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Assessment of Calcium-Oxygen Equilibrium in Liquid Iron PDF
Assessment of Calcium-Oxygen Equilibrium in Liquid Iron PDF
265-269
)
(ega) and the second-order (rga rg•• o interaction parameters between calcium and oxygen
Thefirst-order
in liquid were determined at 1873 K by using the previous data obtained in slag-metal equilibrium
iron
experiments, on the basis of the reciprocal and conversion relationships between mass percent and mole
fraction scales. Thevalues for ega, rg• and rg•, o were obtained as -3 600, 5.7 x I 05 and 2.9 x I 06 jn the range
of {[masso/oCa] +2.51 [masso/oO]} and -990, 4.2x I 04 and 2.1 x I 05 jn the range of {[masso/oCa] +
}
2.51 [massoloO] ~: O.005, respectively, and the validity of these values was discussed.
KEYWORDS:
interaction parameter; equilibrium constant; calcium; deoxidation,
=-
eg•{ [masso/o Ca]
+ (Mc./Mo)[masso/o O] }
rg•{[masso/o Ca]2 (Mc./Mo)2[masso/o O] 2
one can express the calclum deoxidation equilibrium as, - +
log K~+ ~ + ~e~[massoloj] - Iog ac.o
e~.[masso/o i] + 4Mc./. Mo[masso/oO] [masso/o Ca] }
eg.[masso/o
O] - eg•[masso/o Ca]
rco.[masso/o O]2 + (MO+ Mc.)/( IOOMo)eg•[masso/oCa] [masso/o O]
=- - +10gKc* """--"""""""""""""""-""',.............(12)
rg"[masso/o Ca] 2 (rg~c. rg, c.)
- Ca] +
- [masso/o O][masso/o
+10gKc* """""(lO) Since the third term in the right hand side of Eq. (12) is
x ""'
considered to be sufficiently small to be eliminated in
j
where i and represent the components other than O
and Ca, respectively. In the derivation of Eq. (lO), the
comparison with the first and the second terms, Eq. (12)
can be rewritten as,
terms with respect to the self-interaction parameters
and the second-order interaction parameters except those 10g K~+
~e~.[masso/o i]
+ ~e~[massoloj] - Iog ac.o
between calcium and oxygen are neglected.
By using Eqs. (6) to (8) derived in Sec. 2.1. Eq. (lO)
=- eg•{ [masso/o
Ca] + (Mc./Mo)[masso/o O]
c* {[masso/o
}
can be rewritten as - ro Ca] + (Mc./Mo)[masso/o O]}2
2rg"Mc./Mo[masso/o O][masso/o Ca] + Iog Kc. (1 3)
log K~+ ~e~*[masso/o i] + ~e~[massoloJ] - Iog ac*o - '
The values for e~l7) and ac*018) used in this study are
=-
eg•{ [masso/o Ca] (Mc./Mo)[masso/o O]
+
rg•{ [masso/o Ca] 2 (Mc./Mo)2 [masso/o O] 2}
} summarizedin Table I and Fig. l, respectively.
- + The relation between the left hand side of Eq. (1 3) and
Mc./(2Mo)(roc*, o ~rc.o, c* )[masso/o O]2 {[massoloCa] +2.51[massoloO]} is shown in Fig. 2,
-
Mc*)/(200Mg)eg•[masso/o O] 2 indicating a nonlinearity. As can be seen in Eq. (13),
- Mc.(Mo~ therefore, the terms with respect to the second-order
+ {(eco"
+ eco.)/lOO 2(Mo/Mc.rg. + Mc./Morg•)}
- interaction parameter rg* in Eq. (13) have to be taken
x [masso/o Ca][masso/o O] + Iog Kc. ""' """""
(1 l) into account for the calcium-oxygen equilibrium. Slag
where the second term of the right hand side of Eq. (6), compositions for the data used in Fig. are indicated 2
in
-0.0065, was neglected in Eq. (1 l). the CaO-AIO1.5-Si02 phase diagram in Fig. I .
The third and the fourth terms in the right hand side The values for eco" and rg• in Eq. (1 3) determined
were
of Eq. (1 1), which correspond to the second and the third by using the contents of calcium, oxygen and other
terms in the right hand side of Eq. (7), respectively, are components obtained in previous equilibrium exper-
iments,9'12 ~ 15) the respective Interaction parametersl7)
Table l. Interaction parameters at 1873 Ki7) used in the given in Table l, the values for ac*018) and the Kca
present work. value. The value of logKc* was obtained as
- l0.22 at
e~ (ri)
l K
873 by using the thermodynarnic data for the reac-
tions: CaO(s)=Ca(1)+11202 (AG'=434.5kJ/moll9))
and ll202=Q (AG'= I17OOO 2.9T J/g atoml 7))
Al Al 0.045 - -
and the free energy for calcium dissolution in liquid iron
'
O Al
-
3.9 (1.7)
Si -0.131 Ca(1) ~~ (AG'
= = 121 OOO- 35.5 TJ/g
estimated based on the solubility
atom), which was
data20) by assuming
'
Ca Al
- 0.072
Si
- 0.097 regular solution. It should be noted that the values for
eco* and rg• cannot be obtained from the plot of Fig. 2,
acaO SiO 2
( )
S2A6
cs 4O
(0.013)
C3S
C2S AIO1.5
CAS9 Acs2
80 (0.106) (o cn3) 20
CAS5
0.35 Acs4 CA12 Fig. l.
(o,045)
CaO cAs8 CA4 Activities of CaO(s)18) and slag compositions plotted in
(1.0 the CaO-AIOI5-Si02 phase diagram at 1873 K.
20 CA 60 AC 80 AIOI .5
CaO (1.0) (O 11)
(mol "/.)
-o
p~l
/
+ -8 /
/ A CS eJ) -6
O(I~
/ x ACS-2
/
u V ACS-4
cls / ~> CAS-5
~ /
// 1873
K [1 CAS-8
-8 Thermo. calc.
I / + CAS-9
_~ -1O [o/. Al] O.3 aCaO= O.11 OAC :
~,~ -F ["/. Si
J 1.0
Thermo calc
eJ) _~ acaO= I A CA
-10
O O O(]2 OOO4 O006 {] 008 (1.OIO 0.012 -6 -5 -4 -3 -2 -1
r j
i*
Eq. (8). The results are summarized in Table 2. The contents in logarithmic form calculated by the itera-
tive method using the interaction parameters given in
curved lines indicated in Fig. 2 will be explained later. Table 2. Only the solid lines satisfy the condition of
The relations between oxygen and calcium contents
were calculated by the iterative method, using the inter-
{ [mass"/~ Ca] + 2.5 1[mass"/. O]} ~: 0.005.
action parameters given in Table 2. The results, which and calcium calculated for ac*o = were used to draw I
were calculated without taking into account the effect of the lines in Fig. 2
in order to neglect the effects of the
aluminumon oxygen, are shownin Figs. 3and 4for the components other than Ca and O. Although two or
ranges of {[masso/oCa]+2.51[masso/oO]} and three oxygen contents were obtained at a given calcium
~ O.005, respectively. for Experimental results9'i2)
AC content as shownin Figs. 3and 4, these oxygen contents
(ac*o =0.1 and (ac*o
= 1)
CA
slags ar6 also indicated l) fall
on the sameline in Fig. 2. The reason for the devia-
in Fig. 3. Only the solid lines in these figures represent tion of the data points from the calculated lines in Fig.
the relations betweenoxygen and calcium contents which 2is not clear and more detailed studies are required.(9).
satisfy the respective conditions of {[masso/o Ca] + The following relation can be written from Eq.
2.51 [masso/o O]}. It is not clear at present that which of
logKc*+10gac.o~loga0=10gac* "-"""'(14)
the oxygen contents in two or three is real for a given
calcium content. The relations given by Eq. (14) are plotted in Figs. 5
The lines in Fig. 2were obtained by using the contents and 6, inwhich the interaction parameters given in Table
of oxygen and calcium calculated in the respective ranges 2and experimental data in respective ranges shownin
the
of {[masso/o Ca] +2.51[masso/o O]} as shown in Figs. 3 Fig. were used to calculate the values for ao and ac.'
2
and 4. It should be noted that only the contents of oxygen Data obtained by other investigators2~4,6) are als~o
~l []
~ -4 ~>
1873 K
cf)
+ (~)
-12 Cl
OO oo
+ 1873 K
o
~;]
O AC ~
~ o
(J -6
~>
[]
[] C] CA clS AC CA
'-O oC]
ccf
eO
~>:
~D>
[> V
D>
ACS-4
CAS-5
a)
~l
cf)
~
Cl CAS-8
+
OI
c~f
-8 O + cAS-9
+
~:~~)
~
~~o
~~~+
~ V
+
["/~ Al] 0.3
without slag e) ~
~~~~
-12
C~oo
oo
o
~ Gustafss'on ~~ o [][] O
["/~ Si]
1 & Mellberg c\i []
-1O
[ppm Ca] + 251 [ppm OJ 50 ~ Ototani et al +
~~
~
(50 ~14
eo c~
-10 -8 -6 -4 -2 Q +
log
o 0.1 0.2 0.3 0.4 0.5
aca
2[% O] + 1.78[% AI]
Fig. 5.
Aplot forthe relation expressed by Eq.(14) inth range
of {[masso/. Ca] + 2.5 1[masso/o O]
} 0.005. Fig. 7. A plot for the retation expressed by Eq. (17).
j
where i and represent the components other than O
and Al, respectively. The values of eJj used in this study
-3
1873K are given in Table I
~
~1 ~> The authorsl5)
.
lower diagram in Fig. 7was drawn with the sameslope along with those for p~ and p~" given by Eqs. (3)
an~
of the line in the upper diagram. (4), respectively, are substituted into Eq. (A-1). Com-
The value for the equilibrium constant log K15 = 13.80, bining this result with Eq. (6), one obtains the follow-
which was obtained from the intercept of the line shown ing equation after arrangement.
in the lower diagram by using the data except one point
= (Mj/Mi)2ri + Mj/(2Mi)(r~" -
rj. r},j)
I
(2[masso/o O] + .78[masso/o Al]
= 0.425), agrees with the
previous value of 13.3~0.59 by the present authors.15) + Mj(Mi - Mj)/(200M?)eJ,i - Mj/(200Mi)(e - ; ej)
It
can be seen from Fig. 7
that the linearity becomes + (Mi- Mj)/(4.6 x 104Mi) ..............................(A-2)
better by considering the interaction between calcium
and oxygen, although the data points still scatter Since the fourth and the fifth terms in the right hand
significantly. side of Eq. (A-2) are negligibly small, Eq. (7) is deduced.
teraction parameters and the equilibrium constant for value as a function of and eJj,
By coupling with e; rj.
calcium deoxidation. The following conclusions are Eq. (6), one obtains the following relationship.
derived:
= - ei/lOO + 2(Mi/Mj)rj.
r~,i
(1) Based on the reciprocal and conversion relation-
ships with respect to the interaction parameters on mass +e /100+(M M)/(2 3x 104M) .......
(B-1)
percent and mole fraction scales, the relation between Since the third and the fourth terms in the right hand
the second-order interaction parameters ri and rj• was side of Eq. (B-1) are sufficiently small to be neglected,
derived. Furthermore, the value for rJj,i was expressed as Eq. (8) is deduced.
a function of other interaction parameters.
(2) By using previous equilibrium data, the values REFERENCES
1 K
for eg•, rg• and rg",o at 873 were obtained as -3 600, l) s. Kobayashi,Y. omori and K. Sanbongi: Trans. Iron Steel Insl.
5.7 x 105 and 2.9 x 106 in the range of {[masso/o Ca] + Jpn., Il (1971), 260.
2.51 [masso/o O]} and -990, 4.2 x 104 and 2.1 x 2) Y. Miyashita and K. Nishikawa: Tetsu-to-Hagan~, 57 (1971),
l05 in the range of {[masso/oCa]+2.51[masso/oO]} ;~ l 969 .
oxygen contents in calcium deoxidized liquid iron was 5) M, Nadifand C. Gatellier: Rev. Metallurgie-CIT, 83 1986), 377.
Q, Han, X. Zhang, D. Chenand P. Wang:Metal/. Trans. B, 19B
(
described by using the present values for the interac- 6)
(1988), 617.
tion parameters and equilibriurn constant.
7) M. Hillert andM. Selleby: Scand. J. Metall., 19 (1990), 23.
(4) By taking into consideratlon the first-order and 8) M. Tano, H Fujiwara and E. Ichise: Proc, the 8th Japan-Germany
the second-order interaction parameters between calci-
.