Synthesis and microstructure characterization of tetragonal Zr1-xTixO2 (x = 0-1) solid solutions

doi:10.1016/j.jmst.2019.04.013

Abstract

Abstract:

Oxide powders of Zr_1-xTi_xO₂ (x = 0-1) solid solutions with micron-sized particles were synthesized via a solution combustion method. The synthesis process and Zr/Ti molar ratio were optimized to produce powders with the tetragonal crystal structure. X-ray diffraction, Raman spectroscopy and transmission electron spectroscopy results confirm that a full crystallization microstructure with the single tetragonal phase is obtained after calcination at 600 °C while maintaining the crystallite size <30 nm. Zr/Ti oxide mixtures with Zr ≥ 67 mol% exhibit a tetragonal crystal structure and the embedding Ti in ZrO₂ improves the structure stability. The nitrogen sorption results indicate that the powders possess mesoporous morphology with medium specific surface areas ($\widetilde{1}$0-50 m²/g). Chemical stability tests show that these powders are relatively stable with negligible removal of titanium and zirconium after elution by 0.5 mol/L HCl. Density functional theory was used to calculate the most stable structure with low energy for the selected composition.

Key words: Tetragonal, Titanium zirconate, Solid solution, Chemical synthesis

Linggen Kong, Inna Karatchevtseva, Hanliang Zhu, Meng Jun Qin, Zaynab Aly. Synthesis and microstructure characterization of tetragonal Zr_1-xTi_xO₂ (x = 0-1) solid solutions[J]. J. Mater. Sci. Technol., 2019, 35(9): 1966-1976.

Figures/Tables 13

Fig. 1. XRD patterns of (a) ZrO2, (b) Zr0.83Ti0.17O2, (c) Zr0.75Ti0.25O2, (d) Zr0.67Ti0.33O2, (e) Zr0.5Ti0.5O2, (f) Zr0.25Ti0.75O2, (g) TiO2 powders calcined for 4 h at 600 °C.

Fig. 2. XRD patterns of (a) ZrO2, (b) Zr0.83Ti0.17O2, (c) Zr0.75Ti0.25O2, (d) Zr0.67Ti0.33O2, (e) Zr0.5Ti0.5O2, (f) Zr0.25Ti0.75O2, (g) TiO2 powders calcined for 4 h at 700 °C. R and M refer to rutile and monoclinic phase, respectively.

Fig. 3. XRD patterns of (a) ZrO2, (b) Zr0.83Ti0.17O2, (c) Zr0.75Ti0.25O2, (d) Zr0.67Ti0.33O2, (e) Zr0.5Ti0.5O2, (f) Zr0.25Ti0.75O2, (g) TiO2 powders calcined for 4 h at 800 °C. R and M refer to rutile and monoclinic phase, respectively.

Table 1 Lattice parameters (?) of tetragonal materials calcined at 600 °C for 4 h.

Materials	Experiment data		Reference data [5,49,50,51]
	a	c	a	c
ZrO₂	3.599	5.159	3.610	5.168
Zr_0.83Ti_0.17O₂	3.576	5.191
Zr_0.75Ti_0.25O₂	3.569	5.197
Zr_0.67Ti_0.33O₂	3.537	5.228
TiO₂	3.787	9.547	3.785	9.514

Fig. 4. Raman spectra of (a) ZrO2, (b) Zr0.83Ti0.17O2, (c) Zr0.75Ti0.25O2, (d) Zr0.67Ti0.33O2, (e) Zr0.5Ti0.5O2, (f) Zr0.25Ti0.75O2, (g) TiO2 powders calcined for 4 h at 600 °C.

Fig. 5. TEM images (a, d, g), HRTEM images (b, e, h), and SAED ring patterns (c, f, i) for samples ZrO2 (a, b, c), Zr0.75Ti0.25O2 (d, e, f), TiO2 (g, h, i) calcined for 4 h at 600 °C.

Fig. 6. Nitrogen sorption isotherms of powders calcined for 4 h at 600 °C: (a) ZrO2, (b) Zr0.75Ti0.25O2, (c) TiO2.

Table 2 N2 sorption data of powders calcined for 4 h.

Materials	Calcination (^oC)	Surface area (m²/g)	Pore volume (cm³/g)	Pore size (nm)
ZrO₂	600	49.6	0.032	3.2
ZrO₂	800	11.2	0.041	14
Zr_0.83Ti_0.17O₂	600	34.8	0.039	4.9
	700	18.4	0.035	7.6
	800	3.71	0.024	21
Zr_0.75Ti_0.25O₂	600	34.4	0.035	4.8
Zr_0.75Ti_0.25O₂	800	2.01	0.015	29
Zr_0.67Ti_0.33O₂	600	34.0	0.038	4.9
	700	12.9	0.032	9.1
	800	2.81	0.021	29
Zr_0.5Ti_0.5O₂	600	11.3	0.022	6.1
TiO₂	600	9.85	0.021	8.7

Fig. 7. Backscattered SEM images of powders calcined for 4 h at 600 °C: (a, b) ZrO2, (c, d) Zr0.75Ti0.25O2, (e, f) TiO2.

Table 3 Chemical stability of ceramic powders eluted by 0.5 mol/L HCl (element concentration in each 100 mL eluant).

Eluant volume (mL)	TiO₂ (1 g)	ZrO₂ (1 g)	Zr_0.75Ti_0.25O₂ (1 g)
Eluant volume (mL)	Ti (mg/L)	Zr (mg/L)	Ti (mg/L)	Zr (mg/L)
100	0.15	0.09	2.14	0.07
200	0.08	0.02	0.72	0.04
300	0.05	0.03	0.38	0.03
400	0.02	0.01	0.53	0.03
500	0.01	0.01	0.26	0.03
600	0.03	0.02	0.23	0.02
700	<0.01	0.01	0.27	0.03
800	<0.01	0.01	0.20	0.02
900	0.02	0.01	0.42	0.02
1000	<0.01	0.01	0.24	0.02

Table 4 N2 sorption data of powders calcined for 4 h at 600 °C.

Materials	Eluted	Surface area (m²/g)	Pore volume (cm³/g)	Pore size (nm)
ZrO₂	Before	49.6	0.032	3.2
	By 0.1 M HCl	45.7	0.034	4.1
	By 0.5 M HCl	43.7	0.033	4.1
Zr_0.75Ti_0.25O₂	Before	34.4	0.035	4.8
	By 0.1 M HCl	32.7	0.034	4.8
	By 0.5 M HCl	31.0	0.038	4.8
TiO₂	Before	9.85	0.021	8.7
	By 0.1 M HCl	9.88	0.021	8.7
	By 0.5 M HCl	9.90	0.021	9.0

Fig. 8. Energy differences between different replacement configurations for Zr0.75Ti0.25O2.

Fig. 9. DFT optimized the most stable (low-energy) Zr0.75Ti0.25O2 (Zr12Ti4O32): (a) monoclinic, (b) tetragonal, (c) orthorhombic, and (d) high-energy monoclinic structures. Red, green and blue spheres refer to oxygen, zirconium and titanium atoms, respectively.

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Synthesis and microstructure characterization of tetragonal Zr_1-xTi_xO₂ (x = 0-1) solid solutions

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