Research Progress on Carbide Ultra-high Temperature Ceramic Anti-ablation Coatings for Thermal Protection System

doi:10.15541/jim20240317

Abstract

Abstract:

Carbide ultra-high temperature ceramics (UHTCs) have emerged as ideal coating materials for the thermal protection systems of hypersonic vehicles due to their high melting point (>3000 ℃), high hardness, low thermal conductivity, excellent heat resistance, and good chemical stability. This review provides a comprehensive overview of structure and properties of carbide UHTCs, namely TiC, ZrC, HfC, NbC, and TaC. Furthermore, it summarizes recent developments in preparation of carbide UHTC coatings using various methods, including chemical vapor deposition, plasma spraying, and solid-phase reaction. Effects of coating microstructure, composition, structural design, and heat flux on the ablation behavior are analyzed. Data from recent literature corroborate that the added second phase can facilitate formation of complex oxides, generate an oxidation layer during ablation to undergo moderate sintering, protect structural integrity, and enhance oxygen barrier properties. Multi-layer structural designs utilize gradient layering and multi-functional structures, which effectively alleviate thermal stress within the coating, suppress crack propagation, and facilitate synergistic enhancing effects among different layers. Finally, the challenges and opportunities in development of carbide UHTC anti-ablation coatings are prospected.

Key words: hypersonic vehicle, thermal protection system, thermal structure, carbide ultra-high temperature ceramic, anti-ablation coating, review

CLC Number:

TQ174

ZHOU Fan, TIAN Zhilin, LI Bin. Research Progress on Carbide Ultra-high Temperature Ceramic Anti-ablation Coatings for Thermal Protection System[J]. Journal of Inorganic Materials, 2025, 40(1): 1-16.

Figures/Tables 11

References 174

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Carbide	TiC	ZrC	HfC	NbC	TaC
Crystal structure	FCC	FCC	FCC	FCC	FCC
Space group	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225
Lattice parameter/Å	4.334	4.692	4.638	4.470	4.455
Density/(g·cm^-3)	4.899	6.634	12.686	7.803	14.498
Melting point/K	3413	3700	4223	3873	4256
Thermal expansion coefficient (20-1600 ℃)/(×10^-6, K^-1)	8.09	7.32	6.88	7.61	6.90
Thermal conductivity^* at 25 ℃/(W·m^-1·K^-1)	17.9	19.1	20.0	17.4	24.7
Vickers hardness^*/GPa	25.20-30.31	16.40-25.00	18.46-25.12	15.10-23.00	13.90-19.90
Young's modulus^**/GPa	481.4	406.6	498.0	483.9	491.8
Flexural strength^*/MPa	424-545	362-407	343-372	440	338-580
Fracture toughness^*/(MPa·m^1/2)	3.04-5.01	1.90-2.90	2.50-3.39	2.50-3.41	2.70-4.00
Resistivity^*/(μΩ·cm)	83	45	72	50	33

Carbide	TiC	ZrC	HfC	NbC	TaC
Crystal structure	FCC	FCC	FCC	FCC	FCC
Space group	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225	$\mathrm{Fm} \overline{3} \mathrm{~m}$#225
Lattice parameter/Å	4.334	4.692	4.638	4.470	4.455
Density/(g·cm^-3)	4.899	6.634	12.686	7.803	14.498
Melting point/K	3413	3700	4223	3873	4256
Thermal expansion coefficient (20-1600 ℃)/(×10^-6, K^-1)	8.09	7.32	6.88	7.61	6.90
Thermal conductivity^* at 25 ℃/(W·m^-1·K^-1)	17.9	19.1	20.0	17.4	24.7
Vickers hardness^*/GPa	25.20-30.31	16.40-25.00	18.46-25.12	15.10-23.00	13.90-19.90
Young's modulus^**/GPa	481.4	406.6	498.0	483.9	491.8
Flexural strength^*/MPa	424-545	362-407	343-372	440	338-580
Fracture toughness^*/(MPa·m^1/2)	3.04-5.01	1.90-2.90	2.50-3.39	2.50-3.41	2.70-4.00
Resistivity^*/(μΩ·cm)	83	45	72	50	33

No.	Coating	Mass ablation rate/(mg·s^-1)	Linear ablation rate/(μm·s^-1)	Ablation type	Heat flux/ (MW·m^-2)	Ablation time	Ref.
C1	APS ZrC	1.378	-1.928	Oxy-acetylene^*	2.4	60 s	[127]
C2	CVD HfC	0.630	1.020	Oxy-acetylene^*	2.4	120 s	[113]
C3	CVD TaC	1.500	3.240	Oxy-acetylene^*	2.4	30 s	[115]
C4	APS HfC	-0.260	-2.100	Oxy-acetylene^*	2.4	120 s	[141]
C5	APS ZrC	0.060	2.250	Oxy-acetylene^*	2.4	120 s	[169]
C6	CVD HfC	2.020	1.250	Oxy-acetylene^*	2.4	90 s	[155]
C7	APS ZrC	4.020	-8.330	Oxy-acetylene^*	2.4	60 s	[170]
C8	APS ZrC	2.020	5.750	Oxy-acetylene^*	4.2	40 s	[171]
C9	APS ZrC	0.270	0.530	Plasma torch^**	10.0	90 s	[172]
C10	APS ZrC-SiC	0.290	0.080	Oxy-acetylene^*	2.4	120 s	[169]
C11	APS HfC-TaC	0.680	-0.580	Oxy-acetylene^*	2.4	120 s	[74]
C12	APS HfC-Hf₆Ta₂O₁₇	-0.320	-1.350	Oxy-acetylene^*	2.4	120 s	[141]
C13	CVD HfC-SiC	0.153	-0.998	Oxy-acetylene^*	2.4	60 s	[78]
C14	APS HfC-ZrC-TiC	0.180	0.710	Oxy-acetylene^*	2.4	120 s	[135]
C15	APS (Hf_1/4Zr_1/4Ta_1/4Ti_1/4)C	0.810	0.190	Oxy-acetylene^*	2.4	180 s	[173]
C16	APS ZrC-SiHfOC	0.099	0.200	Plasma torch^**	10.0	90 s	[172]
C17	CVD (ZrC/SiC)₃	0.750	-0.028	Oxy-acetylene^*	2.4	60 s	[114]
C18	CVD SiC/TaC/SiC/TaC	0.180	-0.760	Oxy-acetylene^*	2.4	30 s	[115]
C19	CVD (SiC/HfC)₃	0.241	0.120	Oxy-acetylene^*	2.4	120 s	[113]
C20	APS ZrC-SiC/ZrC-Al₂O₃/ZrC-MoSi₂/ZrC	0.231	0.156	Oxy-acetylene^*	2.4	60 s × 3	[148]
C21	APS ZrC/TaC/ZrC	1.040	-1.170	Oxy-acetylene^*	2.4	60 s	[170]
C22	APS ZrC/ZrC-LaB₆/ZrC-SiC	-1.070	-2.890	Oxy-acetylene^*	4.2	40 s	[171]
C23	APS ZrC-SiC/ZrC-ZrO₂/ZrO₂-Y₂O₃	-0.460	-0.950	Oxy-acetylene^*	2.4	90 s × 2	[174]
C24	CVD (SiC/HfC)₄/SiC	0.640	0.530	Oxy-acetylene^*	2.4	60 s × 3	[153]

No.	Coating	Mass ablation rate/(mg·s^-1)	Linear ablation rate/(μm·s^-1)	Ablation type	Heat flux/ (MW·m^-2)	Ablation time	Ref.
C1	APS ZrC	1.378	-1.928	Oxy-acetylene^*	2.4	60 s	[127]
C2	CVD HfC	0.630	1.020	Oxy-acetylene^*	2.4	120 s	[113]
C3	CVD TaC	1.500	3.240	Oxy-acetylene^*	2.4	30 s	[115]
C4	APS HfC	-0.260	-2.100	Oxy-acetylene^*	2.4	120 s	[141]
C5	APS ZrC	0.060	2.250	Oxy-acetylene^*	2.4	120 s	[169]
C6	CVD HfC	2.020	1.250	Oxy-acetylene^*	2.4	90 s	[155]
C7	APS ZrC	4.020	-8.330	Oxy-acetylene^*	2.4	60 s	[170]
C8	APS ZrC	2.020	5.750	Oxy-acetylene^*	4.2	40 s	[171]
C9	APS ZrC	0.270	0.530	Plasma torch^**	10.0	90 s	[172]
C10	APS ZrC-SiC	0.290	0.080	Oxy-acetylene^*	2.4	120 s	[169]
C11	APS HfC-TaC	0.680	-0.580	Oxy-acetylene^*	2.4	120 s	[74]
C12	APS HfC-Hf₆Ta₂O₁₇	-0.320	-1.350	Oxy-acetylene^*	2.4	120 s	[141]
C13	CVD HfC-SiC	0.153	-0.998	Oxy-acetylene^*	2.4	60 s	[78]
C14	APS HfC-ZrC-TiC	0.180	0.710	Oxy-acetylene^*	2.4	120 s	[135]
C15	APS (Hf_1/4Zr_1/4Ta_1/4Ti_1/4)C	0.810	0.190	Oxy-acetylene^*	2.4	180 s	[173]
C16	APS ZrC-SiHfOC	0.099	0.200	Plasma torch^**	10.0	90 s	[172]
C17	CVD (ZrC/SiC)₃	0.750	-0.028	Oxy-acetylene^*	2.4	60 s	[114]
C18	CVD SiC/TaC/SiC/TaC	0.180	-0.760	Oxy-acetylene^*	2.4	30 s	[115]
C19	CVD (SiC/HfC)₃	0.241	0.120	Oxy-acetylene^*	2.4	120 s	[113]
C20	APS ZrC-SiC/ZrC-Al₂O₃/ZrC-MoSi₂/ZrC	0.231	0.156	Oxy-acetylene^*	2.4	60 s × 3	[148]
C21	APS ZrC/TaC/ZrC	1.040	-1.170	Oxy-acetylene^*	2.4	60 s	[170]
C22	APS ZrC/ZrC-LaB₆/ZrC-SiC	-1.070	-2.890	Oxy-acetylene^*	4.2	40 s	[171]
C23	APS ZrC-SiC/ZrC-ZrO₂/ZrO₂-Y₂O₃	-0.460	-0.950	Oxy-acetylene^*	2.4	90 s × 2	[174]
C24	CVD (SiC/HfC)₄/SiC	0.640	0.530	Oxy-acetylene^*	2.4	60 s × 3	[153]