ISIJ International. Vol. 29 (1989), No. 2, pp.

140-147

Mathematical Expression of Phosphorus Distribution in Steelmaking

Process by Quadratic Formalism

Retsu NAGABAYASHl,1)
Mitsutaka HIN02) and ShirO BAN-YA2)
1) Graduate School, Tohoku University Nowat Research and DevelopmentLaboratories, ShunanWorks, Nisshin Steel Co., Ltd.. Tonda,
Shin-nanyo, Yamaguchi-ken, 746 Japan. 2) Department of Metallurgy, Faculty of Engineering. Tohoku University, Aza Aoba. Aramaki,
Sendai, Miyagi-ken, 980 Japan

(Received on June 3. 1988, accepted in the final form on September9, I988)

Phosphorusdistribution between slag and liquid iron has been studied at the temperature range from 1573 to 1953 K.
The slag system of FetO-P205-M.Oy(M.Oy= CaO, MgO,Si02) ternary, and of FetO-P205-CaO-M.Oy(M.Oy MgO,
=
Si02) quaternary were studied to clarify the effect of oxides on the phosphorus distribution equiiibrium at steelmaking
process.
In view of ionic theory, the approximate validity of regular solution model
was examined to formulate the equilibrium
reaction of phosphorus distribution between slag and metal. As the results, it was confirmed that the regular solution
model was satisfied for all the experimental results including the present work and the previous stvdies by other inves-
tigators, except for extreamly high iron oxide region The phosphorus and oxygen contents in liquid iron in equilibrium
with slag can be estimated within the accuracy of ~:10 "/• by the quadratic formalism derived from an assumption of the
regular solution of slag

KEYWORDS:thermochemistry; steelmaking reaction; oxygen distribution: phosphorus distribution; quadratic formalism;

steelmaking slag; activity; regular solution model; mathematical modeling

1 . Introduction (Mg,Fe)O, FetO-P205-Si02 saturated with Si02,

FetO-P205-SiO2-CaO saturated with 2CaO.Si02
Numerouslaboratory studiesl-ro) have been made and FetO-P205-CaO-MgO saturated with (Mg,Fe)O
concerning the equilibriurn of phosphorus distribution to know the effect of oxides on the phosphorus dis-
betweenslag and metal at steelmaking process, but the tribution. The previous data used to check thc ap-
physico-chemical treatment of their results was very plicability of the moclel were the experimental results
different by the investigators. Manyattemptsi'2,9~17) ofthe slag saturated with CaO
by Fischer and Ende,3)
were madein the past to predict the phosphorus con- Peter et al.,4) Kntippel and Tr(5mel and Fritre,6)
et al.,5)
tent in iron in slag-metal equilibrium by meansof those saturated with (Mg,Fe)O by Winkler and
theoretical or empirical slag model. Someof the Chipman,1) Trdmel and Schwerdtfeger8) and Suito
models were successful to evaluate the phosphorus dis- et al.,9) those saturated with Si02 by Trdmel and
tribution ratio over a re_.stricted range of' slag com- Schwerdtfeger,8) those saturated with 2(Ca,Mg)O.
position, but the model
same was inadequate for the Si02 by Balajiva et al.,2) and those by the levitation
data from other sources whenthe composition range melting of Shirota et al.10)
of slag was changed. This is probably due to the fact
that the slag model proposed is not enoughto evaluate
the intcraction between the oxides in slag and the ac-
2. Experimentals
tivities of' slag constituents. The experimental apparatus and procedure are
In the present work the approxlmate validity of almost the same as those of our previous workl8) for
the regular solution mode] Ibr slag
was studied to themeasurementof oxygen clistribution between slag
formulate the equilibrium relation of phosphorus dis- and liquid iron.
tribution for all the experimental results including the The experimental apparatus consists of the purifi-
present work and the previous studies by other inves- cation train ofAr, an alumina tube (0.42 x0.52 x I m)
tigators, in succession to the successfhl application of as a reaction chamber, and a Keramaxclectric re-
the model for the oxygen distribution in steelmaking sistance furnace (8 kVA) for a heating device. The
process. Fe-P alloy of 1.5x 10-2 kg and the premelted syn-
For this purpose, the phosphorus distribution be- thetic slag of (6-8)x 10-3 kg set in a crucible
were
tween slag and liquid iron has been studied at the melted under Ar atmosphere of the flow rate of' I .67 x
temperatures from 1573 to 1953 K. The slag sys- l0-6 Nm3/sat a given experimental temperature until
tem studied at present work were of FetO-P205-CaO the att.ainment to equilibrium. At the end of run,
saturatcd with CaO, FetO-P205-MgO
saturated with the crucible containing the sample was taken out

140 C 1989 ISIJ

 ISIJ International, Vol. 29 (1989), No. 2

from a reaction chamber, and then was quenched established at the sametime.
into water bath to solidifv the liquid iron as quickly
as possible. After that, the crucible was immediate- + Q= (FeO)
Fe (1)
""" """"""
"'(3) (i* *1~g)

ly moved to a chamber of He atmosphere to be AG~= 128_ 090+57.990T18) (J) .........(4)

cooled to room temperature. The slag and metal in
-
~+2.5 (FeO) = (PO (i~*1* g) +2.5Fe .(5)
(i~ *1~g)
(1)
2.*
-)
the quenched crucible were separated J_)y crushing.
The contents of fcrrous iron, total iron and the
other kinds of oxides were determine.d by chemical Kp2 = apo,.*/(ap'a~~.50) """"(6)
"""'
analysis. The time to approach to equilibrium is in- Therefore, the distribution ratio of phosphorus be-
fluenced by the rate of solution of crucible material
into liq_uid slag, and the equilibrium time was about tween slag and liquid iron can be deflned as follows;
9x 102 s in case of CaOcrucible, 3.6x 103 s in case of L'
P=
(o/oP)/[ol)P]
O44 (OAP025)l[(~ P]
Si02 crucible, and 1.44x 104 s in case of cruci- MgO = 0.44 (o/o P205)/[o/o P] ..
(7)
ble. . . . . . . . .. . . .

The MgO crucible was bought from market, and Manymodels have been proposed to express the
the Si02 crucible wasmadefrom pure silica glass tube. ionic nature of liquid slag. The regular solution
The CaOcrLrcible was fabricated from the calcined model of slag has proposed by Lumsdenl9) in 1961.
powder of' 10,/.,FeO-CaO mixture, by stamping with In present work, an attempt has been madeto quan-
the binder oflinseed o_ilkerosene (1 : l) solution, and titatively represent the equilibrium relation of phos-
by firing with C2H2-02flame at 1973 K. According phorus distribution in steelmaking process as a func-
to the recent phase diagram of Ca(_)-FeO system, the tion of temperature and slag composition by the
solid CaOmakes a solid sol_ution containing about model, in continuation of our previous studiesl8,20) on
lO o/o FeO at steelmaking temperature. Therefore, the oxygen distribution in steelmaking process. The
pure wustite powder was added in calcining process activity coefficient of a component i in a multicom-
to stabilize the solid CaO. The CaO-FeO crucible ponent regular solution is expressed by the following
madeby technique was durable for about 3.6x
this equation.
work, but was unable to be used in
l03 s in present
the measurementofvery low oxygen potential. G~=AHi=RTlnr"('.'Sf=0) ..............

RT In Ti = ~: aijX~+ ~:~ (aij+aih -afk)Xj. Xk

3. PhosphorusReaction ' jk '

(8)'
. .

Since the phosphorus dissolved in liquid iron, [Po], where Xj : the cation fraction of the componentj in
is oxidized to (P5+) in the oxidizing process of steel- slag
making, it has been considered that the reaction (Yij : the interaction energy bctween cation i-
product in the dephosphorizing of iron with liquid O-cation j.
slag
maybe phosphorus pentoxide (P205), tricalcium Whenthe of Eq. (8)' is valid to express the
relation
phosphate (3CaO.P205) or tetracalcium phosphate activity of cornponent i in the experiments,
coeflicient
(4CaO.P205) in the molecular theory of slag. On the quadratic formalism of Eq. (8)' can be applied as
the other hand, it is well-known that the liquid slag an approximate expression of activity coefficient of
is
one of the ionic melts, and that the phosphorus in componenti in slag, even if the liquid slag is not real
liquid slag exists as the species of phosphate anion regular solution (S~~~O). This is the similar idea to
(P0~-) containing one atom of phospho_rus. Even in the quaclratic formalism of metallic solution proposed
the ionic theory of slag, however, an equilibrium con- by Darken.21)
stant can not be derived without making some as-
sumption, because of the lack of the enough knowl-
edge concerning the ionic naturc of thc liquid slag.
4. Distribution Ratio of Phosphorus
Moreover, it is theoretically diflicult to determine the Manyof the experiments in the present work were
activities or activity coefficients of ions in the fused carried out over a wide range of FetO content and at
Therefore, in the present work, the hypotheti-
salts.
cal species (P02.5) containing one atom of phosphorus
3 temperatures of 1823, 1873 and 1923K. The
phosphorus distribution ratio is a function of the tem-
was assumedas the reaction product to represent the perature, oxygen potential of the system and the com-
dephosphorizing reaction of liquid iron in view of position of slag, as seen in Eqs. (1) and (5). The
ionic theory. The samcidea is also va,lid in the regu- values of the distribution ratio (o/_nP)jr~/oP] obtained
lar solution model oi' slag described in the later. The at 1873 K
were shownas a function of FetO content
equilibrium relation of phosphorus reaction in the in Figs. to 3. IFig. I
shows the results of FetO-
steelmaking process can be written as follows; P205-M.Oy(MwityhO CaO MgOSIO ) isternary sys
tems saturated oxide M*Oy, which the cruci-
~+2.5Q= (P02.5) (i* sl*g) """""""""(1)
ble material. The distribution ratio in FetO-P205-
Kpl = ap02.*/(ap 'a~'5) ........................(2)
.
CaOslag were the highest among3 ternary systems
In the equilibrium state of the system, the oxygen studied, and the maximum value of the distribution
distribution between slag and liquid iron should also ratio was observed at the range of (massol)FetO)=
be in equilibrium. The following equilibria are lO-20. The maximum phosphorus distribution ra-

141
 ISIT International, Vol. 29 (1989), No. 2

4
Fet
O o + FetO-P205--CaO(Peter et al.)
3
~ ~~++
~~ ~~+
~V~~~~O
O ~e
-p2 ~e~

d'
Ca
S
~(,qa t. O e FetO-P205-CaO(Knuppel et al.)
~ ~~~~\
(,
V FetO- P2O5-CaO(Fischer et al.)
~~l I~ 2 ~ e FetO-P205-CaO
?1•*
FetO- P205 - A FetO-P205-MgO Trdmel et al.
Ngosaf I FetO-P205-Si02
1 A~-A~A_A
_
.

A ~~~LA~~~~L~~Lt~ Present work

~(71 .
Aa-~~:"
~L
FetO- P2O5
J~~-~AA~f_~e,L
-
O FetO-P205-CaO
O o d'll't A FetO-P205-MgO
[] FetO-P205-Si02
It o-po
-T ~
fl
I
Fe
2 5-SiO 2 Sat '

Fig.
---- FetO-P205
1.

Phosphorus distribution ratio between liquid iron

-2
o 20 40 60 80 1OO and FetO-P205MxO?!(MxOy =CaO,MgO,Si02)
slags saturated with solid MxOy at 1873 K.
mass'/. FetO

4 A
massell CaO
mass'/.h4gO
F:eto FetO - CaOsat
3 " F)205
P2 -
OO * 5
ll!~'~~_1 " caoset 3 l$
5 * 10
\'~t~~o
~/z::/i0~2~~\:~t ,h~ 20
D 15 - 25
~L

~~ 2 v =,' Q
2
;~^ A 75
O
,~,,,,
_~9"~C:8~)
\ v:218
t""
,,
a, o
Al o
, /d~!Q
'\
ll
a) O
~
~ >~6
lo
BalaJjva et al CID
o 25
C1, 1
O O mass'l.CaO
V= mass'/. O2
Si FeO-PO
t 25 -SiO 2 sat FetO-P205-MgOsat.
/
o ~2 o
-1
2-3 o 10 20 30 40
A 3~
mass'/. Fet O
-2
Fig. 3. ratio between liquid iron
Phosphorus distribution
O 20 40 60 eo
masso/oFetO and FetO-P205-CaO-MgO slags saturated with
(Mg, Fe)O at 1873 K.
Fig. 2. I)hosphorus distributionratio between liquid iron
and FetO-P205-Si02-CaOslags equilibratcd with
solid 2CiaO.Si02 at 1873 K.
From the above experimental results, it will be
seen that of oxides increasing the phos-
the ability
phorus distribution ratio increases with the order of
tios in each slag system
were L~::~1 OOOin FetO- Si02 FeLO MgO
CaO. However, the sameprop-
P205-CaOslag, L~~(lO FetO-P205-MgOslag, in erty of desulfurizing of iron is the order of Ca0>>
and L~ I in FetO-P205-Si02 slag, respectively. The FetO> MgO > si02'
approximate value of Lf, in FetO-P205 binary slag It
was conflrmed that the phosphorus distribution
will be given by extrapolation of L~-values in 3 each ratio decreased with increasing temperature, but the
slag system to 100 massO/oFetO in Fig. l. The dis- results obtained were omitted from the limited page
tribution ratio in FetO-P205 binary slag of the paper.
was esti-
mated to be L~c~ 1. The distribution ratio in FetO-
P205-Si02-CaOsystem saturated with 2CaO•Si02 5. Equilibrium of OxygenDistribution
is shown in Fig. 2. This series of the measurement
was conducted usin" solid CaOcrucible but the in- In our previous papers, 18,20) it was confirmed that
terface between th~ solid CaOand the liquid the regular solution model of slag was satisfactory for
was
always covered with 2CaO.Si02, as was expected predicting the oxygen content in metal in the equi-
from the phase diagram of CaO-FetO-Si02 system. librium state of steelrnaking process over the wide
The distribution ratio in this slag increased with in- range of silicate slag composition. To establish the
creasing basicity defined with (masso/oCaO)/(massO/o relation for the dephosphorization in steelmak-
same
Si02), and an optimum FetO content, at which the ing process, the validity of the model for phosphate
value of Li, is maximum,was observed at the com- slag should be conflrmed, and the interaction energies
position of (massO/oFetO)~:20. As shown in Fig. 3, between cations and phosphorus ion such as (x(Ca2+_
thc distribution ratio in FetO_-P205-CaO-MgO satu- p5+), (r(Mg2+_p5+) and (t(Si4+_p5+) should be cleter-
rated with (Mg,Fe)O increased from I.j,c::: 10 to L' ::: mined if the model was valid for the data obtained.
l OOOwith increasing CaOcontent, and it was clear The experimental results of oxygen distribution equi-
that CaOand MgO
were not equivalent for the de- libriurn was applied for this purpose.
phosphorizing of iron in steelmaking process. The equilibrium relation oi' FeO-Fe203-P205-CaO

142
 ISIT International, Vol. 29 (1989), No. 2

(l-2-4-5 system) slag with oxygen in metal can be Table 1.

Interaction energies between cations.
written as follows by the model.
Interaction energy, aij (J)
Fe +Q= (FeO)
(1)
"""" (i* *1'g)
""" '
"'(3) ion-ion
Ban-ya Ref. Other investigators
et al.
RT K3 = RT In (aF*o/ao)
In

= RTln (XF*o/ao)+RTln rF*o """"""(9) Fe2+_Fe3+

-
18 660 Lumsden
RTIn rF.o = ~ 18 660XF2.~o,.,~ 31380X[2>02'5 OFujita et al. t~

Fe2+_Na+ + 19 250 25)

-3 1380X~~o~64680X}"o,., Xpo,.5 '
Fe2+_Mg
2+ +33 470 20)
+45 770Xl"ol'5'Xc'o Fe2+_Ca2+ -31 380 20) -48 120 Sommerville et al.

14 640 Fujita et al.

-62 760Xr02 " Xc*o ~a45Xr02'5 ' Xc*o J) (
.(lO)
Fe2+_Mn2+ +7 1ro 26)
-
OFujita et al.,
Bell et al.

In the above equation, a45(Ca2+_p5+) is only an un- -3 350 Martin et al.

- 1760
Fe2+_A13+ Sornmerville et al.
known term to be determined at present work, and
other terms of interaction energy between cations have
Fe2+_Ti4+ -37 660 23) -41 840 Smith et al.,
Martin et al.
been already known20,22-27) as listed in Table 1. By Fe2+_Si4+ -41 840 23) -41 840 Lumsden,
the combination of Eqs. (4), (9) and (lO), the un- Sommerville et al.

knownterm is movedto hand side and the known

left
-28 030 Fujita et al.
terms are written to the right hand side, and the fol- -21 760 Fujita et al.
lowing equation can be given. Fe2+_p5+ -31 380 22)

(~!45(Xc*o/Xp02'5) Fe3+_Na+
- 74 890 25)
Fe3+_Mg2+ -2 930 20)
(1
/Ypo, ,) {R T In (XF.o/ao) ~ 18660X~•.o,.5 Fe3+_Ca2+ -95 810 20) I02 510 Fujita et al.
31 380X~02'5~31380X{2.~o -
Fe3+_Mn2+
- 56 480 26) -12 550 Suito et al.

64 680XF.o,.5' Xp02'5+45 770XF.ol'5 Xc.o '

Fe3+-Ti4+ + 1260 23) + 17 570 Smith et al.

Fe3+_Si4+ +32 640 23) + 13 390 Lumsden

62 760Xl o, Xc*o~ 128 090+57.990T}
* +24 270 Fujita et al.

E YA(J) .......
.........(ll) Fe3+_p5+ + 14 640 22)

If the regular solution model is valid for the data in Na+_Si4+

- II1210
290 25)
this slag,the values of YA in Eq. (ll) should be a Na+_p5+ -50 25)

linear function of the term of (Xc'o!Xpo,.,), Passing Mg2+_Ca2+ Ioo 420 20)
through the origin.
-
Mg2+_Mn2++61 920 27) -23 850 Suito et al.

The oxygen distribution ratio, L0=JVF.to![o/oO], ob- +38 910 Suito et al.

tained in FetO-P205-CaOsystem was shown in Fig. Mg2+_Si4+ -66 940 20)

4, in which the previous data by other investiga- Present
Mg2+_p5+
- 37 660 work
tors3~6,8)
were also illustrated. The present results
were in good agreement with the data by Peter et Ca2+_Mn2+ -92 050 27)
-167 740
16 Sommerville et al.

Kntippel al.5) and Trdmel and Fritre,6) and Ca2+_Ti4+ 360 Sommerville et al.
al.,4) et
133 890
- 138 490 Fujita
obtained by Fischer Ca2+Si4+ 20) ei al.
the oxygen distribution ratios - Prcsent
-
and Ende3) were a little lower than those of others. Ca2+_p5+ -2~)1 040
work
Onthe other hand, the phosphorus distribution ratio Sommerville
Mn2+_A13+
- 20 920
et al.
in the samesystem obtained at present work agreed
well with those by Fischer and Ende,3) Kntlppel et Mn2+_Ti4+ -66 409. Sommcrville et al.

Mn2+_Si4+ -75 310 26) -65 270 Fujita et al.

al.,5) and Tr6mel and Fritre,6) exccpt for those by -76 780 Sommerville et al.
Peter et al.,4) as shown in Fig. l. Therefore, all of 100 420 Sommerville et al.
the present work, our previous work,24) Knuppel et al.5] - 108 780 Suito et al.
Mn2+_p5+ -
and Tr6mel et al.s)
were applied to check the validity
Si4+_A13+ -52 300 Sommerville et al.
of Eq. (1 l). The results obtained were shown in Fig.
5. Four sets of data fit to one straight line passing
Si4+_Ti4+ + I04 600 Martin et al.

Present
through the origin. The slope of a line is the inter- Si4+_p5+ +83 6ao work
action energy between Ca2+ and P5+. The following
interaction energies between cations were given by RTIn rF*o
the sameprocedure.
= - 18 660X~.oi 5~31 380X~o,.5
a (Ca2+_p5+) = _251 040 -41 840X~2io,~3 1380X~*o
a(Mg2+_p5+)=
_ 37 660
(J) .........(12) +33 470X~Igo~64 680XF.ol " Xp02'5
a(Si4+_p5+) + 83 680
= +45 770XF.o, 5 Xo'0+ 17740XF.o, , Xltgo
' '

From the above results, the activity coeflicient of -93 140XF.ol 5'Xsio,+ 188 280Xp02"Xc'o
FeO in the FeO-Fe203-P205-Si02-CaO-MgO slag, +39 750Xpo, , 'XMgo~ 156 900Xro, , 'Xsio,
which are major componentsin steelmaking slag, can + 102 5lOXc'~o'XMg0+60670Xc'~o'Xsio,
be written as follows; +58 570X~lgo'Xsio, '
(J) .(13)

143
 ISIJ International, Vol. 29 (1989), No. 2

8 1.0
o Present work /' : oo ,
6
D KnOppel et
e Tr6rnel
Fischer
et ai

et ai
al

eCI
o
/D AA
l

0.5
v
xyJ)~)
~A

DC~;~0 ,d' A o
+ Peter et a[

~~
J04
'D:n

D
8 o
d,
C!D
o
r)
ol
o
o
ldi~;. /
+0 ~
2 CD

-
o.
5

(:
o
O 0.1
O2 03 0.4 O5 O6 10
NFetO
-1.0 -o 5 o o5 1.0

Fig. 4. Relation between oxygen distribution

(~(rF~JX2+~J~k ((~~Fej+'xFeh~ajk)XjX~=)/2.303RT
ratio and
JYF*tO InCaOsaturated FetO-P205-CaOslags in + Iog (XF..o/XF.to) ~ 446/ T+o. 373
contact with liquid iron at 1873 K. Fet O-P2O.-CaO
* sat. FetO-P205-CaO-MgO
s~t.
O Kntppel et al. A Prcsent work
o O Trdmel et al. FetO-P.O5-Si02-CaO
O Present work e present work (2CaO.Si02 sat.)
D FetO-P205-MgOB
C] Xnoppel et al' at. V Prescnt work
-250 x Present work FetO-P205-Si02-CaO-MgOsat.
o Trdmei et al
FetO-P205-SiO2 sat. Winklcr et al.
IIll~)j~;\leD~'!~:]~ A Ban-ya and NagabayaPshi
[] Trdmel et al. Suito
-500 ~ et al.

J,
C]
I Present work
C!
Fig. 6. Comparison between measured and calculated log
> _ 750
~0' CZlee o rFeto'
Xcao
O ' YA= 251040 (J)
' Xp025
-1000 O
o C]
6. Equilibrium of PhosphorusDistribution
O
O
- 1250
Fromthe above results, the equilibrium relation of
O 2 4 6 8 10 12 dephosphorization with FeO-Fe203-P205-Si02-CaO-
XcaO/Xp02.5 MgO slag can be written as follows;
Fig. 5. Relation between YA and XcaO/Xp02. in FeO-
FcO1.5-P02.5-CaOslags.
~+2.5Q= (P02.5) (i* sl*gl """"""""""""""""'(1)
RT In Kpl = RTln {Xro,.*/(ar' a(2j.5)}
+RT In rp02.5
Since the above equation quadratic formalism, the
.
(17)
minor componentswhich are less than 5mass~/o can
is
RT In rp02.5

be neglected for the approximate calculation. = -3 1380X~.0+14 640X~.ol'5~25 1040X~.o

- 37 660X~g0+83 680Xs2io,+ 1
The reference state of FeOactivity in the model is 920Xh"*o XF.ol'5 '

taken to the hypothetical stoichiometric FeOin which -25 1040XF.o ~ 102 51 XMgo
Xc'*o OX},.o
' '

the regular nature of the solution is kept. However,

the reference state of conventional iron oxide activity
+94 140Xl"o Xslo, ~ 140 590XF.o,.5 Xc.o
' '

is the
pure iron oxide in equilibrium with metallic -20 090XF.ol" XMg0+ 65 680Xl'o, Xsio,
'
5
'

iron. The conversion of the reference state for both

- 188 280Xc*o'XMg0~33470Xc*o
Xs*o
activities is written
as follows25,26) .

+ I 12 960XMgo'Xsio, (J) . ...

........(18)

FetO(~+(1 -t) Fe (s or l)
= FeO
(1, R.S.) According to the all ofexperimental results, the
range
.(14) of slag composition covered the wide range of JV:F*t0
AG'14 = -8540+7.142T (J) ....... ........(15) 0.5 and JVI"o, in whicll the relation of Eqs. (17)

RTIn . ~ o RTln
al aF~0~8 540+7. 142 T (J) and (18) is valid to evaluate the equilibrium constant.
.

.(16) The slag composition for basic steelmaking in practice

is within this range. In order to show the validity
The activity coeflicient of iron oxide in phosphate ofthe model, in Fig. 7, the values ofequilibrium con-
slags obtained by present authors and other inves- stant of Eq. (17), K1'1' calculated from the data ob-
was compared with the values cal-
tigatorsl,5,6,8,9) tained in FetO-P205-CaO slag were plotted as a func-
culated from Eqs. (13) and (16) in Fig. 6. The points tion of (Xc^0+XF~o)iXpo,., at 1873 K. As seen in
of' data lie Fig. 7, the values of log Kpl evaluated by the model
on a line with the slope of unity, and the
of
agreement calculated values with the measuredwas were truely a constant within experimental error over
excellent within the experimental error. the wide range of slag composition. The similar re-
sults
werc given in the other slag systems studied at

144
 ISIT International, Vol. 29 (1989), No. 2

present work. The data obtained by the extensive work of Balajiva

The effect of temperature on the log Kpl evaluated were good example to check the validity of the
et al.2)

by the sameprocedure was shownin F'rg. 8, in which model by Eq. (21 ), because the oxygen content in iron
the data reported by other 5 groups of Winkler and in the equilibrium was not determined in their mea-
Chipman,i) Kntppel et al.,5) Trdmel et al.,6,8) Suito surement. As shown in Fig. 9, the points of data
et al.,9) and Kor28) were also shownby the recalcula- recalculated from the results by Balajiva et al. at
tion. The results obtained by different kinds of slags l 858 Iie on a horizontal line of log K/'2 (1 858 K)=
K
-0.76 within experimental error. Tllerefore, the va-
and by many different investigators were in fairly
good agreement each other, and the following equa- lidity of the model and the accuracy of Eq. (21) were
tions were given. also verified from the data by Balajiva et al. The
effect of tcmperature on the equilibrium constant of
p+2 50 =(PO2.5 )(i* *1*g) """"""" Eq. (5) were shownin Fig. lO, in which the results by
log Kpl_ 17060/T-8.510(a = 0.4) ..... .......(19)
_
'

present authors and other investigators of Winkler

= and Chipman,1) Balajiva et al.,2) Knttppel et al.,5)
AG~1= -326 520+162.883T(o = 13 810) (J)
Trdmel et al.,6,8) Suito et al.,9) and Shirota et al.ro)
were plotted for comparison. The results shown
in

Where, the standard phosphorus oxide in state for Fig. 10 were a little scattered in comparison with
slag is pure liquid hypothetical P02.5 under an as- those in Fig. 8, but be seen that they fairly
it will

sumption of' regular solution, and those for oxygen agreed with each other within the experimental error.
In Fig, I l, the phosphorus distribution ratio L~ cal-
and phosphorus being I o/o by massin iron.
The equilibrium relation of phosphorus in iron culated from the model was plotted against the mea-
with iron oxide in slag can be derived as follows by sured I., f'or the data by present authors and other in-
the combination ot' Eqs. (4) and (20). vestigators.1,2,5,6,8-10) The agreement between both
calculated and measuredvalues was also good within
f n I +2.5Fe(~
E+2.5(FeO)(i**1*g)
= \Pv2.5' (i* *1*g) the experimental error.
.(5)
As similar to the case of the activities of FetO and
FeO in slag, the conversion factor between the ac-
= 328/T-0.936((r =
log Kp2 0.4) ..................(21)

AG~2= 6280+17.908T(or = 13 810) (J) .........(22)

8
6 [og Kp2( 1858 K )=-O 760 ((f=0.4)
8
6 4
2 t_3_cf_______
~~~~~~~~~~~~~~~~~~~~~t3~~Gr_______ ~~
~2
ll $~~~:~~~~~~~~~~~~~ c:
o,
o cq)~Q~ o ~Q~~~Qa)g~cf~~)-oQ-
:(
-8.,~~~Oa~~.~.o DD--dt-.O o
a -2 -~a;~~~~~
(~~ ~ ~ ~ ~ ~~~~d:~~ ~
O -2
~ O Present work -4

D Treme[ et aL -e
-6
e KnUPPet et a[.
-8 2.
-8 o 25 30 3.5 4O
1 8 9 (XcaotXb,1gO~XFeO)'( Xsi02'X p02 )
(XcaO+XFeO)! Xp025 5
Fig. 9. Relation betwcen logKp2and slag basicity in FeO-
Fig. 7. Relation between log Kpl and (Xca0+Xl'*o)/ FeOl.5-1)02.5-Si02-CaO-MgO slags equilibrated
Xpo,.* in FeOFeO1.5P02.5-CaO
slags equilibrat-
with liquid iron and solid 2(Ca, Mg)O•Si02 at
ed with liquid iron and solid CaOat 1873 K. l 858 K froln the data of Balajiva et al.

Temp,K Temp K .

2000 1900 1800 1700 1600 aooo l900 1800 wOO 1600
8 8
present work present work
6 ~ Feo- Feoi 5- PO2.s ~ cao sat.
~Feo - Feol 5- p02s ~ SiOi - Cao 6

4 ~ Feo-FeO15~ P0: s ~ F'Igosat. ~Feo-Feol~-p02

( 2CaOSiOisat
5- CaO- H90sat
)
4
~FeO-Feols~POis~CaO sat
;(
Y FeO-Fe015~PO,s~Si02-CaO
( 2CaoSi02sat.)
~Feo-Feol __
5~pol 5-SiO! sat.
+0d
E] ~Feo-FeOI s~H90 5~P02 sat.
~1
FeO-FeO15-P02 ;-CaO-Mgosat.
log F~p2 = 323/T -O.936
,L
2 ---~~I~~: ~;~~/~ D'/!L/~ 2
~FeO- FeOli~POi.s~Si02 sat. ((f=a 4 +j6_ )
:(
a
~-! _________-
~ ~ ~ i3'$ :(
o ~~~ ~~~~~~:•. ~~~~~~~~~t: _ _ _ _ __

al ol o ~~,~~- It,
~:
J90
~) _{
o o -2 o
-2 ~ Tr5mel et a[. log Kpl = 17060/T -8.510
~ Trdmel al
~ Suito et al.
_jil~~~~~

~ Kor
~HnUppel et al. ((1=0 ~ ) -4
et

-6
~ Winkler et aL
~Ror -e
~ Hn~ppel et aL,
~T
Ba[aiiva et al.

-8
~ Suito et al.
-8
~ Winkler et al.
~ Shirota et al.

O50 o s5 o 60 o 65 o 50 o.55 o 60 o 65
T~t/ 10~aK~t T~1
/ I 0~3 K~1
Fig. 8. Temperature dependenceof log Kpl" Fig. 1O. Temperature dependenceof log Kp2'

145
 ISIT International, Vol 29 (1989), No. 2

k 9

3 -, 1
IS I
I
I

-CL ;~]D o
J 2
x~/~~]

Ix ~
Olo
Lr,
-13
~(V'
,i O
QJ
I' ~L
aJ 1 t~
rU
Al oooo O1 . ~~
l/V'( O _1 5 ov
l~i O I' O
U ~L

-1
-1 7 ~~
IPv
-2
1 O 1 2 3 ~
-1 9
-19 -17
-
Measured [ogL~ -
15 -13 -1 1 - 9

FetOP205-CaO FetO-P205-CaO-MgOsat. 2 r(~(rpjX~+ ~j ~k(crpj+ apk- ajk)XjXk)/2.303RT}

sat .

O Kndppel et al.
A Present work + Iog (Xl~02.5/JVp*0=) + 2754/ T- 12.05
O Trt)mel et al. FetO-P205-Si02-CaO FetO-P205-CaOsat. FetO-P205-CaO-MgOsat.
e Prescnt work (2CaO.Si02 sat.)
FetO-P205-CaO
O Kntippel et al. A Prcsent work
V Present work o Tr6nlel et al. FetO-P205-Si02-CaO
d) Shirota et al. FetO-P205-Si02-Ca0=MgO Present work (2CaO.Si02 sat.)
FetO-P205-MgO
s~t.
e
sat . ~ Winkler el al.
FetO-P205-CaO V Present work
x Present work V Balajiva al.et al.
FetO-I]205-Si02-CaO-MgOsat.
Fet O-P205-SiO2 sat. O Shirota et al.
A Suito et FetO-P205-MgO
sat. (~ Winkler et al.
[] Tr6mel et al.
x Present work V Balajiva et al.
l Present work Fet O-P205-SiO2 sat. A Suito et al.

Fig. 11 Relation between calculated and Ineasured phos-

. L] Tr6mel et al.
phorus distribution. I Present work
Fig. 12. Comparison between measured and calculated
tivitiesof conventional liquid P205 and hypothetical log rF20s'
liquid P02.5 slag is necessary. Turkdogan and
m
Pearsonf3) have derived the standard free energy of
range from basic slag to acid slag.
formation of liquid P205 from solutes in liquid iron as
follows
; 7. Conclusrons
2~ (lo/o)+5Q (1 o/o) P205(Pure liquid) .........(23)
= The phosphorus distribution between slag and liq-
AG'23 = -705 420+556.472T(J) .
...............(24)
uid iron has been measuredto study the approximate
validity of the regular solution model of slag. It
was
The conversion factor can be derived by the combina-
confirmed that the model was satisfied over the wide
tion ofEq. (19) with Eq. (24) as follows;
range of slag composition from basic to acid slag.
P205(1) = 2P02.5 R.S.)
(1, .....................(25) The phosphorus and oxygen contents in iron in equi-
librium with the slag can be evaluated within the ac-
RT In ap,o, = 2RTIn apo*.*+ 52 720
curacy of ~ 10 o/o'
- 230.706 T (
J) .(26)
. . .. .. . .. . ..

Acknowledgements
In Fig. 12, the activity coefncients of P205 directly
derived by applying Eq. (24) to the present data and The authors wish to thank former undergraduate
previous data by other investigatorsl,2,5,6,8-10) students at Tohoku University-Messrs. M. Tobita
were
comparedwith the values estimated from the model and H. Yamaguchi, now Spring Co., Ltd.) Mr. HNK
by using Eq. (25). As shown in Fig. 12, the most T. Tanemo, now Nisshin Steel Co., Ltd., Mr. T.
points of the data showedgood agreement within the Megumi,now Nihon Unisys, Ltd., and M. Mukaida,
experimental error. now Graduate school, Tohoku University-for their
effective assistance in making their experiment.
In the past, the slag models, proposed by Flood
and Grjotheim,12) and Turkdogan and Pearson,13)
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11
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146
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147