Fabrication and properties of Cf/(Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C-SiC high-entropy ceramic matrix composites via precursor infiltration and pyrolysis

In this work, C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C-SiC high-entropy ceramic matrix composites were reported for the first time. Based on the systematic study of the pyrolysis and solid-solution mechanisms of (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C precursor by Fourier transform infrared spectroscopy, TG-MS and XRD, C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C-SiC with uniform phase and element distribution were successfully fabricated by precursor infiltration and pyrolysis. The as-fabricated composites have a density and open porosity of 2.40 g/cm³ and 13.32 vol% respectively, with outstanding bending strength (322 MPa) and fracture toughness (8.24 MPa m^1/2). The C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C-SiC composites also present excellent ablation resistant property at a heat flux density of 5 MW/m², with linear and mass recession rates of 2.89 μm/s and 2.60 mg/s respectively. The excellent combinations of mechanical and ablation resistant properties make the C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C-SiC composites a new generation of reliable ultra-high temperature materials.     

Additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites via paper laminating,direct slurry writing,and precursor infiltration and pyrolysis

In this study, continuous carbon reinforced C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C–SiC high entropy ceramic matrix composites were additively manufactured through paper laminating (PL), direct slurry writing (DSW), and precursor infiltration and pyrolysis (PIP). (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C high entropy ceramic (HEC) powders were synthesized by pressureless sintering and ball milling. A certain proportion of HEC powder, SiC powder, water, binder, and dispersant were mixed to prepare the HEC-SiC slurry. Meanwhile, BN coating was prepared on the 2D fiber cloth surface by the boric acid-urea method and then the cloth was cut into required shape. Additive manufacturing were conducted subsequently. Firstly, one piece of the as-treated carbon fiber cloth was auto-placed on the workbench by paper laminating (PL). Then, the HEC-SiC slurry was extruded onto the surface of the cloth by direct slurry writing (DSW). PL and DSW process were repeated, and a C_f/HEC-SiC preform was obtained after 3 cycles. At last, the preform was densified by precursor infiltration and pyrolysis (PIP) and the final C_f/HEC-SiC composite was prepared. The open porosity of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 7.7, 10.6, and 11.3%, respectively. And the density of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 2.9, 2.7 and 2.3 g/cm³, respectively. The mechanical properties of the C_f/HEC-SiC composites increased firstly and then decreased with the HEC content increase, reaching the maximum value when the HEC volume fraction was 30%. The mechanical properties of the C_f/HEC-SiC composites containing 45, 30 and 15% HEC were as follows: flexural strength (180.4 ± 14 MPa, 183.7 ± 4 MPa, and 173.9 ± 4 MPa), fracture toughness (11.9 ± 0.17 MPa m^1/2, 14.6 ± 2.89 MPa m^1/2, and 11.3 ± 1.88 MPa m^1/2), and tensile strength (71.5 ± 4.9 MPa, 98.4 ± 12.2 MPa, and 73.4 ± 8.5 MPa). From this study, the additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites was achieved, opening a new insight into the manufacturing of ceramic matrix composites.     

Microstructures and oxidation mechanisms of (Zr0.2Hf0.2Ta0.2Nb0.2Ti0.2)B2 high-entropy ceramic

A nano dual-phase powder with great sinterability was synthesized by molten-salt assisted borothermal reductions at 1100 °C using B, ZrO₂, HfO₂, Ta₂O₅, Nb₂O₅ and TiO₂ powders as raw materials. Single-phase (Z_r0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ high-entropy ceramic was prepared by spark plasma sintering using the as-synthesized nano dual-phase powder. Oxidation behavior of the (Zr_0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ ceramic was investigated over the range of 30–1400 °C in air and the result indicated that the rapid oxidation of ceramic began at 1300 °C. The phenomenon could be ascribed to the rapid volatilization of B₂O₃ from oxide scale. A layered structure was formed at the cross section of (Zr_0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ ceramic after oxidation. The relationship between partial pressures of gaseous metal oxides and oxygen partial pressures was calculated, which inferred that the formation of layered structure could be ascribed to the active oxidation of (Zr_0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂, the generation of gaseous metal oxides, their outward diffusion and further oxidation.     

(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high‐entropy ceramics with low thermal conductivity

A novel high‐entropy carbide ceramic, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C, with a single‐phase rock salt structure, was synthesized by spark plasma sintering. X‐ray diffraction confirmed the formation of a single‐phase rock salt structure at 26‐1140°C in Argon atmosphere, in which the 5 metal elements may share a cation position while the C element occupies the anion position. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C exhibits a much lower thermal diffusivity and conductivity than the binary carbides HfC, ZrC, TaC, and TiC, which may result from the significant phonon scattering at its distorted anion sublattice. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C inherits the high elastic modulus and hardness of the binary carbide ceramics.     

The effect of submicron grain size on thermal stability and mechanical properties of high-entropy carbide ceramics

(Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramics (HEC) with a submicron grain size of 400 to 600 nm were fabricated by spark plasma sintering using a two-step sintering process. Both X-ray and neutron diffractions confirmed the formation of single-phase with rock salt structure in the as-fabricated (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C samples. The effect of submicron grain size on the thermal stability and mechanical properties of HEC was investigated. The grain growth kinetics in the fine-grained HEC was small at 1300 and 1600°C, suggesting high thermal stability that was possibly related to the compositional complexity and sluggish diffusion in HEC. Compared to the coarse-grain HEC with a grain size of 16.5 µm, the bending strength and fracture toughness of fine-grained HEC were 25% and 20% higher respectively. The improvement of mechanical properties in fine-grained HEC may be attributed to micromechanistic mechanisms such as crack deflection.     

Diffusion bonding of (Hf0.2Zr0.2Ti0.2Ta0.2Nb0.2)C high-entropy ceramic with metallic Ni foil

To prepare large-sized and complex-shaped components, the feasibility of direct diffusion bonding of (Hf_0.2Zr_0.2Ti_0.2Ta_0.2Nb_0.2)C high-entropy ceramic (HEC) and its diffusion bonding with a metallic Ni foil was investigated, and the interfacial microstructure and mechanical properties of HEC/HEC and HEC/Ni/HEC joints were analyzed. For the direct diffusion bonding, reliable joints with a shear strength of 146 MPa could be achieved when the bonding temperature reached 1500 °C under a pressure of 30 MPa. By introducing a metallic Ni foil as the interlayer, the HEC was successfully bonded at the diffusion temperatures from 1150 °C to 1250 °C under 10 MPa through the formation of Ti₂Ni compound phase. Meanwhile, the HEC(Ni) phase formed by the diffusion of Ni into HEC and Ni(s, s) bulks precipitated in the bonding transition zone. The maximum joint shear strength of 151 MPa was obtained by optimizing the Ni-foil thickness, bonding temperature, and holding time.     

Pressureless sintering and properties of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics: The effect of pyrolytic carbon

A novel (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic was successfully prepared by pressureless sintering at 2200 °C. With increasing content of resin-derived-carbon, the density, and mechanical and thermal properties increased up to a maximum content of 2～4 wt% resin addition, after which further addition was detrimental. All specimens showed high strength (≥347±36 MPa), with the highest value achieving 450±64 MPa, and fracture toughness significantly higher (>20 %) than those of the corresponding monocarbides and Ta_0.5Hf_0.5C, (Ta_1/3Zr_1/3Nb_1/3)C. The thermal conductivity was approximately equivalent to the lowest value of the corresponding mono-carbides, which was assumed to be due to the lattice distortion effect.     

First-principles prediction,fabrication and characterization of (Hf0.2Nb0.2Ta0.2Ti0.2Zr0.2)B2 high-entropy borides

The microstructure and mechanical properties of (Hf_0.2Nb_0.2Ta_0.2Ti_0.2Zr_0.2)B₂ high-entropy boride (HEB) were first predicted by first-principles calculations combined with virtual crystal approximation (VCA). The results verified the suitability of VCA scheme in HEB studying. Besides, single-phase (Hf_0.2Nb_0.2Ta_0.2Ti_0.2Zr_0.2)B₂ ceramics were successfully fabricated using boro/carbothermal reduction (BCTR) method and subsequent spark plasma sintering (SPS); furthermore, the effects of different amounts of B₄C on microstructure and mechanical properties were evaluated. Due to the addition of B₄C and C, all samples formed single-phase solid solutions after SPS. When the excess amount of B₄C increased to 5 wt%, the sample with fine grains exhibited superior comprehensive properties with the hardness of 18.1 ± 1.0 GPa, flexural strength of 376 ± 25 MPa, and fracture toughness of 4.70 ± 0.27 MPa m^1/2. Nonetheless, 10 wt% excess of B₄C coarsened the grains and decreased the strength of the ceramic. Moreover, the nanohardness (34.5–36.9 GPa) and Young's modulus (519–571 GPa) values with different B₄C contents just showed a slight difference and were within ranges commonly observed in high-entropy diboride ceramics.     

Microstructures and mechanical properties of high-entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C ceramics with the addition of SiC secondary phase

The relationships between microstructures and mechanical properties especially strength and toughness of high-entropy carbide based ceramics are reported in this article. Dense (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C (HEC) and its composite containing 20 vol.% SiC (HEC-20SiC) were prepared by spark plasma sintering. The addition of SiC phase enhanced the densification process, resulting in the promotion of the formation of the single-phase high-entropy carbide during sintering. The high-entropy carbide phase demonstrated a fast grain coarsening but SiC particles remarkably inhibited this phenomena. Dense HEC and HEC-20SiC ceramics sintered at 1900 °C exhibits four-point bending strength of 332 ± 24 MPa and 554 ± 73 MPa, and fracture toughness of 4.51 ± 0.61 MPa·m^1/2 and 5.24 ± 0.41 MPa·m^1/2, respectively. The main toughening mechanism is considered to be crack deflection by the SiC particles.     

Hardness and toughness improvement of SiC-based ceramics with the addition of (Hf0.2Mo0.2Ta0.2Nb0.2Ti0.2)B2

The influences of different contents ranging 0–15 wt% of high-entropy boride (HEB) (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ on the mechanical properties of SiC-based ceramics using Al₂O₃-Y₂O₃ sintering additives sintered by spark plasma sintering process were investigated in this study. The results showed that the introduction of 5 and 10 wt% (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ could facilitate the densification and the grain growth of SiC-based ceramics via the mechanism of liquid phase sintering. However, the grain growth of SiC-based ceramics was inhibited by the grain boundary pinning effect with the addition of 15 wt% (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂. The SiC-based ceramics with 15 wt% (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ showed the enhanced hardness (21.9±0.7 GPa) and high toughness (4.88±0.88 MPa·m^1/2) as compared with high-entropy phase-free SiC-based ceramics, which exhibited a hardness of 16.6 GPa and toughness of 3.10 MPa·m^1/2. The enhancement in mechanical properties was attributed to the addition of higher hardness of HEB phase, crack deflection toughening mechanism, and presence of residual stress due to the mismatch of coefficient of thermal expansion.     

High-entropy carbide-based ceramic cutting tools

In this study, a novel high-entropy carbide-based ceramic cutting tool was developed. The cutting performance of three kinds of high-entropy carbide-based ceramic tools with different mechanical properties for the ISO C45E4 steel were evaluated. Although the pure (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8 ceramic cutting tool exhibited the highest hardness of 25.06 ± 0.32 GPa, the cutting performance was poor due to the chipping and catastrophic failure caused by the low toughness (2.25 ± 0.27 MPa m^1/2). The (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8–15 vol% cobalt cutting tool with highest fracture toughness (6.37 ± 0.24 MPa m^1/2) and lowest hardness (17.29 ± 0.79 GPa) showed the medium cutting performance due to the low wear resistance caused by the low hardness. The (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8–7.7 vol% cobalt cutting tool showed the longest effective cutting life of ∼67 min due to the high wear resistance and chipping resistance caused by the high hardness (21.05 ± 0.72 GPa), high toughness (5.35 ± 0.51 MPa m^1/2), and fine grain size (0.60 ± 0.15 μm). The wear mechanisms of the cobalt-containing (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8 ceramic cutting tools included adhesive wear and abrasive wear and oxidative wear. This research indicated that the high-entropy carbide-based ceramics with high hardness and high toughness have potential use in the field of cutting tool application.     

Synthesis and thermal stability of novel high-entropy metal boron carbonitride ceramic powders

High-entropy metal boron carbonitride ceramic powders including (Ta_0.2Nb_0.2Zr_0.2Hf_0.2W_0.2)BCN, (Ta_0.2Nb_0.2Zr_0.2Hf_0.2Ti_0.2)BCN, and (Ta_0.2Nb_0.2Zr_0.2Ti_0.2W_0.2)BCN, were successfully synthesized via mechanical alloying at room temperature. Results show that for the first step of 10 h milling, the amorphous BCN phases are observed. After 24 h of second step milling, the as-synthesized high-entropy ceramics exhibit a single face-centered cubic solid solution structure with high compositional uniformity from nano-scale to micron-scale. When heated to 1500 °C for 30min in flowing Ar, the as-prepared high-entropy ceramic powders still show relatively high thermal stability; however, some metals oxides like HfO₂ and ZrO₂ are detected due to the pre-existing oxides on sample surfaces. After heat treatment, some amorphous phases are still retained. This work suggests a new processing route on the synthesis of high-entropy metal boron carbonitride ceramics.     

Densification and joining of a (HfTaZrNbTi)C high-entropy ceramic by hot pressing

A bulk (Hf_0.2Ta_0.2Zr_0.2Nb_0.2Ti_0.2)C high-entropy ceramic (HEC) with a high density was prepared by hot pressing (HP), and through a robust joining technique, large-sized piece was fabricated. A hot-pressed carbide HEC with a single-phase and homogeneous composition was obtained at the sintering temperatures from 1800 to 1950 °C for 30 min under a pressure of 30 MPa. The influence of sintering temperature on the mechanical properties of the HEC was investigated, and the flexural and compressive strengths were reported. Additionally, the feasibility of active brazing of this HEC was studied and solid joints with high shear strength were obtained by atomic diffusion and chemical reaction at the interface, providing a key approach to fabricate complex components of HECs.     

First-principles study,fabrication, and characterization of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramic

The formation possibility of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic (HHC-1) was first analyzed by the first-principles calculations, and then, it was successfully fabricated by hot-pressing sintering technique at 2073 K under a pressure of 30 MPa. The first-principles calculation results showed that the mixing enthalpy and mixing entropy of HHC-1 were −0.869 ± 0.290 kJ/mol and 0.805R, respectively. The experimental results showed that the as-prepared HHC-1 not only had an interesting single rock-salt crystal structure of metal carbides but also possessed high compositional uniformity from nanoscale to microscale. By taking advantage of these unique features, it exhibited extremely high nanohardness of 40.6 ± 0.6 GPa and elastic modulus in the range from 514 ± 10 to 522 ± 10 GPa and relatively high electrical resistivity of 91 ± 1.3 μΩ·cm, which could be due to the presence of solid solution effects.     

Grain coalescence in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C during spark plasma sintering

High-entropy (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C ceramics (HEC) are fabricated via spark plasma sintering using different die configurations, including the conductive and insulating dies. Compared to the conductive die, the grain sizes of samples sintered in the insulating die are significantly larger, which is attributed to the higher local temperature as a result of the higher current density in the sample. Furthermore, the microstructure evolution and grain growth mechanism of HEC are investigated for the first time. We find that at moderate temperatures (∼1600°C), the grain growth of HEC can occur by a grain coalescence mechanism, forming numerous irregular grains in the porous sample. Three factors are crucial to induce grain coalescence, including the formation of partial melting layers on particle surfaces, nanograin rearrangement via rotation and sliding, and the formation of low-angle grain boundaries. During the final sintering stage, the irregular grains will change into polyhedral shapes by grain boundary migration. These findings are of assistance to better understand and control the microstructure evolution of HEC and other ultrahigh-temperature carbide ceramics.     

Oxidation behavior of high-entropy carbide (Hf0.2Ta0.2Zr0.2Ti0.2Nb0.2)C at 1400–1600 °C

Oxidation behavior of high-entropy carbide (Hf_0.2Ta_0.2Zr_0.2Ti_0.2Nb_0.2)C (HTZTNC) was investigated over temperature range of 1400–1600 °C. Results showed improved oxidation resistance of high-entropy carbide compared with individual carbide ceramics. In oxide layer, Ta₂O₅ and Nb₂O₅ were found to be dominant phases at 1400 °C, whereas ZrTiO₄ and HfTiO₄ were main phases obtained at 1500 and 1600 °C. Moreover, these complex dense oxide layer structures on the surface of HTZTNC at high temperature led to excellent oxidation resistance. The observation of Ti-depleted layer at 1500 and 1600 °C after 20 min of oxidation indicated that oxidation mechanism involved outward diffusion of titanium oxide, which was further confirmed by reoxidation experiments. In sum, these findings are promising for future development of high-entropy ultrahigh temperature ceramics with good oxidation resistance.     

High-temperature oxidation behavior of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics in air

High-entropy metal carbides have recently been arousing considerable interest. Nevertheless, their high-temperature oxidation behavior is rarely studied. Herein the high-temperature oxidation behavior of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy metal carbide (HEC-1) was investigated at 1573-1773 K in air for 120 minutes. The results showed that HEC-1 had good oxidation resistance and its oxidation obeyed a parabolic law at 1573-1673 K, while HEC-1 was completely oxidized after isothermal oxidation at 1773 K for 60 minutes and thereby its oxidation followed a parabolic-linear law at 1773 K. An interesting triple-layered structure was observed within the formed oxide layer at 1673 K, which was attributed to the inward diffusion of O₂ and the outward diffusion of Ti element and CO or CO₂ gaseous products.     

Effects of SiC nanowires and whiskers on high-entropy carbide-based composites sintered at low and high temperatures

This study aimed to investigate the toughening effects of SiC nanowires (SiC_nw) and SiC whiskers (SiC_w) on high-entropy carbide based composites prepared at different temperatures (1600°C and 2000°C). At low temperature (1600°C), SiC_nw and SiC_w maintain their original morphology and properties, and exhibit the good toughening effects. The SiC_nw with larger aspect ratio and more curly wires exhibit a much stronger toughening effect on the (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8 composites reinforced with 15 vol.% SiC_nw, which shows the highest value of fracture toughness about 6.7 MPa∙m^1/2. However, at high sintering temperature (2000°C), SiC_nw and SiC_w are prone to thermal-induced damages, which significantly reduces their mechanical properties, and thus, toughening effects on (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8 composites. The addition of SiC_w, which have better thermal stability at 2000°C, results in the (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8–15 vol.% SiC_w composite exhibiting relatively better fracture toughness, about 3.7 MPa∙m^1/2. Based on the results of the current study, the critical influence of SiC_nw and SiC_w on the toughening of (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8 composites is highly dependent on their high-temperature thermal stability.     

Thermophysical and mechanical properties of novel high-entropy metal nitride-carbides

In this work, a novel (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)(N_0.5C_0.5) high-entropy nitride-carbide (HENC-1) with multi-cationic and -anionic sublattice structure was reported and their thermophysical and mechanical properties were studied for the first time. The results of the first-principles calculations showed that HENC-1 had the highest mixing entropy of 1.151R, which resulted in the lowest Gibbs free energy above 600 K among HENC-1, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)N high-entropy nitrides (HEN-1), and (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy carbides (HEC-1). In this case, HENC-1 samples were successfully fabricated by hot-pressing sintering technique at the lowest temperature (1773 K) among HENC-1, HEN-1 and HEC-1 samples. The as-fabricated HENC-1 samples showed a single rock-salt structure of metal nitride-carbides and high compositional uniformity. Meanwhile, they exhibited high microhardness of 19.5 ± 0.3 GPa at an applied load of 9.8 N and nanohardness of 33.4 ± 0.5 GPa and simultaneously possessed a high bulk modulus of 258 GPa, Young's modulus of 429 GPa, shear modulus of 176 GPa, and elastic modulus of 572 ± 7 GPa. Their hardness and modulus are the highest among HENC-1, HEN-1 and HEC-1 samples, which could be attributed to the presence of mass disorder and lattice distortion from the multi-anionic sublattice structure and small grain in HENC-1 samples. In addition, the thermal conductivity of HENC-1 samples was significantly lower than the average value from the “rule of mixture” between HEC-1 and HEN-1 samples in the range of 300-800 K, which was due to the presence of lattice distortion from the multi-anionic sublattice structure in HENC-1 samples.     

Ablation behavior of high-entropy carbides ceramics (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C upon exposition to an oxyacetylene torch at 2000 °C

The ablation performance of a high-entropy ceramic carbide, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C, was performed by oxyacetylene ablation flame, simulating the extreme service environment at 2000 ºC. Phase and microstructure characterization at multi-length scales was carried out. During ablation, a compositionally and microstructurally complex oxidation layer formed on the ablation surface, which consisted of a combination of (Zr_xHf_1?x)₆(Nb_yTa_1?y)₂O₁₇, Ti(Nb_xTa_1?x)₂O₇, and Ti_x(Zr_aHf_bNb_cTa_1?a-b-c)_1?xO₂. Based on the microstructure information, the ablation mechanisms were proposed considering the oxidation thermodynamics and kinetics. Comparable rates of O inward diffusion and Ti outward diffusion are suggested, and a particular innermost dense layer composed of isolated (Zr_xHf_1?x)₆(Nb_yTa_1?y)₂O₁₇ grains embedded in a continuous Ti(Nb_xTa_1?x)₂O₇ matrix is considered to be beneficial for a better ablation resistance.