MAX phase sample has better hot corrosion resistance compared to CoNiCrAlY sample. According to the results, corrosion kinetics of Cr₂AlC sample followed near-cubic law with diffusion occurring along the grain boundaries. On the other hand, CoNiCrAlY sample followed parabolic kinetics where the diffusion of reactants occurred through the oxide scale. The results indicated that in the Cr₂AlC sample, upon exposure time prolongation, a dense and uniform Cr-rich alumina layer was formed in the surface and Cr₇C₃ phase was created as a sub-layer, while in the CoNiCrAlY sample the oxide layer contained Al₂O₃ and porous spinel oxide phases. In the CoNiCrAlY sample, a considerable volume change and stress occurred during the non-uniform growth of spinel oxide causing the formation of defects such as microcracks which deteriorate its hot corrosion resistance.     

Thermal stability of nanostructured 13 wt% Al2O3–8 wt% Y2O3–ZrO2 thermal barrier coatings

Nanostructured 13 wt% Al₂O₃–8 wt% Y₂O₃–ZrO₂ (13AlYSZ) coatings were developed by atmospheric plasma spraying (APS). The phase structure and the morphology of the 13AlYSZ coatings were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). It was found that the as-sprayed coatings mainly consisted of tetragonal zirconia, with the Al element solid solution in ZrO₂. Heat treatment at 1100 °C increased the average grain size of the ZrO₂ phase from 61 to 120 nm and decreased the porosity from 23.8 to 18%. The addition of the nano-Al₂O₃ can effectively inhibit the grain growth of the zirconia phase. The mechanism on inhibiting the grain growth of nanostructured 8 wt% Y₂O₃–ZrO₂ thermal barrier coatings has been discussed in detail.     

Effect of Al addition on creep resistance of MgO-Al2O3 composite for sliding plate at 1400 °C

MgO-Al₂O₃ composites were prepared using fused magnesia, α-Al₂O₃ micropowder, tubular alumina, metal aluminum and sintered magnesia as raw materials, magnesium aluminate sol as the binder. The creep resistance test was conducted at 1400 °C under 0.2 MPa with insulation for 50 h. The specimens after creep resistance test were characterized and analyzed by XRD, SEM, and EDS to investigate the effect of adding metal aluminum powder on the creep resistance of magnesia based composites as well as its mechanism. The results show that Al-MgO-Al₂O₃ composite has better creep resistance than MgO-Al₂O₃ composite. Power Al is more reactive than AlN, adding Al function is to accelerate both spinel solid solution(containing MgAlON) and AlN-polytype, both are reinforcement phase for MgO-Al₂O₃ composite. The mechanism that metal Al powder improves the creep resistance of the specimen M₂ can be expressed as follows：An oxygen concentration gradient exists in the specimen M₂ from the external areas to the internal areas. The Al in external areas is oxidized into Al₂O₃ and further solid-solves with MgO forming MgAl₂O₄. The oxidation of Al leaves shell structures which can bear some compressive stress, restraining the volume shrinkage. When the oxygen concentration is low, Al is nitrided forming reinforcing phases such as AlN polytype and lamellar-structure MgAlON with reticular distribution, restraining the volume shrinkage of specimen M₂.     

Effects of sintering additives on hot corrosion behavior of γ-Y2Si2O7 ceramics in Na2SO4+V2O5 molten salt

Dense γ-Y₂Si₂O₇ ceramics were prepared by moulding and sintering of pure γ-Y₂Si₂O₇ powders synthesized by adding various additives. Effects of sintering additives on hot corrosion behavior of γ-Y₂Si₂O₇ ceramics in Na₂SO₄ + V₂O₅ molten salts were systematically investigated. Chemical kinetics of corrosion process was also calculated to illuminate the influence of different additives on chemical stability. Results showed that corrosion reaction started at grain boundary due to the loose microscopic network. When the intercrystalline glass phase was completely etched, the molten salts began to contact Y₂Si₂O₇, forming NaY₉Si₆O₂₆ and YVO₄. Compared with Li₂O and MgO, intercrystalline glass phase formed by Al₂O₃ additive had the most compact microscopic network structure, leading to the best chemical stability. Apparent activation energy for hot corrosion reaction of γ-Y₂Si₂O₇ ceramics in pure Na₂SO₄, Na₂SO₄ + 5 wt% V₂O₅, Na₂SO₄ + 10 wt% V₂O₅, Na₂SO₄ + 15 wt% V₂O₅ molten salts was calculated to be 408.16, 373.60, 310.62, and 249.63 kJ/mol, respectively.     

Thermal cycle test performances of environmental barrier coatings of HfO2-SiO2/Yb2Si2O7 in the steam environment at 1475 °C

The novel bi-layer environmental barrier coatings (EBCs) with HfO₂-SiO₂/Yb₂Si₂O₇ structure (70HfO₂-30SiO₂/Yb₂Si₂O₇: 70HS/YbDS, 50HfO₂-50SiO₂/Yb₂Si₂O₇: 50HS/YbDS, molar ratios) was tested in 90%H₂O–10%O₂ conditions between room temperature and 1475 °C in an Al₂O₃ tube furnace, then its performance was evaluated. The YbDS layer was contaminated by alumina impurities under steam conditions. After 22 cycles, the 70HS/YbDS completely separated from the SiC substrate, while the 50HS/YbDS and SiC did not separate, even though cracks formed at the 50HS/SiC interface and the TGO layer. Furthermore, the thermally grown oxide (TGO) layer formed at the HfO₂-SiO₂/SiC interface. Formation and growth of the TGO led to the formation and propagation of cracks at the HfO₂-SiO₂/TGO interface and TGO interior, which was the culprit leading to the failure of EBCs. These results demonstrated that the 50HS/YbDS EBCs have the potential to protect SiC in steam conditions at 1475 °C.     

Hot corrosion behavior of CoWSi/WSi2 coating exposed to Na2SO4+NaCl salt at 900 °C

In this study, the high temperature hot corrosion behavior of a CoWSi/WSi₂ composite coating was investigated. Hot corrosion studies were performed on CoWSi/WSi₂ coated nickel specimens after exposure to a molten Na₂SO₄+NaCl salt environment at 900 °C under cyclic conditions. Thermogravimetric technique was used to establish the kinetics of corrosion. XRD and SEM/EDS techniques were used to analyze the corrosion products. The oxide scale formed on the coating surface was complex and the hot corrosion resistance of coating may be attributed to the formation of oxides and spinels of silicon, cobalt and tungsten. Also, NaCl accelerated the degeneration of the coating because of producing the volatile CoCl₂ and thereby oxygen and sulfur could easily penetrate into the coatings and caused the formation of internal oxide and sulfide.     

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.     

Hot corrosion behavior of Y4Al2O9 ceramics for thermal barrier coatings exposed to calcium-magnesium-alumina-silicate at 1250 °C

The degradation of thermal barrier coatings (TBCs) by calcium-magnesium-alumina-silicate (CMAS) attack has become increasingly dramatic. Y₄Al₂O₉ ceramic, a new potential TBC candidate, has received an increasing attention. In this study, porous Y₄Al₂O₉ ceramic pellets, instead of actual TBCs, are used to investigate the CMAS corrosion resistance at 1250 °C. Results indicate that Y₄Al₂O₉ reacts with CMAS melt to form an impervious sealing layer mainly containing Ca-Y-Si apatite, which could mitigate CMAS further penetration. Once the sealing layer formed, further reaction would occur above the layer accompanying by the recession of sealing layer. This process is probably related to a solid state diffusion.     

Novel synthesis and thermal property analysis of MgO–Nd2Zr2O7 composite

MgO-Nd₂Zr₂O₇composites with ratios of 50–70 vol% MgO were produced via a one-pot combustion synthesis. A suite of characterization techniques, including X-ray diffraction, scanning and transmission electron microscopy were employed to investigate the structural properties while dilatometry, simultaneous thermal analysis and laser flash analysis were used to characterize the thermal properties of the composites. Dense pellets were produced after sintering at 1400 °C with grain sizes between 200 and 500 nm for both phases. The thermal properties of the composites are similar to those produced using standard methods. The composite with 70 vol% MgO was found to have the highest thermal conductivity below 1000 °C, while above this temperature the thermal conductivity was found to be similar and independent of MgO content. This novel synthesis route produces materials which show significant improvements in homogeneity with smaller particle sizes when compared to current standard synthesis techniques without significantly reducing thermal conductivity.