Thermal response, oxidation and ablation of ultra-high temperature ceramics, C/SiC, C/C, graphite and graphite-ceramics

doi:10.1016/j.jmst.2021.06.022

Abstract

Abstract:

Various thermal protection materials exhibit obviously different and complicated thermal response, oxidation and ablation behavior, which are very important for the appropriate design and selection. However, the relative researches are very few currently. In this work, the thermal response, oxidation and ablation behavior of representative thermal protection materials including ultra-high temperature ceramics, C/SiC, C/C, graphite and graphite-ceramic were investigated systematically in strong heat flux, high enthalpy and low-pressure environments. Thermal response of these materials was analyzed based on experimental results and thermal energy balance that accounts for all of the heat transfer processes transporting energy into and out of the surface. Many factors were playing important roles in the thermal response including thermal conductivity, volumetric heat capacity, catalytic efficiency, emissivity and oxidation characteristics of the materials. The importance of each factor not only depends on the material characteristics such as material composition and phase content but also environment parameters including heat flux, enthalpy, pressure and testing time. The comparisons and relationships of oxidation and ablation behaviors for these materials under extreme environments were also illustrated in detail. Furthermore, thermal response and ablation behaviors of pre-oxidized material or repeated tests were also performed to evaluate the effect of pre-treatment on the performance and reusability of thermal protection materials. This work offers guiding significance for the appropriate design and selection of thermal protection materials.

Key words: Thermal protection materials, Ceramic, Thermal response, Oxidation, Ablation

Xinghong Zhang, Baihe Du, Ping Hu, Yuan Cheng, Jiecai Han. Thermal response, oxidation and ablation of ultra-high temperature ceramics, C/SiC, C/C, graphite and graphite-ceramics[J]. J. Mater. Sci. Technol., 2022, 102: 137-158.

Figures/Tables 33

Fig. 1. (a) Sample geometry, (b) test models, and (c) schematic of the plasmatron setup.

Table 1 Test parameters.

Condition	Heat flux (MW/m²)	Enthalpy (MJ/kg)	Pressure (kPa)	Ablation time (s)
1	8.39	31.4	5.5	90
2	7.75	29.8	5.2	100-600
3	7.05	27.7	5.0	200-1000
4	5.84	24.2	4.5	200-2500
5	4.5	22.9	3	200-1000

Table 2 Ablation results of thermal protection materials.

Materials	Conditions	Ablation time (s)	Mass change (g)	Thickness of surface recession (mm)	Maximum surface temperature (°C)
Z	1	90	2.0955	3.72	2859
	2	600	-0.0987	—	2433
	3	600	-0.0699	—	2420
	4	1000	-0.1456	—	2386
ZS	1	90	0.877	1.79	2895
	2	600	0.61	0.65	2397
	3	1000	-0.0175	—	2325
	4	1000	-0.0184	0	1522
	4	2500	-0.0376	—	2256
	4*	1000	-0.0074	-0.06	1720
ZSG	1	90	2.3895	3.28	2932
	2	600	1.3521	1.90	2429
	3	1000	0.0261	—	2388
	4	1000	-0.0154	-0.09	2215
CS	2	200	5.4973	10.87	2517
	3	200	4.5449	9.01	2406
	4	200	2.3332	4.58	2321
	5	200	0.2088	0	1580
	5	900	5.3713	11.81	2198
	5*	1000	0.1704	0.3	1617
CC	1	90	1.7790	2.67	2437
	2	200	3.1969	5.24	2323
	3	200	2.9921	4.93	2246
G	1	90	1.8706	3.13	2435
	2	200	3.4452	6.30	2317
	4	200	2.9681	5.32	2137
GS	2	100	—	—	2486
GS	4	200	—	—	2134
GSZ	2	200	3.5069	6.95	2816
	4	200	0.0426	0.06	1641
	4*	1000	0.4581	1.52	2386

Fig. 2. Surface temperature curves of CC, G, CS, GSZ, ZSG, GS, and Z under different test conditions: (a) CC, G, and (b) CS, GSZ, ZSG, GS, Z.

Fig. 3. Temperature curves of GSZ tested for first and second circles under condition 4.

Fig. 4. Temperature curves of ZS with and without pre-oxidized tested under condition 4 for 1000 s.

Fig. 5. Photographs of thermal protection materials after 90 s ablation under condition 1: (a) Z, (b) ZS, (c) ZSG, (d) CC, (e) G, and (f) ZSG during testing

Fig. 6. Photographs of thermal protection materials after ablation under condition 2: (a) Z, (b) ZS, (c) ZSG, (d) CS, (e) CC, (f) G, (g) GS, (h) GSZ.

Fig. 7. Surface and side images of thermal protection materials after ablation under condition 3: (a, f) Z, (b, g) ZS, (c, h) ZSG, (d, i) CS, (e, j) CC.

Fig. 8. Photographs of thermal protection materials after ablation under condition 4: (a) Z, (b) ZS, (c) ZSG, (d) CS, (e) CC, (f) GS, (g) GSZ (200s), (h) GSZ (200+1000s), (i and j) enlarged photographs of GSZ after 200 s ablation.

Fig. 9. Photographs of CS after (a) 200 s and (b) 900 s ablation under condition 4.

Fig. 10. Photographs of CS during testing under condition 4.

Fig. 11. (a) Photograph of the test model during testing, (b) a schematic of the steady-state energy balance at the surface, and (c) photograph of comparison between C/C and graphite under condition 2.

Table 3 Radiative out the energy of thermal protection materials.

Materials	Conditions	Maximum surface temperature (°C)	Radiative out energy (MW/m²)
Z	1	2859	3.82
	2	2433	2.13
	3	2420	2.09
	4	2255	1.62
ZS	1	2895	4.00
	2	2397	2.02
	3	2325	1.81
	4	2256	1.62
CS	2	2517	3.09
	3	2406	2.63
	4	2321	2.31
CC	1	2437	2.75
	2	2323	2.32
	3	2246	2.05
G	4	2137	1.72
GSZ	2	2816	3.61
GSZ	4	2386	1.98

Fig. 12. Temperature curves and temperature difference of C/C and G at different regions under condition 2: (a) Temperature curves (b) temperature difference.

Fig. 13. (a) Temperature curves of C/SiC and C/C under different conditions, (b) temperature curves of C/SiC and C/C at the beginning of the heating under different conditions.

Table 4 Variations of the surface temperature and radiative energy before and after temperature jump.

Materials	Conditions	Temperature jump (°C)	The change of radiative out energy before and after temperature jump (MW/m²)	The percentage of the energy change in total heat flux
ZS	1	1105	3.18	37.9%
	2	677	1.30	16.7%
	3	654	1.16	16.5%
	4	574	0.96	16.4%
CS	2	828	2.42	31.2%
	3	683	1.91	27.1%
	4	660	1.68	28.8%
GSZ	2	1196	3.61	39.1%
GSZ	4	631	1.21	20.7%

Fig. 14. Temperature curves of ZS and ZSG under condition 1.

Fig. 15. Schematic of surface temperature vs. test time for Si-contained materials exposed to partially dissociated air over a certain heat flux.

Fig. 16. Temperature curves of thermal protection materials under condition 4.

Fig. 17. Schematic of oxidation rate vs. temperature for different materials.

Fig. 18. Photographs of ZrB2 (a) during testing and (b) cooling process under condition 1, and (c, d) Photographs of ZS after deep filtration the testing under condition 3.

Fig. 19. Photographs of ZS after testing under condition 2: (a) integral structure, (b) outside scale was removed, (c) outside scale, (d) reversed outside scale.

Fig. 20. (a-c) SEM images of ZS after testing under condition 2 and (d-g) SEM micrographs of the inner surface for ZS after testing under condition 2 (outside scale was removed).

Fig. 21. Video images of Z during testing under condition 1, and (b) temperature curves of Z at different regions under condition 2 for 600 s.

Fig. 22. Surface morphologies of UHTCs under condition 1: (a) Z, (b) ZS, (c) ZSG.

Fig. 23. Video images of C/SiC during testing under condition 3.

Fig. 24. SEM morphologies of C/SiC composites after test under condition 2: (a) low magnification, (b)-(d) large magnification.

Fig. 25. SEM micrographs of graphite and C/C after oxidation and ablation under condition 1: (a) G, (b) low magnification of CC, (c) high magnification of CC.

Fig. 26. Photographs of thermal protection materials after test under conditions 1 and 2: (a) CC (Condition 1), (b) G (Condition 1), (c) CC (Condition 2), (d) G (Condition 2). The green solid line represents the initial surface contour. The areas between the green solid line and color contours are the materials ablated after tests under conditions 1 and 2.

Fig. 27. Video images of C/C (a) and G (b) during testing under condition 2, and (c) video images of GS during testing and cooling process.

Fig. 28. Video images of GSZ during testing under condition 2.

Fig. 29. (a) SEM micrographs of GSZ in the center, and (b) edge regions after test under condition 2 where the outside oxide scale was flaked off during the cooling process.

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