ISIJ International, Vol. 49 (2009), No. 9, pp.

12981307

Condensation of P2O5 at the Interface between 2CaO SiO2 and

CaOSiO2FeOxP2O5 Slag
Xiao YANG, Hiroyuki MATSUURA and Fumitaka TSUKIHASHI
Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5
Kashiwanoha, Kashiwa, Chiba 277-8561 Japan.
(Received on February 24, 2009; accepted on May 18, 2009 )

In order to clarify the reaction behavior of phosphorus in the multi phase flux, the solid 2CaO SiO2 piece
was reacted with the CaOSiO2FeOxP2O5 slag for 1 to 180 s at 1 573 or 1 673 K. The interfaces between
the original solid and liquid phases were observed and compositions of both phases were analyzed by
SEM/EDS.
The result shows that P2O5 is condensed at the rim layer of 2CaO SiO2 piece very fast in less than 1 s.
The P2O5 condensed phases are identified as the mixture of 2CaO SiO23CaO P2O5 solid solution and the
surrounding liquid slag. After reaction for longer time, the reaction behavior of P2O5 depends on the reaction
temperature and initial slag composition. Reaction temperature and mole ratio of CaO/SiO2 in the initial slag
influence the stability of P2O5 condensed phases. Higher temperature induces the dissolution of P2O5 condensed phases while larger mole ratio of CaO/SiO2 has the opposite effect.
KEY WORDS: multi phase flux; hot metal dephosphorization; dicalcium silicate; P2O5 condensed phase; reaction mechanism.

1.

It is known that 3CaO P2O5 can dissolve into solid

2CaO SiO2 phase6) and many reports confirmed that P2O5
existed in 2CaO SiO2 phase in steelmaking slag.4,712)
Inoue and Suito9) found that the mass transfer of phosphorus from 2CaO SiO2 saturated slag to the 2CaO SiO2
particles was fast and a uniform CaOSiO2P2O5 solid
phase was formed within 5 s. Ito et al.10) and Hirosawa et
al.11) measured phosphorus partition ratio between solid
2CaO SiO2 and molten CaOSiO2FeOxP2O5 slag at hot
metal temperatures. Kitamura et al.12) investigated the P2O5
content in different phases for hot metal dephosphorization
slag and found that partition ratio of phosphorus between
liquid slag and 2CaO SiO2 phase increased as the increase
in the slag basicity. However, the formation mechanism of
phosphate compound in the solid 2CaO SiO2 phase was
explained in few researches.
The authors have clarified the reaction mechanism between solid CaO and slag by dipping solid CaO into
CaOSiO2FeOxP2O5 slag at hot metal temperatures.4,13)
The P2O5 condensed phases were observed partly in the
formed 2CaO SiO2 phase on the surface of solid CaO. The
P2O5 content in the condensed phases increased from
CaOslag boundary toward bulk slag. The reaction between
solid 2CaO SiO2 piece and slag was also studied by dipping solid 2CaO SiO2 piece into CaOSiO2FeOxP2O5
slag.14) However, since the experiments were only conducted at 1 673 K with particular slag composition, an integrated understanding of the formation mechanism of the
phosphate compound in the 2CaO SiO2 phase is still unavailable.

Introduction

In hot metal dephosphorization process, usually the CaObased fluxes are used to form basic slag with high phosphate capacity. Because of the high melting point, solid
CaO does not dissolve completely and remains in the slag,
which causes problems such as increase of slag volume and
difficulty of slag recycling. Fluorspar (CaF2) was commonly used as an additive to promote the melting of CaObased flux. However owing to the release of fluoride ion
from the disposed slag, the use of fluorspar is strictly limited based on the concept of the eco-friendly steel production. Recently it is required to reduce the steelmaking slag
emissions further. Therefore, solid CaO should be utilized
more efficiently without adverse technical and environmental effects.
A lot of studies have been done to clarify the dissolution
behavior of solid CaO into the liquid slag. Schlitt et al.1)
discovered that the dissolution rate of CaO could be
markedly enhanced by increasing the FeO content in
CaOSiO2FeOx slag. The dissolution rate was also found
to vary with different additives such as CaF2, CaCl2, Al2O3
and B2O32) and the size of CaO particle.3) Formation of
2CaO SiO2 layer on the surface of CaO particles was ascertained by many observations,4,5) and the dissolution of
CaO proceeded by migration of molten slag through cracks
on the layers of 2CaO SiO2. The effect of 2CaO SiO2 on
CaO dissolution and dephosphorization should be confirmed to promote the utilization efficiency of CaO in hot
metal dephosphorization process.
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nificantly.13) Accordingly, it is supposed that the influence

of Al2O3 impurity is also limited in the present study. Solid
iron was used to control the oxygen partial pressure determined by the Fe/FeO equilibrium. The solid 2CaO SiO2
piece (0.5 to 1 g, f 101 mm cylinder shape) attached to the
tip of the mullite tube was dipped into the liquid slag and
reacted for 1 to 180 s. Reaction temperature was controlled
at 1 573 or 1 673 K. After the reaction, the solid sample was
quickly taken out from the furnace and quenched by immersing in liquid nitrogen, followed by embedding in the
polyester resin. The surface was polished and the interface
between 2CaO SiO2 and slag was observed and analyzed
by SEM/EDS. Since the electron beam diameter is approximately 0.2 m m, accurate composition of solid particle
smaller than the spot size can not be obtained, and in that
case the measured composition will be the average of compositions of solid particle and that of surrounding liquid
phases.

The present study is aimed to clarify the microscopic reaction behavior of phosphorus at the interface between
solid 2CaO SiO2 and liquid CaOSiO2FeOxP2O5 slag on
the basis of the previous studies. A solid 2CaO SiO2 piece
was reacted with the CaOSiO2FeOxP2O5 slag with different composition at 1 573 or 1 673 K. The interface between the original solid and liquid phases was observed and
analyzed by SEM/EDS. The formation mechanism of P2O5
condensed phase at interface between 2CaO SiO2 and the
P2O5 containing slag was clarified. The influence of temperature and initial slag composition on the condensation behavior of phosphorus was discussed.
2.

Experimental

The CaOSiO2FeOxP2O5 slag was prepared by mixing

the synthesized wustite, CaO obtained by the calcination of
reagent grade CaCO3, reagent grade SiO2 and 3CaO P2O5.
With different FeOx content and CaO/SiO2 mole ratio, three
types of slags were used in the present study as shown in
Table 1. The 2CaO SiO2 piece was prepared by pressing a
mixture of CaO and reagent grade SiO2 on mole ratio of
2 : 1 at 50 MPa, followed by heating at 1 773 K for 24 h.
About 1 mass% of 3CaO P2O5 was also added into the
mixture to prevent the dusting of 2CaO SiO2.
Ten grams of slag were charged in an alumina crucible
(I.D.: 34 mm, O.D.: 38 mm, height: 45 mm) with the coexistence of solid iron (3 g) and melted in a furnace at argon atmosphere. In the previous study on reaction between CaO
and slag at 1 673 K, both the Al2O3 crucible and Fe crucible
were used. The results proved that about 15 mass% of dissolved Al2O3 at maximum does not affect the reaction sig-

3.

Results

3.1. Slag A (FeOx 20.0 mass%, CaO/SiO21.0)

The SEM images of interfaces between solid 2CaO SiO2
and slag A after reaction for 1, 10, 60, and 180 s at 1 573
and 1 673 K are shown in Figs. 1(a) to 1(d) and Figs. 2(a)
to 2(d), respectively. The symbols shown in figures correspond to the positions analyzed by EDS.
The results of EDS analysis for Fig. 1 are listed in Table
2, where the iron oxide is calculated as FeO. At 1 573 K,
only after reaction for 60 and 180 s, the phases of which the
CaO/SiO2 molar ratio is larger than 1.5 while P2O5 content
is over 1.0 mass% can be observed, such as position numbers 3, 6 and 8 in Fig. 1(c), and position numbers 3, 4 and 8
in Fig. 1(d), as labeled by open circles. These phases were
identified as P2O5 condensed phases. On the contrary, few
P2O5 condensed phases were observed after reaction for 1
and 10 s.
It is considered that the condensation of P2O5 was restrained by the formation of the 3CaO 2SiO2 layer which

Table 1. Chemical compositions of slag.

Fig. 1. SEM images of interfaces between 2CaO SiO2 and slag A at 1 573 K.

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Fig. 3. The pattern of EDS analyzing across the interface.

separated the solid 2CaO SiO2 and the slag as shown in

Fig. 1. The compositions of the new layer, position numbers
2, 5 and 7 in Fig. 1(a), position numbers 7 and 9 in Fig.
1(b), position numbers 2, 4 and 10 in Fig. 1(c), position
numbers 2, 7 and 9 in Fig. 1(d), were analyzed that FeO
content is less than 6.0 mass% and mole ratio of CaO/SiO2
approximately equals 1.5. With the increase of reaction
time, the initially uniform layer grew up and split into an
indented appearance. Then, the slag penetrated through the
cracks formed in the layer of 3CaO 2SiO2 and reacted with
solid 2CaO SiO2. Therefore, the P2O5 condensed phases
can be observed after reaction for longer time.
As shown in Fig. 2, the formation of 3CaO 2SiO2 layer
was not observed at 1 673 K, that is different from the case
at 1 573 K. It is considered that the enlarging of liquid area
on the CaOSiO2FeOP2O5 phase diagram at higher temperature avoids the formation of the additional layer. However, the detailed formation mechanism of 3CaO 2SiO2 at
the interface is still not fully understood since the phase diagram for the CaOSiO2FeOP2O5 system is unavailable
yet. In addition the P2O5 condensed phases can be easily
observed even after short reaction time. The composition
analysis by EDS at different positions across the interface
was conducted as the pattern shown in Fig. 3 to observe the
concentration profiles of the main components in the system. An arbitrary reference location was chosen inside the
2CaO SiO2 phase. The composition at each analyzed position is recorded as the function of its distance from the reference location as shown in Figs. 4(a) to 4(d). Similar in
four cases, CaO content is decreasing from 2CaO SiO2 to
slag and FeO content shows the incremental trend while
SiO2 content almost keeps constant. The P2O5 condensed
phases with CaO/SiO2 molar ratio larger than 1.5 and P2O5
content over 1.0 mass% are labeled by open symbols, while
all other phases are labeled with solid symbols. As can be
seen, the condensed phases contain more CaO and P2O5 but
less SiO2 and FeO than surrounding phases.
The solid line is drawn from the tendency in Fig. 4 to describe the changing of FeO content. In order to describe the
location of the P2O5 condensed phases, the area near the interface can be divided into three parts according to the concentration profile of FeO: solid 2CaO SiO2 area (constant
low FeO), solid 2CaO SiO2 and liquid slag coexisting area
(increasing FeO), and slag area (constant high FeO), as
shown in Fig. 5. In the present study, the term liquid slag
means the phase other than solid 2CaO SiO2 phase and
P2O5 contained solid phase, while the slag area denotes

Fig. 2. SEM images of interfaces between 2CaO SiO2 and slag

A at 1 673 K.
Table 2. Results of EDS analysis for Fig. 1.

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Fig. 4. Change of the concentration of components against the position at the interface between 2CaO SiO2 and slag A
at 1 673 K.

come thinner with the increase of reaction time. The solid

area will be shrinking and slag area be expanding. Therefore, it is reasonable to realize that the multi phase area as
the intermediate region between pure solid 2CaO SiO2 and
slag will shift towards the inner 2CaO SiO2 area even without observation.
The P2O5 condensed phases only appear in certain regions, as enclosed by dotted line in Fig. 4. After reaction
for 1 and 10 s, the condensed phases lie in both the multi
phase area and slag area. After reaction for 60 and 180 s,
the condensed phases can only be observed in the multi
phase area. The width of the region with condensed phase
can be obtained by reading the width of the region with
open circles in Fig. 4. With increase of reaction time, the
width firstly expanded before reaction for 10 s, then became
narrower from 10 to 180 s.

Fig. 5. Partition of the area near the interface.

the area distinguished from the solid 2CaO SiO2 and the
intermediate solid and liquid coexisting (multi phase) area.
Since the P2O5 condensed phase is formed very little and
scattered, the existence of the condensed phases in slag area
is not considered while discussing the partition of the area
near the interface. The solid 2CaO SiO2 and liquid slag coexisting (multi phase) area is defined since the compositions of the phases in this area locate in the two phase area
in the CaOSiO2FeO phase diagram. As shown by the
grey field in Fig. 4, the multi phase area is formed by the
penetration of liquid slag into the solid 2CaO SiO2. Because of the dissolution of 2CaO SiO2, the solid will be-

3.2. Slag B (FeOx 30.0 mass%, CaO/SiO21.0)

Slag B contains more FeOx than slag A. The concentration profile of FeO and P2O5 across the interface between
2CaO SiO2 and slag B after reaction at 1 573 and 1 673 K
are plotted in Figs. 6(a) to 6(d) and Figs. 7(a) to 7(d), respectively. No additional layer such as layer of 3CaO 2SiO2
was obviously formed at the interface. The P2O5 condensed
phases can be easily observed after various reaction times
at both temperatures.
At 1 573 K, P2O5 condensed phases were located in only
multi phase area after reaction for 1 s. After longer reac1301

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Fig. 6. Change of the concentration of components against the position at the interface between 2CaO SiO2 and slag B at
1 573 K.

Fig. 7. Change of the concentration of components against the position at the interface between 2CaO SiO2 and slag B at
1 673 K.

tion time, the condensed phases can be observed in both

the multi phase area and slag area. P2O5 content in the
condensed phases shows an increasing tendency from
2CaO SiO2 side to the bulk slag side.
At 1 673 K the condensed phases with lower P2O5 con 2009 ISIJ

tent than that at 1 573 K lay in both areas after reaction for
1 and 10 s. On the other hand, after reaction for 60 and
180 s, the condensed phases were only observed in the
multi phase area. The tendency for the P2O5 content in the
condensed phase is not simplex increasing as that at
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Fig. 8. Change of the concentration of components against the position at the interface between 2CaO SiO2 and slag C at
1 573 K.

Fig. 9. Change of the concentration of components against the position at the interface between 2CaO SiO2 and slag C at
1 673 K.14)

1 573 K.

not considered in the present study. The term slag area is

still used to set the part of slag with constant high FeO content in Fig. 8 as distinguished from the solid 2CaO SiO2
and the intermediate multi phase area formed by slag penetration when discussing the partition of the area near the interface. At 1 573 K, P2O5 condensed phases lay in the intermediate multi phase area after reaction for 1 s, and expanded to slag area after reaction for 10, 60 and 180 s. Similar with slag B at 1 573 K, the P2O5 content in the condensed phase keeps increasing from 2CaO SiO2 side to the
bulk slag side.
At 1 673 K, the condensed phases mostly lay in both
areas. The P2O5 content in the condensed phase shows a

3.3. Slag C (FeOx 20.0 mass%, CaO/SiO21.3)

The mole ratio of CaO/SiO2 in slag C is higher than that
in slag A. The concentration change of FeO and P2O5 with
the position across the interface after reaction at 1 573 and
1 673 K are plotted in Figs. 8(a) to 8(d) and Figs. 9(a) to
9(c), respectively.
Slag C is considered to be not in strictly pure liquid state
at 1 573 K. However, the condensation of P2O5 from liquid
phase in slag C to 2CaO SiO2 can still be observed. The
original solid phases in slag C before reaction can be easily
identified by microscope due to their larger size and were
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tendency of increase-decrease from 2CaO SiO2 side to

bulk slag side.
4.

ized to CaOSiO2P2O5 system and plotted in the ternary

composition triangle as shown in Fig. 10. From these composition triangles, two pieces of information can be obtained: the distance of the composition point to the
2CaO SiO23CaO P2O5 tie line and the P2O5 content in
the condensed phase. Both are the implications of the ratio
of solid solution in the mixture. As more P2O5 rich solid solution is contained in the mixture, the composition point
lies closer to the tie line between 2CaO SiO2 and
3CaO P2O5 and the P2O5 content in the mixture is larger as
well. The variation of P2O5 content in the mixture can also
indicate the change of P2O5 content in the solid solution. In
the present study, both the approaching of the composition
point towards the tie line and the increase of P2O5 content
are regarded as the evidences that P2O5 condensation is promoted, vice versa.
The first indication of these results is the influence of reaction time on the P2O5 condensation. In most cases, the
composition points are approaching the tie line between
2CaO SiO2 and 3CaO P2O5 which is the implication of the
2CaO SiO23CaO P2O5 solid solution. The tendency
shows the progression of P2O5 condensation. With the in-

Discussion

4.1. Formation of P2O5 Condensed Phases

The results indicate that normally the condensation of
P2O5 in the slag happens very fast at the interface between
2CaO SiO2 and slag. The only exception is the case of slag
A at 1 573 K. In this case, an additional 3CaO 2SiO2 layer
was formed and restrained the reaction of P2O5 by separating solid 2CaO SiO2 and molten slag. P2O5 was not condensed until the layer split after certain reaction time.
Previous researches712,14) have already proved the formation of 2CaO SiO23CaO S2O5 solid solution at the interface between 2CaO SiO2 and slag. Accordingly, the P2O5
condensed phases in the present study are identified as the
mixture of 2CaO SiO23CaO P2O5 solid solution and the
surrounding liquid slag because the size of the formed solid
solution particle is not big enough to be detected separately
by the current analysis method. The chemistry of P2O5 condensed phases and the surrounding liquid slag are normal-

Fig. 10. Composition of P2O5 condensed phase at interface between 2CaO SiO2 and slag.

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crease of reaction time, the ratio of solid solution in the

P2O5 condensed phase, which is the mixture of solid solution and liquid slag, is increasing. Therefore, the P2O5
condensed phase turns to be the simplex 2CaO SiO2
3CaO P2O5 solid solution after reaction for longer time.
Reaction temperature influences the reaction rate. Higher
temperature decreases the slag viscosity and improves the
fluidity, which is favored for the mass transfer in the system. The reaction of slag B at 1 673 K is so fast that the
progression of P2O5 condensation with reaction time similar
as that at 1 573 K can not be obviously observed. Comparing the results of slag B at 1 573 and 1 673 K, the P2O5 content in the condensed phase decreases at higher temperature, which implies that P2O5 condensation is promoted at
lower temperature by formation of larger P2O5 content solid
solution or increase of solid solution ratio in the mixture.
However, the dominant mechanism is not clear yet. For slag
A at 1 673 K, the composition point is approaching to the
tie line from 1 to 10 s which means the condensation is proceeding. However, from 10 to 180 s, the P2O5 content in the
condensed phase is decreasing which means that the P2O5
content in the solid solution or the ratio of solid solution in
the mixture is decreasing, as shown in Figs. 4 and 10. Such
tendency educes the possibility that dissolution of condensed phase happened. It is suggested that the condensation proceeded from 1 to 10 s, while after reaction for 10 s
the dissolution of condensed phase happened and hence the
P2O5 content decreased. More reason to explain the dissolution of P2O5 condensed phases will be given in the following section. In a word, higher temperature improves the reaction rate and mass transfer, and also induces the dissolution of P2O5 condensed phases.
The initial slag composition is another factor. Larger
mole ratio of CaO/SiO2 in the initial slag is favored for the
P2O5 condensation. Comparing the results of slags A and C
at 1 673 K, the P2O5 content in the condensed phases is
larger in the case of slag C, which means the condensation
is improved by increasing the CaO/SiO2 ratio. The progression of reaction for slag C at 1 673 K can be apparently noticed dissimilar to slag A at 1 673 K, which indicates that
the dissolution of condensed phases was not as fast. Since
slag C with a larger CaO/SiO2 ratio is closer to the liquidus
saturated by 2CaO SiO2 in the phase diagram than slag B,
it is easier to become saturated with 2CaO SiO2. Therefore,
the formation of P2O5 condensed phases is easier and correspondingly the dissolution of condensed phases into slag is
restrained. On the contrary, the influence of FeO content in
the initial slag can not be clarified yet from the present results.

Table 3. Characteristics of region with P2O5 condensed

phases.

various reaction time. These patterns suggest that more

P2O5 was condensed after longer reaction time for slags B
and C at 1573 K. P2O5 condensed phases were only located
in multi phase area after reaction for 1 s. After reaction for
longer time, the condensed phases turned to be located in
both the multi phase area and the slag area.
The different locations of the P2O5 condensed phases
with reaction time prove that at early period of reaction the
condensed phases are formed in the multi phase area. At
the interface between 2CaO SiO2 and slag, the multi phase
area shifts towards 2CaO SiO2 side along with the continuous dissolution of 2CaO SiO2 into slag as the reaction time
increases. After certain time reaction, the location of the
previously formed condensed phase changes to be slag area
owing to the shift of multi phase area. New condensed
phases are formed in the new multi phase area.
Higher temperature improves the reaction rate. Hence
P2O5 condensed phases can be observed in both multi phase
area and slag area after reaction as short as 1 s in each slag
at 1 673 K. However, higher temperature also enhances the
dissolution rate of P2O5 condensed phases. As for slags A
and B at 1 673 K, the condensed phases turn to be located
only in multi phase area after reaction for 60 and 180 s.
This phenomenon indicates that all of the previously
formed condensed phases dissolved into the slag after certain reaction time. The condensed phases can hardly be observed in slag area as only newly formed P2O5 condensed
phases remains. For slag C at 1 673 K, because of the larger
CaO/SiO2 ratio of bulk slag, the dissolution rate is not fast
enough and thus the condensed phases can still be observed
in slag area even after reaction time for 60 s. The width of
the region with P2O5 condensed phases is shrinking with
the reaction temperature increase from 1 573 to 1 673 K,
which also indicates the dissolution of condensed phases at
higher temperature.

4.2.

Characteristics of the Region with P2O5 Condensed Phases

As shown by the open circles in the SEM images, the
P2O5 condensed phases were not formed as a uniform layer,
but scattered unequally in a certain region at the interface.
The width and location of this region are summarized in
Table 3.
For slags B and C at 1 573 K, the region with P2O5 condensed phases is expanding and P2O5 content in the condensed phases always show the increasing tendency across
the interface from 2CaO SiO2 side to bulk slag side after

4.3. Dissolution of P2O5 Condensed Phases

As stated above, the different locations of P2O5 condensed phases with reaction time and shrinking of the condensed phase region at higher temperature indicate the occurrence of the dissolution of P2O5 condensed phase into
the slag. In addition, the different tendency of P2O5 content
in the condensed phases at different temperature is another
indication of the dissolution of condensed phases. As for
slags B and C at 1 573 K, the P2O5 content in condensed
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phases increases from 2CaO SiO2 side to bulk slag side, as

shown in Figs. 6 and 8. However, the increasing tendency is
not apparent in the case of 1 673 K, as shown in Figs. 4, 7
and 9. The increasing trend for P2O5 content in the condensed phase across the interface should be observed in the
case of condensation behavior, while dissolution brings decreasing trend. At lower temperature, the dissolution is not
dominant, hence the tendency is increasing. At higher temperature, the dissolution becomes more dominant and the
combining effects of both condensation and dissolution result in the distinct tendency. The distinct tendency at higher
temperature is induced by the dissolution of the previously
formed condensed phases.
The mechanism of the dissolution could be explained
from the perspective of P2O5 activity profile. In some cases
(slags A, B and C at 1 673 K), The P2O5 content in the
phases other than the condensed phases (solid symbol represents) near the interface was obviously decreasing with
the increase of reaction time, as shown in Figs. 4, 7 and 9.
For example Fig. 9(a) shows the P2O5 content in the range
of 6position16 m m is as high as over 6.0 mass% after
reaction for 1 s. However after reaction for 60 s as shown in
Fig. 9(c), the P2O5 content in the range 16position
35 m m is less than 2.0 mass%. Similar tendency can also be
observed in Figs. 4 and 7. It is considered that the P2O5 activity being the driving force of P2O5 condensation and dissolution exhibits the similar tendency as the P2O5 content in
the phases other than the condensed phases, as shown in
Fig. 11. At the early period of reaction, there was a sharp
activity gradient between 2CaO SiO2 and slag as denoted
by the dashed line. After the slag turned to be saturated
with 2CaO SiO2 by the dissolution of solid 2CaO SiO2,
P2O5 and CaO in the slag react with solid 2CaO SiO2 to
form solid solution or compound. The condensation at one
place progressed until the P2O5 activity in the condensed
phase equaled that in the surrounding slag phases. With the
increase of reaction time, the previously formed condensed
phase stayed still with little change while the multi phase
area shifted towards the 2CaO SiO2. However, P2O5 activity in the phases other than the condensed phases near the

interface was decreasing after long reaction time on account of the facts that P2O5 was being consumed with continuous formation of new condensed phases while the diffusion of P2O5 from bulk slag to the interface area was not
fast enough to fill the loss, as illustrated by the solid line in
Fig. 11. The difference of the P2O5 activity between the previously formed condensed phase and the surrounding slag
led to the dissolution of P2O5 condensed phases into the
surrounding slag. The first formed condensed phase should
be the first to dissolve into the slag.
4.4.

Reaction Behavior of P2O5 at 2CaO SiO2Slag Interface

The mechanism of reaction between solid 2CaO SiO2
and liquid CaOSiO2FeOxP2O5 slag could be concluded
from the present results as illustrated in Fig. 12.
(1) The solid 2CaO SiO2 dissolves into the slag and
also the slag penetrates into the solid sample. The slag area
near the solid turn to be the region with gradient of
2CaO SiO2 by the dissolution. (Fig. 12(a)).

Fig. 12. Phosphorous behavior at interface between 2CaO SiO2

and CaOSiO2FeOxP2O5 slag (C2S is short for
2CaO SiO2).

Fig. 11. Schematic profile of P2O5 activity across the interface

between 2CaO SiO2 and slag.

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(2) The rim layer of the solid 2CaO SiO2 changes into
multi phase area where solid and liquid phases are coexisting. (Fig. 12(b)).
(3) In the multi phase area, CaO and P2O5 in liquid
phase react with solid 2CaO SiO2 to form the P2O5 condensed phases. (Fig. 12(c)).
(4) Since the solid 2CaO SiO2 continues dissolving
into the bulk slag, meanwhile, the slag continues penetrating into the solid 2CaO SiO2, the multi phase area shifts
towards the side of 2CaO SiO2 and new P2O5 condensed
phases are formed. (Fig. 12(d)).
(5) The previously formed P2O5 condensed phases
would remain (Fig. 12(e1)), partly dissolve (Fig. 12(e2)) or
fully dissolve into the slag (Fig. 12(e3)), depending on the
temperature and slag composition.
Reaction temperature and initial slag composition influence the phosphorous behavior at the interface between
2CaO SiO2 and slag through changing the stability of P2O5
condensed phases. For slags B and C at 1 573 K, the P2O5
condensed phases are very stable and the reaction progresses on the sequences of (a)(b)(c)(d)(e1). For slags
A and B at 1 673 K, the P2O5 condensed phases are easy to
dissolve according to the path (a)(b)(c)(d)(e3). For
slag C at 1 673 K as the stability of P2O5 condensed phases
is intermediate between the two cases above the reaction
path is (a)(b)(c)(d)(e2).
5.

the dissolution of 2CaO SiO2.

(2) For slag A (FeOx 20 mass%, CaO/SiO21) at
1 573 K, a layer of 3CaO 2SiO2 is formed at the interface
and restrained the condensation. After reaction for longer
time, the layer would split into an indented appearance and
P2O5 may react.
(3) The P2O5 condensed phases are identified as the
mixture of 2CaO SiO23CaO S2O5 solid solution and the
surrounding liquid slag.
(4) Higher reaction temperature improves the reaction
rate and mass transfer in the system.
(5) Reaction temperature and CaO/SiO2 mole ratio of
initial slag influence the stability of P2O5 condensed phases.
Higher temperature induces the dissolution of P2O5 condensed phase while larger CaO/SiO2 ratio has the opposite
effect.
REFERENCES
1) W. J. Schlitt and G. W. Healy: Am. Ceram. Soc. Bull., 50 (1971), 954.
2) T. Hamano, M. Horibe and K. Ito: ISIJ Int., 44 (2004), 263.
3) J. Yang, M. Kuwabara, T. Asano, A. Chuma and J. Du: ISIJ Int., 47
(2007), 1401.
4) T. Hamano, S. Fukagai and F. Tsukihashi: ISIJ Int., 46 (2006), 490.
5) S. Amini, M. Brungs and O. Ostrovski: ISIJ Int., 47 (2007), 32.
6) W. Fix, H. Heymann and R. Heinke: J. Am. Ceram. Soc., 52 (1969),
346.
7) H. Suito, Y. Hayashida and Y. Takahashi: Tetsu-to-Hagan, 63
(1977), 1252.
8) H. Ono, T. Masui and H. Mori: Tetsu-to-Hagan, 69 (1983), 1763.
9) R. Inoue and H. Suito: ISIJ Int., 46 (2006), 174.
10) K. Ito, M. Yanagisawa and N. Sano: Tetsu-to-Hagan, 68 (1982),
342.
11) S. Hirosawa, K. Mori and T. Nagasaka: CAMP-ISIJ, 17 (2004), 868.
12) S. Kitamura, H. Shibata and S. Saito: Bulletin of the Advanced Materials Processing Building, IMRAM Tohoku University, 62 (2006), 24.
13) R. Saito, H. Matsuura, K. Nakase, X. Yang and F. Tsukihashi: Tetsuto-Hagan, 95 (2009), 258.
14) X. Yang, H. Matsuura and F. Tsukihashi: Tetsu-to-Hagan, 95
(2009), 268.

Conclusions

The reaction behavior of phosphorus in the multi phase

flux was investigated by analyzing the reaction interface between solid 2CaO SiO2 and liquid CaOSiO2FeOxP2O5
slag at 1 573 and 1 673 K. The influence of reaction temperature and initial slag composition on the P2O5 condensation
was clarified. The results are summarized as follows:
(1) P2O5 condensed phases are firstly formed in the
multi phase area, then turn to be located in the slag area by

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