Preparation and electrical conductivity of (Zr, Hf, Pr, Y, La) O high entropy fluorite oxides

doi:10.1016/j.jmst.2021.07.028

Abstract

Abstract:

A series of compositionally complex fluorite oxides (CCFOs) were prepared by ball milling the mixture of ZrO₂, HfO₂, Y₂O₃, La₂O₃, and Pr₆O₁₁ followed by conventional solid-state sintering. Both XRD and TG-DSC results demonstrated that single-phase (Zr_0.2Hf_0.2Pr_0.2Y_0.2La_0.2)O_2-δ was formed at 1400 °C. Elements in bulk ceramic were uniformly distributed without evident accumulation according to SEM-EDS pictures. TEM results revealed that polycrystalline ceramic powder was assignable to cubic Fm-3m fluorite structure. The electrical conductivity (σ) was measured via EIS technology and activation energy (E_a) of CCFOs was calculated in Arrhenius plots. In the temperature range of 300-750 °C, CCFOs preserved the same conduction mechanism and (Zr_0.1667Hf_0.1667Pr_0.1667Y_0.25La_0.25)O_2-δ possessed higher σ and lower E_a than other high entropy fluorite oxides which is related to the incorporation of Pr element or the connection of cation-V_o complex.

Key words: High-entropy ceramic, Fluorite structure, Electrical conductivity, Cation-size difference

Fengnian Zhang, Fuhao Cheng, Chufei Cheng, Meng Guo, Yufeng Liu, Yang Miao, Feng Gao, Xiaomin Wang. Preparation and electrical conductivity of (Zr, Hf, Pr, Y, La) O high entropy fluorite oxides[J]. J. Mater. Sci. Technol., 2022, 105: 122-130.

Figures/Tables 12

References 55

[1]	Z. Lei, X. Liu, H. Wang, Y. Wu, S. Jiang, Z. Lu, Scripta Mater 165 (2019) 164-169. DOI URL
[2]	W. Xu, H. Chen, K. Jie, Z. Yang, T. Li, S. Dai, Angew. Chem. Int. Ed. Engl. 58 (2019) 5018-5022. DOI URL
[3]	H. Chen, W.W. Lin, Z.H. Zhang, K. Jie, D.R. Mullins, X. Sang, S.-Z. Yang, C.J. Jafta, C.A. Bridges, X. Hu, R.R. Unocic, J. Fu, P. Zhang, S. Dai, ACS Mater. Lett. 1 (2019) 83-88.
[4]	R. Liu, H. Chen, K. Zhao, Y. Qin, B. Jiang, T. Zhang, G. Sha, X. Shi, C. Uher, W. Zhang, L. Chen, Adv. Mater. 29 (2017) 1702712. DOI URL
[5]	S.H. Albedwawi, A.H. AlJaberi, N. Gregory, K. Polychronopoulou, Mater. Des. 202 (2021) 109534. DOI URL
[6]	C.-F. Wu, D.E.S. Arifin, C.-A. Wang, J. Ruan, Polymer 138 (2018) 188-202. DOI URL
[7]	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
[8]	C.M. Rost, E. Sachet, T. Borman, A. Moballegh, E.C. Dickey, D. Hou, J.L. Jones, S. Curtarolo, J.-P. Maria, Nat. Commun. 6 (2015) 8485. DOI URL
[9]	M. Zhang, X. Xu, Y. Yue, M. Palma, M.J. Reece, H. Yan, Mater. Des. 200 (2021) 109447. DOI URL
[10]	K. Chen, Y. Chen, J. Zhang, Y. Song, X. Zhou, M. Li, X. Fan, J. Zhou, Q. Huang, Ceram. Int. 47 (2021) 7582-7587. DOI URL
[11]	Y. Sun, H. Xiang, F.-Z. Dai, X. Wang, Y. Xing, X. Zhao, Y. Zhou, J. Adv. Ceram. 10 (2021) 596-613. DOI URL
[12]	X. Meng, J. Xu, J. Zhu, P. Zhang, A. Rydosz, M.J. Reece, F. Gao, Scripta Mater 194 (2021) 113714. DOI URL
[13]	Y. Li, S. Wang, X. Wang, M. Yin, W. Zhang, J. Mater. Sci. Technol. 43 (2020) 32-39. DOI URL
[14]	A.J. Wright, J. Luo, J. Mater. Sci. 55 (2020) 9812-9827. DOI URL
[15]	A. Amiri, R. Shahbazian-Yassar, J. Mater. Chem. A 9 (2021) 782-823. DOI URL
[16]	H.D. Xu, Z.H. Zhang, J.X. Liu, C.L. Do-Thanh, H. Chen, S.H. Xu, Q.J. Lin, Y. Jiao, J.L. Wang, Y. Wang, Y.Q. Chen, S. Dai, Nat. Commun. 11 (2020) 1-9. DOI URL
[17]	Z.F. Zhao, H. Chen, H.M. Xiang, F.Z. Dai, X.H. Wan, Z.J. Peng, Y.C. Zhou, J. Mater. Sci. Technol. 35 (2019) 2892-2896. DOI URL
[18]	M. Ahn, Y. Park, S.H. Lee, S. Chae, J. Lee, J.T. Heron, E. Kioupakis, W.D. Lu, J.D. Phillips, Adv. Electron. Mater. 7 (2021) 2001258. DOI URL
[19]	H. Zhang, B. Zhao, F.-Z. Dai, H. Xiang, Z. Zhang, Y. Zhou, J. Mater. Sci. Technol. 77 (2020) 58-65. DOI URL
[20]	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
[21]	K.P. Chen, X.T. Pei, L. Tang, H.R. Cheng, Z.M. Li, C.W. Li, X.W. Zhang, L. An, J. Eur. Ceram. Soc. 38 (2018) 4161-4164. DOI URL
[22]	J. D˛abrowa, M. Szymczak, M. Zajusz, A. Mikuła, M. Moździerz, K. Berent, M. Wytrwal-Sarna, A. Bernasik, M. Stygar, K. Świerczek, J.Eur.Ceram. Soc. 40 (2020) 5870-5881.
[23]	E. Bonnet, J.C. Grenier, J.M. Bassat, A. Jacob, B. Delatouche, S. Bourdais, J. Eur. Ceram. Soc. 41 (2021) 4505-4515. DOI URL
[24]	D. Bérardan, S. Franger, A.K. Meena, N. Dragoe, J. Mater. Chem. A 4 (2016) 9536-9541. DOI URL
[25]	J. D˛abrowa, J. Cieślak, M. Zajusz, M. Moździerz, K. Berent, A. Mikuła, A. St˛epień, K. Świerczek, J. Eur. Ceram. Soc. 41 (2021) 3844-3849. DOI URL
[26]	S.J. Skinner, J.A. Kilner, Mater. Today 6 (2003) 30-37.
[27]	M. Pianassola, M. Loveday, J.W. McMurray, M. Koschan, C.L. Melcher, M. Zhu-ravleva, J. Am. Ceram. Soc. 103 (2020) 2908-2918. DOI URL
[28]	A.J. Wright, Q. Wang, C. Huang, A. Nieto, R. Chen, J. Luo, J. Eur. Ceram. Soc. 40 (2020) 2120-2129. DOI URL
[29]	R.D. Shannon, Acta Cryst. A 32 (1976) 751-767. DOI URL
[30]	B. Toby, J. Appl. Crystallogr. 34 (2001) 210-213. DOI URL
[31]	C. Artini, M. Pani, M.M. Carnasciali, M.T. Buscaglia, J.R. Plaisier, G.A. Costa, In-org. Chem. 54 (2015) 4126-4137.
[32]	L. Spiridigliozzi, C. Ferone, R. Cioffi, G. Accardo, D. Frattini, G. Dell’Agli, Materi-als 13 (2020) 558-12.
[33]	H. Chen, Z. Zhao, H. Xiang, F.-Z. Dai, J. Zhang, S. Wang, J. Liu, Y. Zhou, J. Mater. Sci. Technol. 38 (2020) 80-85. DOI
[34]	A.R. Denton, N.W. Ashcroft, Phys. Rev. A 43 (1991) 3161. DOI PMID
[35]	A. Sarkar, R. Djenadic, N.J. Usharani, K.P. Sanghvi, V.S.K. Chakravadhanula, A.S. Gandhi, H. Hahn, S.S. Bhattacharya, J. Eur. Ceram. Soc. 37 (2017) 747-754. DOI URL
[36]	A. Mao, H.-Z. Xiang, Z.-G. Zhang, K. Kuramoto, H. Yu, S. Ran, J. Magn. Magn. Mater. 484 (2019) 245-252. DOI URL
[37]	P. Zhang, X. Liu, A. Cai, Q. Du, X. Yuan, H. Wang, Y. Wu, S. Jiang, Z. Lu, Sci. China Mater. 64 (2021) 2037-2044. DOI URL
[38]	A. Sarkar, B. Eggert, L. Velasco, X. Mu, J. Lill, K. Ollefs, S.S. Bhattacharya, H. Wende, R. Kruk, R.A. Brand, H. Hahn, Apl. Mater. 8 (2020) 051111. DOI URL
[39]	A. Filtschew, K. Hofmann, C. Hess, J. Phys. Chem. C 120 (2016) 6694-6703. DOI URL
[40]	Talip Zeynep, Wiss Thierry, E. Philippe, Jérôme Raison, Dario Paillier, J. Am. Ceram. Soc. 98 (2015) 2278-2285. DOI URL
[41]	A. Sarkar, C. Loho, L. Velasco, T. Thomas, S.S. Bhattacharya, H. Hahn, R. Dje-nadic, Dalton T. 46 (2017) 12167-12176. DOI URL
[42]	M. Guo, J. Lu, Y. Wu, Y. Wang, M. Luo, Langmuir 27 (2011) 3872-3877. DOI URL
[43]	R. Djenadic, A. Sarkar, O. Clemens, C. Loho, M. Botros, V.S.K. Chakravadhanula, C. Kübel, S.S. Bhattacharya, A.S. Gandhi, H. Hahn, Mater. Res. Lett. 5 (2016) 102-109. DOI URL
[44]	M. Anandkumar, A. Lathe, A.M. Palve, A.S. Deshpande, J. Alloys Compd. 850 (2021) 156716. DOI URL
[45]	F. Zhang, M. Guo, Y. Miao, F. Gao, C. Cheng, F. Cheng, Y. Liu, J. Inorg. Mater. 36 (2021) 372-378. DOI URL
[46]	Y. Fan, Z. Wang, Y. Huan, T. Wei, X. Wang, J. Adv. Ceram. 9 (2020) 349-359. DOI URL
[47]	S. Kazlauskas, E. Kazakevičius, A. Kežionis, Solid State Ionics 310 (2017) 143-147. DOI URL
[48]	M. Stygar, J. D˛abrowa, M. Moździerz, M. Zajusz, W. Skubida, K. Mroczka, K. Berent, K. Świerczek, M. Danielewski, J. Eur. Ceram. Soc. 40 (2020) 1644-1650. DOI URL
[49]	M. Balcerzak, K. Kawamura, R. Bobrowski, P. Rutkowski, T. Brylewski, J. Elec- tron. Mater. 48 (2019) 7105-7113.
[50]	A. Nakamura, J.B. Wagner, J. Electrochem. Soc. 133 (1986) 1542-1548. DOI URL
[51]	J. Ramírez-González, A.R. West, J. Eur. Ceram. Soc. 40 (2020) 5602-5611. DOI URL
[52]	D.B. Miracle, O.N. Senkov, Acta Mater 122 (2017) 448-511. DOI URL
[53]	L. Spiridigliozzi, C. Ferone, R. Cioffi, G. Dell’Agli, Acta Mater 202 (2021) 181-189. DOI URL
[54]	S. Jiang, T. Hu, J. Gild, N. Zhou, J. Nie, M. Qin, T. Harrington, K. Vecchio, J. Luo, Scripta Mater 142 (2018) 116-120. DOI URL
[55]	K. Chen, J. Ma, C. Tan, C. Li, L. An, Ceram. Int. 47 (2021) 21207-21211. DOI URL

Oxides	Crystal Structure	Space Group	r_c (Å)	CN
ZrO₂	Tetragonal	P42/nmc	0.84	VIII
HfO₂	Monoclinic	P21/c	0.83	VIII
Pr₆O₁₁	Cubic	-	0.96	VIII
Y₂O₃	Bixbyite	Ia-3	1.019	VIII
La₂O₃	Trigonal	P63/mmc	1.16	VIII
CeO₂	Cubic	Fm-3m	0.97	VIII

Oxides	Crystal Structure	Space Group	r_c (Å)	CN
ZrO₂	Tetragonal	P42/nmc	0.84	VIII
HfO₂	Monoclinic	P21/c	0.83	VIII
Pr₆O₁₁	Cubic	-	0.96	VIII
Y₂O₃	Bixbyite	Ia-3	1.019	VIII
La₂O₃	Trigonal	P63/mmc	1.16	VIII
CeO₂	Cubic	Fm-3m	0.97	VIII

		Secondary Phase
No.	Composition	1300 °C	1350 °C	1400 °C	1450 °C	1500 °C	1600 °C
CCFO1	(Zr_0.2Hf_0.2Pr_0.2 Y_0.2La_0.2)O_2-δ	Major	Major	No	No	No	No
CCFO2	(Zr_0.1667Hf_0.1667Pr_0.1667 Y_0.25La_0.25)O_2-δ	Major	Major	Major	No	No	No
CCFO3	(Zr_0.1429Hf_0.1429Pr_0.1429 Y_0.2857La_0.2857)O_2-δ	-	Major	Minor	Minor	No	No

		Secondary Phase
No.	Composition	1300 °C	1350 °C	1400 °C	1450 °C	1500 °C	1600 °C
CCFO1	(Zr_0.2Hf_0.2Pr_0.2 Y_0.2La_0.2)O_2-δ	Major	Major	No	No	No	No
CCFO2	(Zr_0.1667Hf_0.1667Pr_0.1667 Y_0.25La_0.25)O_2-δ	Major	Major	Major	No	No	No
CCFO3	(Zr_0.1429Hf_0.1429Pr_0.1429 Y_0.2857La_0.2857)O_2-δ	-	Major	Minor	Minor	No	No

		CCFO1	CCFO2	CCFO3
Lattice Parameter (Å)		5.36270	5.36995	5.38075
Transition Temperature (°C)		∼1400	∼1450	∼1500
ΔS_{cation-sublattice}		1.61R	1.58R	1.55R
ρ_exp (g/cm³)		6.58345	6.37967	5.9852
ρ_cal (g/cm³)		6.7366	6.5741	6.4430
Relative density		97.042%	97.727%	92.895%
Electrical conductivity	σ_750 °C (S/cm)	1.38 × 10^-3	1.92 × 10^-3	1.68 × 10^-3
	σ_600 °C (S/cm)	2.89 × 10^-4	5.35 × 10^-4	3.94 × 10^-4
	E_a (eV)	0.78	0.66	0.74
	R²	0.99985	0.99879	0.99989