Calcium-magnesium-alumino-silicate Research Articles

Thermochemical compatibility between Hf6Ta2O17 and Al2O3 at high temperatures for thermal barrier coatings

Hf6Ta2O17 is a potential high-temperature thermal barrier coating (TBC) material with better high-temperature stability and calcium magnesium aluminosilicate (CMAS) resistance than yttria-stabilized zirconia (YSZ). However, the high-temperature compatibility between Hf6Ta2O17 and the thermally grown oxide (mainly α-Al2O3) has not been clarified. The thermochemical compatibility between Hf6Ta2O17 and Al2O3 was investigated by annealing Hf6Ta2O17-Al2O3 composite powders and Al2O3/Hf6Ta2O17 diffusion couples at 1300–1600 °C. At 1300 °C, Hf6Ta2O17 and Al2O3 do not react. Above 1400 °C, Hf6Ta2O17 reacts with Al2O3 to form AlHf3TaO10, forming an intermediate phase layer at the Al2O3/Hf6Ta2O17 interface. The layer thickness gradually increases as the annealing time rises, and Al diffusion causes micro-voids at the Al2O3/AlHf3TaO10 interface. The thermal expansion coefficient of AlHf3TaO10 is much lower than that of Hf6Ta2O17 and Al2O3, resulting in high interfacial thermal stresses. The thermochemical incompatibility between Hf6Ta2O17 and Al2O3 above 1400 °C may exacerbate the failure of Hf6Ta2O17-based TBCs.

The Potential for High Temperature Corrosion in the Naval Operating Environment

In the marine environment, it is especially crucial to have reliable, high-temperature, propulsion materials that will enable increased capabilities, improved engine efficiency, reduced fuel costs, and decreased maintenance/total life cycle costs. Propulsion materials need to resist oxidation, various forms of corrosion, or alternating cycles of oxidation and corrosion. Exploring the creation and development of propulsion materials involves, in part, the understanding of kinetics and thermodynamics of materials interactions and materials stability under marine operating environments and temperatures. In the naval environment, one needs to establish the mechanisms of simple and complex thermochemical and thermomechanical interactions of materials, such as hot corrosion and CMAS (calcium-magnesium-alumino-silicate) attack; and to advance life prediction of both existing and new materials under these scenarios. Most papers in the literature since the 1970s consider sodium sulfate salt as the single specie contributing to hot corrosion. Recent Navy standards for Navy F-76 and similar fuels have dropped the sulfur content down to 15 parts per million (ppm) which many believe will end hot corrosion. However, the deposit chemistry influencing hot corrosion is known to be much more complex consisting of multiple sulfates and silicates. Sulfur species may still enter the combustion via ship’s air intake, which may include seawater entrained in the air. In addition to sodium sulfate, seawater contains magnesium, calcium and potassium salts, and atmospheric contaminants that may contribute to hot corrosion. This paper will cover some of the revised understanding of various forms of various forms of corrosion than may be encountered in Naval gas turbine engines.

Failure behavior study of EB-PVD TBCs under CMAS corrosion and thermal shock cycles

Abstract Calcia-magnesia-alumino-silicate (CMAS) erosion has become a major obstacle, limiting the operating temperature and service life of Thermal barrier coatings (TBCs) in aircraft engines. Constructing simulation environments that replicate TBCs’ working conditions and exploring online, non-destructive detection techniques are reliable approaches to studying coatings’ failure, representing both a global research hotspot and a challenge in this field. The paper presents an initial endeavor to establish a simulation experiment for TBCs in aviation-engine within a CMAS environment. Experimental results show that electron beam physical vapor deposition (EB-PVD) Y2O3-stabilized ZrO2 (YSZ), one of the mainstream TBCs technologies, produced 20% surface spallation after 50 thermal-shock cycles under simulated CMAS corrosion conditions. Testing and analysis of the macroscopic and microscopic structures of the failed samples, combined with SEM, EDS, and XRD findings, revealed significant physical and chemical interactions between the ceramic layer and CMAS deposits, as well as phase transformation within the coatings, leading to substantial alterations in mechanical properties and ultimately causing the failure of EB-PVD YSZ.

A systematic study of thermomechanical properties and calcium–magnesium–aluminosilicate (CMAS) corrosion of multicomponent rare-earth phosphates

A systematic study of thermomechanical properties and calcium–magnesium–aluminosilicate (CMAS) corrosion of multicomponent rare-earth phosphates

High-entropy engineering improved the corrosion resistance of rare earth tantalates

High-entropy RETa3O9 ceramics have garnered significant interest in materials science due to their impressive high melting points and lower thermal conductivity. This study focuses on three types of these ceramics: (La0.2Ce0.2Nd0.2Sm0.2Dy0.2)Ta3O9, (La0.2Ce0.2Nd0.2Sm0.2Tm0.2)Ta3O9, and SmTa3O9.The results indicate that the coefficient of thermal expansion (TEC) for RETa3O9 ceramics remains in the range of approximately 5.94×10-6 K-1 to 6.05×10-6 K-1 when subjected to temperatures from room temperature up to 1400°C. This TEC is notably similar to that of silicon carbide ceramic matrix composites (SiC-CMC), which is essential for compatibility in applications where these materials are used together.Moreover, the study highlights an important finding: after 20 hours of exposure to a CMAS (calcium-magnesium-alumino-silicate) environment at 1300°C, the high-entropy tantalates exhibit significantly reduced susceptibility to corrosion compared to traditional single-component tantalate ceramics. While single-component materials, including SmTa3O9, showed greater degradation, the high-entropy RETa3O9 ceramics maintained their original morphology, free from porosity and cracking.This impressive resistance to CMAS corrosion indicates that the high-entropy design is beneficial in enhancing the durability of tantalates in extreme environments. Consequently, these findings suggest that high-entropy RETa3O9 ceramics hold promise for use as thermal/environmental barrier coating (T/EBC) materials in applications involving SiC-CMCs, potentially leading to improved performance and longevity in high-temperature applications.

Composition engineering of high-entropy rare-earth monosilicates enables remarkable CMAS corrosion resistance

Exploring superior calcium-magnesium-aluminosilicate (CMAS) corrosion resistance is crucial for high-entropy rare-earth monosilicates (HEREMs) as the next-generation environmental barrier coating (EBC) materials. However, related studies are rarely reported. This work presents the exploration of HEREMs with remarkable CMAS corrosion resistance by engineering their compositions. The equimolar 3-to-9 cation high-entropy rare-earth monosilicate (3-9HEREM) specimens were initially prepared using a pressure-less sintering technique; subsequently, their resistance to CMAS corrosion was evaluated at temperatures up to 1,600 °C. The results demonstrate that the 5HEREM specimens possess the best CMAS corrosion resistance among all the as-fabricated specimens, surpassing other reported EBC materials. Such remarkable CMAS corrosion resistance results from the generation of a dense apatite protective layer originating from its low dissolution rate at elevated temperatures.

Influence of Ti3AlC2 additions on CMAS corrosion resistance of porous LaMgAl11O19 abradables

The corrosion of calcium-magnesium-aluminosilicate (CMAS) is a critical degradation mechanism for the hot sections of aircraft engines, particularly affecting abradable components where inherent defects complicate the prevention of rapid CMAS melt penetration. To address this challenge, Ti3AlC2 was incorporated into the porous LaMgAl11O19 abradables at concentrations of 5–20 wt% as both a self-healing agent and sintering aid. Annealing at 1200 °C markedly improved crack closure and pore isolation within the coating, with these effects intensifying with higher Ti3AlC2 concentrations, and resulted in the retention of excess TiO2. CMAS interaction tests conducted at 1300 °C demonstrated that only the abradables with 20 wt% Ti3AlC2 addition significantly reduced the penetration of CMAS melt. This effect is attributed to the densification of the abradables caused by self-healing, which blocks the propagation of CMAS along defect channels, and the role of TiO2 as a nucleating agent that facilitates the crystallization of CMAS and the precipitation of CaAl2Si2O8. The La/Ca ratio in the solid solutions related to LaMgAl11O19 and LaTi2Al9O19 can be used to reflect the corrosion level of platelet-like grains, where a value below 1 is likely to trigger their dissolution.

Corrosion resistance of multicomponent disilicate (Ho0.2Er0.2Tm0.2Yb0.2Lu0.2)2Si2O7 against CMAS and volcanic ash

With the increasing operating temperature of gas turbine engines, calcium-magnesium-aluminosilicate (CMAS) poses a serious threat on environmental barrier coatings (EBCs) applied on hot-sections of aero-engines. Here, we have synthesized a novel multicomponent disilicate—(Ho0.2Er0.2Tm0.2Yb0.2Lu0.2)2Si2O7 (brief to (5RE0.2)2Si2O7), and comparatively studied its performance in the presence of synthesized CMAS and natural volcanic ash at 1400ºC. In comparison with Yb2Si2O7, (5RE0.2)2Si2O7 has a shorter Si-O bond length and a larger RE-O bond length because of the larger average RE3+ radius. After CMAS corrosion, some apatite grains precipitate at the CMAS/(5RE0.2)2Si2O7 interface to develop a loose reaction layer, exhibiting a higher corrosion resistance than Yb2Si2O7. Meanwhile, the consumption of CaO and release of SiO2 during the chemical reaction process increase the viscosity of CMAS to some extent and thus weaken its infiltration propensity. For the volcanic ash case, it directly infiltrates into the interior of (5RE0.2)2Si2O7 along grain boundaries without any reaction due to the relatively low CaO content, exhibiting a more serious attacking behavior. In addition, (5RE0.2)2Si2O7 effectively increases the contact angle of molten volcanic ash due to its lower surface energy. These finds here provide a better understanding for the design and application of next-generation EBC material.

Micro-Nano Dual-Scale Coatings Prepared by Suspension Precursor Plasma Spraying for Resisting Molten Silicate Deposit

Yb-doped Y2O3 stabilized ZrO2 (YbYSZ) coatings, developed through solution precursor plasma spraying (SPPS), are engineered to resist calcium–magnesium–alumino–silicate (CMAS) infiltration by leveraging their unique micro-nano structures. This provides superior anti-wetting properties, crucial for preventing CMAS penetration at high temperatures. The investigation focused on the structural and compositional changes in YbYSZ-SPPS coatings subjected to prolonged thermal exposure at 1300 °C. Results indicate that while the coatings undergo significant sintering, leading to densification and microstructural evolution, the elemental composition and phase stability remain largely intact after up to 8 h of heat treatment. Despite some reduction in CMAS resistance, the coatings maintained their overall protective performance, demonstrating the potential of SPPS coatings for long-term use in high-temperature environments where CMAS infiltration is a concern. These findings contribute to the development of more durable TBCs for advanced thermal protection applications.

Degradation of LaPO4-8YSZ composite thick thermal barrier coatings by molten calcium-magnesium-aluminosilicate

The effect of LaPO4 content on the calcium-magnesium-aluminosilicates (CMAS) corrosion resistance of the plasma-sprayed LaPO4-8YSZ composite coatings at 1250 °C was investigated. The microstructure and corrosion products of the LaPO4-8YSZ composite coatings after CMAS attack was determined by using SEM/TEM/SAED. The results indicated that LaPO4 was segregated at the grain boundaries of the composite coatings and the addition of LaPO4 into 8YSZ coating increased their CMAS reactivity, which led to the formation of planar reaction zone while the CMAS infiltration depth decreased from ∼658 μm to ∼119 μm. The CMAS infiltration depth of the composite coatings firstly increased with LaPO4 addition, reaching its maximum for the composite coating with 5 wt% LaPO4, and then showed a downtrend. For the composite coating with 20 wt% LaPO4, a dense apatite layer formed in the corrosion front, which inhibited CMAS penetration and resulted in the shallowest CMAS infiltration depth among the test samples.

Thermochemical interaction of (Yb0.7Gd0.3)4Hf3O12 ceramic with CMAS melts

The molten calcium-magnesium alumino-silicate (CMAS) deposits degradation of thermal barrier coatings (TBCs) is increasingly severe in advanced turbine engines. In this study, the thermochemical interaction of a promising TBC candidate material, (Yb0.7Gd0.3)4Hf3O12, with CMAS melts at 1300 ℃ and 1500 ℃ was systematically investigated. The apatite and reprecipitated fluorite with high melting points were crystallized rapidly when the ceramic reacted with CMAS melts, resulting in the formation of a dense crystalline layer to suppress further infiltration of CMAS melts. Moreover, as the reaction proceeded, the formation of garnet and cuspidine occurred at 1300 ℃ and 1500 ℃, respectively. The CMAS resistance of (Yb0.7Gd0.3)4Hf3O12 was significantly higher compared to that of Yb4Hf3O12, which could be attributed to the greater volume fraction of apatite and reprecipitated fluorite in the reaction products. The (Yb0.7Gd0.3)4Hf3O12 exhibited high effectiveness in mitigating CMAS infiltration, making it a potential candidate material for thermal barrier coatings.

Effects of molten silicate reactivity on high temperature erosion behavior of plasma sprayed Yb2Si2O7-based EBCs

Particulate/debris damage caused by ingestion of calcium magnesium aluminosilicates (CMAS) hinders the durability of environmental barrier coatings (EBCs) used to protect SiC-based ceramic matrix composite components in next generation gas turbine engines. Similarly, ingestion of any debris in the engine can lead to mechanical damage and recession of coatings due to particulate erosion. Investigating particulate interactions at relevant engine conditions is crucial for determining limiting mechanisms in the operating lifetime of EBCs. This study assessed the effects of extrinsic phase formation and microstructural changes due to CMAS interactions on the erosion durability of Yb2Si2O7-based EBCs in a laboratory-scale combustion facility. CMAS exposures and erosion testing were carried out at 1316°C. Using 60 μm Al2O3 particles as the erodent material, the effects of CMAS loading on erosion durability at various impingement angles were evaluated.

Corrosion resistance and microstructural evolution of Yb-Al-Si-O glass-ceramics under molten Ca-Mg-Al-Si environment at 1350 °C

The intrinsic characteristics of Yb2O3-Al2O3-SiO2 (YbAS) glass-ceramics and their resistance to corrosion by molten calcium magnesium aluminosilicate (CMAS) at 1350 °C were systematically investigated. YbAS glass-ceramics, characterized by diverse compositions, maintaining phase stability over extended durations at elevated temperatures. After CMAS corrosion for 50 h, the main reaction phases were CaAl2Si2O8 and Ca2Yb8(SiO4)6O2, accompanied by multiple ion solid solution garnet in certain components. The glass component positioned along the eutectic line of Yb2Si2O7 and mullite, with an OB value marginally exceeding that of CMAS, exhibits superior corrosion resistance to CMAS. This finding offers valuable insights for the subsequent design of environmental barrier coatings (EBCs).

CaO–MgO–Al2O3–SiO2 corrosion resistance of multi-rare-earth-oxide-doped zirconia thermal barrier coating

As a thermal barrier coating (TBC) material, 8 wt% yttria-stabilized zirconia (8YSZ) exhibits poor resistance against calcium–magnesium–aluminosilicate (CMAS) corrosion. This is caused by the penetration of molten CMAS glass and the depletion of Y3+, which limits the lifetime of 8YSZ. In this study, a multi-rare-earth-oxide-doped zirconia (15 wt% (Lu0.2Yb0.2Dy0.2Gd0.2Y0.2)–ZrO2, denoted as 15LYDGY–SZ) ceramic was prepared to examine its interaction with CMAS. The sluggish diffusion effect and the competition between various dopant elements toward reaction with CMAS effectively slow down the atomic diffusion and limit the transformation of tetragonal phase into monoclinic phase in 15LYDGY–SZ ceramic. Compared with the currently used 8YSZ ceramic, the corrosion resistance of 15LYDGY–SZ to CMAS and its retention rate of fracture toughness after CMAS corrosion are improved. The results show that the multi-rare-earth-oxide-doped zirconia ceramic prepared in this study is a promising candidate material for the development of future TBCs.

Composition-driven superior CMAS corrosion resistance of high-entropy rare-earth disilicates

Achieving superior calcium-magnesium-aluminosilicate (CMAS) corrosion resistance in high-entropy rare-earth disilicates (HEREDs) is crucial to their applications as environmental barrier coatings in aerospace. Stimulated by the vast compositional field of HEREDs, we achieve exceptional CMAS corrosion resistance in HEREDs at elevated temperatures via a composition-driven strategy for the first time. Specifically, the equimolar 3- to 8-cation high-entropy rare-earth disilicate (3–8HERED) samples are first successfully designed and fabricated using a high-throughput pressure-less sintering technique and then their CMAS corrosion resistance up to 1773 K is evaluated. Among all the as-fabricated samples, the as-fabricated 7HERED samples are found to exhibit the best CMAS corrosion resistance. The outstanding CMAS corrosion resistance of the as-fabricated 7HERED samples is primarily attributed to pronounced sluggish diffusion induced by configurational entropy, with the synergistic effect of their chemical activity, which facilitates the formation of dense apatite protective layers. Our work provides valuable ways to design remarkable anti-CMAS corrosion high-entropy ceramics.

Medium-Entropy Monosilicates Deliver High Corrosion Resistance to Calcium-Magnesium Aluminosilicate Molten Salt.

For decreasing the global cost of corrosion, it is essential to understand the intricate mechanisms of corrosion and enhance the corrosion resistance of materials. However, the ambiguity surrounding the dominant mechanism of calcium-magnesium aluminosilicate (CMAS) molten salt corrosion in extreme environments hinders the mix-and-matching of the key rare earth elements for increasing the resistance of monosilicates against corrosion of CMAS. Herein, an approach based on correlated electron microscopy techniques combined with density functional theory calculations is presented to elucidate the complex interplay of competing mechanisms that control the corrosion of CMAS of monosilicates. These findings reveal a competition between thermodynamics and kinetics that relies on the temperatures and corrosion processes. Innovative medium-entropy monosilicates with exceptional corrosion resistance even at 1500°C are developed. This is achieved by precisely modulating the radii of rare earth ions in monosilicates to strike a delicate balance between the competition in thermodynamics and kinetics. After 50 and 100h of corrosion, the thinnest reactive layers are measured to be only 28.8 and 35.4µm, respectively.

Corrosion behavior of Al4SiC4/SiC ceramics exposed to molten calcium‐magnesium‐alumino‐silicate at 1350°C in air

AbstractAl4SiC4 shows excellent heat resistance, thermal shock resistance, machinability, and oxidation resistance. We focused on Al4SiC4‐based ceramics with SiC as a non‐oxide matrix for ceramic matrix composites for aircraft jet engines. In this study, monolithic Al4SiC4 and Al4SiC4/SiC ceramics were fabricated by hot‐pressing, and a corrosion test against molten calcium‐magnesium‐alumino‐silicate (CMAS) was conducted at 1350°C for 12–100 h in air, and their corrosion behavior was investigated. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy results revealed that severe damage was not observed at the interface between CMAS and the samples after the CMAS corrosion test. The recession of Al4SiC4‐100, ‐10, and SiC‐100 after corrosion for 100 h was 80–90 µm, and that of Al4SiC4‐50 was the highest of all samples and the value was 130 µm. The dissolution behavior of the oxidation layer into molten CMAS via a corrosion reaction was dependent on the composition of both the sample and the oxidation layer, the thickness, and the microstructure of the oxidation layers. The dominant mechanism of reaction between CMAS and Al4SiC4‐100, ‐90, and ‐50 samples was concluded to be the dissolution of the oxidation products, while in SiC‐100 and Al4SiC4‐10 samples, the dominant reaction was determined to be direct corrosion of the surface with CMAS.

Thermal properties and calcium-magnesium-alumino-silicate (CMAS) interaction of novel γ-phase ytterbium-doped yttrium disilicate (γ-Y1.5Yb0.5Si2O7) environmental barrier coating material

Rare-earth disilicates are promising candidates for thermal and environmental barrier coatings (TEBC) in gas turbines that safeguard SiCf/SiC ceramic matrix composites (CMCs) from thermal degradation and environmental attacks. Here, we report a systematic investigation on novel TEBC material, γ-Y1.5Yb0.5Si2O7. The γ-phase quarter molar ytterbium–doped yttrium disilicate exhibited low thermal conductivity (1.72 W·m−1·K−1 at 1200 °C) and reduced intrinsic thermal expansion (3.17 ± 0.22 × 10−6 K−1 up to 1000 °C), ensuring promisingly effective thermal insulation and minimized thermal stress with CMC substrates. Using density functional theory (DFT), the heat capacity of γ-Y1.5Yb0.5Si2O7 was predicted higher than that of undoped γ-Y2Si2O7. Comparing these predictions to results calculated using the Neumann–Kopp (NK) rule revealed only minor variations. A metastable CMAS interaction byproduct, cyclosilicate phase Ca3RE2(Si3O9)2, was identified based on energy dispersive X-ray spectrometer (EDS) and electron backscatter diffraction (EBSD) techniques, appearing at 1300 °C but disappearing at 1400 °C. The γ-Y1.5Yb0.5Si2O7 exhibited good CMAS resistance on both dense pellets and sprayed coatings, forming a protective apatite (Ca2RE8(SiO4)6O2) interlayer that effectively hindered CMAS infiltration at evaluated temperatures. The relatively higher Y:Yb atomic ratio (> 3) in the apatite grains indicate differential reactivity with molten CMAS and provides crucial insights into the CMAS corrosion mechanism. These findings highlight the potential of γ-Y1.5Yb0.5Si2O7 as a CMC coating material, emphasizing the need for tailored microstructural optimization as a thermal sprayed coating to enhance long-term performance in extreme gas turbine environments.

Reaction of Yb2SiO5 EBCs against CMAS melts with different composition

Ytterbium monosilicate (Yb2SiO5) has been recognized as environmental barrier coatings (EBCs) material with potential applications for SiCf/SiC. However, the corrosion caused by calcium-magnesium-alumino-silicate (CMAS) has posed significant challenges to the design and application of EBCs. In this study, reaction of Yb2SiO5 EBCs against CMAS melts with different Ca/Si ratios (1.1, 0.75, 0.64, and 0.42) at 1350 °C was investigated. Results showed that the components of CMAS have a significant impact on the corrosion behaviors of the Yb2SiO5 coating. The difference in Ca/Si ratio of CMAS changes the phase equilibrium during the reaction process. The CMAS melts with the highest Ca/Si ratios can form a combination of silico-carnotite (Ca3Yb2(SiO4)3), garnet and two kinds of apatite (Ca2Yb8(SiO4)6O2 and Ca4Yb6(SiO4)6O), whereas the CMAS melts with the lowest Ca/Si ratio is expected to form Yb2Si2O7 phase. With the Ca/Si ratio increasing, the viscosity of CMAS decreased and the aggressiveness of CMAS to Yb2SiO5 coating increased.

Thermochemical interactions between Ca2Sm8(SiO4)6O2 apatite and molten calcium–magnesium-aluminosilicate (CMAS)

Thermochemical interactions between Ca2Sm8(SiO4)6O2 (CSmS) apatite and molten calcium-magnesium-aluminosilicate (CMAS) glass having CaO/SiO2 mole ratio 0.37 have been evaluated. CSmS apatite-CMAS diffusion couples were annealed at 1200, 1300, and 1400 °C for 1–50 h. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high angle annular dark field imaging, selected area electron diffraction and energy dispersive x-ray spectroscopy were used to characterize the phases formed during the reaction. Formation of a distinct cyclosilicate [Ca3Sm2(Si3O9)2] layer was observed at apatite-CMAS interface in couples heat treated at 1200 °C but not at higher temperatures. The cyclosilicate layer nucleated at the apatite-CMAS reaction front, continued to grow into the residual melt and eventually detached from the apatite substrate. Residual CMAS melt became Ca-lean when cyclosilicate was present. Formation of MgCaSi2O6 diopside and dendrites of CaSiO3 wollastonite was also observed within the residual CMAS at 1200 °C. At 1300 and 1400 °C molten CMAS, due to its much lower viscosity, infiltrated the apatite substrate through open pores and along the grain boundaries. Ca2Sm8(SiO4)6O2 apatite thermal/environmental barrier coating has the potential to provide protection against CMAS attack up to about 1200 °C but not at higher temperatures.