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Thermodynamic Assessment of Phase Equilibria in the SrO-Al2O3 System

Article  in  Defect and Diffusion Forum · August 2021

DOI: 10.4028/www.scientific.net/DDF.410.725

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Defect and Diffusion Forum Submitted: 2021-04-24
ISSN: 1662-9507, Vol. 410, pp 725-729 Accepted: 2021-06-07
doi:10.4028/www.scientific.net/DDF.410.725 Online: 2021-08-17
© 2021 Trans Tech Publications Ltd, Switzerland

Thermodynamic Assessment of Phase Equilibria

in the Sro-Al2O3 System
Larisa A. Makrovets1,a*, Olga V. Samoilova1,b and Igor V. Bakin2,c
1
South Ural State University, Chelyabinsk, Russia
2
NPP “Technology”, Chelyabinsk, Russia
a
makrovetcla@susu.ru, bsamoylova_o@mail.ru, cigor.npp.bakin@gmail.com

Keywords: thermodynamic modeling, theory of subregular ionic solutions, SrO–Al2O3 system,

strontium oxide, phase equilibria.

Abstract. Thermodynamic modeling of phase equilibria with the subsequent construction of the
phase diagram of the SrO–Al2O3 system has been carried out. To calculate the activities of the
oxide melt in the course of this work, we used the approximation of the theory of subregular
ionic solutions, with the most optimal values of the energy parameters Q1112 = –104 349:
Q1122 = –217 689; Q1222 = –104 436 J/mole. The results obtained for the liquidus line in this work
are in good agreement with the literature experimental data. In the course of the calculation, the
values of the equilibrium constants for the formation of strontium aluminates from the components
of the oxide melt were estimated.

Introduction
The study of phase equilibria in the SrO–Al2O3 system is of interest due to the fact that this
system is part of the slag phase both in the production of new grades of ferroalloys with strontium
additives [1] and in the production of steels modified with strontium-containing alloys [2–5].
There are data in the literature on the phase diagram of the SrO–Al2O3 system [1, 6–14], which
are quite different from each other. So, according to most authors, five strontium aluminates are
formed in the SrO–Al2O3 system: Sr4Al2O7, Sr3Al2O6, SrAl2O4, SrAl4O7, SrAl12O19. However, in
the work [10], in addition to these compounds, the possibility of the formation of two more
aluminates is discussed – Sr5Al2O8 and Sr4Al14O25; and in the work [11], on the contrary, it is
indicated that there are only four compounds in the studied system (there is no strontium
bialuminate). According to information from different sources, the nature of the melting of the
above compounds (congruent or incongruent) is also different, and the temperatures for both
melting of compounds and for eutectic transformations differ for some authors by almost one
hundred and fifty degrees. Thus, the SrO–Al2O3 system requires additional research, including the
assessment of the phase equilibria from the standpoint of thermodynamic analysis.
The aim of this work is to thermodynamically estimate and calculate phase equilibria in the SrO–
Al2O3 system with the subsequent construction of the phase diagram of this system.

Thermodynamic Modeling
The methodology used by us for thermodynamic modeling of phase equilibria in phase diagrams
of oxide systems is described in detail in the works [15–17].
Briefly, the procedure for modeling oxide systems can be described as follows. According to the
algorithms used, the calculation is based on experimental data (from those presented in the
literature) on the coordinates (composition and temperature) of the characteristic points of phase
diagrams: points of eutectic, peritectic, phase transitions, etc. Taking these data into account, the
parameters of the thermodynamic model selected for the calculation are described, and then the
entire liquidus line or liquidus surface of the system under study is calculated.
The values of the parameters of the used thermodynamic model are determined in the process of
solving systems of nonlinear equations, for which the Newton method is applied. To draw up the

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726 Materials Engineering and Technologies for Production and Processing VII

equations, it is necessary (as mentioned earlier) data on the coordinates of a number of

characteristic points selected on the liquidus line or liquidus surface of the phase diagram. For each
characteristic point, an expression is drawn up that connects its coordinates with the parameters of
the thermodynamic model used to calculation.
The values of the coordinates of the characteristic points can differ according to different
versions of the phase diagram given in the literature. Accordingly, a calculation is carried out for
each of the available options, and then a thermodynamic assessment of the obtained calculated data
is carried out (the parameters of the used thermodynamic model, the calculated values of the
activities of the oxide melt, data on phase transitions (for example, constants characterizing the
process of the transition of a solid into a liquid state), as well as the results of the calculating
liquidus line or liquidus surface). Based on the assessment, the best option is selected, while some
difference in the values of the coordinates of the characteristic points with respect to the original
literature data is possible, if the variation (usually insignificant) leads to an improvement in the
indicators for the thermodynamic evaluation of the results.

Results and Discussion

For the SrO–Al2O3 system, the most optimal results on thermodynamic modeling were obtained
when using the model of subregular ionic solutions [15] with energy parameters to calculate the
activities of the oxide melt: Q1112 = –104 349: Q1122 = –217 689; Q1222 = –104 436 J/mole. The
thermodynamic data on the obtained constants characterizing the process of the transition of a solid
into a liquid state, used in calculating the phase diagram of the SrO–Al2O3 system, are given in
Table 1.
Table 1. Thermodynamic data for reactions of phase transition,
Km is a constant characterizing the process of transition of a solid into a liquid state
log Km = –A/T + B
Number Reaction Source
A B
1* |FeO| = (FeO) 1749 1.059 [18, 19]
2* |SrO| = (SrO) 4229 1.507 [20]
3* |Al2O3| = (Al2O3) 5683 2.447 [18]
4 FeAl2O4 = (FeO) + (Al2O3) 11 366 4.568 [17]
5 Sr4Al2O7 = 4(SrO) + (Al2O3) 9023 –0.908 This work
6 Sr3Al2O6 = 3(SrO) + (Al2O3) 11 797 1.020 This work
7 SrAl2O4 = (SrO) + (Al2O3) 9101 1.533 This work
8 SrAl4O7 = (SrO) + 2(Al2O3) 7653 0.449 This work
9 SrAl12O19 = (SrO) + 6(Al2O3) 16 523 3.546 This work
*
– for pure solids, the constants were recalculated according to the data on the temperature and
enthalpy of melting of these substances.
The results of modeling phase equilibria and the phase diagram of the SrO–Al2O3 system in
comparison with the literature data are shown in Fig. 1 and in Table 2.
According to the thermodynamic assessment, the most stable in the system are five compounds
Sr4Al2O7, Sr3Al2O6, SrAl2O4, SrAl4O7, SrAl12O19, which coincides with the data in [1, 6–9].
Strontium aluminates Sr3Al2O6 and SrAl2O4 have a congruent melting pattern; the other three
compounds are incongruent.
 Defect and Diffusion Forum Vol. 410 727

Table 2. Invariant points in the SrO–Al2O3 system

The nature
Composition,
Phase equilibria of the invariant
ionic fraction Al2O3
t, [°C] Source
transformation
0.347 1690 Massazza F. [6]
0.355 1765 Ye X. [9]
SrO + Sr4Al2O7 + Liquid Peritectic 0.324 1800 Ganits F. [7]
0.333 1880 Starczewski M. [8]
0.333 1880 This work
0.381 1630 Massazza F. [6]
0.392 1731 Ye X. [9]
Sr4Al2O7 + Sr3Al2O6 + 0.368 1781 Shukla A. [10]
Eutectic
Liquid 0.384 1687 Ganits F. [7]
0.374 1780 Starczewski M. [8]
0.374 1780 This work
1660 Massazza F. [6]
1735 Ye X. [9]
1782 Shukla A. [10]
Sr3Al2O6 + Liquid Melting 0.400
1736 Ganits F. [7]
1820 Starczewski M. [8]
1790 This work
0.492 1505 Massazza F. [6]
0.525 1557 Ye X. [9]
Sr3Al2O6 + SrAl2O4 + 0.496 1706 Shukla A. [10]
Eutectic
Liquid 0.496 1560 Ganits F. [7]
0.496 1690 Starczewski M. [8]
0.482 1690 This work
1960 Massazza F. [6]
1960 Ye X. [9]
2016 Shukla A. [10]
SrAl2O4 + Liquid Melting 0.667
1960 Ganits F. [7]
2015 Starczewski M. [8]
2011 This work
0.734 1760 Massazza F. [6]
Eutectic 0.737 1660 Ganits F. [7]
SrAl2O4 + SrAl4O7 + 0.754 1830 Shukla A. [10]
Liquid 0.800 1664 Ye X. [9]
Peritectic 0.800 1830 Starczewski M. [8]
0.800 1830 This work
Peritectic 0.825 1857 Shukla A. [10]
0.852 1780 Massazza F. [6]
SrAl4O7 + SrAl12O19 + 0.843 1704 Ye X. [9]
Liquid Eutectic 0.846 1710 Ganits F. [7]
0.825 1790 Starczewski M. [8]
0.838 1790 This work
0.874 1794 Ye X. [9]
0.920 1962 Shukla A. [10]
SrAl12O19 + Al2O3 +
Peritectic 0.934 1790 Ganits F. [7]
Liquid 0.922 1960 Starczewski M. [8]
0.934 1979 This work
SrO + Liquid Additional point 0.292 2000 This work
Al2O3 + Liquid Additional point 0.951 2000 This work
728 Materials Engineering and Technologies for Production and Processing VII

Fig. 1. Phase diagram of the SrO–Al2O3 system:

–– – calculation, this work; ● – [6]; ○ – [7]; × – [8]; + – [9]; ▲– [10]
The obtained form of the liquidus line has the greatest agreement with the experimental data of
Starczewski M. [8], since according to the calculations, the characteristic points presented by him
on the studied diagram allow obtaining a thermodynamically significant set of calculated data,
including an adequate description of the activities of the oxide melt and the form of the position of
the liquidus line. When using data from other authors, the constants characterizing the process of
the transition of a solid into a liquid state for strontium aluminates have large negative values,
which does not make sense from the standpoint of thermodynamic analysis. It should be noted that
these constants reflect the estimated values of the enthalpies and entropies of formation of these
compounds from the components of the oxide melt and cannot be numerically expressed by large
negative values.

Conclusions
A thermodynamic assessment and calculation of phase equilibria in the SrO–Al2O3 system were
carried out using the theory of subregular ionic solutions. Based on these calculations, a phase diagram
of this system was constructed (the position of the liquidus line was determined). It is shown that,
according to the thermodynamic assessment, the most stable in the system are five compounds
Sr4Al2O7, Sr3Al2O6, SrAl2O4, SrAl4O7, SrAl12O19, which coincides with most of the available literature
data. In the course of the work, the constants characterizing the process of transition of a solid into a
liquid state were estimated. For strontium aluminates, these constants reflect the enthalpies and
entropies of their formation from the components of the oxide melt.
 Defect and Diffusion Forum Vol. 410 729

References
[1] K. Tang, L.K. Jakobsson, K. Hildal, Thermodynamic evaluation of Sr-containing Si metals and
silicate melts for Si–Sr alloy production, J. South. Afr. Inst. Min. Metall. 118(6) (2018) 601-605.
[2] I.V. Bakin, N.A. Shaburova, I.V. Ryabchikov, V.G. Mizin, B.F. Belov, G.G. Mikhailov,
A.V. Senin, Experimental study of refining and modification of steel with Si–Ca, Si–Sr, and Si–Ba
alloys, Steel Transl. 49 (2019) 543-547.
[3] M. Breitzmann, H.-J. Engell, D. Janke, Refining of steel melts using alkaline earth metals, Steel
Res. 59(7) (1988) 289-294.
[4] I.D. Rozhikhina, O.I. Nokhrina, V.I. Dmitrienko, M.A. Platonov, Modification of steel with
barium and strontium, Steel Transl. 45 (2015) 908-912.
[5] I.V. Bakin, G.G. Mikhailov, V.A. Golubtsov, I.V. Ryabchikov, L.E. Dresvyankina, Methods for
improving the efficiency of steel modifying, Mater. Sci. Forum. 946 (2019) 215-222.
[6] F. Massazza, The system SrO–Al2O3, Chim. Ind. (Milan). 41 (1959) 108-115.
[7] F. Ganits, T.Yu. Chemekova, Yu.P. Udalov, The system SrO–Al2O3, Zh. Neorg. Khim. 24(2)
(1979) 471-475.
[8] M. Starczewski, Treatise on solid state reactions in the ternary system SrO–Al2O3–SiO2, Zeszyty
Nauk. Politech. Slask. Chem. 22 (1964) 5-75.
[9] X. Ye, W. Zhuang, J. Wang, W. Yuan, Z. Qiao, Thermodynamic description of SrO–Al2O3
system and comparison with other systems, J. Phase Equilib. Diff. 28 (2007) 362-368.
[10] A. Shukla, Development of a Critically Evaluated Thermodynamic Database for the Systems
Containing Alkaline-Earth Oxides, École Polytechnique de Montréal, Montreal, 2012.
[11] Y.-M. Sung, S. Kim, Sintering and crystallization of off-stoichiometric SrO∙Al2O3∙2SiO2
glasses, J. Mater. Sci. 35(17) (2000) 4293-4299.
[12] M. Capron, A. Douy, Strontium dialuminate SrAl4O7: synthesis and stability, J. Am. Ceram.
Soc. 85(12) (2004) 3036-3040.
[13] A.N. Kogorodskaya, G.N. Shabanova, Thermodynamic database of refractory strontium
aluminates, Collection of Scientific Papers of PJSC “The URIR Named after A.S. Berezhnoy”. 112
(2012) 208-213.
[14] S. Ito, S. Banno, K. Suzuki, M. Inagaki, Phase transition in SrAl2O4, Z. Phys. Chem. 105
(1977) 173-178.
[15] G.G. Mikhailov, B.I. Leonovich, Yu.S. Kuznetsov, Thermodynamics of Metallurgical
Processes and Systems, Moscow Institute of Seel and Alloys Publishing house, Moscow, 2009.
[16] O.V. Samoilova, L.A. Makrovets, E.A. Trofimov, Thermodynamic simulation of the phase
diagram of the Cu2O–Na2O–K2O system, Moscow Univ. Chem. Bull. 73(3) (2018) 105-110.
[17] O.V. Samoilova, L.A. Makrovets, Thermodynamic modeling of phase equilibria in the FeO–
MgO–Al2O3 system, Mater. Sci. Forum. 989 (2020) 3-9.
[18] O. Kubaschewski, C.B. Alcock, Metallurgical Thermochemistry, Pergamon Press Ltd Publ.,
Oxford, 1979.
[19] L.S. Darken, R.W. Gurry, The system iron–oxygen. II. Equilibrium and thermodynamics of
liquid oxide and other phases, J. Am. Chem. Soc. 68 (1946) 798-816.
[20] X. Irgashov, V.D. Tarasov, V.Ya. Chekhovskoy, Thermodynamic properties of strontium
oxide in solid and liquid phases, High Temperature. 23(1) (1985) 86-91.

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