ISIJ International. Vol. 33 (1993), No. 1, pp.

2-1 1

Mathematical Expression of Slag-Metal Reactions in Steelmaking

Process by Ouadratic Formalism Basedon the Regular Solution Model

Shiro BAN-YA
Faculty of Engineering. Tohoku University, Aza-Aoba, Aramaki. Aoba-ku. Sendai. Miyagi-ken, 980 Japan.
(Received on May79. 1992, accepted in final form on July 19. l992)

During the past three decades manytheoretical treatments have been developed to predict the ther-
modynamicproperties melts, In this paper, an attempt has been madeto describe the slag-metal
of silicate
reactions in steelmaking process quantitatively by the relation of quadratic formalism based on the regular
solution model, The approximate validity of the model was quite satisfactory to formulate the reactions of
the oxygen distribution, the ferrous-ferric iron equilibrium, the manganesedistribution, the phosphorus
distribution and the hydroxyl capacity, The prediction of activities of componentsin FetO-CaO-Si02and
FetO-MnO-Si02ternaries are aiso in good agreement with the measurements.
KEYWORDS:
slag-metal reaction; steelmaking; quadratic formalism; regular solution model; oxygen
distribution; ferrous-ferric equilibrium; manganesedistribution; phosphorus distribution; hydroxyl capacity;
thermodynamics; activity.

silicate, phosphate and aluminate slags of multi-

1. Introduction
During the past three decades, the available data for
the physico-chemical properties of metallurgical slags
have been exceedingly improved by the efforts of many
Investigators in the world. The selected values of activity
and chemical properties for numerous binary, ternary
and quaternary oxide melts have been compiled and
published in Germanyl) and Japan.2) However, useful
data in multi-component slags are quite few to describe
the slag-metal reactions in steelmaking process. Many
slag models have been proposed to express the ther-
modynamicproperties of silicate melts. Someof the
models were successful for the mathematical expression
of slag-metal reactions in a restricted range of slag
composition, but the samemodels were inadequate for
the data from other sources obtained at different slag
composition. This is probably due to the fact that the
slag models proposed are not enough to evaluate the
interaction energies between the oxides in slag and
activities of slag constituents.
This paper will summarize the outline of our recent
studies for the application of regular solution model to
formulate the activities of slag constituents, the capacities
of slags and slag-metal reactions concerning steelmaking
processes. The regular solution model of polymeric melts
has been proposed by J. Lumsdem (1961)3) to express
the activities of componentsin FeO-Fe203-Si02slag.
Sommerville have also showedthat the regular
et al.4)
solution model was applicable to describe the activities
of FeO MnO
and in quaternary FeO-MnO-Al203-Si02
component system by the extensive studies of Ban-ya
and his co-workers.2,5~8) According to their works, it
has been shown that the activity coefficient of a com-
ponent in multi-component slag can be described by
the relation of quadratic formalism based on the regular
solution model, even if the liquid silicate melt is not
strictly regular solution. The outline of the treatments
will be described in the next section.
2. Regular Solution Model of Silicate Melts
The most difficult problems related to the nature of
polymeric melts are the fact that the structure of silicate
anions varies with the amountand the kind of co-existing
cations and temperature. In other words, the extent of
the polarization of oxygen ion is affected by the valence
and radius of cations. To avoid this difficult question of
the nature of the silicate melts, Lumsden3)has proposed
the application of simple relation of regular behavior for
oxide mixtures. In the model, it is assumedthat all kinds
of cations such as Cu+, Ca2+ . Fe2+ , Fe3 + , Si4+ and P5+
are randomly distributed in the matrix of oxygen anion,
which is a common anion for all kinds of cations present
in the melts. The composition is expressed with cation
fractions, and the melt is considered to be composedof
oxides of the form such as CuO0.5, CaO, FeO, FeOl.5,
Si02 and P02.5' The activity coefficient of component,
i, in
a multi-component regular solution is expressed by
the following equations:
Gt = Aj~i = RTln yi ........
...........(1)

slag. Recently, the approximate validity of the regular

solution model has been proved for many kinds of RTln yi = ~. c(ijXJ ?+~~(oeij+0e,k ocJk)XJXk .
..,...(2)

jk
C 1993 ISIJ 2
 ISIJ International, Vol. 33 (1993). No, 1
Table l. Interaction energy between cations of major componentsin steelmaking slag, aij. (J)

j Fe2+ Fe3+ Mn2+ Ca2+ Mg2+ Si4 + p5 + A13+

i
Fe2+ 18 660 +7 i lO -3 i 380
- + 33 470 -41 840 -31 380 -41 OOO
- 18660
Fe3+ -95 810 - 2930
56 480 + 32 640
- + 14 640 - 161 080
Mn2+ +7 IIO 56 480 -92050 + 61 920 -75 310
Ca2+ -31 380
-
-95810 -2584 940 83 680
-154
- 92 050
- IOO420 - 166
33 890
- 1040 - 810
Mg2+ + 33 470 -2930 + 61 920 - IOO 420
- 940 - 37 660 -71 130
Si4 + -41 840 + 32 640 -75310 133 890
- 25 - 66 940 + 83 680 - 127 610
- 31380
p5 +
A13+ -41 OOO
+ 14 640 - 84 940
- 541040 37 660
- 130 + 83 680 -261 500
- 1 810
161 080 83 680 -71 127 610 -261 500
- - -

8 Table 2. Interaction energy between cations of other com-

ponents.
7 f
(~e o (i cation)-a cation) aij (J) (i cation)a cation) c(ij (J)
G,
~) o
E 6 Fe - O 4(~
Li + _Si4+ 1 H+_Li +
\- + 1500
~ 142 30
: o -
5 Na+ _Fe2+ + 19 250 H+_Na+ + 9750
c Na+ _Fe3+ H+_K+
o - 74 890 + 13 520
~ 4 Si-O
Na+ Si4 + - II1290 H+Mg2+ + 15800
c Na+ _p5 + -50210 H+_Ca2+ + 15 100
:, (l
K+ _Si4+ - 167 030
81 H+ _Mn2+ -248400
230
o 3 O
o Ti4 +
Ca2+ - 360 H+A13+ - 30 ooo
Ti4+Mn2+ 66 940
- H+_Si4 + +
2 Ti4 +Fe2+
O 20 4O 60 80 I OO
37 660
- H+_p5 + + 7700
Ti4 +_Fe3+
Si02 + 1260
--> mo[•/. Ti4 +_Si4 +
+ 104 600
Fig. l. Coordinationnumberofcationinbinarysilicatemelts.

Table 3. Conversion factors of activities.

Where, Xi is cation fraction, and c(ij is the interaction
energy between cations, i.e., (i cation)-O-a cation). The Reaction Free energy change (J)
reference state of the activity in this case is taken to
hypothetical pure liquid, which has regular nature. )
Fe*O(/ + (1 t)Fe(s or
Si02( p-tr)
- I)= FeO(R.S.) - 8540 + 142T
AG' = 7.

Therefore, the activity coefficient of a component i, in = Si02(R.S.) AG'= +27150 -2.054T

Si02( p-cr) AG'= +27030 -1.983T
multi-component slag can be written with the function = Si02(R.S.)
of slag composition and temperature by Eq. (2), if the
)=
Si02(/ Si02(R.S.)
MnO(s)= MnO(R.S.)
AG'= +17450 +2,820T
AG' = -32470 +26.143T
silicate melts have regular nature. )
MnO(! = MnO(R.S.) AG' = -86860 +51.465T
In this model, it is not so rough approximation to )
Na20(! = 2NaOo.5(R.S.)
CaO(s)= CaO(R.S.)
AG'= -185060 +22.866T
ignore the polymerization/de-polymerization of silicate
AG'= +18 160 -23.309T
CaO(1)= CaO(R.S.) AG' = - 40 880 - 4.703 T
anions. However, the assumption of randomdistribution MgO(s)= MgO(R.S,) AG'= +34350 -16.736T
of cations in the matrix of oxygen anion in silicate melts MgO(!)= MgO(R.S.) AG' = -23 300 + 1.833T
P205(1) 2P025(R.S.) AG'= +52720-230.706T
is
a rough approximation in the treatment. Becauseit is =
known that the coordination number of cations for
6
oxygen ion takes 4, or 8by the lonic radius of cations.
agreement would be able to be given to estimate the
According to the extensive studies of Wasedaet al.,9)
activity value even if the effect of minor componentsless
however, the coordination numbersof cations for oxygen
than 5masso/o were ignored in quadratic formalism.
ions were about 4 to 5 in the middle composition of
binary silicate melts as shownin Fig. 1. Therefore, it is
considered that there is a wide range of regular nature
3. Determination of Interaction Energy and Conversion
in the middle composition of silicate
Factor of Activity
melts containing
manykinds of cations. Manyexperimental results have In order to apply the regular solution model for silicate
shownus that the activity coefficient of silicate melts can melts, one should knoiv the next three matters, (1) the
be approximately expressed with the following Eq. (3), composition range in•which the regular nature is satis-
if this melts is not strictly regular solution: fied, (2) the value of the interaction
energy, and (3) the
conversion factor for the reference states of the activities
RTln yi = ~ oe,JXj2
•• + ~~
jk
(c(,j
-
+ -c(ik ocjk)XjXk
+ I' , .
...(3)
between regular and real solution. These three matters
have been studied by the measurementsof Fe3+/Fe2+
where I' is the conversion factor of activity coefficient Fe2+/Fe equilibria and other sla~~metal reactions
between hypothetical regular solution and real solution. previously. They are listed in Tables 1, and 3. 2
This is similar to quadratic formalism of metallic solution This paper will describe howto determine above three
proposed by Darken.lo) Furthermore, a fairly good matters as one of the examples for the application of

3 C 1993 ISIJ
 ISIJ International, Vol. 33 (1993). No. 1
reference state of the activity from the thermodynamic
view-point, it is also possible to take hypothetical pure
2
liquid silica of regular nature as the reference state of
:~:
silica activity. The conversion factor of silica activity
~ Ieoo from solid pure silica to hypothetical liquid silica of
~
H regular nature wasalready determined as the reaction,13)

-I
o.~

o Lr)
Si02(crist)
= Si02(R.S.), AG' = 27 030 .98T (J), by the
tr).

onj o
d5 thermodynamicstudyl3) of FetO-Si02 binary melt. The
1600 V F)
l O8 0•6 04 combination of this equation with Eq. (6) gives us the
Xsi02 following equations:
40
40
Si02(R.S.) + 3C(s) = SiC(s) + 2CO(g) ......(lO)

O Kay & Tayior P~o/asio.(R,s.)

c o"
(
o
Ksi02(R's.)
= ---""""(1 1)
20 O Baird & Tay[or
20
~;i ~'L~)
~ AGsio,(R.s,)
= 648 700 - 363.7T (J) .
..........(12)
1~~
(E;
l u~
o~
The reference state of silica activity in above equations
o
i~O B/~~~ ~~'\O ~O
~( 5
l
~~tn..
~c: a *eo\--e o_ is hypothetical pure liquid silica of regular nature, which
~~ A ulO
6 ~:
H h
o\ \;\
nj
~ is point
C in Fig. 2. The experimental results seen from

T H
cc oc
oc
~~ the base line CO"strictly satisfy the regular nature. From
o -40
-4(
-20 tf]
results mentioned above, the activity coefficients of silica
- 20
1550'C of different reference states are summarizedas follows:
o 0.1 0.2 0.3

~ (1
- XSi02)
2 RTln ysi02(R's.) = - 133 900(1 - Xsio.)2 (J)
SiO
si02 -> CaO
Fig. 2. Acttvity coefficient or si02 in CaOSi02binary slag RTln ysi02(1 ) = - 133 900(1 - Xsi02)2 + 17450
at 1823 K. + 2.82T (J)
regular solution model. Baird and Talyorll) and Kay RTIn ysio.(,.,*t) = -
.
133900(1 -Xsio.)2+27030
and Taylorl2) have studied the silica activity in molten -1.98T (J)
. ......
..........(13)

CaO-Si02 binary melt by the next gas-slag reaction.

4. OxygenDistribution between Slag and Metal
Si02(crist) + 3C(s) = SiC(s) + 2CO(g) ..........
(4)

Ksi02("ist)= P~o/asi02(*ri*t) --"---"""'(5) The equilibrium relation of FeO-Fe203-MnO-

Si02-MgO-CaO which are major componentsin
slag,
AGsio.(.,i,t)
= 675 700- 365.7T (J) .
..,.........(6)
steelmaking slag, with oxygen in metal can be written as
follows by the model, 5 13 14) using the interaction energies
The results of RTln ysio.(.,ist) obtained were plotted as , ,

-Xsio.)2 in Fig. 213) according to the given in our previous studies:

a function of (1
relationship of binary regular solution. good linear A Fe(1) + O= FeO(R.S.) ....................(14)
relationship wasobserved for the values of Tln ysio.(.,i*t) R
in the range of liquid state and the interaction energy of RTlnK0=RTln(XF*o/ao)+RTlnyF*o """(15)
ac*2' -si+ ' =
~ 33 900 was
(J)
1
given from the slope of the
AG'=128 100-57.99T (J) ................(16)
line. Where, the reference state of silica activity is solid

pure cristobalite which is point in Fig. 2. That is, the

A RTln yF.o = ~ 18660X~.o* = + 7110XM2.0
base line of activity coefficient is the line for the AO - 41
840Xs2iO, 33 470XM2go
+ ~ 31
380Xc2*o
measuredvalues. The conversion of the reference state +44930XF.o*= 'XM.0~93 140XF.o* = Xs,o
of activity from solid pure cristobalite to pure liquid
silica is given by the combination of Eq. (6) with the + 17 740XF.o*.= XMgo+ 45 770XF,o, = Xc.o
' '

reaction,13) Si02(1) Si02(crist), AG' -9 580 +4.80T

= = + 40 580XM*o Xsio . ~ 21 340XM*o XMgo
' '

(J)
.
+67780X M*o'X c.o +58570Xs,o XMgo
Si02(1) + 3C(s) = SiC(s) + 2CO(g) ............(7) + 60 670Xsio, Xc.o + 102 510XMgo Xc*o (J)
' '

.(1 7)
Ksi02(1) P~o/asiO,(1) """--""""""'(8)
= Since the above equation quadratic formalism, the
is
AGsi02(1)=666 100-360.9T (J) .............(9)
.
minor componentswhich are less than 5masso/o can be
The reference state of silica activity in Eq. (9) is neglected for the approximate calculation.
supercooled pure silica, which is point B in Fig. 2. If In Fig. 3,13) the oxygen contents in iron calculated by
the molten CaO-Si02binary slag is really regular solu- aboveequation were comparedwith the measuredvalues
tion, the extrapolation of the experimental results to for the typical measurementsof previous investigators.
(1 -Xsi02)2 =0 should consist with the point in Fig. 2. B Fromthe results, it is confirmed that the oxygen content
Namely, it is known that liqLrid the CaO-Si02 melt in liquid iron in equilibrium with slag can be estimated
100/0 by the model.
satisfies the relationship of quadratic formalism but not within the accuracy of ~
regular solutlon. Since there is not any limitation for the The reference state of FeOactivity in the model is

@1993 ISIJ 4
 ISIJ International. Vol. 33 (1993), No. 1
taken to the hypothetical stoichiometric FeO, in which are referred in Fig. 3. An agreement of both measured
the regular nature of the solution is satisfied. However, and calculated values has been excellent over the wide
the reference state of conventional iron oxide activity is range of slag composition from acid side to basic side
the pure iron oxide in equilibrium with metallic iron. The except for extremely FetO rich region of NF*,o 0.7. >
conversion of the reference state for both activities is

as follows:6,1
written 5) Ferrous-Ferric
5. lron Equilibrium in Slag
FetO(1) +(1 The
- t)Fe(s or /)= FeO(R.S.)
......(18) ferrous-ferric
iron equilibrium in slag is very
important concerning the slag basicity, but the
AG'= -8540+7.142T(J) ...............(19) quantitative treatment of A-ratio Fe3+/Fe2+ has been
=
RTlnaF, o(1) RTlnaF.o(R,s.)~8 540+7,142T(J) . very difficult due to the complicate variation by the slag
.(20) composition and temperature. The A-ratio can be
4,14)
obtained by the model as follows:5,13)
In Fig. the activity of iron oxide, aF.,o, in
FetOCaOSi02 ternary in equilibrium iron with liquid
= FeO(R.S.) + l/4 02(g) .......(21)
FeO1.5(R.S.)
estimated by the model is shown to compare with the
RTln KF* = RTln(XF*o/XF*o* =)+ 0.25RTln P02
experimental results of manyprevious investigators, who
+ RTln( yF*o/ yF.o*.5 ) "" - -""
--(22)
1500
FetO-Si02-cao-Mgo AG'=126820-53.01T(J) ..............(23)
o A
.

cl Shim and Ban-ya The past workers could not formulate quantitatively the
o Suito'Inoue
Takada
and AA
e
vcl ~b
variation of A=Fe3+/Fe2+ by the change of s]ag
ChiPmAa~oA
1'
~
:'
u'
1000
v
A
T~tor
and
wird([er
ChlPman ~L
arx:1

l.• ~ eo:l e
C:l
composition. However, by the application of the regular
solution model, the values of A-ratio in slags are
expressed as follows from Eq, (22):
'u vcl
o JL/~:~Ner///
E log(Fe3 +/Fe2 +)
:/:::;:~~e e' = 6625/T- 2.77 + 0.25 Iog P02
r-l
o
E 500 el +(RTlnyF.o~RTlnyF,oi.5)/(19,1
The Fe203 contents in FetO-CaOand FetO•--CaO-Si02
T) .
.........(24)

~
a e el
by above equation are shownin Fi~• 5,1 3)
slags estimated
LJ
:)
d:L7A
/ FetO - Si02- cao
JLFetters and ChiPman
to confirm the validity
aF**o O.7.
of the mode] at the rang~ of

' G6r[ Oeters and Theexperimental data by Taylor and Chipmanshowed

Schee[
O the higher values for the estimated data by the model,
O 500 1OOO 1500
[ppm O] ca[culated but the points of data by the other investigators of four
Fig. 3. Estimated values for oxygen contents by regular groups agree well each other within the accuracy of
solution model and the measuredvalues in liquid iron ~ IO o/o. The similar
agreement for the ferrous and ferric
equilibrated with FetO-(CaO+MgO)-Si02slags. iron equilibrium was observed in FetO-Na20-(Si02+

Si02
aFet O
o 0'9 - 1
e O'S - 019
C] 0'7 - 0'8
0'2 018
I 0'6 - O' 7
A Ot5 - 0'6
A 0'4 - O'
0'3 - 0'4
5
IF 0'2
- 013 Si02
v O'I - 0'2 014 ~v v
sat
' 0'6
v O -'0'1
O
(Jer
1~~:VllF~ 'r
'~i\S)":I

0~)
l~: \
~,
Q~~(/v
lv /b~A~) ' ~:~piv"'4
$1'1b:~1\'~'vl(~'I):'
~/
~/r'~~ J'b

0'6 ~~
)1I

(t7:~/:;;J:~~ AA- Iha

A/ It;i
L~Clej)Q~S)~b ~3Cc~Q~SI
';~F
t

A ~ l:1
/ i~1;~ I~

J!t,1~
lbp~~ '$ ,.

p
~(
.
's:ej!/

Oi8 ' / cl'\" "_'1" 012

A \
IF
ol
,t
q)l ." Fig. 4.
(~ ~tAA JL
o: o)' ' Estimated values for aF** o(1 by regular solution model
ejlO~t~ ,lJbA
,:~
\ \ cS! Lei
)
and the measured values in Fe,O-CaO•-Si02 slags
( I~l~"~:l]clcllt~"e~D.o J2) 1
equilibrated with liquid iron at 873 K.
CaO 0.2 0.4 0,6 0.8 FetO
NFetO

5 C 1993 ISIJ
 ISIJ International, Vol. 33 (1993), No. 1
NFe203 (ca[.) in FetO-CaO 6
o
(u o O.1 0.2 0.3 0.4 FetO- lvlnOsat ~Si02 ~823 K
(~)'008 4 4
o. C] Ban-ya. Hino & Kikuchi FetO-MnO-Si02sat.
FetO - CaO V FiScher & Bardenheuer
I
X6rber &oel5en
oN l Gurry and Darken O
'1' ~~ 2
th.C'
( 18a3t 2a ~ )
u) FetO - Si 02- CaO u CCl~ _e(tD
0.06 A Fetters and Chipman 0.3 +~Oc:UIOt aa,:l]
o o Tay[or and Chipman
.
O o l]
LLO :~~)
.E
e
e
e
~ Cl~
(, -2 Fet O-MnO-CaO
-NgOsat Si 02
0~Sl
ee ~
t o)
-
u,
0.04
.
o.
2 o
FetO-lvlnO-MgOsat~Si02

e Bell
A Xrings
Winkler
&Schackmann
& Chipman
'1'
Q,
co,1'
-4 (]
. t. O Be[1, Murad & Carter A Suito & Inoue
E o c: e. o
E
~o"~0.02 eo ' FetO- Si02 -CaO ~ 60
LLa,
o Bodsworth
o .1
o
0.2
NSi02
0•4 0•6
o LL(P

o
z o~) . G6rt, Oeters
Z Fig. 6. Relation between equilibrium constant calculated by
and Schee[
regular solution model and Nsio, at 1
823 K.
o O
O O.O 2 0.0 4 O.06 0.0 8 Temp., K
NFe203 (cal.) in FetO - Si02 -CaO 2000 1900 1800
3
FeLO MnOsat~Si02
Fig. 5. Estimated values for NF*,o, by regular solution model Fe jO- MnO-CaOsat.- SiO
2
and the measured values in Fe*O-CaOslags equili- O Fischer ~
Bardenheuer Ban-ya.Hlno & Fujisawa
2 e Ban-ya, Hino Kikuchi & FetO h4nO CaO-Si02
brated with Pco, I atm and in FetO-CaO-Si02slags FetO-lvlnO-Si02sat
O Mavrer & Bischof
=
equilibrated with iron, O~brber &Oeisen
~2 1 ~~~-~
~
ai ~'.
t/io
P205)'6)(Fe,0+MnO)-(Ca0+MgO)-Si02ls) and Oi;~ !
~~uo,
FetO-(CaO+ MgO) (Si02 + p205)1 6) slags.
- ca:
;~:-
0~ o ~' l
9o
6. Equilibrium of ManganeseDistribution Q logKMn=7386/T 34S2 c]
Q1
a -1 o
The equilibrium relation of manganesedistribution Fe ta -MnO-h4gO- Si02
A Bel[ lylurad & Carter Fe tO -lylnO- CaO-lvlgOsat.-Si02
between FeO-Fe203-MnO-Si02-MgO-CaO
slag and
-2 Fe IO-MnO-h4gOsat.~ SiO2 C] Krings &Schackmann
liquid iron can be written as follows:8) A Be[i
l Winkler & Chipman
V 8an-ya, Hino & Fujisawa x suito & Inoue

FeO(R.S.) + Mn Fe(1) + MnO(R.S.) .......(25)

= -3
5,0 5.1
52 5.3 5•4 55 56 5.7
104!T
RTln KM*= RTln[XM*o/(aF.o(R.s.) ' aM*)]
Fig. 7. Temperature dependence of equilibrium constant
+ RTln yM~o(R.s.) """""""-"""(26) calculated by regular solution model.
AG' = - 141 400+66.28T(J) ..............(27)
Inoue and Winkler and Chipman, are also shown by
= 71
RTlnyM.o(R,s.) lOXF2.0 480XF2.0,
~ 56 s The results obtained by different kind of
recalculation.

- 75 31OXs2i02+ 61 920XM2go~ IOO420Xc2*o slags and by

manydifferent investigators are in fairly
30 710XF.o XF.o 26 360XF.o Xsi02 good agreement each other, and the results obtained are
- , =-
' '

expressed by Eq. (27).

+35 560XF,o XMg0~53
560XF,o 'X c*o
As similar to the case of the activities of FetO(!) and
- 164 430XF.o,
s + 8370XF.o, j XMgo ' Xsi02 '

FeO(R.S.) in slag,
the conversion factor between the
- 52 720XF,o, 5 Xc.o + 53 550Xsi02 XMgo ' ' activities of conventional liquid MnO(/) and the
hypothetical liquid MnO(R.S.) in slag is necessary. The
- 33 470Xsi02 Xc*o + 70 290XMgoXc*o .(28)
' (J) '
.

conversion factor can be derived in our previous work

as follows:8)
In Fig. 6,8) the equilibrium constant of manganese
distribution in FetO-MnO-CaO-MgO-Si02 Slag are MnO(1)= MnO(R.S.) ....................(29)

plotted against the silica content to examine the validity AG'= -86860+51.465T (J) ..........,...(30)
of model. The composition of four groups of manganese
calculated in Fig. 6 was within the range of RTln aM.o(1 )= RTln aM~o(R.s,) 86 860 + 51.465T (J)
silicate
~ .

NF*,o and Nsi02 As seen in Fig. 6, the values

.(3
1)
of log KM*evaluated by the model were almost a constant From above relation, the activity coefficients of each
value within experimental error over the wide range of componentin FetO-Si02-MnOslags can be given by
slag composition. the following equations: 15)
The effect of temperature on the log KM*evaluated by
RTln aM.o(*) = 7113XF2.0 56 490XF2,0* = 75 320Xs2io,
the sameprocedure is shown in Fig. 7,8) in which the ~ ~
data, reported by other eight groups of Maurer and
Bischof, Krings and Schackmann,K6rber and Oelsen,
- 30 710XF,o XF.o * * - 26 360XF,o Xsio,
•

.
•

164440XF,o* Xsio, ~32470+25.04T(J)

Bell et al., Bell, Fischer and Bardenheuer, Suito and =
.(32)

C 1993 ISIJ 6
 ISIJ lnternational, Vol. 33 (1 993), No. 1
NlnSi03 Mn2Si04 8
1,0
\j

\1
l;! i 6

\ aSi02(o
l
- cr )
Ifi
/f!
aMno(s)
~2
CL •1~~~~~D_~ _ _ ~ _ ~ _
_t3__(f~
_ _
o.
8 \ tL il'
l
'!

1773 K
:(
ol o
J~~~_OOlaS~.~.O
D~!
' ~ ~~~~d~ ~
6>•-o

o
~ ,/: !i
~ -2 O Present work
o O.6 If!
/ Trdrnel et al
\
C:I

~
O t l'
-6
~nUppel et al.

~ /'
'

- - ~
Abraham
Davies'
Richardson
'
-8
1

= /
7 Mehta'
(XcaO+XFeO)/ Xp025
o 0.4 ~~
/ Fig. lO. Relation between logKpl and (Xc*0+XF.o)/Xpo,
Lr)
/
~
Richardson m
O '( FeO-FeOls~P02,5CaO slags
,

~f ~
equilibrated with
\,
---- Rao'Gaskett liquid iron and solid CaOat 1873 K.
' '
~J
/ \\' Regu[arsotution
o.
2
l r/
ri~

/
/
f \
~
\
_ mode[
_ from the model showedgood agreementwith other data.

~ 7. Equilibrium of Phosphorus Distribution

~
~'~~
~~ The equilibrium relation of phosphorus with FeO-
o Fe203-P20s~Si02-CaO-MgO
slag can be written as
0.4 0.6 o.
8 1.0
follows:7,17)
NM~o
Fig. 8. Comparison of the activities of the components in P+2.50=(P02.5)(R.S.) .................(35)

MnO-Si02slags at 1773 K, RTln Kpi RTln[Xpo, =/(ap ag•5)] '

+ RTln ypo,.=(R :(~6)
S)
Si02

a Feto AG' = - 326 520 + 162.88T (a= 13 810) (J) ...(37)

= 31 380XF2.0+ 14
A 0.10 RTln ypo. 640XF2.0*.=
=(R,s.)
02 08 o 0.30
I O50
25 1040Xc2*o 37 660XM2go + 83 680Xs2io,
A 0.70
~
+ 1920XF.o XF.o, = ~ 251 040XF.o Xc*o •

4
- 102 510XF*o XMgO+ 94 140XF*o XsiO,
o. o.
6
o
'E:s ~ U).
• •

~,': O.
I O.
2 ~~, 140590XF.o* Xc.o 20090XF.o*.='XMgo
03
=
O~ +65680XF.o* Xsio
o.
6
A
A
o O.
5
o.
4 . , ~ 188 280Xc*o •XMgo
l O.
5 - 33 470Xc.o XsiO, '
+ I 12 960XMgOXsiO, • (J)
.

l 0.7 .(38)
08 A
08 02
In order to showthe validity of the model, the value~
of equilibrium constant of Eq, (36), Kpi, calculated from
the data obtained in FetO-P205-CaO slag were plotted
h,InO
o2 0.4
NFeto
o,
6 o.o FetO as a function of (Xc*o + XF.o)/Xp0= at 1873
=
in Fig.
K
10. As seen in Fig, l0,7) the values of log Kpl evaluated
Fig. 9. Comparison of calculated ap.*o(1) with the measured by the model were truly a constant within experimental
one in FetO-Si02-MnOslags in equilibrium with solid
error over the wide range of slag composition. Thesimilar
iron at 1723 K.
results were given in the other slag systems studied at
present work.
RTln aFe,o(1) = 18660XF2eol 5 ~41 842Xs2i02 ~ 7113XM2no The effect of temperature on the log Kpl evaluated by
93 140XFeol Xsi02 + 44 940XFeol,5 XMno the sameprocedure is shownin Fig. Il,7) in which the
- 5
' '

+40590Xslo XMno~8540+7.172T (J) ........(33)
RTln asi02(crist) = ~ 26 360XM2.0~ 41 842XF2eo
+ 32 040XF2eoi 5 ~ 124270XM.o XFeo
+ 13 510XMno'X Feo1 5 +9456XFeo'X Feoi 5
+27030- 1.983T (J)
The activities of the componentsin MnO-Si02binaryi 5)
and FetO-MnO-Si02ternaryl5) slags are shownin Figs.
8 and 9 respectively. The values of activity estimated
data reported by other five groups of Winkler and
Chipman, Kntippel et al., Trdmel et al., Suito et a/, and
Kor are also shownby recalculation. Theresults obtained
' by different kinds of slags and by many different
investigators were in fairly good agreement each other,
, .
and Eq, (37) was given.
(34)
.
...............,................,. The equilibrium relation of phosphorus in iron with
iron oxide in slag can be derived as follows by the
combination of Eqs. (16) and (37):
7 C 1993 ISIJ
 ISIJ International, Vol. 33 (1 993) , No. 1
8
e
~ Feo- Feot s ~ P02'5 - Cao sat. ~Feo - Feol 5~ p02'5 - Si 02 - cao
(
2CaoSi02sat.)
~ Feo-Feol s~ P02 5-hJ490sat, ~Feo - Feo],5-p02 5- Cao-N90sat Prese n t
work
4 ~ Feo-Feols~P02s~Si02sat f3CF
_
D D
2 ~-~I~~~;~'~o~~~~~:~~~~~~/C] D ~'----

~( ______i8
al o
o
-2
~ Trdmel et al iog ~pl = 17060l T- 8. 51
o
-4 ~ HnUppel et al,
( ~=0.4 )
-6 ~ Winkler et al
~ ~or

-8
~Suito et al
Fig. Il.
Temperature dependenceof log Kpl ,

o. 50 0.55 o 60 o 65
T~1
/ 1ri~3
v
L/~1
r\

8
6
~Feo -Feol 5-p02 5-cao sat. ~ Feo-Feol 5-p02.5- Si02-c ao
( 2cao,si02sat )
~Feo - Feol 5- p02,s~N90sat •
~ Feo- FeoL5- Pol s~ c ao -M gosat '
present
wor k
4~ Feo- Feol 5~ poi.!~Si02 sat

2 iog Kp2= 3281T-O936

(\'
'~ _~_Cf = O~,_4__)_
_t_3cf
~( JD~,0:~;{~~o ~~~~~~_ ____ ___ ___ _

(7)
O o-~_~~~if-Itr~~~~ ____i______{_______~_ c]

o D
-2 -- ~~~i5~cr~~

-4 ~Trdmel et al
~ suito et al
~ xor

_6 ~ Knuppel et al.
~ Ba[aiiva et al

~8
~ winkler et al
~ shirota et al
Fig. 12.
Temperature dependenceof log Kp2'

O 50 O 55 O 60 o 65
T~1
/ 10 3K 1

formation of liquid P205 from solutes in liquid iron as

E+ 2.5(FeO) (in slag)
)
= (P02, s) (R.S.) + 2.5Fe(1...(39) follows:

AGp2=6 280+17.908T ((T= 13 810) (J) .....(40) 2P(1 o/o)+50(1 o/o)=P205 (pure liquid) .....(41)
.

The effect of temperature on the equilibrium constant AG41= -705 420+556.472T (J) .
..........(42)

of Eq. (39) is shownin Fig. 12. in which the results by The conversion factor can be derived as follows by the
present authors and other investigators of Winkler and combination of Eq. (40) with Eq. (42):
Chipman, Balajiva et al., Kntppel et al., Tr6mel et al.,
Suito et al., Kor, and Shirota et al. are plotted for P205(1)=2P02.5(R.S.) .......
..........(43)

comparison. The results shown in Fig. 12 are a little RTln ap,0=(1 )= 2RTln apo, =(R.s.) + 52 720
scattered in comparison with those in Fig. l, but it will
I -230.706T (J) ...... .........,,(44)
be seen that they fairly agree with each other within the .

experimental error. In Fig. 13, the phosphorus dis- In the past, the slag models, proposed by Flood and
tribution ratio L~ calculated from the model is plotted Grjeftheim,19) and Turkdogan and Pearsonl8) were
against the measuredL~ for the data by present authors enough accurate to predict the phosphorus content in
and other investigators. The agreement between both metal and the phosphorus distribution ratio betweenslag
calculated and measuredvalues was also good within the and metal for basic slag, but the models of the sameidea
experimental error. were not successful to predict the oxygencontent in metal
As similar to the case of the activities of FetO(1) and and the oxygen distribution between slag and metal.
FeO(R.S.) in slags, the conversion factor between the However, in the approximate application of the regular
activities of conventional liquid P205 and hypothetical solution model, the both oxygen and phosphorus
liquid P02.5 in slag is necessary. Turkdogan and contents in metal and the distribution ratios of oxygen
Pearsonl8) have derived the standard free energy of and phosphorus can be estimated within the error of

C 1993 ISIJ 8
 ISIJ International, Vol. 33 (1993), No. 1
4 40
AGH02p=
~19800• 26.32 T(J)
3 e _lO
A_/
-CL
J 2 :(:c
~~ o
OIO

li L 20 cl~l
.~/~]
1:~
1
~Vl ~
o: _/:A
QJ
e O CaO-Si02
re
Al
5/V1
oo
oo ~
og: ~ KO0.5-Si02
l~iO dl o e NaO0.5-Si02
U [] LiOo.5-Si02
-1
o
1400 1600 1800

- 22
T (K)
- 1 O 1 2 3 4 Fig. 14. Temperature dependenceof free energy of solution
Measured logL~ of hydrogen in silicate melts.
FetO P205- CaOsat. FetO-P205- CaO-~lgOsat.
o ~nUppei et ai. A present work 0,02
o Tr~mel et al. FetO-P205-Si02-CaO Kurkjian & Russell
e
FetO-P205-CaO
Present work ( 2CaO•Si02 sat )
A KO0.5-Si02(1 573 K)
v Present work
o Shirota et al. FetO-P205-Si02 - CaO-hdgOsat. e NaO0.5-Si02 590X) (1

[] Li O0.5-Si02 (1573 X)
FetO-P205-~lgOsat. Winkler et al.
x present work V Baiajiva et al.
FetO-P:205 -Si02sat. A Suito et ai.
calcuiated
D Trdmel et a[.
I Present work I
uo 0.01
Fig. 13. Relation between calculated and measured phos- A e
Al(//
phorus distribution. eA
~10 o/o
over the wide range from basic slag to acid slag. e-e'~eD/

8. Estimation of Hydroxyl Capacity

o
An attempthas been madeto estimate the hydroxyl O O.
2 O4 O.6 0.8

capacity by the regular solution model. The equilibrium XMO0.5

relation of water vapor solubility in silicate melts is Fig. 15. Comparison of CbHcalculated by regular solution
written as follows: model with CbHmeasured in alkaline metal silicate
melts.
l /2 H20(g) = HO0.5(R.S.) . .. . .... . ..... ...
(45)
0.016
RTln KH20= RTln XHo. = ~ 1/2 Iog PH,o lr
O /
+ RTln yHo...(R.s.) """""""""'(46) llo
430-1 873 K) / /
AG~,o=
~ 19 800 + 26.32T
(J) (1
..(47) nlF/ /
l:)
vQ) l o
/1F /
/1~ O
Therefore, hydroxyl capacity is expressed as follows: 0,008 VIZ
V/V ~)
fO
e~~F:~tl~flrl(DV
RTln CbH= RTln KH,o~ RTln yHo..=(R.s.) /1(D:S~~~)~~/
I
*O 1'F

=RTlnKH=0~~0cH
,X,
V //
/
/
-~~(oe H_,, +c(H_j-oeiJ)X,XJ ......(48) /
•. O
ij O 0.008 0.016

The values of free energy of Eq. (45) are shownin Fig. C' (measured)
OH
14 for the four kinds of binary silicates of Si02-MO
(M0=CaO,Na20, K20, Li20)20-22) systems. The CaO-Si02 CaO-SiO2-AI O
23
results obtained in Fig. 14 is expressed with Eq. (47). In e lguchi et a[
O Iguchi et a[.
Na20-Si02 e sachdev et a[.
Fig. 15, the estimated hydroxyl capacity of binary silicate Q) Russet[ I Ban-ya et al.

melt is shownwith the experimental data of Kurkjian & 1) Kurkjian & Russell CaO-Si02-MgO
Russell20) to confirm the validity of the model. There are
K20-SI02 v lguchi & Fuwa
v Kurkjian & Russe[1 A Sosinsky et al.
minimumvalues of hydroxyl capacity for three kinds of L 20-Si02 A Ban-ya et al.
silicate melts at the composition of NMOO=0.4, and a l Kurkjian & Russe[[ CaO-Si02-MnO
s c Iguchi & Fuwa
good agreement is observed for both ~;:easured and Fig. 16 Comparison of estimated values of Cb}1 by regular
calculated values. Figure 16 showsapproximate validity solution model and the measuredvalues in molten
of the model for the hydroxyl capacity for CaO- silicate slags.

9 C 1993 ISIJ
 ISIJ International, Vol. 33 (1993), No. 1

40 lv'lg2'
e

o
Cao Mgo '
cao Feo
tvl~g.O.

~:,~f
'
4 Fe203
_2 O
IP3 "Mn2tNa \e *1

\
22~~g ~je0203J~•S~/0/2~~~'IFeo Fe
/ o
.23 A[3+0
O
'
.
2
cMago?F~;g:I~~g2L/~i~/ ~2F~OS~02 Fe e
-2 5
3Cao' SiO'--~0
'~Q ~,Feo
\FeO'Si02
2Mgo'Si02
'Ti02
'
~:
1_2
,5 o Fe3
\\\
~(/02Cad.Si02 ~;
O +4
I Na20'Fe203
~S
q,
LL
p5'
\ e\\ Ca2
acao SiO2
l
'
// Ti4*
o -40 L e
E -5 O e Si

.Na20 2Si020 OA[2 03 Si02 '

\ e Ban-ya et ai
J
Fe203' P205 o Others
.

!sej

5 l Ferrite 02 Na20 02 O25 O50 O.7 5 1.00

(~)
-7
ONa20•S i 02 rMz'
O Si[icate
o(~ e phosphate Fig. 18. Relation between interaction energies and cation
I L~ Others radii.
~
-1
oo e 3lvlgO P20
ion and London's force, but their theoretical treatment
cao'p205 e is not known even in present day. However, they are
e 4cao'p205
-125

e 3lcao'p205
/ O
e 3Na2O•P25
affected by the valence and radius of cation. Therefore,
Fig. 1814) shows the relationship
valence for the oeF... of
of ionic radius and
the example of many
_M.. as one
e ~cao p205
-75 -50 -25 o
interaction pararneter. good correlation is also foundA
o(jj xj Xj(kJ ) amongthe ionic radius, valence and interaction pa-
rameter except for Ti4+. From these results, it is con-
Fig. 17. Correlation between interaction energies and the firmed that the values of interaction energy obtained
heats of formation of complex oxides at 298 K. is not only
parameter for curve fitting.

S02,2i 22) Na O S02,20) K20-Si02,20) Li20-Si02,20) 10. Conclusion

CaO-Si02-A12203,23.24)
CaOSi02Mg025,26) and
CaO-Si02Mn02
7)
systems.
The application of regular solution model for silicate
melts was studied to espimate the activities of slag
constituents, the capacity of slag and slag-metal reactions
9. Correction of the Interaction Energy with Other
concerning steelmaking process. it was confirmed that
Physico-chemical Properties
the model was satisfied over the wide range of slag
The interaction energy between cations can be written composition from basic to acidic sides. The content of
as follows in the regular solution: the elements dissolved in iron in equilibrium with the
slag can be estimated within the accuracy of ~: 100/0.
c(ij=(ZN012)(2Uij- Uii- Ujj) , .
..........(49)

where Uij is the bond Acknowledgments

energy of (i cation)-O-(j cation)
ion pair, and Z
and No are coordination number of The author wishes to thank Drs. M. Hino and F. Ishii,
cation and Avogadro's number respectively. The value and manycolleagues in our laboratory for their effective
of ceij should have close correlation with other assistance in completing this paper.
physico-chemical properties of oxides.
Theheat of mixing of multicomponent regular,solution REFERENCES
can be expressed as follows: l) SlagAtlas, VDEh,VerlagStahleisen M. B. H. Dtisseldorf, (1981).
2) Chemical Properties of Molten Slags, ed. by S. Ban-ya and M.
=V
AHM ~ cc..X.X.
LL. * J *J . ...
..........(50)
3)
Hino. ISIJ, Tokyo, (1991).
J. Lumsden: Physical Chemistry of Process Metallurgy, Part I,
iJ Interscience, NewYork, (1961).
As a rough approximation of Eq. (50), the heat of 4) I. D. Sommerville, I. Ivanchev and H. B. Bell: Chemical
formation of binary complex oxide. AH298, can be Metallurgy of lron and Steel, Iron Steel Inst., London, (1973).
written as follows: 5) S. Ban-ya and J.-D, Shim: Can. Metall. Q., 23 (1983), 319,
Tetsu-to-Hagan~, 67 (1981), 1735, 1745.
AH298~c(,,X.X.. ......,...(51) 6) S. Ban-ya, M. Hino and H. Takezoe: Trans. Iron Steel Inst. Jpn.,
'J *
' J ...
25 (1985), I122.
Figure 176) shows the relationship between the heat of 7) R. Nagabayashi, M. Hino and S. Ban-ya: ISIJlnt., 29 (1989), 140.
formation of binary complex oxides, AH298, and the 8) M. Hino, I. Kikuchi, A, Fujisawa and S. Ban-ya: Proc. 5th Int.
interaction energy related to these complex oxides. A lron and Steel Cong., ISIJ, Tokyo, (1990), 264,
good correlation is found between them, especially in the 9) Y. Waseda.Y. Shiraishi and J. M. Toguri: J. Jpn. Inst, Met., 43
(1979), 1009.
range lower than AH298= - 41 .8 kJ.
It is said that the bond lO) L, S, Darken: Trans. Metal!. Soc., AIME, 239 (1967), 80, 90.
energy of (i cation)-O-(j cation) l l) J.D. Baird and J. Taylor: T,'ans. Fa,'aday Soc., 54 (1958), 527.
consists of the coulombic force, polarization of oxygen
12) D. A. R. Kayand J. Taylor: Trans. Faraday Soc., 56 (1960), 1372.

C 1993 ISIJ 10
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13) S. Ban-ya and M. Hino: Tetsu-to-Hagan~, 74 (1988), 1701. Hagan~, 53 (1967), 91.
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l 5) S. Ban-ya, M. Hino and N. Yuge: Tetsu-to-Hagan~, 71 (1 985), 853.
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l 6) R. Nagabayashi, M. Hino and S. Ban-ya: Tetsu-to-Hagan~, 74 23) S. Ban-ya, Y, Iguchi and S. Nagata: Tetsu-to-Hagan~, 71 (1985),
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11
C 1993 ISIJ