Thermodynamic Modeling of MgO-Al2O3-TiO2 System

doi:10.19691/j.cnki.1004-4493.2021.03.004

China's Refractories ›› 2021, Vol. 30 ›› Issue (3): 17-22.DOI: 10.19691/j.cnki.1004-4493.2021.03.004

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Thermodynamic Modeling of MgO-Al₂O₃-TiO₂ System

Oksana M. BORYSENKO¹^,^*(), Galina M. SHABANOVA¹, Sergey M. LOGVINKOV², Lgor A. OSTAPENKO³

1 Kharkiv Polytechnic Institute, National Technical University, Kharkiv 61002, Ukraine
2 Simon Kuznets Kharkiv National University of Economics, Kharkiv 61166, Ukraine
3 TOV “Druzhkivskiy Vognetrivkiy zavod”, Druzhkovka 84293, Ukraine

Online:2021-09-15 Published:2021-11-26
Contact: Oksana M. BORYSENKO
About author:Oksana M. Borysenko is a docent, and a doctoral candidate of the Department of Ceramics, Refractory Materials, Glass and Enamels Technology of Kharkiv Polytechnic Institute of National Technical University in Ukraine, majored in technical sciences. Her field of scientific interests embraces refractory nonmetal materials, multicomponent system condition diagrams, solid phase exchange reactions and their conjugation, and the self-organization of phases into dissipative structures. She had more than 130 scientific publications.

Abstract

Abstract:

This scientific paper gives consideration to the information on the structure of the triple component system, in particular MgO-Al₂O₃-TiO₂ that serves as a basis for the production of thermal resistance materials. The structure of such binary systems as MgO-Al₂O₃, Al₂O₃-TiO₂, MgO-TiO₂ was described and the data available for the MgO-Al₂O₃-TiO₂ system were given. Thermodynamic data on all the system compounds were also presented and used for the computation of a change in the free Gibbs energy in the temperature range form 800 K to 1 900 K for the basic exchange reactions. It was established that the triangulation of the MgO-Al₂O₃-TiO₂ system was changed in the three temperature intervals: in the temperature range lower than 1 537 K TiO₂ existed as the polymorphous modification, i.e. anatase; in the temperature range from 1 537 K to 2 076 K TiO₂ existed as a polymorphous modification in form of rutile and tialite was stable; and at the temperatures above 2 076 K the availability of stochiometric compound of Al₄TiO₈ was possible. In the temperature range lower than 1 537 K the two-phase equilibra of Al₂O₃-MgTi₂O₅, MgTi₂O₅-MgAl₂O₄, MgTiO₃-MgAl₂O₄, and Mg₂TiO₄-MgAl₂O₄ were stable; in the temperature range from 1 537 K to 2 076 K the two-phase equilibria of MgTi₂O₅-Al₂TiO₅, MgTiO₃-Al₂TiO₅, MgTiO₃-Al₂O₃, MgTiO₃-MgAl₂O₄, and Mg₂TiO₄-MgAl₂O₄ were stable, and above 2 076 K the MgTi₂O₅-Al₂TiO₅, MgTi₂O₅-Al₄TiO₈, Al₄TiO₈-MgTiO₃, Al₄TiO₈-Mg₂TiO₄, Al₄TiO₈-MgO, and Al₄TiO₈-MgAl₂O₄ systems were stable.

Key words: phase equilibria, change in Gibbs free energy, triangulation, magnesium aluminate spinel, tialite, geikielite, carroite, qandilite

Oksana M. BORYSENKO, Galina M. SHABANOVA, Sergey M. LOGVINKOV, Lgor A. OSTAPENKO. Thermodynamic Modeling of MgO-Al₂O₃-TiO₂ System[J]. China's Refractories, 2021, 30(3): 17-22.

Figures/Tables 7

References 14

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Compound	-ΔH⁰_{298 K}/ (kJ · mol^-1)	ΔS⁰_{298 K}/ [J · (mol · K)^-1]	C_p = a + bТ + c'T^-2 /[J · (mol · K)^-1]			Reference
Compound	-ΔH⁰_{298 K}/ (kJ · mol^-1)	ΔS⁰_{298 K}/ [J · (mol · K)^-1]	a	b×10³	-с×10^-5	Reference
Al₂O₃	1 676.057 7	50.95	115.02	11.80	35.06	[11, 12, 13]
MgO	601.241	26.924	42.59	7.28	6.19	[11, 12]
TiO₂ anatase	912.53	34.727	44.225	15.062	7.782	[11]
TiO₂ rutile	943.492	49.915	74.6	2.092	17.698	[11]
MgAl₂O₄	2 297.02	80.58	153.97	26.78	40.92	[11]
MgTiO₃	1 571.93	74.56	118.37	13.27	27.32	[11, 14]
Mg₂TiO₄	2 163.55	115.10	154.64	35.73	28.83	[11]
MgTi₂O₅	2 507.89	138.91	170.21	38.49	30.75	[11]
Al₂TiO₅	2 607.47	109.62	182.55	22.18	46.91	[11]
Al₄TiO₈	4 194.883	211.576	395.84-1.1634×10⁷×Т^-2--1 925.3Т-0.5+1.505×10⁹×Т^-3			[5]

Compound	-ΔH⁰_{298 K}/ (kJ · mol^-1)	ΔS⁰_{298 K}/ [J · (mol · K)^-1]	C_p = a + bТ + c'T^-2 /[J · (mol · K)^-1]			Reference
Compound	-ΔH⁰_{298 K}/ (kJ · mol^-1)	ΔS⁰_{298 K}/ [J · (mol · K)^-1]	a	b×10³	-с×10^-5	Reference
Al₂O₃	1 676.057 7	50.95	115.02	11.80	35.06	[11, 12, 13]
MgO	601.241	26.924	42.59	7.28	6.19	[11, 12]
TiO₂ anatase	912.53	34.727	44.225	15.062	7.782	[11]
TiO₂ rutile	943.492	49.915	74.6	2.092	17.698	[11]
MgAl₂O₄	2 297.02	80.58	153.97	26.78	40.92	[11]
MgTiO₃	1 571.93	74.56	118.37	13.27	27.32	[11, 14]
Mg₂TiO₄	2 163.55	115.10	154.64	35.73	28.83	[11]
MgTi₂O₅	2 507.89	138.91	170.21	38.49	30.75	[11]
Al₂TiO₅	2 607.47	109.62	182.55	22.18	46.91	[11]
Al₄TiO₈	4 194.883	211.576	395.84-1.1634×10⁷×Т^-2--1 925.3Т-0.5+1.505×10⁹×Т^-3			[5]

Reaction number	ΔG /(kJ · mol^-1), Temperature /K
Reaction number	800	1 000	1 200	1 400	1 600	1 800	1 900
0	-	-	-	0.715	-0.558	-1.640	-2.094
1^**	-	-	-	4.459	4.025	3.129	2.484
2^**	-	-	-	-	-	-129.484	-145.566
3^*	-106.866	-124.409	-143.450	-163.683	-	-	-
3^**	-	-	-	-0.702	-0.308	-0.228	-0.322
4^**	-	-	-	0.013	-0.867	-1.868	-2.416
5^**	-	-	-	-	-	-139.481	-155.370
6^*	-57.037	-66.189	-76.144	-86.639	-	-	-
6^**	-	-	-	-5.149	-5.102	-5.226	-5.223
7^**	-	-	-	19.675	15.322	10.427	7.849
8^**	-	-	-	-	-	-125.271	-142.687
9^*	-35.824	-47.031	-59.216	-72.140	-	-	-
9^**	-	-	-	9.349	6.653	3.756	2.234
10^**	-	-	-	29.314	29.667	30.088	30.320
11^**	-	-	-	-	-	-75.568	-89.896
12	-	-	-	-11.027	-8.978	-6.944	-5.936
13	-	-	-	-10.312	-9.536	-8.584	-8.031
14	-	-	-	4.187	2.318	0.398	-0.572
15	-	-	-	-	-	257.828	289.522
16	-	-	-	-	-	123.801	139.698
17	-	-	-	-	-	132.784	147.157
18^**	-	-	-	3.054	3.407	2.673	1.840
19	-21.213	-19.157	-16.928	-14.499	-11.855	-8.982	-7.458
20	-35.218	-30.345	-25.017	-19.402	-13.615	-7.740	-4.791
21	-	-	-	-	-	-404.102	-229.125
22	-	-	-	-	-	-273.356	-303.490
23	-	-	-	-	-	-396.760	-443.761
24	-	-	-	-	-	-105.656	-120.216
25	-	-	-	-	-	-140.464	-174.482

Reaction number	ΔG /(kJ · mol^-1), Temperature /K
Reaction number	800	1 000	1 200	1 400	1 600	1 800	1 900
0	-	-	-	0.715	-0.558	-1.640	-2.094
1^**	-	-	-	4.459	4.025	3.129	2.484
2^**	-	-	-	-	-	-129.484	-145.566
3^*	-106.866	-124.409	-143.450	-163.683	-	-	-
3^**	-	-	-	-0.702	-0.308	-0.228	-0.322
4^**	-	-	-	0.013	-0.867	-1.868	-2.416
5^**	-	-	-	-	-	-139.481	-155.370
6^*	-57.037	-66.189	-76.144	-86.639	-	-	-
6^**	-	-	-	-5.149	-5.102	-5.226	-5.223
7^**	-	-	-	19.675	15.322	10.427	7.849
8^**	-	-	-	-	-	-125.271	-142.687
9^*	-35.824	-47.031	-59.216	-72.140	-	-	-
9^**	-	-	-	9.349	6.653	3.756	2.234
10^**	-	-	-	29.314	29.667	30.088	30.320
11^**	-	-	-	-	-	-75.568	-89.896
12	-	-	-	-11.027	-8.978	-6.944	-5.936
13	-	-	-	-10.312	-9.536	-8.584	-8.031
14	-	-	-	4.187	2.318	0.398	-0.572
15	-	-	-	-	-	257.828	289.522
16	-	-	-	-	-	123.801	139.698
17	-	-	-	-	-	132.784	147.157
18^**	-	-	-	3.054	3.407	2.673	1.840
19	-21.213	-19.157	-16.928	-14.499	-11.855	-8.982	-7.458
20	-35.218	-30.345	-25.017	-19.402	-13.615	-7.740	-4.791
21	-	-	-	-	-	-404.102	-229.125
22	-	-	-	-	-	-273.356	-303.490
23	-	-	-	-	-	-396.760	-443.761
24	-	-	-	-	-	-105.656	-120.216
25	-	-	-	-	-	-140.464	-174.482

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Thermodynamic Modeling of MgO-Al₂O₃-TiO₂ System

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References 14

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