Thermodynamics of Phase Equilibria in FeO-TiO2-Al2O3 System

doi:10.19691/j.cnki.1004-4493.2022.02.008

China's Refractories ›› 2022, Vol. 31 ›› Issue (2): 40-44.DOI: 10.19691/j.cnki.1004-4493.2022.02.008

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Thermodynamics of Phase Equilibria in FeO-TiO₂-Al₂O₃ System

Oksana M. BORYSENKO^*(), Sergey M. LOGVINKOV, Galina M. SHABANOVA, Andrii A. IVASHURA, Alla M. KOROHODSKA

Kharkiv Polytechnic Institute, National Technical University, Kharkiv 61002, Ukraine

Online:2022-06-15 Published:2022-07-05
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 discusses the information on the structure of the three-component system FeO-TiO₂-Al₂O₃, which is necessary for the creation of heat-resistant oxide materials. The structure of binary systems: FeO-Al₂O₃, FeO-TiO₂, and Al₂O₃-TiO₂ is described, and the data on the FeO-TiO₂-Al₂O₃ system are presented. The thermodynamic data of all compounds of the system are given, on the basis of which the change in the Gibbs free energy in the temperature range of 8 00-1 900 K for twenty-one exchange reactions was calculated. It has been established that the triangulation of the FeO-TiO₂-Al₂O₃ system changes in five temperature ranges: up to 1 408 K (TiO₂ exists in the polymorphic modification-anatase), 1 408-1 537 K (TiO₂ exists in the polymorphic modification-rutile and pseudobrookite is stable), 1 537-1 630 K (thialite is stable), 1 630-2 076 K (rearrangement cannot occur) and above 2 076 K (the presence of the stoichiometric compound Al₄TiO₈ is allowed). Two-phase equilibria up to 1 408 K are stable: Al₂O₃-FeTiO₃, FeTiO₃-FeAl₂O₄, and FeAl₂O₄-Fe₂TiO₄; in the temperature range of 1 408-1 537 K: FeAl₂O₄-TiO₂, FeAl₂O₄-FeTi₂O₅, FeAl₂O₄-FeTiO₃, and FeAl₂O₄-Fe₂TiO₄; in the temperature range of 1 537-1 630 K: FeAl₂O₄-TiO₂, FeAl₂O₄-FeTi₂O₅, FeAl₂O₄-FeTiO₃, FeAl₂O₄-Fe₂TiO₄, and FeAl₂O₄-Al₂TiO₅; in the temperature range of 1 630-2 076 K: FeTi₂O₅-Al₂TiO₅, Al₂TiO₅-FeTiO₃, FeTiO₃-Al₂O₃, FeTiO₃-FeAl₂O₄, and FeAl₂O₄-Fe₂TiO₄; over 2 076 K: FeTi₂O₅-Al₂TiO₅, FeTi₂O₅-Al₄TiO₈, Al₄TiO₈-FeTiO₃, Al₄TiO₈-Fe₂TiO₄, Al₄TiO₈-FeO, and Al₄TiO₈-FeAl₂O₄.

Key words: phase equilibria, change in Gibbs free energy, triangulation, hercynite, ulvospinel, ilmenite, pseudobrookite, thialite

Oksana M. BORYSENKO, Sergey M. LOGVINKOV, Galina M. SHABANOVA, Andrii A. IVASHURA, Alla M. KOROHODSKA. Thermodynamics of Phase Equilibria in FeO-TiO₂-Al₂O₃ System[J]. China's Refractories, 2022, 31(2): 40-44.

Figures/Tables 9

References 10

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Compound	-ΔH⁰_{298 K}/ (kJ · mol^-1)	ΔS⁰_{298 K} / [J · (mol · K)^-1]	Cp =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	115.072	11.80	35.06	[6-8]
FeO	272.044	60.752	48.785	8.37	2.80	[6-7]
TiO₂ anatase	912.53	34.727	44.225	15.062	7.782	[6]
TiO₂ rutile	943.492	49.915	74.6	2.092	17.698	[6]
FeTiO₃	1 236.37	105.86	116.61	18.24	20.04	[9]
FeTi₂O₅	2 190.7	145.6	192.59	22.01	31.00	[6]
Fe₂TiO₄	1 510.42	163.18	139.5	63.10	14.23	[6]
FeAl₂O₄	1 982.4	106.3	156.48	26.15	31.34	[9]
Al₂TiO₅	2 607.47	109.62	182.55	22.18	46.91	[6]
Al₄TiO₈	4 194.883	211.576	395.84-1.163 4×10⁷×Т^-2- (-1 925.3)×Т^-0.5+1.505×10⁹×Т^-3			[4]

Compound	-ΔH⁰_{298 K}/ (kJ · mol^-1)	ΔS⁰_{298 K} / [J · (mol · K)^-1]	Cp =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	115.072	11.80	35.06	[6-8]
FeO	272.044	60.752	48.785	8.37	2.80	[6-7]
TiO₂ anatase	912.53	34.727	44.225	15.062	7.782	[6]
TiO₂ rutile	943.492	49.915	74.6	2.092	17.698	[6]
FeTiO₃	1 236.37	105.86	116.61	18.24	20.04	[9]
FeTi₂O₅	2 190.7	145.6	192.59	22.01	31.00	[6]
Fe₂TiO₄	1 510.42	163.18	139.5	63.10	14.23	[6]
FeAl₂O₄	1 982.4	106.3	156.48	26.15	31.34	[9]
Al₂TiO₅	2 607.47	109.62	182.55	22.18	46.91	[6]
Al₄TiO₈	4 194.883	211.576	395.84-1.163 4×10⁷×Т^-2- (-1 925.3)×Т^-0.5+1.505×10⁹×Т^-3			[4]

Reaction number	ΔG /(kJ · mol^-1)
Reaction number	800 K	1 000 K	1 200 K	1 400 K	1 600 K	1 800 K	1 900 K
1	-	-	-	-	-	-134.198	-149.324
2	-4.728	-3.969	-3.414	-2.835	-2.279	-1.780	-1.560
3	-13.643	-10.378	-7.088	-3.790	-0.493	2.801	4.446
4^*	40.445	50.675	61.770	73.492	-	-	-
4^**	-	-	-	-7.998	-6.614	-5.138	-4.367
5	-	-	-	-	-	-120.179	-136.612
6	23.039	20.869	18.713	16.560	14.402	12.237	11.151
7	-	-	-	-	-	-106.178	-122.732
8	-	-	-	28.945	27.996	26.238	25.031
9	-	-	-	-	-	-136.999	-157.771
10	9.215	6.408	3.673	0.955	-1.786	-4.582	-6.007
11	-	-	-	-	-	-127.835	-141.756
12	-32.588	-32.826	-32.600	-31.781	-30.276	-28.019	-26.591
13	-	-	-	-17.354	-17.054	-16.418	-15.969
14	4.787	2.438	0.258	-1.880	-4.066	-6.362	-7.568
15	-22.858	-16.786	-10.761	-4.745	1.293	7.383	10.453
16	-60.748	-61.682	-61.786	-60.726	-58.273	-54.258	-51.623
17	-	-	-	13.160	10.948	8.497	7.175
18	-	-	-	50.104	45.560	39.874	36.574
19^*	-7.857	-17.849	-29.170	-41.711	-	-	-
19^**	-	-	-	39.779	36.891	33.158	30.959
20^*	94.534	11.729	130.629	150.775	-	-	-
20^**	-	-	-	-12.205	-12.735	-13.079	-13.182

Reaction number	ΔG /(kJ · mol^-1)
Reaction number	800 K	1 000 K	1 200 K	1 400 K	1 600 K	1 800 K	1 900 K
1	-	-	-	-	-	-134.198	-149.324
2	-4.728	-3.969	-3.414	-2.835	-2.279	-1.780	-1.560
3	-13.643	-10.378	-7.088	-3.790	-0.493	2.801	4.446
4^*	40.445	50.675	61.770	73.492	-	-	-
4^**	-	-	-	-7.998	-6.614	-5.138	-4.367
5	-	-	-	-	-	-120.179	-136.612
6	23.039	20.869	18.713	16.560	14.402	12.237	11.151
7	-	-	-	-	-	-106.178	-122.732
8	-	-	-	28.945	27.996	26.238	25.031
9	-	-	-	-	-	-136.999	-157.771
10	9.215	6.408	3.673	0.955	-1.786	-4.582	-6.007
11	-	-	-	-	-	-127.835	-141.756
12	-32.588	-32.826	-32.600	-31.781	-30.276	-28.019	-26.591
13	-	-	-	-17.354	-17.054	-16.418	-15.969
14	4.787	2.438	0.258	-1.880	-4.066	-6.362	-7.568
15	-22.858	-16.786	-10.761	-4.745	1.293	7.383	10.453
16	-60.748	-61.682	-61.786	-60.726	-58.273	-54.258	-51.623
17	-	-	-	13.160	10.948	8.497	7.175
18	-	-	-	50.104	45.560	39.874	36.574
19^*	-7.857	-17.849	-29.170	-41.711	-	-	-
19^**	-	-	-	39.779	36.891	33.158	30.959
20^*	94.534	11.729	130.629	150.775	-	-	-
20^**	-	-	-	-12.205	-12.735	-13.079	-13.182

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Thermodynamics of Phase Equilibria in FeO-TiO₂-Al₂O₃ System

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