Preparation of nanostructured Gd2Zr2O7-LaPO4 thermal barrier coatings and their calcium-magnesium-alumina-silicate (CMAS) resistance

Nanostructured 30 mol% LaPO₄ doped Gd₂Zr₂O₇ (Gd₂Zr₂O₇-LaPO₄) thermal barrier coatings (TBCs) were produced by air plasma spraying (APS). The coatings consist of Gd₂Zr₂O₇ and LaPO₄ phases, with desirable chemical composition and obvious nanozones embedded in the coating microstructure. Calcium-magnesium-alumina- silicate (CMAS) corrosion tests were carried out at 1250 °C for 1–8 h to study the corrosion resistance of the coatings. Results indicated that the nanostructured Gd₂Zr₂O₇-LaPO₄ TBCs reveals high resistance to penetration by the CMAS melt. During corrosion tests, an impervious crystalline reaction layer consisting of Gd-La-P apatite, anorthite, spinel and tetragonal ZrO₂ phases forms on the coating surfaces. The layer is stable at high temperatures and has significant effect on preventing further infiltration of the molten CMAS into the coatings. Furthermore, the porous nanozones could gather the penetrated molten CMAS like as an absorbent, which benefits the CMAS resistance of the coatings.     

ZrO2-doped YTaO4 as potential CMAS-resistant materials for thermal barrier coatings application

In this contribution, the ZrO₂-doped YTaO₄ (Zr_xY_0.5−x/2Ta_0.5−x/2O₂ (x = 0, 0.1, 0.2, 0.28)) are proposed as potential CMAS-resistant materials for TBCs. The corrosion behavior of those materials under CMAS attack are investigated from thermodynamics and kinetics. The results show that all compositions have the much better CMAS resistance than the classical Gd₂Zr₂O₇. After 50 h corrosion at 1300℃, the corrosion depth in ZrO₂-doped YTaO₄ bulks is about 50–80 µm (for a 20 mg/cm² CMAS deposition) in contrast with ~140 µm in Gd₂Zr₂O₇ bulk. The CMAS corrosion mechanism of ZrO₂-doped YTaO₄ is elucidated, and the excellent CMAS resistance is attributed to the rapid formation and followed thickening of dense reaction product layer. Furthermore, the effects of ZrO₂ doping content on CMAS resistance of YTaO₄ is discussed. It is elucidated that ZrO₂ doping can inhibit the precipitation of apatite, decrease the consumption of CMAS melt, and change the morphology of dense reaction layer. In summary, minor doping of ZrO₂ can ensure the excellent short- and long-term CMAS resistance, but heavy doping of ZrO₂ will degrade the long-term CMAS resistance.     

Calcium-magnesium-alumina-silicate (CMAS) resistance characteristics of LnPO4 (Ln = Nd,Sm, Gd) thermal barrier oxides

Calcium-magnesium-alumina-silicate (CMAS) attack has been considered as a significant failure mechanism for thermal barrier coatings (TBCs). As a promising series of TBC candidates, rare-earth phosphates have attracted increasing attention. This work evaluated the resistance characteristics of LnPO₄ (Ln = Nd, Sm, Gd) compounds to CMAS attack at 1250 °C. Due to the chemical reaction between molten CMAS and LnPO₄, a dense, crack-free reaction layer, mainly composed of Ca₃Ln₇(PO₄)(SiO₄)₅O₂ apatite, CaAl₂Si₂O₈ and MgAl₂O₄, was formed on the surface of compounds, which had positive effect on suppressing CMAS infiltration. The depth of CMAS penetration in LnPO₄ (Ln = Nd, Sm, Gd) decreased in the sequence of NdPO₄, SmPO₄ and GdPO₄. GdPO₄ had the best resistance characteristics to CMAS attack among the three compounds. The related mechanism was discussed based on the formation ability of apatite phase caused by the reaction between molten CMAS and LnPO₄.     

Synthesis and characterization of ytterbium oxide: A novel CMAS-resistant environmental barrier coating material

Demand for more powerful aircraft promotes development of ceramic matrix composites and environmental barrier coating (EBC). A promising EBC material, ytterbium oxide (Yb₂O₃), was fabricated by hot pressing, and its properties were systemically investigated. The evaluation of thermal properties provides a baseline for the application of Yb₂O₃ on SiC_f/SiC or Al₂O_3f/Al₂O₃ composites. The performance in water vapor and molten calcium–magnesium–aluminosilicate (CMAS) environments indicates its excellent durability in harsh environment. Compared with rare-earth silicates, the thermochemical interactions between ytterbium oxide and CMAS changed greatly with the absence of silicon oxide. Reactions of ytterbium oxide with CMAS form several reaction products, including apatite, garnet, and silicocarnotite. The crystallization of garnet and silicocarnotite could effectively consume and solidify the CMAS melt, which prevents the melt infiltration and mitigates the further corrosion.     

Gadolinium oxide solubility in molten silicate: dissolution mechanism and stability of Ca2Gd8(SiO4)6O2 and Ca3Gd2(Si3O9)2 silicate phases

Improvement of the calcium-magnesium aluminosilicate (CMAS) infiltration mitigation concept in thermal barrier coatings (TBC) requires fundamental data on thermochemical reaction involving rare-earth oxide candidate as ZrO₂ alloying element. This study investigates, through a model approach, Gd₂O₃ dissolution at 1200 °C in a synthetic model CAS melt (64.4SiO₂–9.3Al₂O₃–26.4CaO mol. %) and the stability of the precipitated Gd-apatite Ca₂Gd₈(SiO₄)₆O₂ and Ca₃Gd₂(Si₃O₉)₂ cyclosilicate phases. The two Gd-rich silicates have been synthesized by solid-state reaction and then characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The interactions of Gd₂O₃, Gd-apatite and Gd-cyclosilicate with CAS have been observed by scanning electron microscope (SEM) after various times of contact at 1200 ̊C, giving information about dissolution/precipitation processes. Dissolution kinetics has been evaluated by electron probe microanalysis (EPMA) measurements in the CAS melt. A discussion is finally provided concerning the thermodynamic stability of all phases of the system and confronted with kinetics considerations.     

Protocol for selecting exemplary silicate deposit compositions for evaluating thermal and environmental barrier coatings

A protocol for selecting representative silicate compositions for comparative testing of gas turbine coating materials is presented. It begins with a curated dataset of compositions of engine deposits and naturally occurring siliceous debris including volcanic ashes, sands, and dusts. The compositions are first reduced to the five major oxides—those of Ca, Mg, Fe, Al, and Si—and then distilled further using principal component analysis and k-means clustering. The process ultimately yields four classes of possible deposits with common chemical characteristics. Each class is represented by a composition centroid and a range in Ca:Si ratios. Key thermophysical properties of the possible deposits are calculated and related to the glass network connectivity, characterized by the Si:O ratio. Finally, deposits from each of these classes are compared in terms of their reactions with prototypical thermal and environmental barrier oxides, with due consideration of the effects of composition variations within each deposit class. The protocol is, in principle, adaptable to datasets compiled by OEMs and researchers in gas turbine coatings.     

Corrosion resistance and thermal-mechanical properties of ceramic pellets to molten calcium-magnesium-alumina-silicate (CMAS)

Because gas turbine engines must operate under increasingly harsh conditions, the degradation of thermal barrier coatings (TBCs) by calcium-magnesium-alumina-silicate (CMAS) is becoming an urgent issue. Mullite (3Al₂O₃·2SiO₂) is considered a potential material for CMAS resistance; however, the performance of mullite in the presence of CMAS is still unclear. In this study, mullite and Al₂O₃–SiO₂ were premixed with yttria stabilized zirconia (YSZ) in different proportions, respectively. Porous ceramic pellets were used to conduct CMAS hot corrosion tests, and the penetration of molten CMAS and its mechanism were investigated. The thermal and mechanical properties of the samples were also characterized. It was found that the introduction of mullite and Al₂O₃–SiO₂ mitigated the penetration of molten CMAS into the pellets owing to the formation of anorthite, especially at 45 wt% mullite/55 wt% YSZ. Compared with Al₂O₃–SiO₂, mullite possesses a higher chemical activity and undergoes a faster reaction with CMAS, thus forming a sealing layer in a short time. Additionally, the thermal expansion coefficient, thermal conductivity, and fracture toughness of different samples were considered to guide the architectural design. Considering the CMAS corrosion resistance, thermal and mechanical performance of TBCs systematically, a TBC system with a multilayer architecture is proposed to provide a theoretical and practical basis for the design and optimization of the TBC microstructure.     

Growth kinetics of apatite layer evolved from calcia-magnesia-aluminosilicate (CMAS) hot corrosion reaction of (Y1-xYbx)2SiO5 ceramics at elevated temperatures of 1673 K and 1773 K

Calcia-magnesia-aluminosilicate (CMAS) corrosion behaviors of hot-pressed (Y_1-xYb_x)₂SiO₅ ceramics at 1673 K and 1773 K have been investigated. The main corrosion product of nonstoichiometric Ca-RE-Si-O apatite phase evolves with increasing temperature or prolonging corrosion time. The growth of apatite layer at 1673 K follows approximately a linear rate law, however it follows a proximately parabolic rate law at 1773 K. The growth rate of the apatite layer at 1773 K is lower than that at 1673 K in the process of interaction between CMAS and rare-earth monosilicates. Yb-doping mediates the CMAS corrosion resistance of Y₂SiO₅ effectively by changing the growth rate of apatite layer and the composition of formed apatite phase. This work provides new insights on compositional regulation of (Y_1-xYb_x)₂SiO₅ EBCs materials to resist CMAS corrosion.     

Interactions between Ca2Gd8(SiO4)6O2 apatite and calcium-magnesium-aluminosilicate (CMAS) at elevated temperatures

High temperature corrosion behavior of Ca₂Gd₈(SiO₄)₆O₂ (CGdS) apatite has been investigated in the presence of molten calcium-magnesium-aluminosilicate (CMAS) glass having the composition 21.9 CaO - 4.3 MgO - 5.4 Al₂O₃ - 63.0 SiO₂ - 4.3 Na₂O - 0.8K₂O - 0.1 Fe₂O₃ (weight %). CGdS apatite powder was prepared by solid state synthesis from constituent oxides. Pellets of CGdS apatite + CMAS mixed powder and CGdS-CMAS diffusion couples were annealed at 1200, 1300, 1400, and 1500 °C for 1 and 20 h in ambient atmosphere. Development of phases in heat treated specimens was characterized using various analytical techniques as 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. In both pellets and diffusion couples, monoclinic cyclosilicate Ca₃Gd₂(Si₃O₉)₂ formed from reaction of apatite with CaO in the CMAS melt only in samples heat treated at 1200 °C for 1 and 20 h or at 1300 °C for 1 h. Triclinic CaSiO₃ and monoclinic diopside MgCaSi₂O₆ were also observed in samples annealed at 1200 and 1300 °C. At 1400 and 1500 °C, because of its low viscosity, CMAS infiltrated along the pores and grain boundaries of the apatite substrates in diffusion couples. Phase compositions predicted from thermochemical computation were in good agreement with those observed experimentally. Ca₂Gd₈(SiO₄)₆O₂ apatite has the potential for being an effective T/EBC in circumventing the penetration of molten CMAS up to about 1300 °C but not at higher temperatures.     

Thermochemical interactions between CMAS and Ca2Y8(SiO4)6O2 apatite environmental barrier coating material

Thermochemical interactions between Ca₂Y₈(SiO₄)₆O₂ apatite, a potential environmental barrier coating (EBC) material, and a synthetic CMAS having the composition 23.3 CaO - 6.4 MgO - 3.1 Al₂O₃ - 62.5 SiO₂ - 4.1 Na₂O - 0.5 K₂O - 0.04 Fe₂O₃ mole % were investigated. Pellets of apatite + CMAS powder and hot-pressed apatite disc-CMAS couples were annealed at 1200–1500 °C for 1–50 hours in air. Powder X-ray diffraction (XRD) was used to identify the phases present. Polished cross-sections of the heat treated pellets and diffusion couples were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), high angle annular dark field (HAADF) imaging, selected area electron diffraction (SAED), and energy dispersive X-ray spectroscopy (EDS). Ca₃Y₂(Si₃O₉)₂ cyclosilicate, apatite, and amorphous phases were present in the samples heat treated at 1200 and 1300 °C, whereas no cyclosilicate was detected in samples annealed at 1400 and 1500 °C. A distinct cyclosilicate layer was observed at the apatite-CMAS interface in the diffusion couples heat treated at 1200 and 1300 °C. However, at 1400 and 1500 °C, due to its much lower viscosity, CMAS quickly infiltrated the apatite substrate through pores and along the grain boundaries and no cyclosilicate was observed; the apatite grains dissolved in molten CMAS followed by re-precipitation of apatite needles within an amorphous phase on cooling.     

Thermophysical properties of Yb2O3 doped Gd2Zr2O7 and thermal cycling durability of (Gd0.9Yb0.1)2Zr2O7/YSZ thermal barrier coatings

(Gd_1−xYb_x)₂Zr₂O₇ compounds were synthesized by solid reaction. Yb₂O₃ doped Gd₂Zr₂O₇ exhibited lower thermal conductivities and higher thermal expansion coefficients (TECs) than Gd₂Zr₂O₇. The TECs of (Gd_1−xYb_x)₂Zr₂O₇ ceramics increased with increasing Yb₂O₃ contents. (Gd_0.9Yb_0.1)₂Zr₂O₇ (GYbZ) ceramic exhibited the lowest thermal conductivity among all the ceramics studied, within the range of 0.8–1.1 W/mK (20–1600 °C). The Young's modulus of GYbZ bulk is 265.6 ± 11 GPa. GYbZ/YSZ double-ceramic-layer thermal barrier coatings (TBCs) were prepared by electron beam physical vapor deposition (EB-PVD). The coatings had an average life of more than 3700 cycles during flame shock test with a coating surface temperature of ∼1350 °C. Spallation failure of the TBC occurred by delamination cracking within GYbZ layer, which was a result of high temperature gradient in the GYbZ layer and low fracture toughness of GYbZ material.     

Apatite and garnet stability in the Al–Ca–Mg–Si–(Gd/Y/Yb)–O systems and implications for T/EBC: CMAS reactions

This work advances the understanding of the influence of rare earth (RE) ion radius on the stability and extent of the garnet solid solution phase in the (ytterbia/yttria/gadolinia)-calcia-magnesia-alumina-silica systems. Guided by the crystal chemistry and charge neutrality constraints, selected compositions in the notional garnet stability field were synthesized, equilibrated at 1400°C, and characterized to determine the equilibrium phases and their compositions. The results show a significant reduction in the stability of the silicate garnet relative to apatite with increasing RE ion radius. Apatite was not observed for any composition in the Yb-containing system, the Y-containing system formed both garnet and apatite, and there was no evidence of silicate garnets in the Gd-containing system. However, despite the apparent differences in stability relative to apatite, the extent of the garnet solid solution increases only slightly for the Yb- compared to Y-containing systems. The quantitative microchemical analysis suggests that Mg²⁺ prefers the octahedral site over the dodecahedral site in the garnet structure, and that the solubility of Mg²⁺ in the dodecahedral site increased in the system containing Yb³⁺ compared to Y³⁺. The results are discussed for their relevance to reactions between RE-containing thermal and environmental barrier coatings and CMAS-type silicate deposits.     

Synthesis and thermophysical properties of ATa2O6 (A = Co,Ni, Mg,Ca) tantalates with robust CMAS resistance

A new family of ceramic environmental/thermal barrier coating (E/TBC) materials, that is, ATa₂O₆ (A = Co, Ni, Mg, Ca), for high-temperature applications, are investigated and reported in this study. We focus on the synthesis and features of crystal structures, and on the mechanical and high-temperature properties. ATa₂O₆ oxides have an extraordinary phase stability (up to 1300°C), and their thermal expansion coefficients (6.2–7.3 × 10⁻⁶ K⁻¹) match those of SiC fiber-enhanced SiC ceramic matrix composites (3–7 × 10⁻⁶ K⁻¹). Their low thermal conductivities (min: 1.15 W·m⁻¹·K⁻¹) root in the slow phonon spreading speed and fierce phonon-phonon scattering process, and they will provide exceptional thermal insulation. Moreover, their hardness (5.6–8.8 GPa), toughness (1.4–1.9 MPa·m^1/2), and moduli (100–210 GPa) have good comparability with current E/TBCs. We propose the 33CaO-9MgO-13AlO_1.5-45SiO₂ (CMAS) corrosion mechanisms of ATa₂O₆ ceramics, and their robust CMAS resistance relies on the phase stability of CaTa₂O₆ oxides. The excellent high-temperature properties ensure that ATa₂O₆ can be used as E/TBCs to provide thermal insulation and CMAS corrosion protection.     

Phase stability and thermal conductivity of RE2O3 (RE=La,Nd, Gd,Yb) and Yb2O3 co-doped Y2O3 stabilized ZrO2 ceramics

Y₂O₃ stabilized ZrO₂ (YSZ) has been considered as the material of choice for thermal barrier coatings (TBCs), but it becomes unstable at high temperatures and its thermal conductivity needs to be further reduced. In this study, 1 mol% RE₂O₃ (RE=La, Nd, Gd, Yb) and 1 mol% Yb₂O₃ co-doped YSZ (1RE1Yb–YSZ) were fabricated to obtain improved phase stability and reduced thermal conductivity. For 1RE1Yb–YSZ ceramics, the phase stability of metastable tetragonal (t′) phase increased with decreasing RE³⁺ size, mainly attributable to the reduced driving force for t′ phase partitioning. The thermal conductivity of 1RE1Yb–YSZ was lower than that of YSZ, with the value decreasing with the increase of the RE³⁺ size mainly due to the increased elastic field in the lattice, but 1La1Yb–YSZ exhibited undesirably high thermal conductivity. By considering the comprehensive properties, 1Gd1Yb–YSZ ceramic could be a good potential material for TBC applications.     

Resistance of pure and mixed rare earth silicates against calcium-magnesium-aluminosilicate (CMAS): A comparative study

Rare earth silicate environmental barrier coatings (EBCs) are state of the art for protecting SiC ceramic matrix composites (CMCs) against corrosive media. The interaction of four pure rare earth silicate EBC materials Yb₂SiO₅, Yb₂Si₂O₇, Y₂SiO₅, Y₂Si₂O₇ and three ytterbium silicate mixtures with molten calcium-magnesium-aluminosilicate (CMAS) were studied at high temperature (1400°C). The samples were characterized by SEM and XRD in order to evaluate the recession of the different materials after a reaction time of 8 hours. Additionally, the coefficient of thermal expansion (CTE) was determined to evaluate the suitability of Yb silicate mixtures as EBC materials for SiC CMCs. Results show that monosilicates exhibit a lower recession in contact with CMAS than their disilicate counterparts. The recession of the ytterbium silicates is far lower than the recession of the yttrium silicates under CMAS attack. Investigation of the ytterbium silicate mixtures exposes their superior resistance to CMAS, which is even higher than the resistance of the pure monosilicate. Also their decreased CTE suggests they will display better performance than the pure monosilicate.     

Orthorhombic to tetragonal polymorphic transformation of YTa3O9 and its inhibition through the design of high-entropy (Y0.2La0.2Ce0.2Nd0.2Gd0.2)Ta3O9

To explore the mechanism of phase transformation, YTa₃O₉ was prepared by an integrated one-step synthesis and sintering method at 1500 °C using Y₂O₃ and Ta₂O₅ powders as starting materials. High-temperature XRD patterns and Raman spectra showed that a phase transformation from orthorhombic to tetragonal took place in YTa₃O₉ through the bond length and angle changes at 300–400 °C, which caused a thermal conductivity rise. To inhibit the phase transformation, a high-entropy (Y_0.2La_0.2Ce_0.2Nd_0.2Gd_0.2)Ta₃O₉ (HE RETa₃O₉) was designed and synthesized at 1550 °C using the integrated solid-state synthesis and sintering method. In tetragonal structured HE RETa₃O₉, phase transformation was inhibited by the high-entropy effect. Furthermore, HE RETa₃O₉ exhibited low thermal conductivity, and its tendency to increase with temperature was alleviated (1.69 W/m·K, 1073 K). Good phase stability, low thermal conductivity and comparable fracture toughness to YSZ make HE RETa₃O₉ promising as a new thermal barrier coating material.     

Thermodynamic Modeling of the HfO2–La2O3–Al2O3 System

Based on phase equilibria, thermodynamic, and crystal structure data, the thermodynamic modeling of HfO₂–La₂O₃–Al₂O₃ system is presented. Liquid phase is described by the modified quasichemical model considering the short‐range ordering in liquid solution. Solid solutions are described by the ionic sublattice model considering respective crystal structure. The model (La³⁺, Hf⁴⁺)₂(Hf⁴⁺, La³⁺)₂(O^2?, Va)₆(O^2?)₁(Va, O^2?)₁ successfully describes the structure defect, homogeneity range, and thermodynamic property of pyrochlore solid solution. A set of optimized model parameters is obtained which reproduces most experimental data well. Isothermal sections, liquidus and solidus projections, and Scheil reaction scheme are constructed.     

The phase stability and thermophysical properties of InFeO3(ZnO)m (m = 2, 3, 4, 5)

The phase stability and thermophysical properties of InFeO₃(ZnO)_m (m = 2, 3, 4, 5) compounds were investigated, which are a general family of homologous layered compounds with general formula InFeO₃(ZnO)_m (m = 1–19). InFeO₃(ZnO)_m (m = 2, 3, 4, 5) ceramics were synthesized using cold pressing followed by solid-state sintering. They revealed an excellent thermal stability after annealing at 1450 °C for 48 h. No phase transformation occurred during heating to 1400 °C. InFeO₃(ZnO)₃ exhibited a thermal conductivity of 1.38 W m⁻¹ K⁻¹ at 1000 °C, which is about 30% lower than that of 8 wt.% yttria stabilized zirconia (8YSZ) thermal barrier coatings. The thermal expansion coefficients (TECs) of InFeO₃(ZnO)m bulk ceramics were in a range of (10.97 ± 0.33) × 10⁻⁶ K⁻¹ to (11.46 ± 0.35) × 10⁻⁶ K⁻¹ at 900 °C, which are comparable to those of 8YSZ ceramics.     

Thermal radiation and cycling properties of (Ca,Fe) or (Sr,Mn) co-doped La2Ce2O7 coatings

La₂Ce₂O₇ with low thermal conductivity as a potential candidate of thermal barrier coatings (TBCs) was co-doped with (Ca, Fe) or (Sr, Mn) in order to further improve its thermal radiation at high temperatures. The microstructure, chemical composition, infrared emission properties (reflection and absorption properties) and thermal cycling lifetime of the coatings were respectively investigated. The results revealed that La_2-xCa_xCe_2-xFe_xO₇₊δ and La_2-xSr_xCe_2-xMn_xO₇₊δ coatings had defected fluorite structure and their infrared emittances were much higher than that of the parent La₂Ce₂O₇. The superior infrared emission could be ascribed to the enhancement of the intrinsic absorption (electron transition absorption), free-carrier absorption and impurity absorption as well as lattice vibration absorption. However, the thermal cycling lifetime of La₂Ce₂O₇ coatings presented a reduction after the (Ca, Fe) or (Sr, Mn) substitution, primarily due to the decrease in the fracture toughness and the increase in the thermal conductivity.