Trans. Indian Inst. Met.

TP 2245
Vol.61, No. 6, December 2008, pp. 473-475

Calcium Treatment Of Liquid Steel –

Assessment Of Deoxidation Constant
Ahindra Ghosh
Formerly with the Department of Materials and Metallurgical Engineering
Indian Institute of Technology, Kanpur 208016, India
E-mail : ahindra258@yahoo.co.in
(Received 1 August 2007 ; in revised form 6 June 2008)

Although assessed value has been employed in some of our

ABSTRACT thermodynamic analyses work2,3 and reported in reviews4,5
and brief mentions were made, but the assessment procedure
Calcium treatment of liquid steel is practised for better product has not yet been elaborated in any publication.
quality and prevention of nozzle-clogging. Calcium is a powerful
deoxidizer and desulphurizer. Several studies have been 2. THERMODYNAMICS OF DEOXIDATION
reported in literature on thermodynamics of reactions of calcium REACTIONS
upon addition into liquid steel. These have been either
experimental measurements or theoretical analyses or both. Upon addition of a deoxidizer (Mn, Si, Al, Ca etc.) to liquid
The present author and his co-workers have done some steel in ladle during secondary steelmaking, or in the finishing
thermodynamic analyses and calculations for deoxidation of stage of an Electric Furnace bath, the deoxidizer reacts with
steel by some deoxidizers, including calcium. An important oxygen, as represented by the following generalized
component of any work involving thermodynamics, is reaction.
assessment of literature data for selection of reliable values
of the same. This paper reports the assessment exercise, x[M] + y [O] = (MxOy) (1)
carried out by the present author on deoxidation constant for
calcium. where, [M] and [O] denote deoxidizer and oxygen dissolved
in molten steel, and (MxOy) is the oxide product (i.e. the
inclusion, if you so wish).
1. INTRODUCTION
The equilibrium relation for reaction (1) is:
Calcium treatment of liquid steel started for prevention of
nozzle clogging in aluminium-killed plain carbon steels. Now-
a-days, it is done extensively also for inclusion modification
(
­° a M x O y ½°
K 'M = ®
)
¾
to improve properties of the product. Calcium is a powerful °̄ [h M ]x [h O ]y °¿ eq (2)
deoxidizer and desulphurizer. Thermodynamics is the principal
theoretical tool for prediction and control of calcium addition.
Therefore large number of studies have been carried out on where K′M is equilibrium constant. aMxOy is activity of MxOy
thermodynamics of deoxidation and desulphurization of liquid in Raoultian standard state. hM, hO are activities of dissolved
steel by calcium. M and O respectively in molten steel in 1 wt.pct. standard
state.
From time-to-time, the present author and his co-workers
carried out experimental and theoretical investigations of If the deoxidation product is pure (Al2O3, SiO2 etc.), then
deoxidation of liquid steel, where thermodynamic analyses aMxOy= 1. Again,
constituted a part of the program. Thermodynamic
calculations require reliable experimental thermodynamic data. hM = fM.WM, hO = fO.WO (3)
For deoxidation by a single deoxidizer (simple deoxidation),
these data are deoxidation constant (KM),where M is symbol where W is wt. pct., and f is activity coefficient. For very
for the deoxidizer, and interaction coefficients (e i j ) of dilute solution, fM = 1, fO = 1, i.e. hM = WM, hO = WO.
concerned solutes dissolved in liquid steel. Often, it
required fairly elaborate assessment exercises for selection Combining the above,
of reliable data. For an idea of the kind of activities undertaken
for this, the paper by Ghosh and Murthy1 may be referred 1
to. [WM]x [WO]y = =KM = deoxidation constant (4)
K 'M
There have been large discrepancies amongst investigators
for strong deoxidizers (e.g. Al, Ti, Zr, V, Ce, Ca etc.). For some Deoxidation constant varies with temperature as:
of these, such as Al, through several experimental
measurements and assessment exercises, discrepancies have,
A
by and large, been resolved, and we have fairly reliable log KM = - +B (5)
values of KM and ei j. However, for calcium deoxidation, T
confusions and controversies still exist, although there have
been some convergence of views. The present paper reports where T is temperature in Kelvin, A and B are empirical
critical assessment of KM for calcium (i.e. KCa). constants.
474 l Ahindra Ghosh : Calcium treatment of liquid steel – assessment of deoxidation constant

3. THERMOCHEMICAL ESTIMATION OF (1) 10 to 30 kJmol-1 error in compiled thermodynamic tables

K Ca for standard free energy of formation of CaO 10

Ghosh and Naik2 carried out thermodynamic modelling for (2) Some uncertainty in free energy of dissolution of
deoxidation of liquid steel by Ca-Si-Al and Mg-Si-Al. Since calcium in liquid iron9.
these are complex deoxidizers, and the deoxidation products
M
are oxide solutions of CaO, SiO2, Al2O3 and MgO, additional 4. DETERMINATION OF KM AND e O FROM
data were required on activity- composition relationships in EXPERIMENTAL DATA OF DEOXIDATION
oxide solutions. But we are not concerned about this in the EQUILIBRIUM
present paper. The deoxidation constant for calcium was
calculated with the help of thermochemical data taken from From Eqs.(2 and (3), for pure oxide as the deoxidation
compilations by Elliott et al6,7, as follows. product, the general definition of K M is :

Ca (g) + ½O2 (g) = CaO (s) (6) [hM]x x [hO]y = KM (10)

ΔG60 = -7.867 x 105 + 191.35 T Jmol-1 i.e. log KM = x log hM + y log hO

M .W + eO .W ]
= x [ log WM + eM
½O2 (g) = [O] wt % (7) M M O
+ y [ log WO + eM O
O .WM + e O .WO] (11)
ΔG70 = -117230 - 2.89 T Jmol-1

Ca (g) = [Ca] wt % (8) Rearrangement of Eq.(11) yields :

ΔG80 = -39481 + 49.4 T Jmol-1 log KM – x log WM – y log WO - WO [y eOO + x eO

M]

Combination of Eqs.(6), (7) and (8) yielded

′′ = y eMO .WM + x eMM .WM
= log K M
= WM [ y eM M
O + x eM ] (12)
CaO (s) = [Ca]wt% + [O]wt% (9)
″ is ‘Apparent’ deoxidation constant.
Where, KM
ΔG90 = 6.3 x 105 - 144.84 T Jmol-1

As per convention, it is understood that the values of ΔG0 Experimental measurements of deoxidation equilibria in Fe-
correspond to free energy changes for standard states of M-O ternary system yield values of [W M ] and [W O] at
reactants and products. From Eq.(9), equilibrium with the oxide M xO y at the temperature of
measurement. The results are plotted as log KM″ vs. WM at
constant temperature. From measurements on binary Fe-M
ΔG90 32903 and Fe-O solutions, values of eMM and e O are known. e O is
log KCa = − =− + 7.56 (10) M
related to eO
O M
. Therefore, from experimental data, K M and
2.303RT T M
eO can be determined on the basis of Eq.(12).
Equation (10) gives a value of KCa = 9.84 x 10-11 at 1600oC
If Eq.(12) gives a straight line, then eM
O can be determined
(i.e. 1873 K), which is traditionally taken as normal
from the slope, and is intercept at [WM ]→0 .If it is a curved
steelmaking temperature in steelmaking thermodynamics.
line, then the limiting slope is to be found out, since, by
M
Values of interaction coefficients related to calcium definition, eO is mathematically rigorous at [WM ]→0 .
deoxidation were hardly available, and hence these were
For pure oxide product, the most popular is to plot log [WO]
assumed to be zero.
as function of log [WM]. If all interactions are ignored, then
Table 1 presents some thermochemical estimates of KCa at Eq.(4) is applicable, and it can be rewritten as :
1873 K.
log [WO] = log KM - log [WM] (13)
Table 1
which gives a straight line. Figure 1 shows such plots for
Thermochemical estimates of KCa at 1873K from different
some deoxidizers 1,4. Although the lines are approximately
sources
straight at low wt % [M], these are basically non-linear. Such
non-linearity is due to interaction between dissolved
Source (Year) K Ca x 1011
deoxidizer and dissolved oxygen in liquid iron.
Ghosh and Naik2 (1983) 9.84
Kulikov 8 (1985) 9.3
As Figure1 shows that the curves exhibit minima. More
powerful is the deoxidizer, more the minima shifts towards
Japan Society Compilation9 (1984) 11.0 lower concentration of M. This has been ascribed to large
Turkdogan10 (1991) 4.6 negative values of eMO . More powerful is the deoxidizer, more
M
negative is eO . St.Pierre et al11 and some others carried out
mathematical analyses, and demonstrated it quantitatively.
While the first three values in Table 1 are fairly close, the last
one is about half of the others. Possible sources of
However, for strong deoxidizers ( Al, Ti, Zr, V, Ca, Ce etc.),
discrepancy are :
concentrations of dissolved oxygen and deoxidizer element

Trans. Indian Inst. Met., Vol. 61, No. 6, December 2008

 Ahindra Ghosh : Calcium treatment of liquid steel – assessment of deoxidation constant | 475
at equilibrium with the deoxidation product are very low. This
poses the following problems, viz.
(1) large errors in chemical analyses of dissolved O and M
(2) difficulty of attainment of equilibrium in reasonable time
after addition of deoxidizer
(3) reaction of the dissolved deoxidizer with the crucible
and consequent difficulty of attainment of stable
equilibrium.
Therefore, the plots of log KM ″ vs.[WM], or, log [WO] vs. log
[W M ] are characterized by large scatters. Hence, the
M Ca
procedure for estimation of KM and eO from experimental
data called for mathematical modelling involving computer-
oriented numerical methods. Ghosh and Murthy1 used all
data sets of the plots of log KM ″ vs. [WM] for this purpose,
for deoxidation by Cr, Al, Ti, V, and Zr. They included the
M
second –order interaction coefficient (rO ) as well. Then the
M M
estimated best-fit values of KM, eO and rO were employed
for construction of best-fit curves of log [WO] vs. log [WM].
Figure 1 shows the curves.
There have been some other experimental work and
theoretical analyses by other investigators. A recent one is
by Jung et al 12 . Ghosh and Murthy also recommended
analytical equation for easy calculations1,4, as follows.
M
log KM = x(logWM + eM .WM)
M 2
+ y(logWO + eOM.WM + rO .WM ) (14)
The above exercises have been able to standardize values of
M Eq.(10), seems to be fairly all right.
KM and eO for some strong deoxidizers, such as aluminium.
However, the situation with respect to calcium deoxidation is
not yet satisfactory, because Ca is a much more powerful
deoxidizer, as compared to, for example, Al. Therefore, the
concentrations of dissolved Ca and O in liquid iron at
equilibrium with CaO are extremely low, thus making chemical
Fig. 1 : Some deoxidation equilibria in liquid iron at 1873 K1,4
analyses very difficult and unreliable. This is being further
elaborated in the next section.
5. DISCREPANCIES IN VALUES OF KCa AND
e OCa FROM EXPERIMENTAL
MEASUREMENTS OF DEOXIDATION
EQUILIBRIUM FOR CALCIUM
There have been several published papers, reporting values
of e OCa and K Ca , extracted from experimental results of
deoxidation equilibrium for calcium in liquid iron. The
findings of several studies have been reviewed in some
publications9,13 . At 1873 K, the value of KCa, reported by
various investigators ranged from 10-5 to 10-10 approximately,
and those for eO were also found to vary over a very wide
range, from -60 to -9000. These clearly demonstrate
unreliability of the above.
Therefore, although the present paper is concerned with
calcium deoxidation, the curve for calcium cannot be included
in Figure 1 because thermochemical estimates have been
considered as reliable for KCa, and interaction coefficients
have been ignored ( see Sec.3), and hence Eq.(4) is applicable
for this. Therefore, Figure 1 only provides illustration of kind
of results we obtain for deoxidizers from experimental
M
determination of KM and eO , and application of Eq.(14).
6. CONCLUSIONS
• Only thermochemical estimation of deoxidation constant
for calcium deoxidation of liquid steel is reliable.
• The log KCa versus temperature relationship, estimated
by Ghosh and Naik 2 from thermochemical data, i.e.
• In view of large uncertainty in eCa O , and likely in other
interaction coefficients involving dissolved calcium in
liquid steel, it is desirable to ignore all interactions, as
done by Ghosh et al2, and use Eq.(4) as the basis of
calculation.
REFERENCES
1. Ghosh A, Murthy G V R, Trans Iron and Steel Inst. Japan, 26
(1986) 629.
2. Ghosh A, Naik V, Tool & Alloy Steels, 17 (1983) 239.
3. Choudhary S K, Chandra S, Ghosh A, Tata Search (2002) 95.
4. Ghosh A, Secondary Steelmaking – Principles and Applications,
CRC Press, Boca Raton, Florida, USA (2000) Ch.5.
5. Ghosh A, Trans Indian Inst. Met., 59 (2006) 635.
6. Elliott J F, Gleiser M, Thermochemistry for Steelmaking, vol.1,
Addision – Wesley Publishing Co., Reading, Mass, USA (1960).
7. Sigworth G K, Elliott J F, Metal Science, 8 (1974) 298.
8. Kulikov I S, Izv.Akad.Nauk SSSR. Met., 6 (1985) 9.
9. The Japan Soc. For The Promotion of Science, The 19 th
Committee on Steelmaking, Steelmaking Data Sourcebook,
(revised ed.), Gordon and Breach Science Publishers, New York,
(1986) 79.
10. Turkdogan E T, Steel Research, 62 (1991) 379.
11. St.Pierre G R, Blackburn R D, Trans. Met. Soc. AIME, 242
(1968) 2.
12. Jung I, Decterov S A, Pelton A D, Met. and Mat.Trans B, 35B
(2004) 493.
13. Kimura T, Suito H, Met. and Mat. Trans B, 25B (1994) 33.
Trans. Indian Inst. Met., Vol. 61, No. 6, December 2008