ISIJ International, Vol. 50 (2010), No. 6, pp.

822829

Distribution of P2O5 between Solid Solution of

2CaO SiO23CaO P2O5 and Liquid Phase
Farshid PAHLEVANI, Shin-ya KITAMURA, Hiroyuki SHIBATA and Nobuhiro MARUOKA
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577
Japan. E-mail: farshid@tagen.tohoku.ac.jp
(Received on February 5, 2010; accepted on April 6, 2010 )

It is desirable to decrease the phosphorous content of steel and the amount of slag in steel rening. For
satisfying this requirement recently, the importance of multiphase slag in steel rening has been given considerable attention. Normally, hot metal dephosphorization slag consists of the CaOSiO2FeOP2O5 system, and the industrial operation is mainly carried out in the dicalcium silicate (C2S) saturated region. It is
well known that C2S forms a solid solution with the main product of dephosphorizationtricalcium phosphate (C3P)at the treatment temperature over a wide composition range, and a high distribution ratio of
P2O5 between the solid solution and the liquid phase has been reported. In order to determine the ruling
factors on the distribution ratio, the inuences of MgO, MnO, and Al2O3 were investigated for various slag
compositions in the case of FeO or Fe2O3 as the iron oxide. First, a mixture of a standard regent was heated
to the melting temperature in order to produce homogenous liquid slag. Next, it was cooled down to a semisolid state: during cooling, the solid solution of C3PC2S was precipitated under the equilibrium condition.
For clarifying the inuence of slag composition on the distribution ratio, the ruling factors on the activity coefcient of P2O5 in the solid solution and liquid slag phase were evaluated. It is the contention of this research that the activity coefcient of P2O5 in the solid solution was largely inuenced by P2O5 and the total
solved oxide content of the solid solution. (log g P2O5SS )cal was obtained empirically in order to represent the activity coefcient in the solid solution. On the other hand, the activity coefcient of P2O5 in the liquid phase
was strongly inuenced by the CaO content of the liquid phase. On the basic of these correlations, it was
shown that the CaO content of the liquid phase and (log g P2O5SS )cal are the ruling factors on distribution ratio.
KEY WORDS: distribution ratio; activity coefcient of P2O5; added oxide to slag; multi phase slag; steel rening.

1.

the liquid slag phase) indicated that P2O5 is concentrated in

the solid solution with a high distribution ratio.4,5) Kitamura
et al.6,7) pointed out the importance of a solid solution in
achieving efcient dephosphorization. Based on their results, it may be considered that dicalcium silicate and its
solid solution with tricalcium phosphate can act as a sink
for phosphorus and lower the phosphorus content of the liquid phase, which make it more capable for future dephosphorization.
Some researches, consider steelmaking slag as a source
of phosphorus.2) The C2SC3P solid solution in the slag,
which has high phosphorus content, can be used as an alternative source of phosphorus. Therefore, if steelmaking slag
is to be used as an alternative source of the phosphate ore, it
is important to increase the distribution ratio of phosphorous between the liquid slag and the solid solution.
Recently, Kitamura et al.6,7) studied the effect of P2O5
content of the CaOSiO2Fe2O3P2O5 slag system on the
distribution ratio of phosphorus and also claried the inuence of oxides such as MgO and MnO on the distribution
ratio. Shimauchi et al.7) found that if the P2O5 content is
sufciently high and other conditions such as T Fe are controlled in order to obtained a high distribution ratio, the

Introduction

Since steel come in use under various conditions its

phosphorus content must be as low as possible in order to
ensure that it is of high quality. Because of that, the demand
for the production of low-phosphorus steel has been increasing, however production of low-phosphorous steel
cause production of large amount of slag in the steel rening process. Recently, because of the increasing concern for
environmental conservation, much attention has been devoted to the hot metal dephosphorization process as a
means to decrease the amount of slag generated, reduce the
production cost, and increase the productivity during the
production of high-purity steel.
Normally, hot metal dephosphorization slag consists of
the CaOSiO2FeOP2O5 system, and the industrial operation is mainly carried out in the dicalcium silicate (C2S) saturated region. It is well known that C2S forms a solid solution with the main product of dephosphorizationtricalcium phosphate (C3P)at the treatment temperature over a
wide composition range.13) Measurements of the distribution ratio of P2O5 between the solid and liquid phases in
semisolid slag (coexistence of the solid solution phase in
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concentration of C3P in the solid solution can be increased

to 100%. They also indicated that there is no signicant effect of the addition of MgO and MnO on the distribution
ratio of P2O5.
In this research effect of different oxides in the slag system on the distribution ratio of P2O5 was studied. Because
most industrial slags contain Al2O3, in this research rst,
effect of different Al2O3 contents in the CaOSiO2Fe2O3
P2O5 slag system was studied. Then based on the pervious
results of the authors effect of changing the iron oxide in
the slag system from Fe2O3 to FeO was studied. Effect of
different P2O5 contents in the CaOSiO2FeOP2O5 slag
system on the distribution ratio of phosphate and also the
inuence of oxides such as MgO, MnO, and Al2O3 on the
distribution ratio was investigated. On the basic of these
data and their analysis by a regression method, an equation
is proposed to evaluate the activity coefcient of P2O5 in a
solid solution. Finally, the ruling factors on the distribution
ratio were discussed.
2.

C and on the CaOSiO2FeO phase diagram for samples D,

E, F and G. The desired criterion for the used slag systems
was that the slag should be in a homogenous liquid state at
1 673 K in the case of FeO and 1 873 K in the case of Fe2O3
and it should be in a semisolid state at 1 573 K in the case
of FeO and 1 673 K in the case of Fe2O3.
The mixed regents containing FeO were placed in a steel
crucible with dimensions of F 10 mm20 mm and those
containing Fe2O3 were placed in a Pt crucible with dimensions of F 5 mm5 mm. The steel crucible was heated in
an electric resistance furnace up to 1 673 K for producing
FeO-containing slag and the Pt crucible was heated up to
1 873 K in an electric resistance furnace for producing
Fe2O3-containing slag. Each crucible was maintained at its
above mentioned temperature for 60 min in order to produce a homogenous slag in liquid phase. Then, FeO-contained slag was cooled to 1 573 K at a cooling rate of
3 K/min and Fe2O3-contained slag was cooled to 1 673 K at
a cooling rate of 10 K/min. Each crucible was maintained at
its particular temperature for 60 min so as to produce semisolid slag (solid solution of C2SC3P in equilibrium with
liquid slag). Finally, the slag sample thus produced was
quenched in oil. The heat treatment pattern of samples is
shown in Fig. 2. It should be mentioned that when FeO was
used as iron oxide, the heat treatment was performed in an
Ar atmosphere, and in the case of Fe2O3, it was performed
in an air atmosphere.
The quenched sample was mounted and analyzed by following a standard metallographic procedure. The composition of each phase was measured by using an EPMA (electron probe micro analyzer). Because the average particle diameter of the solid solution phase exceeded 10 m m and the
liquid phase became glassy after quenching their composition could be directly analyzed by EPMA. Then, the distribution ratio of P2O5 (LP) was calculated by Eq. (1).

Experimental Procedure

Regent-grade SiO2, Fe2O3, Fe, CaCO3 and [3CaO P2O5]

Ca(OH)2 were used to produce slag in this experiment.
First, CaCO3 was heated to 1 273 K for 60 min under an air
atmosphere in an Al2O3 crucible so as to produce CaO.
Next, for the conditions that require FeO, Fe was mixed
with Fe2O3 and heated to 1 673 K for 60 min under an Ar atmosphere in an iron crucible so as to produce FeO. Then,
the reagents were mixed in various ratios in order to produce the CaOSiO2FeOP2O5 or CaOSiO2Fe2O3P2O5
slag system. For investigating the effect of other elements
on the distribution ratio of phosphorous, Al2O3, MgO and
MnO were added in some cases. Table 1 shows the different mixing conditions which was used in this research. Figure 1 also shows the composition range of the used slag on
the CaOSiO2Fe2O3 phase diagram for samples A, B, and

Table 1. Mixing conditions of slag (mass%).

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Fig. 1. Mixing conditions of slag are shown on the ternary (a) CaOSiO2Fe2O3 phase diagram for the case in which
Fe2O3 was used and (b) CaOSiO2FeO phase diagram for the case in which of FeO was used.

Fig. 2. Experimental conditions for precipitation of C2SC3P solid solution, with (a) Fe2O3 used as the iron oxide, and (b)
FeO was used as the iron oxide.

LP

3.

(%P2O5 ) SS
............................(1)
(%P2O5 ) L

3.1.

Effect of Al2O3 on the CaOSiO2P2O5Fe2O3 System

Figure 3 shows the effect of adding different oxides on
the distribution ratio of P2O5 for different T Fe in the liquid
phase. The results of adding MgO and MnO to the slag system were taken from pervious paper by Shimauchi et al.7)
As compared with the results of adding MgO and MnO to
the CaOSiO2P2O5Fe2O3 slag system, the addition of
Al2O3, caused LP to become large in the low T Fe condition.
If the activity of P2O5 in a solid solution does not change
widely, LP depends on the basicity of the liquid phase. In
Fig. 4, the CaO content of the liquid slag was selected to
represent the index of slag basicity. LP decreased on the addition of MgO and MnO, but it did not change on the addition of Al2O3.

Results

From microstructural study of samples, it is clear that in

the case of FeO contained slag at 1 673 K and in the case of
Fe2O3 contained slag at 1 873 K the samples was in uniform
liquid phase which cause uniform glassy structure in the
quenched samples. Also at 1 573 K for FeO contained slag
and 1 673 K for Fe2O3 contained slag solid solution phase
was precipitated under all experimental conditions. In some
cases, because of high FeO content, pure Fe phase was also
precipitated in addition to the solid solution phase. The
composition and area fraction of the precipitated phase and
matrix are summarized in Table 2. This table also presents
the distribution ratio of P2O5 (LP) and the average composition of samples after precipitation of Fe and solid solution.
For calculating the average composition, rst, the area fraction of each phase was calculated by image analyzing the
microstructure of samples. Then, based on the composition
of each phase, which was obtained from EPMA analysis the
average composition under each mixing condition was calculated. It should be mentioned that, for some cases in
Table 2 the sum of area fraction for matrix and precipitated
solid solution is not equal to one. In these cases this difference refers to area fraction of precipitated Fe phase.
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3.2.

Comparison between CaOSiO2P2O5Fe2O3 and

CaOSiO2P2O5FeO Systems
Figure 5 shows the distribution ratios at different T Fe
contents by changing the iron oxide in the slag system. As
shown for high T Fe content, LP of the CaOSiO2P2O5
FeO system is lower than that of the CaOSiO2P2O5
Fe2O3 system.
Figure 6 shows the inuence of the CaO content of the
liquid phase on the distribution ratio. The difference between two systems becomes more clear. Inoue5) has showed
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Table 2. Composition of liquid and solid phase in slag (mass%).

Fig. 3. Inuence of adding Al2O3 on the P2O5 distribution

ratio between the liquid and solid solution phases at
different T Fe contents in liquid phase.

Fig. 4. Changes produced in the P2O5 distribution ratio between the liquid and
solid solution phases by adding MgO, MnO and Al2O3 at different CaO
contents in liquid phase in the case of Fe2O3 as iron oxide.

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Fig. 5. Inuence of different iron oxides on the P2O5 distribution

ratio between the liquid and solid solution phases at different T Fe contents in liquid phase in the case of Fe2O3
as iron oxide.

Fig. 8. Activity coefcient of P2O5 vs. P2O5 content of the solid

solution for two types of iron oxides (Fe2O3 and FeO).

when FeO is used as iron oxide. By comparing this gure

with Fig. 4, it is found that the effect of adding MgO, MnO
or Al2O3 on LP is smaller in the case of CaOSiO2P2O5
FeO system than that in the case of CaOSiO2P2O5Fe2O3
system.
4.

Discussion

In order to achieve better understanding of the phenomenon of distribution of P2O5 between the solid solution and
the liquid slag phase and to nd out the effect of different
oxides, the results of the present research and the previous
research by Shimauchi et al.7) was used for this discussion.
Because the liquid slag phase and solid solution are in
equilibrium the activities of P2O5 in the solid solution and
liquid phase are same. Then, the observed distribution ratio
is proportional to the activity coefcient of P2O5 in each
phase, as shown in Eq. (2). Where a is the activity; g , the
activity coefcient; and k, the coefcient for the conversion
of the mass percentage to the mol fraction. Subscripts
P2O5(Liq) and P2O5(SS) denote the activities and activity coefcients of P2O5 in the liquid phase and the solid solution,
respectively.

Fig. 6. Change produced in the P2O5 distribution ratio between

the liquid and solid solution phases by changing the used
iron oxide at different CaO contents in liquid phase.

LP

aP O P2O5( L )
PO
(%P2O5 ) SS
k 2 5( SS )
k 2 5( L ) ...(2)
P2O5( SS )
aP2O5( L ) P2O5( SS )
(%P2O5 ) L

The activity of P2O5 in the liquid phase was calculated by

using a regular solution model,8) and from that the activity
coefcient of P2O5 in solid solution was calculated.
4.1. Activity Coefcient of P2O5 in Solid Solution
Figure 8 shows the relation between the activity coefcient of P2O5 and the P2O5 content of the solid solution
when Fe2O3 or FeO is used as the iron oxide. From these results, it can be said that the activity coefcient increases
with increasing the P2O5 content. In addition, it is clear
from the gure that the activity coefcient is larger in the
case of FeO than that in the case of Fe2O3.
Figure 9 shows the effect of the added oxide on the activity coefcient of P2O5 in solid solution in the case of
Fe2O3 iron oxide. Figure 10 also shows this effect in the
case of FeO as iron oxide. The addition of MgO and MnO
causes an increase in the activity coefcient of P2O5, while

Fig. 7. Changing on the P2O5 distribution ratio between the liquid and solid solution phase by adding MgO, MnO and
Al2O3 at different CaO content in liquid phase in the case
of FeO as iron oxide.

that the temperature dependence of LP is very small, acordingly it is expected that a change in LP will be caused by the
change in the slag system (Fe2O3 or FeO).
3.3.

Effect of Added Oxides in the CaOSiO2P2O5

FeO System
Figure 7 shows the effect of adding different oxides

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Fig. 10. Effect of different added oxides on the relation between

the activity coefcient of P2O5 and the P2O5 content of
solid solution in CaOSiO2P2O5FeO system.

Fig. 9. Effect of different added oxides on the relation between

the activity coefcient of P2O5 and the P2O5 content of
solid solution in CaOSiO2P2O5Fe2O3 system.

Table 3. Composition of the solid solution phase (mass%) and the activity coefcient of P2O5.

that of Al2O3 leads to a decrease in the activity coefcient.

Table 3 summarizes the composition of the solid solution
and the activity coefcient of P2O5 in the solid solution for
all the samples. The results for the CaOSiO2P2O5Fe2O3
slag system are taken from the previous research by Shimauchi et al.7) From Table 3, it is clear that in the
CaOSiO2P2O5Fe2O3 slag system, the solid solution is
pure 2CaOSiO23CaOP2O5 when the Fe2O3 content is less

than 2%. However, in the CaOSiO2P2O5FeO slag system, the FeO content of the solid solution is 38%. Further,
in the case of Al2O3 addition, the Al2O3 content of the solid
solution is less than 1%, but in the case of MgO and MnO
addition, the MgO and MnO content is 17%. Therefore,
the presence of an oxide other than CaO, SiO2, and P2O5 in
a solid solution (solved oxide) will inuence the activity
coefcient of P2O5.
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For more precise understanding of the effect of a solved

oxide on the activity coefcient of P2O5 its relation with the
total solved oxide content in the range of 2733% of the
P2O5 content was extracted. This relation is shown in Fig.
11. After analyzing these data by a regression method the
correlation between the oxide content and the activity coefcient of P2O5 was evaluated and is presented in Eq. (3).

oxides on this relation; a good relation is observed, except

in the case of Al2O3 addition to the slag. Although Al2O3
is known as a neutral oxide, in the regular solution
model,8) the interaction parameter between P5 and Al3
(261 500 J) has almost the same value as that between P5
and Ca2 (251 040 J). Therefore, in the present calculation, the addition of Al2O3 lowers the activity of P2O5 in the
liquid slag. In order to conrm the validity of this conjecture, the interaction parameter of Al3 must be evaluated in
the future.
As discussed before, the P2O5 content and the solved
oxide content of a solid solution have large inuence on the
activity coefcient of P2O5 in the solid solution. From the
conditions under which the total solved oxide content was
lower than 1.5%, an equation was formulated for calculating the activity coefcient of P2O5 in the pure
2CaO SiO23CaO P2O5 system. By combining this equation with Eq. (3) the relation between and the oxide content
was obtained (Eq. (4)).

log P2O5 ,SS 1.4305 W 1 / 2 17.567 ..............(3)

where W is the total solved oxide content (in mass%) in the
solid solution.
4.2.

Partition of P2O5 between Liquid Slag and Solid

Solution
The distribution ratio of P2O5 is proportional to the ratio
of the activity coefcients of P2O5 in the two phases. Based
on the above discussion, because the activity coefcient of
P2O5 in the solid solution changes with the P2O5 content
and the solved oxide, nding a simple relation between the
distribution ratio and T Fe would be limited.
As shown in Figs. 4, 6, and 7, there is a good relation between the distribution ratio and the CaO content of the liquid phase. Figure 12 shows the relation between the activity coefcient of P2O5 and CaO content of the liquid phase;
the activity coefcient was calculated by the regular solution model. Figure 13 shows the effect of different added

(log P2O5 ,SS )cal 0.0409(%P2O5 ) SS

(1.4305 W 1 / 2 17.567) 1.227 ...(4)
where (log g P2O5,SS)cal indicates the logarithm of the activity
coefcient of P2O5 in a solid solution. Figure 14 summarizes the relation between (log g P2O5,SS)cal which was calcu-

Fig. 13. Effect of different added oxides on the relation between

the activity coefcient of P2O5 and the CaO content of
the liquid phase.

Fig. 11. Effect of total oxide content except CaO, SiO2, and P2O5
on the activity coefcient of P2O5 in the solid solution.

Fig. 12. Relation between the activity coefcient of P2O5 and the
CaO content of the liquid phase for two types of iron
oxides (Fe2O3 and FeO).

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Fig. 14. Relation between (log g P2O5,SS)cal and logarithm of activity coefcient of P2O5 in solid solution.

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the solid solution and the liquid slag phases was measured
for various slag compositions. In order to clarify the inuence of slag composition on the distribution ratio, the ruling factors on the activity coefcients of P2O5 in the solid
solution and liquid phase were evaluated. By this research,
it was claried that the activity coefcient of P2O5 in a solid
solution was largely inuenced by the P2O5 content and the
solved oxide content of the solid solution. (log g P2O5,SS)cal
was obtained empirically in order to represent the activity
coefcient of P2O5 in a solid solution. On the other hand,
the activity coefcient of P2O5 in a liquid phase was inuenced by the CaO content of the liquid phase. On the basis
of these correlations, it was shown that the CaO contentment of a liquid phase and (log g P2O5,SS)cal are the ruling factors on distribution ratio.

Fig. 15. Relation between the distribution ratio of P2O5 and the
CaO content of the liquid at different (log g P2O5,SS)cal.

Acknowledgment
We would like to gratefully acknowledge the ISIJ and
Steel Industry foundation for the advancement of environmental protection technology which provide the nancial
support of this research.

lated from Eq. (4) and the logarithm of the activity coefcient of P2O5 in the solid solution for all data presented in
Table 3.
From the above discussion, it is seen that the activity coefcient of P2O5 in liquid slag is governed by the CaO content of the liquid phase and the activity coefcient of P2O5
in solid solution is inuenced by (log g P2O5,SS)cal. Therefore,
the distribution ratio can be controlled by these factors.
Figure 15 shows the relation between the distribution ration of P2O5 and the CaO content of the liquid phase, for
solid solutions with different value of (log g P2O5,SS)cal. A
fairly good relation is obtained in this case.
5.

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Conclusion

By changing the iron oxide from Fe2O3 to FeO and by

adding, different oxides such as Al2O3, MnO, and MgO the
effect of oxides on the distribution ratio of P2O5 between

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