Deoxidation of
steel
The main sources of Oxygen in steel
are as follows:
•Oxygen blowing (example: Basic Oxygen Furnace);
•Oxidizing slags used in steel making processes(example: Electric
Arc Furnace
•Atmospheric oxygen dissolving in liquid steel during pouring
operation.
•Oxidizing refractories (lining of furnaces and ladles);
•Rusted and wet scrap
Solubility of oxygen in steel
Solubility of oxygen in molten steel is 0.23% at 1700°C. However it decreases
during cooling down and then drops sharply in Solidification reaching 0.003%
in solid steel.
Oxygen liberated from the solid solution oxidizes the steel components (C,
Fe, alloying elements) forming gas pores, blowholes and non-metallic
inclusion entrapped within the ingot structure. Both blowholes and inclusions
adversely affect the steel quality.
In order to prevent oxidizing of steel components during solidification the
oxygen content should be reduced.
Deoxidation classification
Deoxidation of steel is a steel making technological operation, in which
concentration (activity) of oxygen dissolved in molten steel is reduced to a
required level.
There are three principal deoxidation methods:
•Deoxidation by metallic deoxidizers
•Deoxidation by vacuum
•Diffusion deoxidation
Deoxidation by metallic deoxidizers
This is the most popular deoxidation method. It uses elements forming strong
and stable oxides. Manganese (Mn), Silicon (Si), Aluminum (Al), Cerium (Ce),
Calcium (Ca) are commonly used as deoxidizers.
Deoxidation by an element (D) may be presented by the reaction:
n[D] + k[O] = (DnOk)
The equilibrium constant KD-O of the reaction is:
KD-O = aox/(hDn x hOk)
or
hDn x hOk = 1/log KD-O = log D
Deoxidation by metallic deoxidizers
where:
aox - activity of the oxide (DnOk) in the resulted non-metallic inclusion;
hD - activity of the deoxidizer in liquid steel;
hO - activity of oxygen in liquid steel.
The equilibrium constant of a deoxidation reaction is determined by the steel temperature:
log KD = -AD/T + BD
where:
AD, BD - characteristic parameters determined for the particular deoxidizer D; T - steel temperature,
(K), KD = Deoxidation constant
Deoxidation by metallic deoxidizers
Deoxidant Deoxidation product Concentration of KD (1600⸰C)
(D) Deoxidizer
Al Al2O3 >10-5 2.51 × 10-14
C CO 2.39× 10-3
FeCr2O4 <3 2.39× 10-6
Cr
Cr2O3 3.0-8.0 8.72× 10-5
Cr3O4 >8 2.23× 10-5
Mn FeO-MnO (l) <0.2 0.3102
FeO-MnO (s) >0.2 0.19
Si SiO2 2.11× 10-5
Ca CaO 9.84× 10-11
A. Ghosh, A. Chatterjee, Ironmaking and Steelmaking, PHI learning, 2008
Deoxidation by metallic deoxidizers
Wt.% of O in equilibrium with 0.1 % D [1600 °C]
Deoxidiz Wt.% of O
er
Mn 0.413
Si 0.0145
Al 1.35 × 10-3
Ca 9.84 × 10-10
Ca is strongest and Mn is weakest deoxidizer
A. Ghosh, A. Chatterjee, Ironmaking and Steelmaking, PHI learning,
2008
Kinetics of deoxidation
Lecture 24: Principles of Deoxidation, NPTEL
A. Ghosh: Principles of secondary processing and casting of steel, (1990)
Kinetics of deoxidation
Particle radius > 10-4 cm, velocity for flotation is higher enough for
separation as compared to finer particles.
Moelwyn Hughes : Physical Chemistry, (1961), 1212, Pergamon Press,
New York.
Deoxidation by metallic deoxidizers
According to the degree of deoxidation Carbon steels may be subdivided
into three groups:
Killed steels - completely deoxidized steels, solidification of which does
not cause formation of carbon monoxide (CO). Ingots and castings of killed
steel have homogeneous structure and no gas porosity.
•Semi-killed steels - incompletely deoxidized steels containing some
amount of excess oxygen, which forms carbon monoxide during last
stages of solidification.
Deoxidation by metallic deoxidizers
• Rimmed steels - partially deoxidized or non-deoxidized
low carbon steels evolving sufficient amount of carbon
monoxide during solidification. Ingots of rimmed steels
are characterized by good surface quality and
considerable quantity of porosities.
Deoxidation by metallic deoxidizers
Volumetric contraction
during solidification
Steel Deoxidation: Part One, Total Materia, 2008
Deoxidation by metallic deoxidizers
Killed Steel Semi-killed Steel Rimmed Steel
%C : > 0.30% %C : 0.15-0.30% %C ≤ 0.15%
Forging, Carburizing Structural steel, Plate Steel sheet, flat
steel manufacturing product fabrication
Capped Steel :
1.Category of rimmed steel.
2.% C : ~ 0.15%.
3.Capping of the ingot.
4.Less gas evolution than rimmed steel.
5.Less gas voids.
6.Cast Iron cap is provided at mould top.
7.Used for manufacturing wires, bars, flat products.
Deoxidation in vacuum
Method of deoxidation in vacuum utilizes carbon dissolved in steel as the deoxidizer according
to the equation:
[C] + [O] = {CO}
where:
[C] and [O] - carbon and oxygen dissolved in liquid steel; {CO} - gaseous carbon monoxide.
The equilibrium constant of this chemical reaction is expressed as follows:
KCO = pCO/(aC x aO)
Deoxidation in vacuum
where:
pCO - partial pressure of carbon monoxide in the atmosphere; aC and aO - activities of
carbon and oxygen in liquid steel.
Temperature dependence of KCO is insufficient.
For approximate calculations the following equation may be used:
log KCO =(1160/T)+2.003
T = 1873 K
[C]*[O] = 0.002386*pCO at 1600°C
Steelmaking Data Sourcebook, in: The Japan Society for Promotion of Science, The 19th Committee
on Steelmaking, Gordon and Breach Science Publishers, Montreux, 1988
Deoxidation in vacuum
• Vacuum treatment of molten steel decreases the partial pressure of CO,
which results in shifting equilibrium of the reaction of carbon oxidation.
• Bubbles of carbon monoxide form in the liquid steel, float up and then they
are removed by the vacuum system.
In addition to deoxidation vacuum treatment helps to
remove Hydrogen dissolved in liquid steel. Hydrogen diffuses into the CO
bubbles and the gas is then evacuated by the vacuum pump.
Deoxidation in vacuum
• Vacuum deoxidation is used mainly in Ladle refining.
• Steels deoxidized in vacuum are characterized by homogeneous structure,
low content of non-metallic inclusions and low gas porosity.
• Vacuum treatment is used for manufacturing large steel ingots, rails, ball
bearings and other high quality steels.
Diffusion deoxidation
Oxygen dissolves in both steel and slag. Equilibrium between the two systems may be
presented by the equation:
[O] = (O)
The equilibrium constant of the reaction:
KFeO = a[O]/a(O) or a[O] = KFeO*a(O)
Thus reduction of the oxygen activity (concentration) in steel may be achieved by
decreasing the oxygen activity in the slag. Therefore deoxidation of slag is required.
Diffusion deoxidation
Carbon (coke), silicon, aluminum and other elements are used for
slag deoxidation.
Since deoxidizers in the diffusion method are not introduced directly
into the steel melt, oxide non-metallic inclusions do not form.
Diffusion deoxidation allows to produce steel less contaminated by
non-metallic inclusions.
https://www.ispatguru.com/
Environment/slag
Slag/liquid steel
Liquid steel/slag
Bulk steel
deoxidation
Z. Deng and M. Zhu, Deoxidation Mechanism of Al-Killed Steel during Industria
Refining Process, ISIJ International, 54 (7) (2014) 1498–1506.
Z. Deng and M. Zhu, Deoxidation Mechanism of Al-Killed Steel during Industria
Refining Process, ISIJ International, 54 (7) (2014) 1498–1506.
