UDK 669.1:666.187:669.
787 ISSN 1580-2949
Izvirni znanstveni ~lanek MATER. TEHNOL. 35(3-4)105(2001)
V. GROZDANI]: REOXIDATION OF STEEL BY ADDING AN OVERCRITICAL CONCENTRATION OF DEOXIDIZER
REOXIDATION OF STEEL BY ADDING AN
OVERCRITICAL CONCENTRATION OF DEOXIDIZER
PONOVNA OKSIDACIJA JEKLA Z DODATKOM NADKRITI^NE
VSEBNOSTI DEOKSIDANTA
Vladimir Grozdani}
University of Zagreb, Metallurgical Faculty, Aleja narodnih heroja 3, 44103 Sisak, Croatia
Prejem rokopisa - received: 2000-09-20; sprejem za objavo - accepted for publication: 2001-06-16
At deoxidation of molten steel using silicon or aluminium appears an paradox. Namely, increasing concentration of deoxidizer
in the melt over some critical value results in increase of dissolved oxigen. Thermodynamical conditions for appearance of this
phenomenon has been discussed in detail.
Key words: deoxidation, reoxidation, deoxidiser content
Dezoksidacija staljenega jekla s silicijem ali aluminijem lahko privede do paradoksa. S pove~anjem vsebnosti dezoksidanta nad
neko kriti~no mejo se opa`a pove~anje vsebnosti raztopljenega kisika. Analizirani so termodinami~ni pogoji, ki privedejo do
tega pojava.
Klju~ne besede: dezoksidacija, reoksidacija, vsebnost dezoksidanta
1 INTRODUCTION So the deoxidation ability of silicon depends on its
concentration and the temperature of the metal, but also
Deoxidation is the removal of excess oxygen from on the activity aSiO2. At high temperature and the some
molten metal. The procedure involves adding materials value of [%Si], [%Mn] and [%C], its deoxidation ability
with a high affinity for oxygen, the oxides of which are is something smaller than that of carbon, but conside-
either gaseous or readily form slags 1. The deoxidation of rably higher than manganese.
steel is usually performed by adding Mn, Si and Al, or At some point during the increase in the concentra-
rarely by adding Cr, V, Ti, Zr and B. The deoxidation of tion of silicon in the Fe-Si melt the minimum concentra-
molten steel exhibits a paradox. By increasing the tion of oxygen [%O]min is obtained, any further increase
concentration of deoxidizer in the melt over some critical in [%Si] results in an increase of [%O]. At first sight this
value reoxidation of steel takes place. A few examples of suggests that the product of the activity coefficients
the reoxidation of steel by adding the usual deoxidizers (f0Si)2fSiSi decrease faster than the increase of [%Si]. The
(Si and Al) are examined in this paper. result of that is that, in agreement with the expression for
the equilibrium constant (2), the extreme value for the
2 REOXIDATION OF STEEL BY ADDING concentration of silicon [%Si]extr. corresponds to the
SILICON minimum concentration of [%O]min..
When calculating the critical value of [%O]min. and
Silicon is a strong deoxidizer. If [%Si] ≥ 0.2, [%C] ≤ [%Si]extr. it is necessary to express equation (2) in the
0.15, and the temperature of the melt is 1873 K the following way
allowing reaction is possible:
1 1 1
[Si] + 2[O] = ( SiO 2 ) (1) ln[%O] = ln a SiO 2 − ln K Si − O − ln[% Si] -
2 2 2
The equilibrium constant of the reaction (1) is 1
- ln f Si − ln f OSi
Si
(4)
a SiO 2 2
K Si − O = (2)
[% Si][%O] f Si f O2
2
The logarithms of the coefficients of activity are:
If the standard state is solid silica, then in the thermo- ln f OSi = 2.3 log f OSi = 2.3e OSi [% Si] (5)
dynamic calculation for the deoxidation of steel by
means of silicon aSiO2 is taken as being equal to one. ln f SiSi = 2.3 log f SiSi = 2.3e SiSi [% Si] (6)
According to Kramarov 2 if the slag is saturated with
silica then: and the interaction parameters are eOSi = -0.133 and eSiSi
1 31000 = 0.098. The interaction parameters eO0 and eSi0 are
log K Si − O = log = − 1215
. (3) neglected because the concentration of oxygen is
[% Si][%O] f Si f O
2 2 T
relatively small (log fOO ≈ 0, log fSiO = eSiO[%O] ≈ 0,
MATERIALI IN TEHNOLOGIJE 35 (2001) 3-4 105
V. GROZDANI]: REOXIDATION OF STEEL BY ADDING AN OVERCRITICAL CONCENTRATION OF DEOXIDIZER
and follows fOO ≈ 1 and fSiO ≈ 1), and the activity is very strong, and fO is <1. The equilibrium concentra-
aSiO2=1. tion of oxygen in the melt may be expressed with:
To obtain [%Si]extr. it is necessary to take the first 1
derivative of the concentration of oxygen divided by the [%O] = (13)
[ ] O Al
2 Al 3
concentration of silicon and set the equation equal to
3
% Al ( f ) K
zero under specific conditions:
An analysis of the equation (13) shows that at some
∂ ln[%O] 1 e Si increment of the concentration of aluminium the activity
=− − 2, 3 Si − 2, 3e OSi = 0 (7)
∂[% Si] 2[% Si] 2 factor fOAl decreases faster than [%Al]2/3 increases. The
result is that at some value of [%Al] the [%O]min. is
The second derivative is greater than zero: obtained. A further increase in [%Al] results in an
∂ 2 ln[%O] 1 increase of [%O].
=− >0 (8) To obtain [%Al]extr., the first derivative of the
∂[% Si] 2[% Si]
2 2
logarithm of the concentration of oxygen divided by the
Consequently, the function has a minimum. The concentration of aluminum must be set equal to zero:
concentration of silicon at which [%O] is a minimum: ∂ 2 ln[%O] 1
=− − 2.3e OAl = 0 (14)
1 ∂[% Al] 3[% Al]
[% Si]eksrt. = −2, 3e Si − 4,6e Si (9)
Si O
0.29
On the basis of the quoted value of the interaction [% Al] ekstr.
=−
e OAl
(15)
parameters for T=1873 K and aSiO2=1 [%Si]extr. a value of
2.59% is obtained. In that case fSiSi = 1.794 and fOSi = According to Kulikov 3, interaction parameter e0Al =
0.452. For steel melts there is also the influence of the -1.17, which corresponds to [%Al]extr. = 0.248. According
other elements on fSi and fO. At 1873 K the equilibrium to formula (13) the minimum concentration of oxygen
constant KSi-O = 25099. The minimum concentration of [%O]min = 1.35×10-4 % is obtained.
oxygen in the melt is:
1 4 CONCLUSION
[% Si]min = (10)
K Si [% Si] f SiSi ( f OSi ) 2
During the deoxidation of steel with common
By inserting reasonable values into equation (10) a deoxidizers, Si and Al, a paradox occurs. For a particular
minimum concentration of oxygen [%O]min = 6.5×10-3 % concentration of deoxidizer there exists a minimum
is obtained. concentration of oxygen dissolved in the steel which
increases with an increase in the concentration of the
deoxidizers. This is explained by the fact that in the
3 REOXIDATION OF STEEL BY ADDING equation for the equilibrium constant the factor of
ALUMINIUM activity decreases faster than the increment of the value
The deoxidation of steel by aluminum proceeds of the concentration of dissolved deoxidizer. For the
according to the reaction: deoxidation of steel with silicon the critical concen-
tration of Si is 2.59%, which corresponds to a minimum
2[ Al] + 3[O] = ( Al 2 O3 ) (11) concentration of oxygen of 6.5×10-3 %. In the case of
The equlibrium constant may be determined from: aluminum, the critical concentration of Al dissolved in
a Al2 O 3 the steel is 0.248%, which corresponds to a minimum
log K Al − O = log (12) concentration of oxygen of 1.35×10-4 %, under the
[% Al] [%O] f Al2 f O3
2 3
defined conditions (T=1873 K, aSiO2=1, aAl2O3=1,
neglected influence of other elements present in the
At 1873 K the equilibrium constant KAl-O = 4.9×1013. melt).
In the calculation it is assumed that aAl2O3 = 1, because at
a small value of [%Al] (0.001-0.01) the equlibrium
concentration (%FeO) in the slag is neglected, so the 5 REFERENCES
products of deoxidation are solid Al2O3 or an oxide 1
D. C. Gould, AFS Metalcasting Dictionary, American Foundrymen’s
phase saturated with aluminia. The coefficient of activity Society, Des Plaines, 1968.
of aluminum f Al = f AlAl f AlO ≈ 1, and the coefficient of 2
A. D. Kramarov, A. N. Sokolov, Elektrometallurgija stalji i ferro-
oxygen f O = f OO f OAl ≈ f OAl , which is an approximation, splavov, Metallurgija, Moskva, 1976.
because the influence of the other elements present on fO 3
I. S. Kulikov, Raskislenije metallov, Metalurgija, Moskva, 1975.
106 MATERIALI IN TEHNOLOGIJE 35 (2001) 3-4
