Activities of SiO2 and Al2O3 and Activity Coefficients of FetO

and MnO in CaO-SiO2-Al2O3-MgO Slags

HIROKI OHTA and HIDEAKI SUITO

The activities of SiO2 and Al2O3 in CaO-SiO2-Al2O3-MgO slags were determined at 1873 K along
the liquidus lines saturated with 2CaO z SiO2, 2(Mg,Ca)O z SiO2, MgO, and MgO z Al2O3 phases
using a slag-metal equilibration technique. Based on these and previous results obtained in ternary
and quaternary slags, the isoactivity lines of SiO2 and Al2O3 over the liquid region on the 0, 10, 20,
30, and 40 mass pct Al2O3 planes and those on the 10 and 20 mass pct MgO planes were determined.
The activity coefficients of FetO and MnO, the phase boundary, and the solubility of MgO were also
determined.

I. INTRODUCTION activity coefficients of FetO and MnO and the solubility of

THE activities of components in ladle slags, which con-
sist of a CaO-SiO2-Al2O3-MgO system with a high
CaO/SiO2 ratio, are the most indispensable for the ther-
modynamic analysis of ladle refining processes such as de-
sulfurization, deoxidation, and other aspects. Rein and
Chipman[1] determined the activities of SiO2 on the 10, 20,
and 30 mass pct MgO planes of this system at 1873 K from
the measurements of silicon distribution between slags and
Fe-Si-C alloys saturated with either graphite or silicon car-
bide under PCO 5 1 atm. However, their slag compositions
are less basic than those used in ladle refining processes.
The activity coefficients of FetO and MnO in CaO-SiO2-
Al2O3-MgO slags with compositions of low SiO2 and high
CaO contents are also a basic prerequisite for the thermo-
dynamic understanding of the reduction of FetO and MnO
in a ladle slag by the addition of Al, reoxidation of Al, and
desulfurization. Tsao and Katayama[2] measured the activity
coefficients of FetO in CaO (34 to 47 mass pct)—SiO2 (8
to 18 mass pct)—Al2O3 (22 to 41 mass pct)—MgO (10 to
15 mass pct) slags at 1873 K using a slag-metal equilibrium
technique in an MgO crucible. The activity coefficients of
FetO in the range of 2 to 3 mass pct FetO were determined
as 3.2 to 4.5 from the contents of analyzed oxygen. The
present authors previously measured the activity coeffi-
cients of FetO[3,4] and MnO[4] in a CaO-SiO2-Al2O3-FetO
(,5 mass pct)-MnO (,10 mass pct) system at 1873 K
using an Al2O3 or CaO crucible. As a result, it was found
that the activity coefficients of FetO increased with an in-
crease in SiO2 content, while those of MnO decreased with
a decrease in CaO content.
The activities of components in CaO-SiO2-Al2O3[5] and
CaO-Al2O3-MgO[6] systems were assessed at 1873 K in pre-
vious articles. This work is a continuation of previous
investigations. The activities of SiO2 and Al2O3 in CaO-
SiO2-MgO and CaO-SiO2-Al2O3-MgO slags at the compo-
sitions saturated with the 2CaO z SiO2, 2(Mg, Ca)O z SiO2,
MgO, and MgO z Al2O3 phases were determined at 1873 K
using a slag-metal equilibration technique. Furthermore, the
HIROKI OHTA, Research Associate, and HIDEAKI SUITO, Professor
are with Institute for Advanced Materials Processing, Tohoku University,
Sendai 980, Japan.
Manuscript submitted January 3, 1997.
MgO were also obtained.
II. EXPERIMENTAL
Eight grams of CaO-SiO2-MgO-FetO (0.07 to 1.2 pct)-
MnO (0.2 to 1.9 pct) or CaO-SiO2-Al2O3-MgO-FetO (0.04
to 0.9 pct)-MnO (0.03 to 2.2 pct) slag and 30 g of Fe
containing 0.0006 to 1.9 pct Si, 0 to 0.03 pct Al, and 0.04
to 1.3 pct Mn were melted at 1873 K for 1 to 3 hours in
CaO and MgO crucibles and then quenched by water. In
previous slag-metal equilibrium experiments using CaO-
Al2O3,[4] CaO-Al2O3-MgO,[6] and CaO-Al2O3-SiO2[5] slags,
the time for attainment of equilibrium was confirmed to be
within 1 hour. All compositions in this article are given in
mass pct. The contents of the elements in metal and slag
phases were determined by chemical analyses. Details of
the experimental method and chemical analyses are given
in the previous article.[7]
III. RESULTS AND DISCUSSION
In this paper, CaO-SiO2-MgO slags are denoted as CSM-
1 and CSM-2; CaO-SiO2-Al2O3-MgO slags saturated with
the 2CaO z SiO2 or 3CaO z SiO2 phase are denoted as SC-
1 to SC-5; and those saturated with MgO, 2(Mg,Ca)O z
SiO2, and MgO z Al2O3 are denoted as M-1 to M-4, MS-1,
and MA-1 to MA-3, respectively. It is noted that a molten
slag is not necessarily saturated with a crucible material
such as MgO. It may be saturated with another phase such
as MgO z Al2O3, depending on the initial slag composition.
The CSM-2, SC-1 to SC-5, MS-1, and MA-1 to MA-3 slags
and metal compositions are given in Table I. The chemical
compositions of the CSM-1 and M-1 to M-4 slags and
metal phases were given in the previous article.[7]
A. Activity of SiO2
Silicon deoxidation can be given as
Si 1 2O 5 SiO2 (s) [1]
DG71 5 2581,900 1 221.8 T J/mol[9,10]
The activities of SiO2 were calculated from Eq. [1] using

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 29B, FEBRUARY 1998—119

 Table I. Chemical Compositions of Metal and Slag Phases at 1873 K

[Al] Metal Slag

Soluble Insoluble [TzSi] [Mn] [Ca] [Mg] [TzO] (CaO) (SiO2) (Al2O3) (MgO) (MnO) (FetO)
(Mass Ppm) (Mass Pct) (Mass Ppm) (Mass Pct)
SC-1
2.9 1.2 0.0563 0.0461 ,0.05 0.35 31.5 49.2 35.4 8.6 5.9 0.129 0.367
1.7 1.6 0.0189 0.183 ,0.05 0.25 47.9 48.7 33.4 9.8 5.7 0.861 0.593
21.8 1.6 1.04 0.520 10.4 5.2 25.4 49.0 34.6 9.2 5.7 0.306 0.157
23.6 0.8 1.37 0.396 0.55 2.4 10.3 48.7 34.8 9.5 5.7 0.307 0.168
SC-2
1.4 0.6 0.0100 0.0421 ,0.05 0.17 30.1 47.9 26.3 19.7 4.9 0.0527 0.307
,0.1 1.4 0.0016 0.196 ,0.05 ,0.05 72.4 50.4 24.2 18.7 5.1 0.562 0.597
66.8 1.5 1.03 0.886 1.3 2.6 10.4 53.2 22.5 18.3 4.9 0.108 0.0940
66.4 0.7 1.24 1.14 6.3 2.3 15.2 49.7 24.9 19.6 5.1 0.149 0.154
SC-3
2.7 0.8 0.0124 0.0788 ,0.05 0.49 24.2 54.6 22.5 13.6 8.8 0.105 0.140
1.0 0.7 0.0008 0.211 ,0.05 ,0.05 87.8 56.2 19.2 13.8 8.3 0.755 0.772
83.4 1.3 1.12 0.852 3.2 4.2 14.6 53.1 21.0 16.8 8.8 0.0910 0.0887
87.5 0.7 1.16 1.21 1.2 10.8 16.0 53.6 21.2 15.5 8.5 0.141 0.398
SC-4
0.9 ,0.1 0.0008 0.186 ,0.05 0.65 45.9 56.5 14.6 19.3 7.9 0.219 0.415
1.2 0.8 0.0006 0.283 ,0.05 0.58 62.8 57.4 13.8 18.7 7.8 0.403 0.932
139 ,0.1 0.922 1.02 0.53 7.7 12.2 56.1 15.5 20.4 7.7 0.0301 0.0587
214 0.3 1.17 1.30 1.9 12.2 13.4 58.3 13.6 20.2 6.9 0.0321 0.0363
SC-5
2.0 0.8 0.0187 0.0506 ,0.05 1.9 27.7 47.5 29.8 9.5 11.9 0.0451 0.200
,0.1 0.7 0.0040 0.312 ,0.05 0.41 54.4 47.1 31.0 8.2 11.6 0.759 0.452
61.0 2.2 1.04 0.859 1.6 3.3 33.5 48.3 29.2 8.9 12.4 0.148 0.173
88.5 1.4 1.21 0.974 1.3 3.5 15.0 47.0 30.2 9.5 12.0 0.103 0.326
MS-1
2.6 0.2 0.220 0.425 ,0.05 0.87 29.9 13.2 40.9 9.8 32.5 2.15 0.606
3.5 0.2 0.590 0.572 0.28 0.76 19.8 13.4 42.5 9.3 31.7 1.91 0.326
8.2 0.1 1.54 0.466 0.29 1.2 12.6 13.3 41.8 11.3 32.2 0.746 0.193
MA-1
1.3 0.3 0.0836 0.188 ,0.05 0.20 25.6 21.8 30.6 17.2 28.3 0.766 0.501
14.0 0.1 0.438 0.779 ,0.05 ,0.05 13.9 21.6 32.3 16.4 28.0 1.02 0.329
29.0 4.4 1.07 1.02 0.22 ,0.05 9.3 19.7 31.2 20.1 28.4 0.782 0.263
MA-2
3.7 0.3 0.0848 0.277 ,0.05 ,0.05 26.1 21.1 27.5 27.2 22.0 0.866 0.486
24.6 ,0.1 0.508 0.291 ,0.05 0.25 15.1 20.1 26.2 29.5 23.0 0.300 0.254
63.8 ,0.1 1.27 0.851 ,0.05 0.66 9.6 18.1 25.0 32.3 23.4 0.695 0.200
MA-3
12.6 0.6 0.101 0.189 0.14 0.67 16.6 23.7 27.5 37.4 9.9 0.432 0.477
69.1 0.2 1.01 0.220 ,0.05 ,0.05 8.7 25.7 23.4 40.3 10.6 0.224 0.272
109 1.1 1.60 0.217 1.1 0.19 13.2 25.1 22.0 40.8 10.8 0.101 0.218
CSM-2
— — 0.509 0.0437 ,0.05 0.98 33.2 13.1 52.1 — 32.6 0.615 1.01
— — 0.547 0.0776 ,0.05 0.71 28.2 12.2 50.6 — 34.0 0.950 1.16
— — 1.10 0.368 ,0.05 0.41 19.3 12.6 50.0 — 34.8 1.90 0.399

the DG71 value, the contents of O and Si, and the respective
interaction coefficients[9] for fO and fSi, where fi is the activ-
ity coefficient of element i in Henry’s state, referred to as
1 mass pct. The interaction coefficients of Ca and Mg for
fO, obtained from a previous report,[7] are used. The results
for the SC-1 to SC-5 and M-1 to M-4 slags and those for
the MS-1, MA-1 to MA-3, and CSM-1 and CSM-2 slags
are plotted against total Si contents in logarithmic form in
Figures 1 and 2, and are given in Table II along with the
standard deviation. The reason for the use of total Si con-
tent instead of acid-soluble Si content will be described
later. It can be seen that the aSiO2 values at the compositions
of [pct T z Si] .1 are considerably high for some of the
slags, despite the fact that Mn was added to approach the
equilibrium from supersaturation.
By using the aSiO2 values in the CaO-SiO2-MgO (CSM-
1 and CSM-2) and CaO-SiO2-Al2O3-MgO (SC-1 to SC-5,
M-1 to M-4, MS-1, and MA-1 to MA-3) slags given in
Table II and those in the CaO-SiO2 (CS),[11] CaO-SiO2-
Al2O3 (CSA),[3–5,12,13] and CaO-SiO2-Al2O3-MgO (CASM)[14]

120—VOLUME 29B, FEBRUARY 1998 METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table II. Activities of SiO2 and Al2O3 and Activity
Coefficients of MnO and FetO

Slag Log aSiO2 Log aAl2O3 LoggMnO LoggFetO

SC-1 21.6850.08 21.5750.09 0.3850.10 0.6950.02
SC-2 22.4350.04 21.7650.09 0.7350.07 0.7950.08
SC-3 22.5350.04 21.7050.01 0.7150.07 0.9250.11
SC-4 23.0650.11 21.8250.14 1.0350.03 0.6950.21
SC-5 22.2550.06 21.4050.16 0.8050.09 0.8950.01
M-1 22.1150.09 21.4750.10 0.6250.03 0.7450.02
M-2 21.7750.10 21.4350.14 0.6450.08 0.6650.09
M-3 22.4450.11 21.3050.12 0.8350.06 0.7250.12
M-4 22.4450.13 20.9450.08 0.8250.10 0.4850.13
MS-1 21.1450.07 21.7650.22 0.1650.04 0.4750.02
MA-1 21.6150.05 21.1750.11 0.3150.07 0.4150.14
MA-2 21.5350.12 20.6350.14 0.3550.07 0.4650.09
MA-3 21.8150.18 20.6750.04 0.2150.12 0.31
CSM-1 22.0250.11 — 0.4850.19 0.8750.24
CSM-2 20.8150.12 — 20.1950.13 0.1850.05

Fig. 1—Activity of SiO2 plotted against total Si content in mass pct in

logarithmic scale.

Fig. 3—Comparison of observed activities of SiO2 and Al2O3 with

Fig. 2—Activity of SiO2 plotted against total Si content in mass pct in
logarithmic scale.
slags calculated from Eq. [1], the aSiO2 values were ex-
pressed as a function of slag composition using a multiple
regression analysis as follows:
log aSiO25 0.036 (pct MgO) 1 0.061 (pct Al2O3)
1 0.123 (pct SiO2) 2 0.595 (pct SiO2)/
(pct CaO) 2 6.456 (R 5 0.85)
where R is the correlation coefficient.
Activities of SiO2 were first expressed as a linear func-
calculated ones from Eqs. [2] and [5], respectively.
tion of the slag component, but it was found that this func-
tion could not reasonably well explain the experimental
data. Accordingly, the fourth term in the right-hand side
of Eq. [2] was added. It is noted that Eq. [2], which is
utterly an empirical formula, can be applied only to 10 to
60 pct CaO-10 to 50 pct SiO2-O to 50 pct Al2O3-0 to 30
[2] pct MgO slags. The relationship between the calculated
aSiO2 value from Eq. [2] and the observed value in loga-
rithmic form is shown in the upper diagram of Figure 3,
where the correspondence between the two is within the
experimental scatter.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 29B, FEBRUARY 1998—121

Fig. 4—(a) and (b) Activities of SiO2 on 0 and 10 mass pct Al2O3 planes.
Fig. 5—Activities of SiO2 on 20 mass pct Al2O3 plane.
The aSiO2 values obtained from the present and previ-
ous[14] results along the liquidus lines are shown on the 0,
10, 20, 30, and 40 pct Al2O3 planes of the CaO-SiO2-Al2O3-
MgO phase diagram[15,16] in Figures 4 through 6. The isoac-
tivity lines for SiO2 calculated from Eq. [2] are indicated
by solid lines over the liquid region along with those ob-
tained based on the results by Rein and Chipman,[1] which
are represented by dashed-dotted lines. The aSiO2 values in
previous studies for the CaO-SiO2[11] binary slag and the
CaO-SiO2-Al2O3[1,3,4,12] and MgO-SiO2-Al2O3[1] ternary slags
122—VOLUME 29B, FEBRUARY 1998
Fig. 6—(a) and (b) Activities of SiO2 on 30 and 40 mass pct Al2O3 planes.
are also indicated. The data given by brackets correspond
to those estimated by extrapolation.
The isoactivity lines by Rein and Chipman[1] indicate that
the aSiO2 values decrease slightly by the replacement of CaO
by MgO for a given SiO2 content. This trend is different
from the present ones derived by Eq. [2]. Such inconsis-
tency is observed particularly at the slag compositions with
0, 10, and 20 pct Al2O3, as shown in Figures 4 and 5. At
a constant content of SiO2 for a given Al2O3 content, the
aSiO2 value is expected to increase with the replacement of
CaO by MgO due to the fact that MgO is less basic than
CaO. The isoactivity lines of SiO2 on 10 and 20 pct MgO
planes reported by Rein and Chipman[1] and those derived
from Eq. [2] are shown in the upper diagrams of Figures 7
and 8, along with the present and previous[14] results.
B. Activity of Al2O3
The exchange reaction with respect to Al and Si between
slag and metal is expressed as follows:
Al 1 3/4 SiO2 (s) 5 3/4 Si 1 1/2 Al2O3 (s) [3]
DG73 5 2164,600 1 26.8 T J/mol[9,10]
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 7—(a) and (b) Activities of SiO2 and Al2O3 on 10 mass pct MgO
plane.
The following relation is obtained using the equilibrium
constant of Eq. [3], K3:
log [pct Al] 5 (3/4) log [pct Si] 1 log (fSi3/4 / fAl)
[4]
1 log {aAl2O31/2 / (K3 z aSiO23/4)}
Total Al contents are plotted against total Si contents in
logarithmic form in Figure 9. Instead of acid-soluble Al (Si)
content, total Al (Si) content is used in this work because
acid-insoluble Al (Si) is considered to be the secondary
inclusion precipitated during solidification. Further details
of this have been given elsewhere.[17,18] It can be seen from
Figure 9 that the data points follow approximately the lines
having a slope of 3/4, as predicted from Eq. [4], even for
the data points at the compositions of [pct T z Si] . 1.
Although these data points deviate considerably from the
lines in the plot of log aSiO2 vs [pct T z Si], as shown in
Figures 1 and 2, this finding is consistent with the previous
observations[3,12,13] in which the aAl vs aSi relation in loga-
rithmic form shows the linearity without respect to the pres-
ence of supersaturated oxygen. The data points obtained in
the range of low Si levels deviate from the line. This is due
to the scattering of the values of analyzed Al for such a
low Si level.
The activities of Al2O3 were calculated from Eq. [4] us-
ing the average values of aSiO2 given in Table II and the
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 8—(a) and (b) Activities of SiO2 and Al2O3 on 20 mass pct MgO
plane.
respective interaction coefficients[9] for fSi and fAl. The re-
sults are plotted against total Al contents in Figure 10. It
can be seen that the aAl2O3 values in the very low concen-
tration range of [ppm T z Al] ,10 deviate considerably due
to the uncertainty of the analyzed Al contents, which mark-
edly influence the calculation of the aAl2O3 values. Therefore,
the experimental data with [ppm T z Al] .10, except for
those of the MS-1 slag, were used for the evaluation of
aAl2O3. These results are summarized in Table II along with
the standard deviation.
By using the aAl2O3 values in the present CaO-SiO2-Al2O3-
MgO (SC-1 to SC-5, M-1 to M-4, MS-1, and MA-1 to MA-
3) slags and those in previous CaO-SiO2-Al2O3 (CSA)[3–
5,12,13]
and CaO-SiO2-Al2O3-MgO (CASM)[14] slags calcu-
lated from Eq. [4], the aAl2O3 values were expressed as a
function of slag composition using a multiple regression
analysis as follows:
log aAl2O3 5 {20.275 (pct CaO) 1 0.167 (pct MgO)}/(pct SiO2) [5]
1 0.033 (pct Al2O3) 2 1.560 (R 5 0.89)
Activities of Al2O3 were first expressed as a linear function
of slag component, but it could not well explain the exper-
imental data. It was found that the aAl2O3 values expressed
by Eq. [5] fit the data with the correlation coefficient R 5
0.89. The relations between the calculated aAl2O3 from Eq.
VOLUME 29B, FEBRUARY 1998—123
Fig. 9—Relation between total Al content in mass ppm and total Si content
in mass pct in logarithmic scale.
Fig. 10—Activity of Al2O3 plotted against total Al content in mass ppm
in logarithmic scale.
[5] and the observed value in logarithmic form are plotted
in the lower diagram of Figure 3.
The present and previous[14] results along the liquidus
lines are shown on the 10, 20, 30, and 40 pct Al2O3 planes
of the CaO-SiO2-Al2O3-MgO phase diagram[15,16] in Figures
11 and 12. The isoactivity lines for Al2O3 calculated from
124—VOLUME 29B, FEBRUARY 1998
Fig. 11—(a) and (b) Activities of Al2O3 on 10 and 20 mass pct Al2O3
planes.
Eq. [5] over the liquid region and the aAl2O3 values in the
respective ternary systems[1,3–5,12,13] are given. The data sat-
urated with the MS-1 slag shown in the upper diagram of
Figure 11 is significantly different from the calculated
value. This is due to the scatter of Al content, which is
below 10 ppm. The data given by brackets correspond to
those estimated by extrapolation. The isoactivity lines for
Al2O3 from Eq. [5] are shown on the 10 and 20 pct MgO
planes of the CaO-SiO2-Al2O3-MgO phase diagram[15,16] in
the lower diagrams of Figures 7 and 8, along with the pres-
ent and previous[1,6,14] results. Activity of Al2O3 can be also
estimated from the SiO2 isoactivity curves using the Gibbs–
Duhem relation. The present authors[6] determined the ac-
tivities of Al2O3 in a CaO-Al2O3-SiO2 system using this
method. In the present CaO-Al2O3-SiO2-MgO system, how-
ever, the values for the integration limit on the Gibbs–Du-
hem relation are not accurately determined. For this reason,
this method was not used in this work.
It should be pointed out that the activities of MgO in the
slags saturated with the MgO z Al2O3 phase can be esti-
mated from the reaction MgO (s) 1 Al2O3 (s) 5 MgO z
Al2O3 (s), DG7Spinel 5 218,800 2 6.3 T J/mol[1] using the
aAl2O3 values. The aAl2O3 value at the MgO and MgO z Al2O3
double-saturated composition using the free energy change
for MgO z Al2O3 was calculated as 0.14, which agreed with
the present value. Similarly, the activities of CaO at the
slag compositions saturated with the 2CaO z SiO2 phase can
be obtained from the reaction 2CaO (s) 1 SiO2 (s) 5 2CaO
z SiO2 (s), DG7C2S 5 2118,800 2 11.3 T J/mol[19] using the
aSiO2 values.
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 12—(a) and (b) Activities of Al2O3 on 30 and 40 mass pct Al2O3
planes.
C. Activity Coefficient of MnO
Slag-metal reaction with respect to Mn and Si can be
expressed as follows:
Mn 1 1/2 SiO2 (s) 5 MnO (s) 1 1/2 Si
DG76 5 2800 1 17.4 T J/mol[9,10,20]
The activity coefficients of MnO relative to the solid
standard state, gMnO, were calculated from Eq. [7] using the
equilibrium constant of Eq. [6], K6, the average values of
aSiO2 given in Table II, and the respective interaction coef-
ficients[9] for fMn and fSi.
log gMnO 5 log {[pct Mn]/[pct Si]1/2} 1 log (fMn/fSi1/2)
1 log {azK6zaSiO21/2/(pct MnO)}
where a is the constant related to the conversion from mol
fraction of MnO to mass pct. Although a is a function of
slag composition, it is regarded to be approximately con-
stant under the present experimental condition. The gMnO
values are plotted against the MnO contents in logarithmic
form in Figures 13 and 14 for SC-1 to SC-5 and M-1 to
M-4 slags and MS-1, MA-1 to MA-3, CSM-1, and CSM-
2 slags, respectively. These values are also given in Table
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 13—Activity coefficient of MnO plotted against MnO content in mass
pct in logarithmic scale.
[6]
Fig. 14—Activity coefficient of MnO plotted against MnO content in mass
pct in logarithmic scale.
[7] II along with the standard deviation. The gMnO values cal-
culated from the reaction Mn 1 O 5 MnO (s), DG7 5
2288,100 1 128.3 T J/mol,[20] using the contents of Mn
and O and the respective interaction coefficients,[9] agreed
with those calculated from Eq. [7] for the data except the
value for supersaturated oxygen.
By using the gMnO values in the present CaO-SiO2-Al2O3-
MgO (SC-1 to SC-5, M-1 to M-4, MS-1, and MA-1 to MA-
3) slag and the previous CaO-SiO2-Al2O3 (CSA)[4] and
CaO-SiO2-Al2O3-MgO (CASM)[14] slags containing less
than 10 pct MnO, the gMnO values were expressed as a func-
VOLUME 29B, FEBRUARY 1998—125
Fig. 15—Comparison of observed activity coefficients of MnO and FetO
with calculated ones from Eqs. [8] and [10], respectively.
tion of slag composition using a multiple regression anal-
ysis as follows:
log gMnO 5 0.019 (pct CaO) 1 0.023 (pct MgO)
[8]
2 0.023 (pct SiO2) 1 0.129 (R 5 0.88)
The relations between the calculated value from Eq. [8]
and the observed value in logarithmic form are shown in
the upper diagram of Figure 15, in which the present results
for the CaO-SiO2-MgO (CSM-1 and CSM-2) slag, the pre-
vious results[4] for the CaO-Al2O3 (AC, CA) and CaO-SiO2
(CS) slags with (pct MnO) ≤7, and those for the CaO-SiO2-
Al2O3 (CSA) slag, obtained at 1923 K by Abraham et al.[21]
and Mehta and Richardson,[22] are also included. It can be
seen that the data points agree well with the gMnO values
calculated from Eq. [8].
The present and previous[14] experimental data along the
liquidus lines are shown on the 0, 10, 20, 30, and 40 pct
Al2O3 planes of the CaO-SiO2-Al2O3-MgO phase dia-
gram[15,16] in Figures 16 and 17. The iso-gMnO lines calcu-
lated from Eq. [8] are plotted over the liquid region, along
with previous results[4] in the CaO-SiO2-Al2O3 system. The
data given by brackets correspond to those estimated by
extrapolation. It can be seen that the gMnO values decrease
with an increase in SiO2 content for a given Al2O3 content.
The isoactivity coefficient lines for MnO from Eq. [8] are
shown on the 10 and 20 pct MgO planes of the CaO-
SiO2-Al2O3-MgO phase diagram[15,16] in the upper diagrams
of Figures 18 and 19, along with the present and previ-
ous[6,14] results. It can be seen from the upper diagram of
126—VOLUME 29B, FEBRUARY 1998
Fig. 16—(a) and (b) Activity coefficients of MnO on 0 and 10 mass pct
Al2O3 planes.
Figure 18 that the gMnO values increase with an increase in
the (pct CaO)/(pct SiO2) ratio, except for the compositions
with low SiO2 and high Al2O3 contents.
D. Activity Coefficient of FetO
The reaction of Si with FetO in slag can be expressed by
2 FetO (1) 1 Si 5 SiO2 (s) 1 2 Fe (1) [9]
DG79 5 2349,700 1 124.2 T J/mol[9,10,23]
The activity coefficients of FetO, gFetO , relative to the liq-
uid standard state, were calculated from the DG79 value, the
average values of aSiO2 given in Table II, and the respective
interaction coefficients[9] for fSi, using Eq. [7] with respect
to gFetO. The results are plotted against total Si contents in
Figure 20 and are summarized in Table II. The gFetO values
can also be estimated from the contents of analyzed O from
the reaction Fe (l) 1 O 5 FetO (l), DG7 5 2116,100 1
48.79 T J/mol.[23] These results, except for the data at su-
persaturation, are in agreement with those from Eq. [9].
By using the gFetO values in the present CaO-SiO2-
Al2O3-MgO (SC-1 to SC-5, M-1 to M-4, MS-1, and MA-
1 to MA-3) slag and previous CaO-SiO2-Al2O3 (CSA)[3,4]
and CaO-SiO2-Al2O3-MgO (CASM)[14] slags, the gFetO val-
ues were expressed as a function of slag composition using
a multiple regression analysis as follows:
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 17—(a) through (c) Activity coefficients of MnO on 20, 30, and 40
mass pct Al2O3 planes.
log gFetO 5 {0.676 (pct MgO) 1 0.267 (pct Al2O3) 2 19.07}/ [10]
(pct SiO2) 1 0.0214 (pct CaO) 2 0.047 (R 5 0.59)
The relations between the calculated value from Eq. [10]
and the observed value are shown in the lower diagram of
Figure 15, in which the results for the present CaO-SiO2-
MgO (CSM-1 and CSM-2) and the previous CaO-SiO2
(CS)[4] slags are also included.
The gFetO values along the liquidus lines and the iso-
gFetO lines over the liquid region on the 0, 10, 20, 30, and
40 pct Al2O3 planes of CaO-SiO2-Al2O3-MgO phase dia-
gram[15,16] are shown in Figures 21 and 22. The gFetO values
decrease with an increase in SiO2 content at compositions
for a given low Al2O3 level, but they increase with increas-
ing MgO content for a given high Al2O3 level. The isoac-
tivity coefficient lines for FetO from Eq. [10] are shown on
the 10 and 20 pct MgO planes of the CaO-SiO2-Al2O3-MgO
phase diagram[15,16] in the lower diagrams of Figures 18 and
19, along with the present and previous[6,14,24] results. It can
be seen from the lower diagram of Figure 18 that the
gFetO values increase with an increase in CaO content at the
compositions of (pct SiO2) .20, but they tend to decrease
with an increase in CaO content at the compositions of (pct
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 18—(a) and (b) Activity coefficients of MnO and FetO on 10 mass
pct MgO planes.
SiO2) ,20. More detailed study is necessary in this com-
position range.
E. Phase Boundary and Solubility of MgO
The liquidus lines on the 0, 10, 20, and 30 pct Al2O3
planes shown in Figures 4 through 6 are those by Osborn
et al.[15] Those on the 40 pct Al2O3 plane shown in the lower
diagram of Figure 6 were obtained by extrapolation based
on the results obtained by Cavalier and Sandreo–Dendon.[16]
The present and previous[14] slag compositions fall approx-
imately on the liquidus lines except for the line saturated
with the MgO z Al2O3 phase.
The liquidus lines on the 10 pct MgO plane shown in
Figure 7 are those by Cavalier and Sandreo–Dendon,[16] but
those on the 20 pct MgO plane shown in Figure 8 were
obtained by extrapolation based on the results obtained by
Osborn et al.[15] The present and previous[14] slag compo-
sitions saturated with 2CaO z SiO2, MgO, and MgO z Al2O3
phases on the 10 pct MgO plane are significantly different
from the results reported by Cavalier and Sandreo–Den-
don,[16] as shown in Figure 7, but those on the 20 pct MgO
plane agree with those reported by Osborn et al.,[15] as
shown in Figure 8. The disagreement observed in Figure 7
may be partly due to the fact that liquidus lines change
drastically with an increase in MgO content, as shown in
VOLUME 29B, FEBRUARY 1998—127
 Fig. 20—Relation between FetO and total Si content in mass pct in
logarithmic scale.

Fig. 19—(a) and (b) Activity coefficients of MnO and FetO on 20 mass
pct MgO planes.

Figures 7 and 8, and the results by Osborn et al.[15] are

different from those by Cavalier and Sandreo–Dendon.[16]
In the parallel projection method in which the composi-
tions in a quaternary system can be represented by a two-
dimensional representation, a given point on a saturated
plane is projected onto the basal plane of the CaO-Al2O3-
SiO2 system parallel to the edge CaO-MgO. As a result,
the point in the tetrahedron can be plotted in a (CaO 1
MgO) 2 Al2O3-SiO2) quasiternary diagram.
The present and previous[2,14] results are shown in Figure
23, in which the heavy and light lines represent the phase
boundaries and the iso-MgO solubility lines, respectively.
The lines for 5, 10, and 15 pct MgO were determined
mainly from the data by Cavalier and Sandreo–Dendon,[16]
but that for 20 pct was determined from the data of Osborn
et al.[15] The present and previous[14] results in the MgO or
MgO z Al2O3-saturated phase are in agreement with these
lines. The phase boundaries were estimated mostly from the
results by Osborn et al.[15] It can be seen from the iso-MgO
solubility lines that, with an increase in Al2O3 content for
a given SiO2 content, the solubility of MgO in the MgO-
saturated phase increases to the MgO-MgO z Al2O3 double-
saturated phase boundary and, thereafter, decreases in the Fig. 21—(a) and (b) Activity coefficients of FetO on 0 and 10 mass pct
MgO z Al2O3-saturated phase. Al2O3 planes.

128—VOLUME 29B, FEBRUARY 1998 METALLURGICAL AND MATERIALS TRANSACTIONS B


Fig. 22—(a) through (c) Activity coefficients of FetO on 20, 30, and 40
mass pct Al2O3 planes.
Fig. 23—Iso-solubility lines of MgO plotted in the (CaO 1 MgO)-SiO2-
Al2O3 quasiternary diagram.
METALLURGICAL AND MATERIALS TRANSACTIONS B
IV. CONCLUSIONS
By using a slag-metal equilibration technique, the activ-
ities of SiO2 and Al2O3, the activity coefficients of FetO and
MnO, and the phase boundaries in a CaO-SiO2-Al2O3-MgO
slag were determined at 1873 K. The aSiO2 values were
found to agree with those by Rein and Chipman and the
phase boundaries are also in reasonable agreement with pre-
vious results. Comparison could not be made with respect
to the aAl2O3, because no data are available for the activities
of Al2O3 in the present slag. It can be said, however, from
the results for the aAl2O3 values in the respective ternary
slags, that the aAl2O2 values are satisfactory. In the present
work, the activities of MgO and CaO could not be deter-
mined. If accurate thermochemical data on the respective
interoxide compounds are available, these activities can be
estimated based on the activities of SiO2 and Al2O3.
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