Ablation behaviour of (Hf-Ta-Zr-Nb)C high entropy carbide ceramic at temperatures above 2100 °C

doi:10.1016/j.jmst.2021.09.064

Abstract

Abstract:

The ablation behaviour of (Hf-Ta-Zr-Nb)C high entropy carbide (HEC4) was studied at temperatures above 2100 °C using a plasma flame gun in air. The microstructures, phase and chemical compositions of the HEC4 samples were investigated after ablation. The mass ablation rate of the HEC4 samples increased with increasing ablation time from 0.21 mg cm^-2 s^-1 for 60 s to 0.45 mg cm^-2 s^-1 for 120 s. Compared to the mono- and binary carbides with commonly decreased mass and thickness after ablation, the HEC4 samples with the increased mass and thickness after ablation showed good resistance to mechanical scouring at such high temperatures and an oxidation controlled ablation mechanism. The ablation processes mainly include the oxidation of the carbide, the phase separation of the oxides, the melting of oxides, and the diffusion of oxygen. A composition gradient in the oxide layer was detected due to the different melting temperatures of the different oxides; Nb-Ta rich oxides formed at the front surface melted and became enriched at the edge of the samples, and the Zr-Hf rich oxides were enriched in the centre of the samples. The oxide layer with complex compositions and phase distributions acted as an effective ablation barrier.

Key words: High entropy carbides, Transition metal carbides, Ultra-high temperature ceramics, Ablation resistance

Yichen Wang, Buhao Zhang, Chengyu Zhang, Jie Yin, Michael J. Reece. Ablation behaviour of (Hf-Ta-Zr-Nb)C high entropy carbide ceramic at temperatures above 2100 °C[J]. J. Mater. Sci. Technol., 2022, 113: 40-47.

Figures/Tables 11

Fig. 1. SEM image and photo of HEC4.

Table 1. Ablation rates (LAR and MAR) of HEC4 and a comparison for a range of carbides.

Materials	Conditions of ablation test	LAR (μm s^-1)	MAR (mg cm^-2 s^-1)	Refs.
HEC4-60	Plasma flame, ∼2100 °C, 60 s, 1.3 MW m^-2	8.5 ± 5	0.21	This work
HEC4-120	Plasma flame, ∼2100 °C, 120 s, 1.3 MW m^-2	4.8 ± 3	0.45	This work
HfC	Oxyacetylene flame, ∼2500 °C, 60 s, 2.4 MW m^-2	-0.73	-0.031	[30]
HfC	Oxyacetylene flame, ∼2900 °C, 180 s,	-11.0	-0.56	[28]
Ta_0.8Hf_0.2C	Plasma flame, ∼2100 °C, 90 s, 4.0 MW m^-2	-3.5	/	[31]
ZrC-SiC coating	Plasma flame, ∼2700 °C, 300 s, 3.0 MW m^-2	0.15	-0.11	[32]
Ta-Hf-C coating	Oxyacetylene flame, ∼2100 °C, 30 s, 4.2 MW m^-2	-0.94	-0.082	[29]

Fig. 2. SEM images and photos of morphologies of (a) HEC4-60 and (b) HEC4-120.

Fig. 3. XRD spectra of the front surface of HEC4-60 and HEC4-120.

Fig. 4. BSE images of the ablated front surface of the centre of (a, b) HEC4-60 and (c, d) HEC4-120; and (e) EDS maps of the square in (d).

Table 2. Possible alternate phase matches for the XRD results in Fig. 3.

Symbol	Indicated phase	PDF number	Possible alternate oxides
♣	TaZr_2.75O₈	42-0060	(Nb, Ta)(Zr, Hf)_2.75O₈ [37]
♦	Nb₂Zr₆O₁₇	09-0251	(Nb, Ta)₂(Zr, Hf)₆O₁₇ [22,23,38]
♥	Ta₂O₅	21-1198	(Nb, Ta)₂O₅ [39]
♠	HfO₂	43-1017	(Zr, Hf)O₂ [20, 40]

Fig. 5. XPS spectra of the centre/middle/edge of HEC4-120.

Fig. 6. SEM images of the cross section of the centre of (a) HEC4-60 and (b) HEC4-120; (c) and (d) are the corresponding EDS results of the red rectangles in (a) and (b), respectively. The front surface of the samples is at the top of all of the images.

Fig. 7. BSE images and EDS results from a cross section of the centre of the ablated specimens: (a) HEC4-60; (b) HEC4-120; (c) EDS results of points in (a and b); and (d) EDS results of points though the oxide layer of HEC4-120 in (b). The front surface of the samples is at the top of all of the images.

Fig. 8. (a) BSE image of the cross section of the edge of HEC4-120; (b) BSE image of the red square in the near surface layer in (a); (c) EDS results of points in (a) and (b). The front surface of the samples is at the top of all of the images.

Fig. 9. Schematic diagram of ablation mechanism model for HEC4.

References 45

[1]	P. Sarker, T. Harrington, C. Toher, C. Oses, M. Samiee, J.-.P. Maria, D.W. Brenner, K.S. Vecchio, S. Curtarolo, Nat. Commun. 9 (2018) 4980. DOI URL
[2]	E. Castle, T. Csanádi, S. Grasso, J. Dusza, M. Reece, Sci. Rep. 8 (2018) 8609. DOI URL
[3]	F.Z. Dai, B. Wen, B. Gao, Q. Zou, Y. Sun, Q. Yang, D. Tian, H. Xian, Y. Zhou, J. Mater. Sci. Technol. 43 (2020) 168-174. DOI URL
[4]	H. Xiang, Y. Xing, F.Z. Dai, H. Wang, L. Su, L. Miao, G. Zhang, Y. Wang, X. Qi, L. Yao, H. Wang, B. Zhao, J. Li, Y. Zhou, J. Adv. Ceram. 10 (2021) 385-441. DOI URL
[5]	B. Ye, T. Wen, K. Huang, C.Z. Wang, Y. Chu, J. Am. Ceram. Soc. 102 (2019) 4344-4352. DOI URL
[6]	D. Liu, A. Zhang, J. Jia, J. Meng, B. Su, J. Eur. Ceram. Soc. 40 (2020) 2746-2751. DOI URL
[7]	K. Wang, L. Chen, C. Xu, W. Zhang, Z. Liu, Y. Wang, J. Ouyang, X. Zhang, Y. Fu, Y. Zhou, J. Mater. Sci. Technol. 39 (2020) 99-105. DOI
[8]	B. Ye, T. Wen, M.C. Nguyen, L. Hao, C.Z. Wang, Y. Chu, Acta Mater. 170 (2019) 15-23. DOI URL
[9]	K. Kaufmann, D. Maryanovsky, W.M. Mellor, C. Zhu, A.S. Rosengarten, T.J. Har-rington, C. Oses, C. Toher, S. Curtarolo, K.S. Vecchio, Npj Comput\. Mater. 6 (2020) 42.
[10]	Y. Wang, T. Csanadi, H. Zhang, J. Dusza, M.J. Reece, R.Z. Zhang, Adv. Theory Simul. 3 (2020) 2000111. DOI URL
[11]	Y. Sun, F. Chen, W. Qiu, L. Ye, W. Han, W. Zhao, H. Zhou, T. Zhao, J. Am. Ceram. Soc. 103 (2020) 6081-6087. DOI URL
[12]	X. Yan, L. Constantin, Y. Lu, J.F. Silvain, M. Nastasi, B. Cui, J. Am. Ceram. Soc. 101 (2018) 4486-4491. DOI URL
[13]	H. Chen, H. Xiang, F.Z. Dai, J. Liu, Y. Lei, J. Zhang, Y. Zhou, J. Mater. Sci. Technol. 35 (2019) 1700-1705. DOI
[14]	T.J. Harrington, J. Gild, P. Sarker, C. Toher, C.M. Rost, O.F. Dippo, C. McElfresh, K. Kaufmann, E. Marin, L. Borowski, Acta Mater. 166 (2019) 271-280. DOI
[15]	T. Csanadi, E. Castle, M.J. Reece, J. Dusza, Sci. Rep. 9 (2019) 10200. DOI URL
[16]	L. Feng, W.T. Chen, W.G. Fahrenholtz, G.E. Hilmas, J. Am. Ceram. Soc. 104 (2021) 419-427. DOI URL
[17]	X. Han, V. Girman, R. Sedlak, J. Dusza, E.G. Castle, Y. Wang, M. Reece, C. Zhang, J. Eur. Ceram. Soc. 40 (2019) 2709-2715. DOI URL
[18]	J.F. Justin, A. Jankowiak, Ultra High Temperature Ceramics: Densiﬁcation, Prop- erties and Thermal Stability (2011) 1-11.
[19]	M.J. Gasch, D.T. Ellerby, S.M. Johnson, Ultra High Temperature Ceramic Com- posites, in: N.P. Bansal (Ed.), Handbook of Ceramic Composites, Springer US, Boston, MA, 2005, pp. 197-224.
[20]	B. Ye, T. Wen, D. Liu, Y. Chu, Corros. Sci. 153 (2019) 327-332. DOI URL
[21]	Y. Wang, R.Z. Zhang, B. Zhang, O. Skurikhina, P. Balaz, V. Araullo-Peters, M. J. Reece, Corros. Sci. 176 (2020) 109019. DOI URL
[22]	B. Ye, T. Wen, Y. Chu, J. Am. Ceram. Soc. 103 (2020) 500-507. DOI URL
[23]	L. Backman, J. Gild, J. Luo, E.J. Opila, Acta Mater. 197 (2020) 81-90. DOI URL
[24]	Y. Tan, C. Chen, S. Li, X. Han, J. Xue, T. Liu, X. Zhou, H. Zhang, J. Alloys Compd. 816 (2020) 152523. DOI URL
[25]	L. Backman, J. Gild, J. Luo, E.J. Opila, Acta Mater. 197 (2020) 20-27. DOI URL
[26]	Y. Wang, M.J. Reece, Scr. Mater. 193 (2021) 86-90. DOI URL
[27]	J. Dusza, P. Švec, V. Girman, R. Sedlák, E.G. Castle, T. Csanádi, A. Koval číková, M. J. Reece, J. Eur. Ceram. Soc. 38 (2018) 4303-4307. DOI URL
[28]	Z. Peng, W. Sun, X. Xiong, Y. Xu, Z. Zhou, Z. Zhan, H. Zhang, Y. Zeng, Corros. Sci. (2021) 109623.
[29]	Z.Y. Tan, W. Zhu, L. Yang, Y.C. Zhou, Q. Wu, L.J. Gong, Surf. Coat. Tech. 403 (2020) 126405. DOI URL
[30]	N. Ni, W. Hao, T. Liu, L. Zhou, F. Guo, X. Zhao, P. Xiao, Ceram. Int. 46 (2020) 23840-23853. DOI URL
[31]	B. Zhang, J. Yin, J. Zheng, X. Liu, Z. Huang, J. Dusza, D. Jiang, J. Eur. Ceram. Soc. 40 (2020) 1784-1789. DOI URL
[32]	T. Liu, Y. Niu, C. Li, X. Pan, M. Shi, X. Zheng, C. Ding, Corros. Sci. 145 (2018) 239-248. DOI URL
[33]	L. Pienti, D. Sciti, L. Silvestroni, A. Cecere, R. Savino, J. Eur. Ceram. Soc. 35 (2015) 1401-1411. DOI URL
[34]	J. Gild, M. Samiee, J.L. Braun, T. Harrington, H. Vega, P.E. Hopkins, K. Vecchio, J. Luo, J. Eur. Ceram. Soc. 38 (2018) 3578-3584. DOI URL
[35]	F. Li, L. Zhou, J.X. Liu, Y. Liang, G.J. Zhang, J. Adv. Ceram. 8 (2019) 576-582. DOI URL
[36]	G.V. Samsonov, in: G.V. Samsonov (Ed.), The Oxide Handbook, Springer US, Boston, MA, 1973, pp. 36-223.
[37]	G. Hautier, C. Fischer, V. Ehrlacher, A. Jain, G. Ceder, Inorg. Chem. 50 (2011) 656-663. DOI URL
[38]	S.J. McCormack, W.M. Kriven, Acta Crystallogr. B 75 (2019) 227-234. DOI PMID
[39]	H. Wang, S. Wang, Y. Cao, W. Liu, Y. Wang, J. Mater. Sci. Technol. 60 (2021) 147-155. DOI URL
[40]	J. Tang, F. Zhang, P. Zoogman, J. Fabbri, S.W. Chan, Y. Zhu, L.E. Brus, M.L. Steiger- wald, Adv. Funct. Mater. 15 (2005) 1595-1602. DOI URL
[41]	C. Gasparrini, R.J. Chater, D. Horlait, L. Vandeperre, W.E. Lee, J. Am. Ceram. Soc. 101 (2018) 2638-2652. DOI URL
[42]	C. Zhang, B. Boesl, A. Agarwal, Ceram. Int. 43 (2017) 14798-14806. DOI URL
[43]	L. Zhao, D. Jia, X. Duan, Z. Yang, Y. Zhou, J. Eur. Ceram. Soc. 32 (2012) 947-954. DOI URL
[44]	H. Wang, Y. Cao, W. Liu, Y. Wang, Ceram. Int. 46 (2020) 11160-11168. DOI URL
[45]	J. Yuan, W. Song, H. Zhang, X. Zhou, S. Dong, J. Jiang, L. Deng, X. Cao, Mater. Lett. 247 (2019) 82-85. DOI URL