Process metallurgy

Thermodynamic assessment of the AI deoxidation reaction in liquid iron

Jeong-Do Seo, Seon-Hyo Kim and Kwang-Ro Lee

The deoxidation reaction of aluminum in liquid iron has been investigated thermodynamically using Ab03 crucible at 1873 K under Ar
atmosphere as a fundamental study for the accurate control of inclusions in the ladle refining process. In addition to the equilibrium con-
stant log KAI f0t. the aluminum deoxidation reaction, the first-order and second-order interaction parameters between aluminum and oxy-
gen were experimentally determined in the concentration range of aluminum up to 1 %. The temperature dependence of the equilibrium
constant and the first-order interaction parameter eti was also obtained: log KAI =12.32 - 474001T, e~l =15.57 - 365001T.
The equilibrium relation between aluminum and oxygen contents in the aluminum deoxidized iron by applying interaction parameters and
the equilibrium constant determined in this work satisfies fairly well the equilibrium data over the whole concentration range of aluminum
considered.

Thermodynamlsche Bewertung der AI·Desoxldatlonsreaktlon In Eisenschmeizen. Die Desoxidationsreaktion mit Aluminium in

Eisenschmelzen wurde thermodynamisch untersucht. Grundlegende Studien in einem Ab03- Tiegel bei 1873 K in Ar-Atmosphara sollten
Erkenntnisse iiber die EinschluBkontrolle wahrend der Pfannenbehandlung Iiefem. Erganzend zur Gleichgewichtskonstanten fOr die
Aluminiumdesoxidation, log KAl' wurden auch die Wechse!wirkungsparameter erster und zweiter Ordnung von Aluminiumund Sauerstoff
fUr Aluminiumkonzentrationen bis zu 1% experimentell ermittelt. Die Temperaturabhangigkeit der Gleichgewichtskonstanten und des
Wechselwirkungsparameters erster Ordnung, eti ' lieB sich zu log KAI
. = 12.32 - 474001T, .eti = 15.57 - 36500fTbestimmen.
Die Gleichgewict:ltsbeziehung zwischen Aluminium- und Sauerstoffgehalten in AI-desoxidierten Eisenschmelzen, die mit diesen Wech-
selwirkungsparametern bzw. Gleichgewichtskonstanten bestimmt wurden, geniigt den Gleichgewichtswerten iiber dem gesamten, be-
trachteten Aluminiumkonzentrationsbereich gut.

Aluminum is commonly used as a strong deoxidizer in Experimental

steelmaking process. Its utilization as a deoxidizer, how-
ever, is somewhat limited due to the formation of AI-
related inclusions in liquid iron. When the aluminum con-
taining steels are tapped into the cast mould through the
refractory nozzle, the build-up of non-metallic oxides such
as Ah03 and MgO·Ah03 in the nozzle leads to a break-
down of the whole casting system. Therefore the control of
non-metallic inclusions in the refining stage is of great
importance to produce high-quality clean steels economi-
cally. The reliable thermodynamic data .of aluminum de-
oxidation equilibria should be established to control effi-
ciently the formation of non-metallic inclusions associated
with aluminum. Despite the extensively performed previ-
ous works [1...14] on the aluminum deoxidation equilibria,
some uncertainty still exists on the equilibrium data. Most
works have been carried out over the narrow range of very
low aluminum concentrations' at 1873 K. Furthermore, the
thermodynamic data previously reported are very incon-
sistent according to the aluminum concentration range
considered.
In this work, the limitation of validity for the first-order
interaction parameter between aluminum and oxygen in
iron was investigated at 1873 K under the aluminum con-
centration range up to 1 %. Not only the first-order and the
second-order interaction parameters between aluminum
and oxygen but the equilibrium constant for aluminum
deoxidation reaction was estimated at 1873 K by a multi-
ple regression method using the published data and the
present experimental results. The validity of these values
was also discussed.
Jeong-Do Seo, graduate student; Professor Seon-Hyo Kim; Dr. Kwang-
Ro Lee, research assistant, Materials Science and Engineering, Pohang
University of Science and Technology, Pohang, Korea.
The equilibrium study was carried out at 1873 K in a
LaCr03 resistance furnace equipped with a fused alumina
tube with a diameter of 50 mm. The tube was sealed at
both ends with water cooled metal sections. The tempera-
ture was measured by a thermocouple of PtRh6/PtRh30
controlled with an accuracy of 2 K. Argon gas was flown
after purifying through H2S04, P20S, Mg(CI04)2 and a
bed of Ti-granules at 650°C.
High-purity electrolytic iron ([%0] = 0.0035, [%AI] =
0.0003, [%C] = 0.001, [%Si] < 0.001) of 40 g was initially
melted in the Al203 crucible (026x55H) under a deoxi-
dized Ar atmosphere. An appropriate amount of Fe-20%AI
was added into the iron melt. The melt was stirred for
about 2 h by an Ah03 rod at 30 min intervals in order to
facilitate the deoxidation reaction. To eliminate oxide
inclusions by flotation the melt was maintained under
unstirring condition for at least 1 h. After reaching equili-
bration, the crucible was taken out of the furnace and
quenched rapidly in a He gas stream, followed by water
quenching. The quenched sample was sliced into a plate
shape and then sectioned to small pieces for oxygen and
aluminum analysis.
The total oxygen content of a sample was determined by
a method of inert-gas fusion-infrared absorptiometry. In
the case of oxygen analysis of the samples containing a
significant amount of aluminum, it is recognized that the
vaporized aluminum from the sample reacts with CO gas
to form the AhO vapour which condenses at lower tem-
peratures. This phenomenon results in the analytical error
of real oxygen contents. In order to eliminate these ana-
lytical shortcomings, the Sn bath-Ni capsule method cou-
pled with the double graphite crucibles was employed for
the samples containing more than 0.3 % aluminum. The

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Process metallurgy

analytical method relating to the soluble- or insoluble- Table 1. Chemical composition of metal employed in this work
aluminum concentrations in metal was described in detail Aluminum mass contents in % oxygen mass contents in %
elsewhere [9]. The soluble- and insoluble-aluminum solu- 0,0002 0.0110
tions were prepared individually and then mixed together 0.0875 0.0014
in a 50 ml mass flask in order to determine the total alumi- 0.1300 0.0008
num content in a mixed solution by the inductively cou- 0.2056 0.0007
pled plasma emission spectrometry. 0.2674 0.0008
0.3146 0.0008
Results and discussion 0.3728 0.0018
0.7207 0.0017
The deoxidation reaction for aluminum is expressed by 0.9873 0.0011

Ah03 (s) = 2 [AI] + 3 [0] (1)

Table 2. The previously reported values of interaction parameters
The equilibrium constant, KAI of reaction (l), the appar- between aluminum and oxygen and equilibrium constant of alumi-
num deoxidation reaction at 1873 K
ent equilibrium constant, K~l (= [%AI]2 • [%0]3) and the
AI AI logKAl references
activity coefficient of component i, Ii in liquid iron with eo ro
respect to I % Henrian standard state are correlated as a -4.60 - -13.90 [I]
form of following equation: -1.00 - - [3]
-3.90 - -13.25 [6]
log KAI = 2 10gfAI + 3 logfo + log K~I - log a AIz03 -5.25 - -13.22 [8]
-4.05 - -13.30 [II]
.
= log K~I + 2 (e1\[%i] + e~d%O] + r1\[%Al]2 -5.54 -14.01 [12]
-3.90 1.70 -13.30 [16]
+ r~1 [%0]2 + r~IAI [%O][%AID + 3 (eg [%0]
+ e~1 [%Al] + r~1 [%Al]2 + rg [%0]2 = -e~l {3[%AI] + 2(MAl/Mo)[%0]} - r~l {3[%AI]
+ rg· AI [%O][%Al] ) + 2 ~ (e~1 [%i] + r~ [%i]2 + 2(MAI / Mo)[%O] }2 + r~1 {6[%AI]2 + 2[%0]2
t.]

+ 2(MAl/Mo)[%0][%AI]} + log KAI. (4)

+ r~tl [%i][%Al] + r~{ [%i][%jD
The equilibrium chemical compositions of metal are
+ 3 ~ (eb [%i] + rb [%i]2 + r~o [%i][%O]
t.] given in table 1. The experimental equilibrium data be-
(2) tween aluminum and oxygen at 1873 K are plotted in fig-
+ r& [%i][%jD - log a AIz03
ure 1. In order to have I % Henrian standard state applied,
where i and j represent the components other than oxygen the data selection was only limited to the aluminum con-
and aluminum, respectively. [%i] represents mass content centrations up to 1 %.
of component i. If the second-order interaction parameter terms between
The aluminum deoxidation equilibrium can be finally aluminum and oxygen become abbreviated in equation (4),
written as equation (3) according to the relationship de- the following simplified equation can be expressed:
rived by Lupis et al. [15]:

log KAj - log K~I - 2 ~

, (e~1 [%i] + ell [%Al] 3.5 ....-....---.---.----.-..---r--.--..,.-r--~-..-.....,
3.0
+ r~1 [%i]2) - 3 ~ (e6 [o/oj] + eg [%0] 2.5
]
2.0
+ r6 [o/oj]2) + log a AIZ03 = e~1 {3[%AI]
5' 1.5
+ 2( MAI/Mo )[%O]} + r~1 {3[%AI]2 S.
.!::lI 1.0
+ 2(MAI/Mo)2[%0]2 + IO(MAI/Mo)[%O][%AI]} (3) J 0.5

where M is the atomic mass fraction of the respective

0.0 •
0
PnlIIent
Fruehan[6]
component. -0.5 [] Rhodo[7]
-1.0 A Dimi1rov [12]
Equation (3) can be rearranged as:
0 Suito [9] 1873K
-1.5
log K~I + 2 L, (e~1 [%i] + e11 [%AI] -2.0 L -..........L...--'---L---I_.l.-..a-...I-..........--L---'...........
-5 -4 -3 -2 -I o 1
+ r~1 [%i]2) + 3 L (e6 [o/oj] + eg [%0] log[%Al]
]

Figure 1. Experimental data of aluminum and oxygen equilibrated

+ r6 [o/oj]2) - log a AIZ03 in liquid iron at 1873 K

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Process metallurgy

log K~l + 2 L (e~l [%i] + e~1 [%Al]

-5 .----.---,.-~--.---.--_r_-~___,
i
+ r~l [%i]2) + 3 L (e6 [%i] + eg [%0]
o j

+ r6 [o/'!i]2) - log aAl203

+ = - e~l {3[%AI] + 2 (MAl/Mo)[%O])}
;!:, g + log KAI. (5)
l es - Calculated
-J o~ • Present
'-' + -15 o FruebaD The relation between the left-hand-side (LHS) of equa-
':;: o tion (5) and 3[%AI] + 3.37[%0] term in the right-hand-
w-es Rhode
N
+
·....0
..
A
<>
Dimitrov
Suito
side is plotted in figure 2 using the values of e~:, eg
:J H~ -20 I...-~_--L --'-_--,-_-'-_"""'----'
along with the contents of aluminum, oxygen, and the
other components from the present experimental results
J ~ 0 234
and previously reported data. A non-linear relationship
3[o/oAI] + 3.37[%0]
exists with an intercept value of log KAI. This result indi-
Figure 2. The relation between the LHS of equation (5) and
cates that the equilibrium between aluminum and oxygen
3[%AI]+3.37[%O] term
in liquid iron can not be explained only by first-order in-
teraction parameters given in the table 2 without consid-
ering the higher order interaction parameters. The interac-
5r----.---,.---.---.---.--...--~___, tion parameters e~l, r~1 and log KAI could be estimated
using equation (3) by a multiple regression analysis as
o follows:
+ log KAI = -12.96 ± 0.14,
':I-. -5
~
.;::
~ -10 e~1 = -4.09 ± 0.41, r~l = 2.67 ± 0.47,
- Calculated

~ • Present
... -15 o FruebaD e~l = -6.90 ± 0.69, r~l = 7.60 ± 1.34,
+ C Rhode

~...
~
-20
A
<>
Dimitrov
Suito r~l,O (r~I'o) = 9.05 ± 1.59 (9.05 ± 1.59). (6)

2 3 4 The curved line indicated in figure 2 was obtained from

3[o/oAl] + 3.37[%0] equation (4) using the values of the equilibrium constant
and interaction parameters obtained in this work.
Figure 3. Relation between the LHS otequatlon (5) plus the sec-
Transferring the second-order interaction parameter
ond-order interaction parameterterms and 3[%AI]+3.37[%O] term
terms in equation (4) to the LHS, the relation between the
LHS and 3[%AI] + 3.37[%0] terms is then reasonably
plotted as a straight line in figure 3. The line is well satis-
fied with the reported data and present experimental results
0 over the concentration range considered.
The relation between aAI(obs) and aAl(cal) is shown in
figure 4. The values of aAI(obs) were determined directly
-1
"......
from the contents of solutes using the available values of
'"
'8 various interaction parameters. On the other hand, the
'-' -2 values of aAI(cal) were calculated from equation (7) using
~ the equilibrium constant and the values of a Al203 and ao
OIl
.s -3 •
0
Present
Fruehan determined in this work:
0 Rhode
/1 Dimitrov
-4 log KAI + log a Al203 - 3 log ao = 2 log aAI (7)
e Suito

-5 Il::.-""---L.......... _ _- - '
--JL....-..i..-...J....--'-~_"----....L.-
where ao and aAI denote the activities of oxygen and alu-
-5 -4 -3 -2 -1 0 minum in liquid iron relevant to the 1 % Henrian standard
log aAl (cal) state, respectively. It can be seen from figure 4 that the
corresponding values of aAI(obs) and aAI(cal) are reasona-
Figure 4. Plotofthe relation between aAI(obs) determined directly
from the contents of solutes as well as the available values of bly in good agreement with each other. This result implies
various interaction parametersand aAI(cal) determined from equa- that the values of interaction parameters experimentally
tion (7) estimated in this work seem to be reliable.

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Process metallurgy

function of temperature can be derived:

Dca
-2
0.2 0.4 0.6
[o/oAl]
Figure 5. Plot of the logarithmic activitycoefficient of oxygen as a
function of aluminum contentin liquid iron
The activity coefficient of oxygen, fa is plotted as a
function of aluminum concentration in figure 5. The val-
ues of log fa show a linear relationship up to 0.2 % AI.
This result indicates that the consideration of first-order
interaction parameters for the activity calculation could be
only valid in the concentration region of [%AI] < 0.2 %,
where the effect of second-order interaction parameter
terms could be negligible. However, at higher aluminum
concentrations the log fa is no longer a linear function of
aluminum content and the effect of second-order interac-
tion parameters on the activity becomes more significant.
The determination of temperature dependence of the
equilibrium constant, log KAI for the deoxidation reaction
and the first-order interaction parameter, e~1 is graphi-
cally shown in figures 6 and 7 used only for the previ-
ously reported data and present result, respectively. In
those figures the relatively low-to-high range of aluminum
concentrations "{ere adapted from the reported data. From
the slope and intercept values in figures 6 and 7, the equi-
librium constant and first-order interaction parameter as a
•
0
Present
Fruehan
log KAI = 12.32 - 474001T, (8)
D Rhode
eoAl = 15.57 - 365001T. (9)
A Dimitrov
0 Suito
The values of log KAt and e~t at 1873 K are found to be
-12.99 and -3.92, respectively. The fact that these values
• obtained from equations (8) and (9) agree well with those
determined earlier using equation (3) confirms the validity
of equations (8) and (9).
The equilibrium relations between aluminum and oxy-
gen contents are shown in figure 8, which were calculated
from equation (2) by the iterative method with interaction
0.8 1.0 1.2 parameters and equilibrium constants. It is shown in this
figure that most of the calculated lines from the results of
other investigators [6; 8; 11; 12] who only considered first-
order interaction parameters seem to be generally incon-
sistent with the experimental data. The calculated line for
the results of Sigworth et al. [16] who considered first- and
second-order interaction parameters fits the experimental
data more closely, but seems to deviate largely from the
data at the high aluminum concentration range of 0.2 <
[%AI] < 1 %. However, the calculated line taking into
consideration interaction parameters and equilibrium con-
stant determined in this work satisfies fairly well the equi-
librium data over the whole concentration range consid-
ered. This finding also assumes that equation (6) represents
the convincing values of equilibrium constant and interac-
tion parameters.
Conclusions
The deoxidation reaction of aluminium in liquid iron
was assessed thermodynamically at 1873K using the pre-
viously reported data and present experimental results. The
equilibrium constant, KAt for the aluminum deoxidation
reaction and the values of first- and second-order interac-
tion parameters between aluminum and oxygen in liquid
iron were derived by a multiple regression method as fol-
lows:

-6

-7 •
0
Present
FIUeban 0 •
0
Present
FlUeban
-8 D d'Entremont [31 D d'Entremont
D
-I D
A McLean [I] A McLean
-9
0 Kobayashi [5] 0 K.obayashi
D -
-10 v Swisher [4] -2
:(
ll< <0
CU
l'>O -11 -3 e
.!a
-12
-4
-13
log K AI - 12.32 - 47,400rr -5 e~ = 15.57 - 36,500IT
-14
-15 L -........-L-.........---I_"--....L...-..........- - ' - - - - " _ L -.........-1 ·6
4.4 4.6 4.8 5.0 5.2 5.4 5.6 4.4 4.6 4.8 5.0 5.2 5.4 5.6
Iff (x 10 4
) Iff (x 10~
Figure 6. Temperature dependence of equilibrium constants for Figure 7. Temperature dependence of first-order interaction para-
the aluminum deoxidation reaction metersbetween aluminum anq oxygen in liquid iron

52 steel research 69 (1998) No.2

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Process metallurgy

3.0 log KAI = 12.32 - 474001T,

alolp, =1
2.5 Al
eo = 15.57 - 365001T.
2.0 ./
1.5 The equilibrium relation between aluminum and oxygen
~ 1.0
contents in the aluminum deoxidized iron could be ther-
o modynamically well described over the concentration
j; 0.5
o range up to 1 % with the first- and second-order interaction

== l
Experimental data
DO 0.0 parameters as well as the equilibrium constant determined
..s -0.5 in this work .
....... .Dimitrov Calculated
-1.0 (A 01337; received: 05. August 1997)
-_._.- Coo [lIJ values
-1.5 --- Gustafsson [8J References
-2.0 - - Sigworlh [16]
-2.5 l.-.-I----"_....L..---o-_.L.-.-I-----I_-'----I.._.........--' [I] McLean, A.; Bel/, H B.: 1. Iron and Steel Inst, 203 (1965), p.
-4 -3 -2 -1 0 123/30.
[2] Mcl.ean, A.; Ward, R. G.: J. Iron and Steel Inst. 204 (1966), p.
log[o/oAl]
8111.
Figure 8. Comparison of experimental data with thermodynami- [3] d'Entremont, J. C: Guernsey, D. 1.; Chipman, J.: Trans. Met Soc.
cally calculated relation between aluminum and oxygen contents AIME 227 (1963), p. 14/17.
for the equilibrated liquid iron at 1873 K [4] Swisher. J. H: Trans. Met Soc. AIME 239 (1967), p. 123/24.
[5] Kobayashi, K; Omori. Y.; Sanbongi, K: Tetsu-to-Hagane 53
(1967), p. 141/44.
log KAI = -12.96 ± 0.14, [6] Fruehan, R. J.: Metallurg. Trans. I (1970), p. 3403/10.
[7] Rhode, 1. E.; Choudhury. A.; Wahlster, M.: Arch. Eisenhiittenwes.
42 (1971), p. 165/74.
e~1 = -4.09 ± 0.41, r~1 = 2.67 ± 0.47, [8] Gustafsson, s, Mel/berg. r-o.. Scand. J. Metall. 9 (1980), p.
111/16.
[9] Suito, H; Inoue. H; Inoue. R.: ISH Int. 31 (1991), p. 1381/88.
e~1 = -6.90 ± 0.69, r~1 = 7.60 ± 1.34, [10] Holcomb, G. R.; St. Pierre, G. R.: Metallurg. Trans. 23B (1992), p.
789/90.
[II] Cho, S. w.; Suito, H: ISH Int. 34 (1994), p. 177/85.
r~I,O (r11'0) = 9.05 ± 1.59 (9.05 ± 1.59). [12] Dimitrov, S.; Weyl. A.; Janke. D.: steel res. 66 (1995), p. 3/7.
[13] St. Pierre, G. R.: Metallurg. Trans. 8B (1977), p. 215/17.
The temperature dependence of the equilibrium constant [14] Steelmaking Data Source Book, rev. edn. Jap. Soc. Promot. Sci.,
Gordon and Beach Sci. Pub!., New York/London/ParisIMon-
and the first-order interaction parameter, e~1 by using treaux/Tokyo/Melboume, 1988, p. 45/53.
previously reported data and present results were also [15] Lupis, C. H P.; Elliott. 1. F.: Acta Metal!. 14 (1966), p. 529/38.
obtained: [16] Sigworth, G. K; Elliott. J. F.: Metal, Sci. 8 (1974), p.298/310.

steel research 69 (1998) NO.2 53