Design, Preparation and Properties of Carbon Fiber Reinforced Ultra-High Temperature Ceramic Composites for Aerospace Applications: A Review

Abstract

Abstract:

Carbon fiber reinforced ultra-high temperature ceramic (UHTC) composites, consisting of carbon fibers embedded in a UHTC-matrix or a C-SiC-UHTC-matrix, are deemed as the most viable class of materials that can overcome the poor fracture toughness and thermal shock resistance of monolithic UHTC materials, and also improve the oxidation resistance and ablation resistance of C/C and C/SiC composites at ultra-high temperatures. In this review, we summarize the different processing routes of the composites based on the UHTC introducing methods, including chemical vapor infiltration/deposition (CVI/D), precursor infiltration and pyrolysis (PIP), reactive melt infiltration (RMI), slurry infiltration (SI), in-situ reaction, hot pressing (HP), etc; and the advantages and drawbacks of each method are briefly discussed. The carbon fiber reinforced UHTC composites can be highly tailorable materials in terms of fiber, interface, and matrix. From the perspective of service environmental applications for engine propulsions and hypersonic vehicles, the material designs (mainly focusing on the composition, quantity, structure of matrix, as well as the architecture of carbon fibers, UHTCs and pores), their relevant processing routes and properties (emphasizing on the mechanical and ablation properties) are discussed in this paper. In addition, we propose a material architecture to realize the multi-function through changing the distribution of carbon fibers, UHTCs and pores, which will be an important issue for future development of carbon fiber reinforced UHTC composites.

Key words: Carbon fiber composites, Ceramic matrix composites (CMC), Ultra-high temperature ceramic (UHTC), Ablation

Tang Sufang,Hu *Chenglong,*. Design, Preparation and Properties of Carbon Fiber Reinforced Ultra-High Temperature Ceramic Composites for Aerospace Applications: A Review[J]. J. Mater. Sci. Technol., 2017, 33(2): 117-130.

Figures/Tables 15

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Property/material	C	SiC	HfC	ZrC	TaC	HfB₂	ZrB₂
Molecular weight (g/mol)	12.01	40.10	190.54	103.23	192.96	200.11	112.84
Density (g/cm³)	2.2	3.2	12.7	6.6	14.5	11.2	6.1
Melting point (°C)	3550 (sublimation)	2700	3890	3540	3880	3380	3245
Thermal expansion (ppm/°C)	2.5 (PyC)	4.3 (6H)	6.8	7.3	6.6	6.3	5.9
Thermal conductivity (W/(m °C))	150	125	22	20	22	104	85
Specific heat (J/(g °C))	0.84	0.58	0.20	0.37	0.19	0.25	0.43
Hardness (kg/mm²)	20	2500	2300	2700	2500	2800	2300
Young's modulus (GPa)	—	448	350-510	350-440	285-560	480	489
Poisson's ratio	—	0.168	0.18	0.191	0.24	0.21	0.16
Oxidation temperature (°C)	~450	~1200	~800	~600	~750	~800	~700

Property/material	C	SiC	HfC	ZrC	TaC	HfB₂	ZrB₂
Molecular weight (g/mol)	12.01	40.10	190.54	103.23	192.96	200.11	112.84
Density (g/cm³)	2.2	3.2	12.7	6.6	14.5	11.2	6.1
Melting point (°C)	3550 (sublimation)	2700	3890	3540	3880	3380	3245
Thermal expansion (ppm/°C)	2.5 (PyC)	4.3 (6H)	6.8	7.3	6.6	6.3	5.9
Thermal conductivity (W/(m °C))	150	125	22	20	22	104	85
Specific heat (J/(g °C))	0.84	0.58	0.20	0.37	0.19	0.25	0.43
Hardness (kg/mm²)	20	2500	2300	2700	2500	2800	2300
Young's modulus (GPa)	—	448	350-510	350-440	285-560	480	489
Poisson's ratio	—	0.168	0.18	0.191	0.24	0.21	0.16
Oxidation temperature (°C)	~450	~1200	~800	~600	~750	~800	~700

Materials	Fabrication method	Density (g/cm³)	Flexural strength (MPa)	Ablation method	Temperature		Time (s)	Ablation rate
Materials	Fabrication method	Density (g/cm³)	Flexural strength (MPa)	Ablation method	Flame	Surface	Time (s)	Ablation rate
C/C-HfC	CVI?+?PIP	2.01	132	Plasma generator	—	~2537?K	240?s	0.55?mg/(cm²s)^[36] 5.31?µm/s
C/C-HfC	In-situ reaction?+?TCVI	1.80	~65	Oxyacetylene	—	~1900?°C	60?s	~2.0?mg/(cm²s)^[73] ~0.7?µm/s
C/C-ZrC	In-situ reaction?+?TCVI	1.81	—	Small solid rocket hot-fire	~3380?K	—	3-4?s	~10?µm/s^[68]
C/C-TaC	CVI	3.53	—	Oxyacetylene	>2000?K	—	120?s	~20?mg/s^[92]
C/ZrC	PIP?+?RMI	—	63^[54]	Oxyacetylene	~3100?°C	~2100?°C		0.6?mg/s^[53] 1.9?µm/s
C/ZrC	CVI?+?RMI		172	Oxyacetylene	—	~2600?°C	270?s	0.56?mg/(cm²s)^[52] 0.24?µm/s
C/C-ZrC-SiC	CVI?+?PIP	2.19	—	Plasma	—	~2200?°C	300?s	0.55?mg/s^[93] 1.77?µm/s
C/C-SiC-ZrC	CVI?+?RMI	1.86	—	Oxyacetylene	~2300?°C	—	30?s	0.24?mg/s^[48] 1.33?µm/s
C/ZrC-SiC	PIP	2.04	—	Oxyacetylene	~3000?°C	—	80?s	0.32?mg/(cm²s)^[94] 16?µm/s
C/ZrC-SiC	In-situ reaction	~2.1	290	Plasma	~2400?K	~2400?K	600?s	0.9?µm/s^[67]
C/ZrB₂-ZrC -SiC	PIP	2.28	248	Plasma	—	~2300?K	300?s	10?mg/s^[16] 2?µm/s
C/SiC-SiBC	LPCVI?+?SI+ LSI?+?CVD	2.2	276^[95]	—	—	—	—	—
C/ZrC-SiC	PIP	2.11	136	Oxyacetylene	~3000?°C	~2700?°C	40?s	8.8?mg/s^[45] 23?µm/s
C/ZrC-SiC	PIP?+?RMI	2.94	101.5	Oxyacetylene	——		30?s	13?mg/s^[46] 22?µm/s
C/ZrC-SiC	PIP	1.99	—	Oxyacetylene	~3100?°C	~2200?°C	90?s	8.9?mg/s^[44] 13.6?µm/s
C/ZrB₂-SiC	PPI?+?CVI	2.4	148	Arc wind tunnel	~2000?°C	~1250?°C	650?s	-0.114?µm/s[76]^;[77]
C/SiC-TaC	SI?+?CVI	—	—	Oxyacetylene	—	—	20?s	0. 9?mg/s^[96] 6.8?µm/s
C/SiC-TaC	SI?+?PIP	5.67	211	Oxyacetylene	~3100?°C	~2100?°C	60?s	17?mg/s^[65] 13?µm/s
C/SiC-ZrB₂-TaC	SI?+?PIP+ CVI	2.35	255	Oxyacetylene	~3000?°C	—	20?s	26?µm/s^[97]
C/HfB₂-SiC	HP	7.24	~350^[75]	—	—	—	—	—

Materials	Fabrication method	Density (g/cm³)	Flexural strength (MPa)	Ablation method	Temperature		Time (s)	Ablation rate
Materials	Fabrication method	Density (g/cm³)	Flexural strength (MPa)	Ablation method	Flame	Surface	Time (s)	Ablation rate
C/C-HfC	CVI?+?PIP	2.01	132	Plasma generator	—	~2537?K	240?s	0.55?mg/(cm²s)^[36] 5.31?µm/s
C/C-HfC	In-situ reaction?+?TCVI	1.80	~65	Oxyacetylene	—	~1900?°C	60?s	~2.0?mg/(cm²s)^[73] ~0.7?µm/s
C/C-ZrC	In-situ reaction?+?TCVI	1.81	—	Small solid rocket hot-fire	~3380?K	—	3-4?s	~10?µm/s^[68]
C/C-TaC	CVI	3.53	—	Oxyacetylene	>2000?K	—	120?s	~20?mg/s^[92]
C/ZrC	PIP?+?RMI	—	63^[54]	Oxyacetylene	~3100?°C	~2100?°C		0.6?mg/s^[53] 1.9?µm/s
C/ZrC	CVI?+?RMI		172	Oxyacetylene	—	~2600?°C	270?s	0.56?mg/(cm²s)^[52] 0.24?µm/s
C/C-ZrC-SiC	CVI?+?PIP	2.19	—	Plasma	—	~2200?°C	300?s	0.55?mg/s^[93] 1.77?µm/s
C/C-SiC-ZrC	CVI?+?RMI	1.86	—	Oxyacetylene	~2300?°C	—	30?s	0.24?mg/s^[48] 1.33?µm/s
C/ZrC-SiC	PIP	2.04	—	Oxyacetylene	~3000?°C	—	80?s	0.32?mg/(cm²s)^[94] 16?µm/s
C/ZrC-SiC	In-situ reaction	~2.1	290	Plasma	~2400?K	~2400?K	600?s	0.9?µm/s^[67]
C/ZrB₂-ZrC -SiC	PIP	2.28	248	Plasma	—	~2300?K	300?s	10?mg/s^[16] 2?µm/s
C/SiC-SiBC	LPCVI?+?SI+ LSI?+?CVD	2.2	276^[95]	—	—	—	—	—
C/ZrC-SiC	PIP	2.11	136	Oxyacetylene	~3000?°C	~2700?°C	40?s	8.8?mg/s^[45] 23?µm/s
C/ZrC-SiC	PIP?+?RMI	2.94	101.5	Oxyacetylene	——		30?s	13?mg/s^[46] 22?µm/s
C/ZrC-SiC	PIP	1.99	—	Oxyacetylene	~3100?°C	~2200?°C	90?s	8.9?mg/s^[44] 13.6?µm/s
C/ZrB₂-SiC	PPI?+?CVI	2.4	148	Arc wind tunnel	~2000?°C	~1250?°C	650?s	-0.114?µm/s[76]^;[77]
C/SiC-TaC	SI?+?CVI	—	—	Oxyacetylene	—	—	20?s	0. 9?mg/s^[96] 6.8?µm/s
C/SiC-TaC	SI?+?PIP	5.67	211	Oxyacetylene	~3100?°C	~2100?°C	60?s	17?mg/s^[65] 13?µm/s
C/SiC-ZrB₂-TaC	SI?+?PIP+ CVI	2.35	255	Oxyacetylene	~3000?°C	—	20?s	26?µm/s^[97]
C/HfB₂-SiC	HP	7.24	~350^[75]	—	—	—	—	—

	Density (g cm^-3)	Flexural strength (MPa)	TC (24.5?°C) (W m^-1?K^-1)	Linear ablation rate (µm/s)
Integrated composites	1.65?±?0.05	260?±?31	3.29?±?0.25	0.79(1000?s)
Dense C/SiC	2.10?±?0.1	310?±?30	9.4?±?0.40	1.40(400?s)